JPRS ID: 8753 USSR REPORT CHEMISTRY

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• Content Type: REPORTS

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6 NOVEMBER i9T9 CFOUO i179) i OF i
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JPRS L/8753
6 November 197~
USSR Re ort
p
CHEMI~TRY
CFOUO 1 /79)
F~IS FOREIGN BROADCAST INFORMATION SERVICE
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NOTE
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- given by source.
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,
NOTICE
Beginning with this issue, this report will contain addi-
tional mater'ial under the new subject category "Chemical
Industry and Related Equipment" which heretofore had been
. included in the JPRS serial, "USSR REPORT: INDUSTRIAL -
AFFAIRS."
We expect the periodicity of this report to increase s~ib-
stantially with the addition of this material.
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- JPRS L/8753
6 November 1979
USSR REPORT
CHEMISTRY
(FOUO i/~9)
This serial publication contains articles, abstracts of articles and news
items from USSR scientific and technical journals on the specific subjects
_ reflected in the table of contents.
~ Photoduplications of foreign-language sources may be obtained from the
_ P'hotoduplication Service, Library of Congress, Washington, D. C. 20540.
Requests should provide adequate identification both as to the source and '
- the individual article(s) desired. _
CONTENTS PAGE
~
. BUILDING MATERIAL6
~ -
llth Mendeleyev Congress on General and Applied Chemistry--
, Plenary Reports .
(V. I. Dobuzhinskiy; XI MIIVDELEYEVSKIY S"EZD PO
OBSHCHEY I PRIKLADNOY KHIMII: FI.,IIVARNYYE DOIff~4DY,
1977) 1.
Norms for Consumption of Materials and Parts Per Million
Rubles Worth of Es~;imated Construction and Installation
Work: Chemical and Petrochemical Industries
(NOF.~~iY RASHIiODA MATERIALOV I IZDELIY NA 1 MLN. -
RUB. SMETNOY STOIMOSTI STROITEL'NO-MONTAZHNYKH
RABOT--KHIMLCHESKAYA PROMYSFII~ENNOST',
NEFTEKHIMICHESKAYA PROMYSHI~EPINOST', 1979) 12
CHENIICAL IlVDUSTRY
- The PTG.tional Chemica,l Industry at the End of the Tenth
Five-Year Plan -
(T. I. Sin,yukova; KEiIb~CHESKAYA INDUSTRIYA STRANY
V KONTSE DESYATOY PYATILETKI, 1979) 14
. - a- [III - USSR - 21B S&T FOUOJ
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CONTIlVTS (Continued) p~$e
FOOD TECHNOLOGY
Collected Papers on Protein and Peptide Chemistry
(Kon:~tsntin Titovich Poroshin; IZBRANNYYE TRUDY
V OBLASTI KHIMII BELKA I PEPTIDOV, 1977) 1.F
FUEL CELLS
Regenerative Fuel Elements
_ (L. I. Kvasnikov, R. G. Tazetdinov; REGENERATI~TPJYYE
'~OPLNNYYE ELF~rY, 1978) 17
ORGANOPHOSPHORUS COMPOUNDS _
Stereospecificity of Inter~,ction of Chair Form of
Thiopyrophosphonates With Ace~tylcholine Esterase
(I. A. Nuretdinov, et al.; IZVESTIYA AKADEMII NAUK
SSSR--SERIYA KHIMCCHESKAYA, 1979) 20
PETROLEUM PROCESSING 1^ECHNOLOGY -
llth Mendeleyev Congress on General an d Applied Chemistry--
Plenary Reports
(V S. Fedorov; XI M~IVDELEYEVSKIY S"EZD PO
UBSHCHEY I PRIKI,ADNOY HIiIML2; PLENARNYYE DOKI~ADY,
1977) 22
PHOSPHORUS INDUSIRY
lith Mendeleyev Congress on C,eneral and Ap~lied Chemistry--
Plenary Reports
(S. I. Vol'f~ovich; XI MENDELE7EVSKIY S"EZD PO
OBSHCHEY I PRIKLAIAVOY KHIMII: PLIIVARNYYE DOKLADY, _
1977) 34
RADIATION CHEMLSTRY
Chemical Protection of Organic Systems Against Zonizing
Radiat ion -
(Mikhail Fedorovich Romantsev; KHIMICHESKAYA
ZASHCHITA ORGANIG`~iESKIKH SIS~'EM OT IOIVIZIRUYUSHCHEGO
IzLUCI~NIYA, 1978) 56 ~
PLANT SAFEr.CY
Safety Rules for Plants Producing Organic Chemical Reagents
(Yu. N. Slesarev, et al.; PRAVII,A BEZOPASNOSTI DLYA ~
PROIZVODSTV ORGANICHESKIKH KHIMICHEgKIKH gEAHI'1VOV,
1978) 58
- b -
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CONTENTS (Continued) pa,ge
WATER TREA^1MENT
Water Treatment by Reverse Osmosis and Ultrafiltration
(A~ A. Yasminov, et al.; QBRABOTKA VODY OBRATNOM
OSMOSOM I ITL'TRAFIL'TRATSIYEY, 1978) 60
- c - �
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BUILDIIVG MATERIALS
11T:i MENDELEYEV CONGRESS ON GENERAL AND APPLIED CHEMISTRY--PLENARY REPORTS
Moscow XI MENDELEYEVSKIY S"EZD PO OBSHCHEY I PRIKLADNOY KHIMII: PLENARNYYE
- DOKLADY in Russian 1977 signed to press 30 May 77 pp 128-138
[Article by V. I. Dob uzhinskiy: "Scientific-Technical Problems of the -
Development of the Building Materials Industry"]
[Text] Developing and improving the building materials industry--the
_ mate rial-technical base of construction--is of decisive importance for the
fulfillment of the vast program of construction work in the USSR. -
The production of building materials, parts and structures is concentrated
in varioiis sectors of the industry. The main building materials are: -
cement and other binders, wall materials, asbestos-cement items, building
ceramics, heat- and soun d-proofing materials, construction and industrial
glass, etc. They are produced mainly at the enterprises of the system of
the USSR Miriistry of Construction Materials Industry.
The building maCerials industry of the Soviet Union, with respect to the
absolute production volume of basic building materials (cement, window glass,
asbestos cement items, precast ~einforced concrete) has surpassed the largest
, capitalist countries; 2.4 million people are working in it. Industrial-
production fixed capital constitutes about 21 billion rubles.
Silicate building materials--cement, glass, reinforced concrete, asbestos
cement, clay and silica brick, etc.--predominate in our country. The pro-
portion of the output of the chemical industry and metallurgy is small in
the overall balance of physical construction resources, but it is growing
and will con~tinue to grow in the future through increasing the production
of building materials on the basis of polymers, ecnnomical shapes of rolled
ferrous metals, aluminum, and wooden glued structures.
The following tasks are set for the present and the next five-year plan.
Expanding the output of new building materials.
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Develo~ing ac accelerated rates the production of cement, using the dry
method, on the basis of the newest industrial processes. Increasing the
output of high-grade and special types of cement--quick-hardening, pre-
stressed and decorative.
Expanding the assortment and increasing the production of glass, including
_ measured window, plate, heat-reflecting and architectural-construction glass.
Introducing highly productive processes of two-stage forming of strips of
glass and high-temperature founding of glass masses.
Increasing the production of large structures and individual asbestos cement
items, as well as efficient heat- and sound-insulating materials. ~
Expanding the assortment and raising the quality of finishing and facing
materials. Increasing the output of ceramic tiles, porous aggregates,
items made of porous concretes, and also local building materials. Making
broader use in the production of building materials of raw materials
obtained as hy-products and industrial wastes. Mechanizing and ~utomating
the proc~uction of wall materials.
The collectives of the enterprises and organizations of the ministry have
fulfilled ahead of schedule the assignments for the Ninth Five-Year Plan
_ for ~ ale of output, growth of labor productivity and profits.
In the five years the total volume of industrial production rose by 42.2
percent. Some 507 million r.ubles worth of products above the plan were ~
' sold: Labor productivity increased by 34.9 percent, and profits--by
81.7 percent, which exceeds the assignments of the five-year plan. About
nine-ten ths of the increase in output was obtained through raising labor ~
productivity.
Implementing measures specified by the program for technical reequipment in
the Ninth Five-Year Plan made it possible to increase the output of products
at existing plants with lower capital investments, as compared with new
construction.
The scientists play a large role in the progress achieved by the building
materials industry. The Central Committee of the Commvnist Party of the
Soviet Union and the Soviet Government, in showi.ng concern at all stages of
socialist construction for outstripping development rates for the building
materials industry, at the same time took measures to establish research
and planning institutes, develop sectorial science and organize the training
. of skilled scientific and engineering personnel at the key chemical and
technological, p.olytechnical and construction VUZ's in the country.
A considerable amount of scientific work is now being done at 33 scientific
research institutes of the ministry, from research studies to putting the
achievements into production. In collaboration with the workers of plants
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and planning and tune-up organizations, the collectives of the sectorial
scientific research institutes are successfully solving specific prohlems
of technical progress in industry. The ties are being made stronger
between the sectors of science and the research organizations of related
sectnrs and th e scien tists of WZ's and institutes of the USSR Academy of
_ Sciences. The USSR Ministry of the Construction Materials Industry and the
USSR Ministry of Higher and Secondary Specialized Education have worked out
a plan in accordance with which 110 scientific research projects are now
being carried out.
Prominent scientists, well-known far beyond the borders of the Soviet Union,
have laid the basis for domestic science of silicates. The fundamental
research of A. A. Baykov, D. S. Belyankin, P. P. Budnikov, I. V.
_ Grebenshchikov, N. N. Kachalov, I. I. Kitaygorodskiy, N. A. Toropov and
~other eminent scientists and teachers has made a great contribution to
world science.
We will discuss some of the most important developments of domestic science
- with respect to silicates, introduced into production, and the tasks facing
Lndividual se ctors of the building materials industry, the fulfilling of
_ which requires that large-scale scientific research be performed.
~ ihe science of cement and the technique of cement production were enriched
� by the research and development of a complete industrial p rocess with wide-
- scale use of the wastes of other sectors of industry.
The production ef slag Portland cement was organized for the first time on
a large scale using acid blast-furnace slags. A broad range of special new
types of cement was created. The prestige of Soviet scientists and produc-
tion workers in this field was confirmed at the Sixth International Congress
on Cement Chemistry held in Moscow in September 1974.
Theoretical work on the application of the general laws of heat transfer
_ and combustion to thermal processes in rotary furnaces, an d studies on the
movement of material and formation of clinker made it possible to establish
a scientific method of calculating furnaces and their structures:
Large-scale research was performed in the field of the theory of clinker-
formation and hydration.
Considerable progress was achieved in accelerating cement setting by chang-
ing the composition and structure of the clinker of fine grist and intro-
ducing additiues--setting accelerants--which made it possible to create a
whole group bf special cements, including fast-setting and high-strength
cements. It should be noted that the product lisc of cements put out by
industry satisfies the most varied demands of construction.
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The first automated production control system using the Tsement-1 electronic -
, computer was developed and put into operation at the Sebryakovskiy Cement
Flant.
High-power main lines for producing cement by the advanced "dry" mettiod,
with furnaces with a capacity of 3,000 tons a day were constructed and put
into operation. Highly produr_tive self-pulverizing mills and slag dryers,
new in principle, are being successfully put into operation, and have five
times the productivity of those formerly used.
Right now the scientific research organizations of the cement industry are
working on the design of a new industrial process for obtaining clinker at
a low temperature, are developing a domestic design for decarbonization
reactors which make possible a 1.5-2-fold increase in the capacity of the
rotary furnaces with cyclone heat exchangers, and are studying the problems
- of intensifying tlie work of the furnaces.
Extensive new studies will be made in the field of creating high-strength
cements that possess unified industrial-construction properties.
The study of concrete and reinforced concrete developed by Soviet researchers
has gai.ned worldwide r.enown.
Fundamental research has been performed on hydration and set:.ing of binders
and the kinetics of concrete setting under conditions of thermal processing,
serving as the basis for developing an industrial process for reinforced -
concrete items.
Theoretical and experimental work on studying the role of the cement block
and its effect on the structure and physical-chemical properties of con-
cretes made it possible to design an efficient production process based on
precise calculation c~f the relations of the basic properties of the con-
cretes (including high-strength), mixtures snd set articles.
Concrete will become more resistant to chemicals and freezing, its tensile
strenQth will be increased and its setting time reduced. The use of
additives that improve the properties ~f the concrete will be expanded. '
A concrete serength of 1400 kg/cm2 will become common, and for special
p urposes concretes will be developed that have even greater strength.
Truly promising from th e technical standpoint is reinforcing cement with
- high-strength and chemieally resistant crystalline filaments made of
silicates, which ti~ill increase the strength 5-10-fold with a considerable
reduction in the weight. Formulas for cement-resistant fiber glass are
be~ng developed. Obviously, in the near future the industrial output of
concrete based on glass-cement will be developed.
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The glass ~ndustry is characterized hy the large scale of scientific
research and planning-design work. At the Scientific Research Institute
of Glass and its branches, the Institute of Silicate Chemistry of the USSR
Academy of Sciences, the Institute uf Glass Fiber and Glass Plastics, the
Institute of Quartz Glass, ut the departments of the Moscow Institute of
- ChemIcal Technology imeni D. I. Mendeleyev and other chemical-technolafiical
Vif%'s, in scientific organizations of the Academies of Sciences of the
Uk raine, Belorussia, Georgia, Armenia, Lithuania, at the scientific
research institute of the Konstantinovskiy Avtosteklo Plant, and in the
laboratories of major glass plants, research is being performed on all
~ types of building, commercial and packaging glass, glassware, devitrified
glass, slag devitrified glass and quartz glass.
Soviet scientists have enriched world science with respect to glass through
their work on creating glass resistant to chemically corrosive reagents,
- with high and low electric resistance, with various softening points,
increased mechanical strength, glass that permits rays of a certain wave
length to pass through, with given values of light refraction, dispersion
and coefficient of thermal expansion.
Soviet scientists and engineers have developed control of the crystalliza-
tion of glass on a product ion scale, which made it possible to obtain
' materials with given chemical and physical properties--devitrified glass
and slag devitrified glass, which are already being widely used in industry
an~ construction due to their strength indicators, chemical resistance and
high aging resistance.
A great deal of work has been done to intensify g~ass-making processes.
Methods of continuous founding and production of items made f rom crystal
and colored glass, decorated with rare-earth elements, permitting the
production cycle to be reduced 10-fold and the fuel consumption cut in
- half, have been designed and put into widescale production. The puoduction
process for plate glass using the method of two-stage forming on a band of
molten metal has come into wide use. The introduction of the new method
increased labor productivity 3.25-fold, made it possible to reduce the
production cost by 68 percent and raised the capacity of the equipment
2.3-fold, with a simultaneous reduction in capital expenditurese As a
result ~f replacing ohsolete equipment with new equipment, a production
area equal to 16,000 square meters was freed. The introduction of the
- first iine made it possib le to obtain a yearly economic saving equal to
21.4 million rubles.
Tt?e research outlined in th e glas~ industry should lead to profound quali-
ta tive changes in the very nature of the production.
Work will continue on solving the most important problems involved in
intensifying glass production, with widescale introduction of automation,
- with the design of new structures for furnaces and glass-making machines
~ an d the design and introduction of new formulas for glass and methods for
their thermal and industrial processing.
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A great deal of attention will be paid to the problem of strengthening
glass. It i:~ already possible to obtain glass fibers with extremely high
strength under lahoratory cond~tions. In practical work, however, glass
stren~th proves to he considerably lower because of microfissures on the
surface which are increased when exposed to the environment. Research is
- being performed on strengthening glass by applying metal oxides to the
surfar.e layer before the glass is annealed, and methods are being developed
for using an ion-exchange process, as well as methods of strengthening on
the basis of combining hardening, etching and film coatings. Research is
to be done on intensifyir.g the strengthening processes in supersonic and
_ electric fields.
The result of this research is obtaining and industrial developing of pro-
duction of new types of glass that will be 10-fold stronger, and should
approach quartz with respect to the expansion coefficient and thermal
properties. Items made from this glass will be included in the composition
of engineering structures and building structures.
The USSR asbestos cement industry, the largest in the world, deve3oped on
the basis of broadly explored scien ti�ic research and planning-design work.
A consideratale amotmt af varied industrial equipment and mechanized flow
lines has been designed and manufactured, and this made it possible to
or~anize the production of discharge pipes withstanding a pressure of up to
15 atmospheres and large ashestos cement slabs. A thorough study was made
of the fundamentals of the effect of the chemical-mineralogical composition
snd dispersab ility of cement on the production process for asbestos cement.
A great deal of work has been done on the use of short-fibered types of
_ asbestos from various deposits.
In this field, enlisbing modern physical chemistry methods, the nature of
- the aggregative cohesiveness of as~estos fibers will be studied and efficient
methods and equipment will be worked out to fluff up the asbestos. Methods
will be devised to regulate the surf ace properties of the asbestos that will
enst~re the prcducibility of large asbestos cement slabs an d long�discharge
pipes.
Methods new in principle are being developed for making asbestos cement
items using the principles of extrusion and rolling.
Research will be carried out on strengthening items by introducing polymers
into the con~position, as well as th rough partial replacement of the asbestos
with mineral fibers.
~ The ceramics production process has been radically refdrmed. In the field
of ceramics technology classic works of both Russian and foreign scientists
- of the nineteenth. and first half of the twentieth century are widely known.
The achievements of Soviet science in the field of developing new production
processes for ceramic tiles are particularly undisputed. This was preceded
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by tl~e study of fundamental theoretical pra'~lems of the physical chemistry
c~f silicates and ceramic thermotechnics.
The introduction of scientifically substantiated high-speed systems of
drying and annealing ceramic tiles, combined with design developments, made
it possible to design mechanized flow lines with spray dryers and glazing-
drying conveyo rs and slot roller-hearth furnaces surpassing all the processes
kno~an in other countrie.s with respect to their technical-econo mic indicators. -
Suffice to say that the process makes it possible to reduce the production
cycle from 65 to 72 hours t~ 1 hour.
Now the problem is posed of increasing the impact strength of ceramic items
through reinfo rcement and selecting the cooling and annealing systems. The
possibility of future development of plastic ceramic building materials will
con~titute serious competition for metal and concrete. Work is to be done
to organize th e output of thinner tiles, using the wastes from other sectors
of industry.
Technical progress in the soft roofing materials and waterproofing materials
_ industry was implemented mainly through the construction of large-scale new
enterprises provided with modern i.ndustrial equipment. Work is to be done
to develop the pruduction of various types of roofing and waterproofing
materials based on glass, to use reinforcement of ruberoid with polymeric
or mineral fibers to increase its life, to use copolymers of bitumen, to
develop new, nonrolled roofing materials (compositions) based on latex,
polyurethane foam, etc. and to increase the strength of roofing materials
for repeated bending and tensile rupture. The production of ruberoid with
a flexible covering layer, perforated ruberoid and foam waterproofing
materials is b eing organized on an industrial scale.
The prestige of Soviet scientists in the study, development and widescale
use of items made from silicate concretes with autoclave setting is widely
known.
Soviet scientists have developed the theory of.hydrothermal setting of cal-
careous-siliceous materials, and have studied the conditions for the forma-
tion of calcium hydrosilicates in the process oF autoclave processing.
A new sector being developed--the production of large items made of auto-
clave setting concretes--is a great technical achievement for scientists
and experience d practical workers in our country. A new production process
for items made of porous concretes, using vib ration, is now being worked
out and put into operation.
= Theoretical studies and experimental-industrial work on silicate concretes
~ with autoclave setting will be thoroughly developed in the future; par-
tict~lar importance is attributed to the nature of the processes of the
~ reaction of lime and siliceous components an~ to the study of the effect of
new cementing formations on the properties of large items, which will make
it possible in practical work to ensure the obtaining of a product with
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properties assigned in advance. Highly productive, fiilly mechanized and _
automated industrial lines will be designed and put into operation to manu- ~
facture enclosing and supporting structures, completely piant finished,
made of poroi~s and dense silicate concretes with "room-size" measurements.
- Systematic scientific-experimental research has been developed at a number
of scientific researclt institutes of porous aggregates and li~htweight _
concretes based on them. Scientific fundamentals have been worked out for
the production process for claydite, aggloporite, slag pumice, per~ite and
schungizite. Work is being done on comprehensive use of the ashes from�.
thermal electric power stations and, in particular, obtaining cinder agglo- -
porite gravel on their basis. A production process is being worked out for
annealing claydite in a suspended state and from the fusion of silicate
materials, as well as a process for cinder gravel in aggregates of the
boiling layer.
A number of ineasures have been implemented in the wall materials industry
to intensify the industrial processes and mechanize p roduction.
There are plans for a fun damental improvement in the industrial process and
- the designing of automated plants, provided with highly productive equipment
and automated control systems, and supervision and optimization of the indus-
trial processes for the production of ceramic caall materials and silicate
brick, ensi~ring an increasE in labor productivity by 6-10-fold and a sharp
improvement in the quality of the output.
Scientific research work to impr.ove the production process and develop new
types of efficient insulating materials has been developed on a broad scale.
Along with the development of production of items with increased rigidity
and solidity made of natural raw mate~ials, the thermal-insulation and
_ sound-insulation fiberglass materials industry will be considerably developed.
_ There have been considerable ch anges in the production structure of mineral-
ized items. The relative proportion of commercial cotton wool has been ~
suhstantially reduced and the proportion of items made from it has been _
� correspondingly increased [as published]. The production of efficient -
mineralized items is being developed. Mass production of acoustic tiles
made of the Silakpor brand porous concrete has been organized.
The output of tested mineralized items makes it possible to expand the use
_ of rhe existing lightweight structures and to develop new typeG of efficient
structural members, as for example, triple-layer panels for apartment -
houses and industrial buildings, lighter-weight brick walls, etc. The r.e-
placement of claydite concrete (also a thermal-insulating�material) wicth
mineral slabs in the multilayer panels of exterior walls makes it possible
to reduce the weight of 1 square meter of panel 5-fold and to reduce the
total cost of the construction of the facilities by 20 perr_ent.
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I
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Extremely important theoretical research, experimental and industrial-test
work is tm be done, directed toward developing a fiber-f orming unit that
ensures obtaining nonreguline mineral fiber with complete processing of
the melt, toward developing aii automatic all-purpose smelting unit using
g~~s or liquid fuel, ensuring the production of a silicate f usion from vari-
- ous types of raw material and toward developing automated conveyor lines
for the production of building structures, fully plant finished, on the
basis of mineralized items with increased rigidity.
The youngest science is the science of polymer building materials. The
VNIIstroypolimer Scientific Research Institute, specialized in this field,
in conjunction with a number of scientific organizations of the chemical and
petrochemical industry, worked out a production process and certain types of
equipment for producing various rolled materials, tiles and mastics, using
polyvinyl chloride materials, without a base, as well as using a fabric and
thermal-insulating basis. Efficient constru~tion designs were developed for _
insulating buildings on the basis of polymers and synthetic resins, and gas-
filled plastics were manufactured on the basis of them. Polyvinyl acetate
mastics and polymer-cement and plastic-concrete formu]_as were developed.
A considerable amount of work is being done on expanding the raw material
. resources for polymer building materials from the wastes of the petro-
- chemical industry. ,
Developing building materials from plastics will proceed along the lines
of increasing their structural strength, life and fire-resistance. A wide
range of decorative thermal- and sound-insulating materials, items for
sanitation equipment, structures and materials for walls and floors will
_ be produced on the basis of plastics and synthetic resins.
' ividescale use of polyurethane and polyvinyl chloride will make it possible
to produce slabs on the basis of flat and embossed asbestos cement sheets,
with a rigid mineral and gypsum base, and reinforced fiber glass (trimming
material,.imita.ting natural stone, wood, etc.).
Varying types of laminated structures made from asbestos cement sheets, _
panels made from lightweight concretes, plastoconcretes, breccia, mosaic
tiles from marble wastes, granite, etc. will be produced on the basis of -
resins of the epoxy type.
The use of resins of the melamine-formaldehyde type and various copolymers
~ and latexes will make it possible to increase substantially, 2-2.5-fold,
the resistance and life of soft roofing materials. -
The fire-resistance of plastics will obviously be increased hy introducing
components that are combustion inh.ibitors. "
It has now been established that introducing polymers into various building
materials gives a fundamental improvement in their properties. On this
basis new organo-mineral materials may be obtained in which the negative
~ properties of polymers are neutralized.
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It is very efficient to inject polymers into the pores and capillaries of -
already finished building materials (concrete~ ashestos cement, cer.amics),
and impregnating concrete with monomers, with subsequent special processin~,
- incrcas~s thc~ crushing stren~th from 200-30~ tc, 1200-1500 k~s/cm2, tht.
strength of the clay brick reaches 1000 kgs/cm2 and the transverse strength
of asbestos cement--500 kgs/cm2, This new production process will be widely ~
developed'.
Studies directed toward nature protection and the optimum use of natural
_ resources, includin g the purification of sewage and introduction of
- advanced systems in water recycling, occupy an important place in the _
scientific research program. Theoretical studies and experimental work on
drawing industrial wastes and by-products from other sectors of the national
economy into the production of building materials are being expanded and -
intensified.
Using finely pulverized raw material masses in maximally rigid mixtures,
with additives of surfactants, using vibration mixing, may fundamentally
change the production process for a number of building materials.
In the future, extensive new studies will be made to develop the theory of
processes of forming hardness and thermal transformations in materials -
, created on the basis of phosphate binders.
The problem of obtaining materials with assigned properties, when using
microadditives to raw material or a finished product, and with a directed
chan~e in the crystalline structures~ through the conditions for cooling
the tusions or agglomerates is extremely interesting.
The tremendous progress made in chemistry has made it possible to reevaluate
the long known fact of the presence of polymers among inorganic compounds.
In addition to silica, polymeric compounds are formed by.aluminum, phos-
phorus, sultur and other elements. -
Building materials such as glass, ceramics and cement have inorganic poly-
mers as cheir basis. Glass ceramic materials--devitrified glass--a typical
polymerical material obtained on the basis of silica--may serve as an
example.
We expect that, as the result of the work of scientists in the field of
� study of the structure of glass, ceramics, cement and silicate concrete,
compoi.m ds will be obtained that make possible a multiple increase in the
strengtfi, chemical resistance and other properties of these materials.
The workers in the USSR building materials industry will constantly put
into effect the new ideas based on tfie achievements of science and tech-
- nolog,y of all sectors of tfie national economy and fundamental research in
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chemistry and other sciences, and will develop processes that are new in
- principle, thus solving th e extremely important problem posed for the Soviet
people by the Central Committee of the Communist Party of the Soviet Union
of accelerating the rates of technical progress in all the sectors of the
country's national economy.
COPYRIGHT: Izdatel'stvo "Nauka", 1977
12151 -
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BUILDING MATERIALS
NORMS FOR CONSUMPTION OF MATERIALS AND PARTS PER MILLION RUBLES WORTH OF
ESTIMATED CONSTRUCTION AND INSTALLATION WORK: CHEMICAL AND PETROCHEMICAL
INDUSTRIES
Moscow NORMY RASKHODA MATERIALOV I IZDELIY NA 1 MLN. RUB. SMETNOY STOIMOSTI
STROITEL'NO-MONTAZHNYKH RABOT--KHIMICHESKAYA PROMYSHLENNOST', NEFTEKHIMICHES-
KAYA PROMYSHLENNOST' in Russian 1979 signed to press 20 Nov 78 pp 4, 47
[Annotation and table of contents from book issued by Gosstroy and Gosplan
USSR; Stroyizdat, 19,000 copies, 27 pp]
[TextJ These norms were developed by planning organizations of the USSR Min-
i.stry of the Chemical Industry and Ministry of the Petroleum Refining Industry
together with the Scientific Research Instit~ite of Construction Economics,
Gosstroy USSR, on the basis of the most economical current designa and with
reference to the requirements of the "Technical Regulations for Economical
Use of Main Construction Materials."
- The following planning organizations took part in developing the norms:
Giprokhim [chemical plant planning institute], Goskhimproyekt [institute for
_ planning chemical enterprise facilities], Gosgorkhimproyekt [mining and chemi-
cal enterprise planning institute], Lengorkhimproyekt [Leningrad mining and
chemical enterprise planning institute], GIAP [nitrogen and synthetics indus-
tries planning institute], Promstroyproyekt [general construction and sanitary
engineering planning institute] (Moscow, Kiev), Giproplast [plastics and semi-
finished products enterprise planning institute], Giproiv [synthetic-fiber
enterprise planning institute], Giproorkhim [organic intermediates, dyestuffs
and reagents enterprise planning institute], GIPI-LKP [paint and varnish in-
dustry planning institute] (Moscow, Leningrad), Gipropolimer [plastics indus-
try planning institute], Giprokislorod [oxygen industry planning institute],
gi.prokhimreaktiv [chemical reagents enterprise planning institute]. (Donetsk,
K1-,ar'kov), Giprokauchuk [synthetic rubber industry planning institute] (Moscow),
Rezinoproyekt [rubber industry planning institute] (Moscow, Yaroslavl') and
GPI Santekhproyekt [sanitary engineering planning institute].
/ -
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Contents pgge
General S
Norms for Consumption of Materials and Parte per Million Rubles
Worth of Estimated Construction and Inatallation Work 9
Steel, pipes for steel constructions, aluminum-alloy shaped
sections and sheets, and steel cables 9
' Cement, concrete and mortar, asbestos cement slabs 13
Lumber, fiberboard and particle board, plywood, parquet............ 17
Glass, linoleum, ceramic tile 21
Petroleum asphalt 25
Sanitary-engineering items, heating radiators and convectors,
ribbed pipe . 28
Roll materials, plastic materials, drying oils, white pigments,
cement-fibrolite and arbolite slabs, door units, flooring '
boards 32
Gypsum board, rock wool, rock-wool products, brick, limestone,
quarry stone, crushed stone, gravel and s2nd 36
Appendix 1. Territorial coefficients and calculated duration of
winter period and winter outdoor temperature 40
Appexdi.x 2. Coefficients for consumption norms for steel, cement
and other materials per million~rubles of estimated
construction and installation work to be done i~.z -
earthquake-prone regions 44
Appendix 3. Procedure for calculating corrections to the tiorms for
consumption of materials per million rubles worth of
estimated construction and installation work involving
construction during the winter 46
COPYRIGHT: Stroyizdat, 1979 .
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CHEMICAL INDUSTRY
THE NATTONAL CHEMICAL INDUSTRY AT THE END OF THE TEN'TH `r'IVE-YEAR PLAN
Moscow KHIMICHESKAYA INDUSTRIYA STRANY V KONTSE DESYATOY PYATILETKI in Russian _
1979 signed to press 24 May 79 pp 2, 62
[Annotation and table of contents from book by T. I. Sinyukova, Znaniye, 40,800
capies, 64 pp]
[Text] This booklet discusses the role of the chemical industr.y in the coun-
try's economy and its growing importance in the world economy. It is shown that
as a result of changes in the raw materials base, the product breakdown and its
utilization, and also of international division of labor, the increase of
foreign trade and other factors, a geography of the chemical industry has devel-
oped. The shifts in distribution of the sector over the last 20 years are eval-
uated. The nature of the sector during the lOth Five-Year Plan is analyzed, the.
development of the chemical industry in the individual union republics and regions
- of the European and Eastern economic zones is analyzed, and the largest current
construction projects are discussed.
This booklet is intended for a wide range of readers: scientists, propagandists,
teachers and students in upper classes.
Contents Page
Introduction 3
Chapter 1. The Chemical Industry: A Component of the Country's
National Economic Complex 5
1. The role of the chemical sector in the industry of the USSR...... 5
2. Extending the process of chemicalization 9
3. New trends in utilizing the country's resource potential in
the chemical industry 12
Chapter 2. Featuxes of the Current Geography of the USSR's Chemical
Industry 16
l. Development of the geography of the chemical industry in the
period 1958-1978 16
2.~ Integration processes and the distribution of the chemical
industry 22
3. The chemical industry and problems of environmental protection... 26
� 14
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Chapter 3. Ways of Developing and Locating the Chemical Industrv in
the Tenth Five-Year Plan 29 ~
1. Development.of the chemical industry under conditions of
intensifying production 29
2. Main features of the distribution of the chemical industry....... 35
3. The chemical industry in the union republics and economic regions 39 ~
Bibliography 61
8480
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FOOD TECHNOLOGY _
COLLECTED PAPERS ON PROTEIN AND PEPTIDE CHEMISTRY
Dushanbe IZBRANNYYE TRUDY V OBLASTI KHIMII BELKA I PEPTIDOV in Russian 1977,
signed to press 5 May 77 pp 2, 202 ~
[Annotation and table of contents from collection of papers by Konstantin
Titovich Poroshin, edited by.Academician (Tadzhik SSR) P. M. Solozhenkin;
' Izdatel'stvo "Donish", 600 copies, 203 pp]
[Text] These papers deal with a critical problem of modern bioorganic chemis-
try: thE chemistry of proteins and peptides, whose significance stems from
the variety of biological functions which they perform in the living or~anism. .
The book dealswith four main areas: investigation of the chemistry of proteins
and their hydrolysates; investigation of polycondensation of inethyl and ethyl
esters of amino acids and peptides; syntheses of activated esters of peptides,
and through them of regular polypeptides, and the use af these polypeptides to
simulate the structure of certain proteins; and the synthesis of alkaloid-
peptide compounds.
The book is intended for a wide range of specialists working in bioorganic
chemistry, natural products chemistry, microbiology, biophysics and biology.
Contents Page
Preface 3
Konstantin Titovich Poroshin: A Short Sketch of His Life and
Scientific Activity 5
Chapter 1. Investigation of the Structure of Protein [3 papers]........ 11
Chapter 2. Kinetics and Chemistry of the Condensation Reactions of
Alpha-Amino Acid Esters [8 papers] 41
Chapter 3. Regular Polypeptides Which Simulate the Structure of
Certain Proteins [18 papers] 93
Chapter 4. Alkaloid-Peptide Compounds [5 papers] 179
COPYRIGHT: Izdatel'stov "Donish",_1977
8480 ' - 16
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FUEL CELLS
REGENERATIVE FUEL ELEr1ENTS
Moscow REGENERATIVNYYE TOPLIVNYYE ELEMENTY in Russian 1978 signed to press
22 December 1977 pp 2, 167-168
[Annotation and table of contents from book by L. I. Kvasnikov and R. G.
Tazetdinov, Atomizdat, 1600 copies, 168 pp]
[Text] Regeneration of the working components of electrochemical energy con-
verters--fuel cells (TE)--makes it possible to create a new class of power pro- -
duction systems. The present book is devoted to analysis of the operating pro-
ceases in power production units using regenerative fuel cells (RTE). It pro-
vides a classification of the various types of regenerative fuel cells and
describes their main characteristics. Particular attention is devoted to sys-
tems with thermal regeneration of components: thermoelectrical convertera
(TEKhP) of fuel into electrical energy [thermocells]. The use of the tech-
niques of nonequilibrium thermodynamics makes it possible to obtain relatively
precis2 and at the same time general equations for the main parameters of the
operating process. The range of components and electrolytes for different
types of regenerative fuel cells is discussed, along with the kinetics of the
working processes in thermocells and power systems based on them.
The book is intended for physicists, electrochemists and engineers dealing with
problems of nonmechanical energy conversion and processes in high-temperature
fuel cells with fused-salt and solid electrolytes.
Contents Page
Foreword ~ 3 :
List of symbols not explained in the text 5
Chapter 1. Main Types of Regenerative Fuel Cells....... 7
1.1 The development of work with refenerative fuel cells............ 7
1.2 Main classifications of regenerative fuel cells 9
1.3 Thermoelectrochemical converters 11
1.4 Concentration rhermoelectrochemical converters [thermocells]
� with different-temperature electrodes 15
17
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1.5 Thermocells with chemical circuits 21
1.6 Thermocells with different-temperature electrodes 27
1.7 Regenerative fuel cells with photochemical, nuclear-chemical,
chemical and electrical regeneration of components 28
Chapter 2. Thermodynamic Four~dations of the Operating Processes of
Thermoelectrochemical Converters 35
2.1 Use of the main equations of the thermodynamics of irreversible
processes for analysis of thermocells 35
2.2 Voltage loads on thermocells 38
2.3 The EMF of thermocells 43
2.4 The thermal efficiency of thermocells 51
2.5 Concentration thermocells 52 -
2.6 Thermocells with chemical circuits 68
2.7 Thermocells with different-temperature electrodes 72
Chapter 3. Working Components and Electrolytes of Thermocells.......... 75
3.1 Main requirements for working components and electrolytes of
~ thermocells 75
3.2 Working components and electrolytes of concentration thermo-
cells and their properties 78
3.3 Working components and electrolytes of thermocells with
� chemical circuits 93 ~
3.4 Working components and electro.lytes of thermocells with
different-temperature electrodes 97
Chapter 4. Main Laws Governing Kinetic Processes in Thermocells....... 101
4.1 The generalized volt-ampere characteristic and power of
thermocells 101
4.2 The generalized formula for the efficiency of thermocells........ 104
4,3 Differential equations for energy and mass exchange in
thermocells 106
Chapter 5. Kinetics of Operating Processes in Some Types of Thermocells 109
5.1 Irreversible changes of electrochemical potential in con-
centration thermocells based on binary mixtures with
regeneration by volatilization of the active substance......... 109
5.2 Thermal losses and efficiency of concentration therniocells
based on binarq mixtures with regeneration by vaporization
o� the active substance 116
5.3 Calculation models of concentration thermocells based on
binary mixtures with regeneration by vaporization of the
active substance 120
~ 5.4 Characteristics of,the main types of concentration thermocells
using binary mixtures with regeneration b}~ vaporization of
the active substance 135
5.5 Analysis of irreversible losses in single-component
� concentration thermocells 138
5.6 Characteristics of the kinetics of concentration thermocells
using binary mixtures with regeneration by vaporization of
the second component 144
- 5.7 Kinetics of thermocells with chemical circuits 146
- 18
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Chapter 6. Cha-racteristics of Regenerative Fuel Cells with Photo-
chemical, Nuclear-Chemical, Chemical and Electrical
Regeneration 148
6.1 Characteristics of photoelectrochemical converters 148
6.2 Characteristics of nuclear-electrochemical converters............ 149
6.3 Characterics of chemoelectrochemical converters 151
6.4 Characteristics of electrical-electrochemical converters......... 152
Chapter 7. Power Installations Using T�hermocells 154
7.1 Types and structures of nuclear power units with thermocells..... 154
7.2 Power units based on cancentration thermocells with regenera-
tion by vaporization of second component 155
7.3 Power units based on concentration thermocells with regenera- ~
tion by vaporization of the active substance 156
7.4 Selection of parameters and optimization of nuclear power
units with thermocells 158
Bibliography 168
COPYRIGHT: Atomizdat, 1978
8480
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ORGANOPHOSPIi0RU5 COMPOUNDS
- trDC 541.515:542.91:547.;5~.42
S~EFEOSPECIFICITY OF INTERA.CTION OF CHAIR FORM OF THIOPYROPHOSPHONATES WITH
ACETYLCHOLINE ESTERASE
Moscow IZVESTIYA AKADEMII NAUK SSSR--SERIYA KHIMICHESKAYA in Russian No 5,
1979 Pp 116~+-116~ manuscript received 10 Jan 79
- [Article by I. A. Nuretdinov, N. A. Buina, Ye. V. Bayan dina, F. G. Sibgat-
ullina and D. N. Sadkova, Institute of Organic and Physical Chemistry
imeni A. Ye. Arbuzov, Kazan' Branch, USSR Acaderqy of Scienees]
[Text] ~e biological activity of orbanophosphorus insecticides is deter-
- mined, by and large, by their ability to inhibit vitally imF~rtant insect
enzymes. Problems of making organophosphorus insecticides more selective
axe important in pesticide chemistry today [1].
We found that optically active thiopyrophosphates--with the general formula
R(RO)P(S)~-P(0)(OR)R (I) (R = C2H5)--prepared by the reaction of and
(-)-0-ethylethylthiophosphonic acid with dicyclohe~ylcarbodiimide based on
[2]--exhibit stereospecificity upon reacting with acetylcholinesterase of
bull erythrocytes (ACE, creatine phospY:ate 3.1.1.7, Olayne Plant). Listed
in the table are some data on the properties of thiopyrophosphonates (I)
we prepared along with the constants of ACE inhibition with these compounds
~g _
- 40
coonNgo- ~ b~ I E�L~ ( d) x,c to-~,
a~ r~ xe ~~x0![, 96 d~ n
p [a] p O.~p a/Hxf~ ~MOni
t~RCaorw
f(ta) fl0,0 f,i467 4!690 -l9,53 +8,Q5 -90, -25 3.69
~h ~(Isj 87,5 i.i4i6 l,4690 YaqelY7 T-ii,75 0,~
l .e )
Determined by potentiometric titration according to [3]. Elemental
analysis is satisfactory. �
Key: a. Compound
b. Yield, percent e. Racemate
c. for initial acid f. Ia
d. liters/minute'mole~' g� Ib
h. Ic
" 20
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These data show that the configuration of the phosphorylating fragment of
thiopyrophosphates (I) strongly affects their reaction with ACE. The strong-
est inhibitor of ACE is (Ia), eight times stronger than the isomer (Ib); the
racemate (Ic) ranks intermediate between the optical isomers (Ia) and (Ib).
BIBLIOGRAPHY
1. Mastryul~ova, T. A., and Kabachnik, M. I. ZH. VSES. KHIM. 0-VA IM. D. I. ~
MENDELEYEVA, Vol 23, 1978, p 160.
_ 2. Mikolajczyk, NI. CHEM. BER., Vol 99, ~966, p 2083.
3. Yakovlev, V. A., and Volkova, R. I. DOKL. AN SSSR, Vol 128, 1959,
p 843.
[91-10123]
COPYRIGHT: Izdatel'stvo "Nauka", "Izvestiya AN SSSR, Seriya Khimicheslcaya",
1979 -
10123
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PFTR OLEUM PROC~SSING TECHNOLOGY
11TH MENDELEYEV CONGRESS ON GENERAL AND APPLIED CHEMISTRY--PLENARY REPORTS
Moscow XI MENDELEYEVSKIY S"EZD PO OBSHCHEY I PRIKLADNOY KHIMII: PLENARNYYE
DOKLADY in Russian 1977 signed to press 30 May 77 pp 70-81
_ [Article by V. S. Fedorov: "Basic Directions of Scientific-Technical
Progress in the USSR Petrochemical and Petroleum Refining Industry"]
[Text] An important event such as the llth Mendeleyev Congress on General
a.nd Applied Chemistry is an integral part of the nationwide struggle for
further development of our national economy. The successful completion of
the Ninth Five-Year Plan showed the greatness of the labor victory of the
Soviet people and the fruits of the gigantic political and organizational
work that is being daily and painstakingly performed by our Communist Party,
its Leninist Central Committee and the Politburo, headed by Comrade L. I.
Brezhnev, general secretary of the Central Committee.
~ The collectives of the enterprises and scientific research and planning and
design institutes of the petroleum refining and petrochemical industry, by
using fundamental research and theoretical work, in cooperation with *.he
institutes of the USSR Academy of Sciences, laboratories of the higher
schools and organizations of the All-Union Chemical Society imeni D. I.
Mendeleyev, have created the true prerequisites in industry for fulfillment
of the Directives of the 24th party congress and goals of the Ninth Five-
Year Plan.
About eight-tenths of the increase in production is ensured through raising
labor productivity, which has approximately doubled.
A substantial production and scientific-technical potential has been created
in the past years. New petroleum refineries and large petrochemical com-
plexes and plants for the production of tires and industrial rubber and
asbestos items have been put into operation.
The main portion of the growth of the industrial potential has been obtained
by increasin~ the capacities, modernizing and expanding existing production
facilities and enterprises:
22
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- Over nine-tenths of the entire increase in capacities for primary petroleum
refining has been obtained through this;
The entire increase in the production of rubber in volume will be abtained
only through increasing the capacity of and modernizing the existing plants;
The tire production capacities will increase 2.1-fold as against the last
five-year plan and over one-third of the increase will be obtained at the
_ existing plants.
Modernizing and expanding the existing plants made it possible to exceed
the assignments of the Ninth Five-Year Plan with respect to increase in
output for ea.ch ruble of capital investments by over 25 percent, and to
obtain an output ~rom petroleum refining, petrochemistry and shale refining
worth a total of over 8G0 mlllion rubles. In these results too we can see
the actual expression of the true force of scientific-technical progress.
The lOth Five-Year Plan, said L. I. Brezhnev, should above all be a five-
year plan of quality, a five-year plan of efficiency.
The main lever for successfully solving this fundamental problem of the new
five-year period has been and remains scientific-technical progress and its
even more intensive acceleration in all areas of petroleum refining and
petrochemistry. The growing demand for petroleum refining output requires
that petroleum refining be soundly increased in the forthcoming five-year
per.iod.
Just as in the years of the Ninth Five-Year Plan, this problem will be
solved through modernizing and expanding the existing plants. At the same
time, in order to bring the petroleum product production facilities closer
to the places of their concentrated consumption, completion of construction
of six or seven new plants will be accelerated. Petroleum refining will be
developed at high rates in the Ukraine, Belorussia, Turkmeniya and the
Lithi~anian SS R. Today, when mentioning this, it is particularly gratifying
to stress the fact that in the lOth Five-Year Plan the output of petro-
chemical products will increase 7-fold and t~ao major petrochemical complexes -
and a tire industry giant in the south and north of Kazakhstan will be put
, into operation.
The h igh growth rates of petroleum refining in the lOth Five-Year Plan are
ensured by a reliable raw materials base, but major changes will take place
in its qualitative structure--the proportion o.f sour crude and high-sulfur _
petroleum will increase to 80 percent in 1980. This thoroughly complicates
the production process for motor and boiler fuels and makes it more capital-
intensive.
The technical revolution has enriched our industry with powerful technical
devices for forming the structure, quality and properties of motor and
boiler fuels, lubricants an d~raw materials for chemistry and petrochemistry -
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made from types of crude petroleum of any qualitative structure, as well as
with the potential to change, by means of catalytic conversions, the output
- of many of these products as opposed to their natural content in petroleum.
It is by using these precise devices that we were able, in the Ninth Five-
- Year Plan, to ensure an increase in the production of high-octane gasolines
when refining low-octane and sour crude oils by over 3-fold. Here too, the
conversion of essentially all the systems of catalytic cracking from
amorphous aluminosilicate to highly efficient catalysts containing zeolite
is very important. If this were not~.done, we would have had to censtruct
an additional five or six new systems, spending up to 50 million rubles for
this purpose.
In order to realize fully the potential for using catalysts cont`aining
zeolite, work is now being done to create in the future new, more efficient
systems of catalytic cracking of heavy distillate and residual raw material
with a unit capacity of up to 2.5-3.0 million tons a year, using new ver-
sions of catalysts containing zeolite.
Increasing the efficiency of catalytic systems of the reforming process had
a substantial influence on the growth rates of production of high-octane
gasolines, and along with this, of aromatic hydrocarbons. The Al1-Union
Scientific Research Institute of Petrochemical Processes developed new
bimetallic polyfunctional catalysts, series KR, the introduction of which,
as was shown by experiment at the Novo-Ufa and Kirishi Plants, made it pos-
sible to raise to 83-87 percent the output of gasolines with an octane num-
ber of 95-97 (according to the research method) and reduce the pressure of
the process to 15-17 atmospheres, as opposed to 35-40 in catalytic systems
of the first and second generations. Work is now being done to prepare the
conversion of exi.sting and newly constructed reforming units to these effi-
cient catalytic systems.
_ The conclusion of a large complex of scientific research and planning and
design work will be the design of a highly efficient process of catalytic
reforming ensuring a yield of up to 90 percent gasolines with an octane -
number up to 100, with the pressure of the process up to 10-15 atm., and
the transition to constructing reforming units with a unit capacity of up
to 2.0-2.5 million tons a year.
Great importance is attributed in the industry to accelerating the completion
of developments and the introduction of the isoreforming process, which,
combined with catalytic reforming, will make it possible to produce hj.gh-
octane gasoline without using alkylate, which reduces the construction
volume of systems for its production.
Developing and improving domestic systems of catalytic processing of sour
crude and high-sulfur fractions of petroleum in a hydrogen medium resulted
in outstanding achievements in the production of new, thermostable reactive -
~ fuels for all types of aircraft, as well as to an increase in the output of
low-sulfur diesel fuels. Now tao, great perspectives are being opened up
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in this fielci by the new GK-35 and GD-80 catalysts containing zeolite,
created by the VIJIINP [All-Union 5cientific Research Tnstitute of Petroleum
and Gas Processing and the Production of Synthetic Liquid Fuel] and the
Institute of Catalysis of the Siberian Branch of the USSR Academy of
Sciences. The first increases the bulk speed of the hydrorefining process
1.5-1.8-fold, which will make it possible, at low expenditures, to increase
the capacities ot the existing units for hydrorefining of diesel fuels by
10-11 million tons; the second increases the bulk speed of hydrorefining of
gasoline fractions 9-10-fold. These new catalysts will be very important
- for the powerful new catalytic reforming systems being planned. ~
- The catalytic systems and industrial process of hydrocracking of heavy
vacuum gas oil, developed by the VNIINP, opened up great potentials for
producing base-stock oils with a viscosity index from 110 to 140, made from
sour crude oils. This is very important. The point is that, by using the
valuable natural properties of the oil fractions, with the aid of the pro-
cess now used both in our country and abroad, it is possible to obtain, even
from the best varieties of petroleum (and among them--petroleum from new
deposits in Western Siberia and Kazakhstan) oils with a viscosity index of
not over 95-110.
Putting ir.to operation the systems created f.or the hydroisomerization process
will ensure the production of oils with low viscosity values at temperatures
below zero and a high yield of them from fractions of high-paraffin
petroleum.
The introduction of these processes that we are planning will make it pos-
sible not only to raise th e quality of the base-stock oils, but also to '
thoroughly expand the raw material resources for their production.
In the field of lubricants technical progress is above all observed in
developing the production and use of special highly efficient additives.
The indt~stry is now producing more than half of the motor oils with these
individual heteroatomic compounds, complex in their structure, possessing _
specific proper.*_ies, and intensifying the cleansing, corrosion-inhibiting,
oxidation-inhibiting, dispersive, viscosity and other specially assigned
properties of mineral oils.
In the lOth Five-Year Plan the production of additives is being increased
1.8-fold, which fully pruvides for the national economy's need for high-
quality lubricants.
P-fuch has been done and is being done. The interests of this work, however,
require an even closer uniting of the efforts of the scientists of the USSR
Academy of Sciences, scientific research institutes and planning-design
organizations of the industry, to overcome the lagging behind in this field
through reinforcing thE scientific-technical bases by means of a detailed
study of the action of lubricants. There must be a search for new types of
multifunctional, highly efficient additives and special synthetic oils on
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- the basis of element-contairiing organic compounds that have higher bonding
energy and, as a result, high thermostahility, ensuring normal operation Qf
mechanisms in a broad range of temperatures, and able to withstand the
effect of. the space vacuum, radiation and resist all types of corrosive
mediums.
- Now, when the outlines of the vast development of industry in 1976-1980 are
appearing, we and the specialists in the petroleum and chemical machine
building field are faced with the task of accelerating the developmenr, and
~ design of highly productive equipment, in order to take an even large.r step
in the direction of optimum expansion of industrial Lm its, bearing i~1 mind
the transition to construction of units for primary petroleum refining with
a capacity of up to 12 million tons, instead of the 6-8 million tons that
now hold the principal place in the construction of new and modernization
of existing plants, which will make it possible to double or triple the unit
capacities of the secondary processes. These powerful systems are a step
forward in the cause of increasing the efficiency of capital investments
and prodi~ction.
It is quite clear that expanding the unit capacity of the equipment has a
_ limit, determined by th e technical potentials. In this connection an impor-
tant means to further increasing the efficiency is the optimum unification
of a number of logically interrelated industrial processes in the form of -
unified compact corabined block-units with a high capacity, with automated
control systems. This progressive trend has been broadly developed.
The principle of combining ha~ been carried out in the GK-3 type deep
petroleum refining units. With the construction of this type of unit in
accordance with the pattei*n: primary and vacuum distilling--catalytic -
cracking--vis-breaking tars, as compared with the collection of analogous
patte rns based on local un its with a similar capacity, the capital expendi-
tures and metal consumption were reduced 1.6-fold, and the building area--
4.5-fold, and the number of workers was reduced almost 3-fold. The yearly
efficiency from operating this system in Angarsk was about 17 million rubles,
mainly through the increase (by over 22 percent) in the output of motor
fuels when refining Romashkinskaya petroleum as compared with the usual
pattern.
For plants with light refining of petroleum, even more powerful type LK-6u
units were developed and are now being used in accordance with the pattern:
desalinization--stabilization--primary petroleum refining--reforming--
hydrorefining with a gas f ractionation system. This unit, recently put into
operation at one of the plants, by refining up to 6-8 million tons of sour
crude or high-sulfur petroleum a year, will produce gasoline with an octane
number no lower than 93, thermostable reactive and low-sulfur diesel fuel
u(in amounts that are essentially at the level of their natural content in
crude oil) and also mazut as boiler fuel (with a sulfur content depending
on the petroleum being refined, f rom 2.7 to 4.5 percent).
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Certain other plants are now being constructed on this technical base. The
assembly of ~he plant's capacity based on units of this type will soundly
reduce the capital- and metal-intensiveness and labor-intensiveness in the
process of operation and, ultimately, will ensure high efficiency in pro-
duction and good quality for the motor fuels.
An important scientific-technical and economic problem is that of the effi-
ciency of using the petroleum itself. In this connection too, by regarding
mazut and its high-molecular fraction components as the second, basic raw
material for the production of all types of modern motor fuels, oils and
raw materials for petrochemistry, and by developing the scientific-technical
bases for the study and testing of the operation of the GK-3 and LK-6u units,
research and planning-design work will be carried out on a broad scale in
the industry in the direction of designing powerful multipurpose combined
units for thorough, virtually residue-free refining of mazut, and when
_ necessary, the production of low-sulfur boiler fuels.
_ ,
Today's achievements of science and technology in the field of catalytic
break-up of high-molecular mazut fractions in a hydrogen medium open up
- a true potential for solving this problem, important in the economic aspect.
Recently completed on the basis of catalytic systems designed by VNIIIVP,
VNIIneftekhim [All-Union Scientific Recearch Institute of Petrochemical
Processes], GrozNIl [Groznyy Petroleum Scientific Research Institute],
Lengiproneftekhim [Leningrad State Institute for the Planning of Petro-
chemical Processes] and the Planning-Design Association is the preplanning
development of the expansion of one of the plants already under construction
to 24 million tons of deep petroleum refining a year, in accordance with th e
system: petroleum refining on type LK-6u units--hydrodesulfurization of the
mazut--its vacuum distillation--catalytic cracking--coking of low-sulfur
vacuum residue--hydrocracking of heavy distillates--ensures the output of
high-octane gasolines, thermostable and low-sulfur fuels to 78-82 percent
and of raw materials for petrochemistry and the productior, of low-sulfur
electrode coke~to 9=10 percent. The system introduced for thorough refining
reduces the consumption of crude oil per ton of motor fuels up to 1.2-1.3
tons, as against 2.3 tons in the case of light refining, oriented toward
primary production of boiler fuel. In other words, to produce equal amounts
of motor fuels, in the case of light refining, not 24.0, but 44-46 million
tons of petroleum are required, or 20-22 million tons more. This is no
small difference. It considerably exceeds the level of petroleum extraction
in Baku at the present time.
Therefore, the problem of thorough refining of mazut is above all the prob-
lem of ttighly efficient use of the petroleum--this unique and at the same
time irreplaceable natural weaith of our native land. Both the resources
of it and their use should be treated carefully--as is required hy the law
on undQrground resources recently passed by the USSR Supreme Soviet. The
road toward this is now being laid by the achievements of scientific and
technical progress in the field of refining heavy petroleum fractions,
concentrated in mazuts--the residues of primary petroleum distillation.
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It is quite clear that intensifying petroleum refining will inevitably give
rise to a reduction in the production of mazut, the proportion of which in _
the country's fuel-energy balance is still high. A reduction of mazut in
the fuel-energy balance therefore requires a certain compensation tt~rough
the use of.other fuel-energy resources, namely gas, the prospected reserves
of which several times exceed the resources of oil, coal, hydraulic power
and the power from the heat-emitting components of nuclear electric power
stations.
The problem of heavy catalytic refining of mazuts is an important one, and,
at the same time, capital-intensive and complex from the technical stand-
point. Here, perhaps the main concern is the task of ensuring high effi-
ciency in the productivity of the catalytic stages of refining the mazut,
as well as reliable and modern equipment design of the processes for the
h eavy refining unit, on the one hand, and on the other--the use of catalysts
with a high degree of activeness and stability.
In speaking of this, I should like to emphasize the idea that obviously,
the actual catalysts of each stage of the block-unit or local units--
hydrodesulfurization and other catalytic processes of heavy mazut refining
--persistently require more delicate treatment. The point is that the
metals contained in the mazuts, particularly vanadium, as well as the
' nitrogen compounds, give rise to the irreversible deactivation of the
catalysts, and asphaltenes, in turn adsorbed in the catalysts, lead to -
their intensified clogging with coke and consequently, to a reduction in
the efficiency of the catalytic system as a whole. In order to realize
to the maximum the potentials of the catalysts at all stages of the block-
unit, we must, figuratively speaking, above all surmount a kind of "coking
barrier," through introducing a stage of preliminary processing of the
mazut, I would say, a stage of integral preparation of the mazuts that
nesures thorough removal of the siilfur, nitrogen, metals, asphaltenes and
other substances accompanying them that deactivate the catalysts, and thus
opens the way to efficient use of modern methods of catalytic refining of
mazuts.
In a word, there is to be scientific-technical research and development of
an optimum method of preliminary preparation of the mazut. .One of these
methods may prove to be the process of high-temperature adsorption
deasphaltization and demetallization of the mazut, using a circulating
adsorbent either on the basis of coarse-pore aluminum oxide or on the
basis of other adsorbents with a high coking capacity.
As is shown by experiment, thorough extraction ef inetals and asphaltenes in
this case proceeds with quite high selectivity and relatively low losses of
liquid fractions in the form of gas and coke. This or another method of
preliminary preparation of the mazut, depending on the specific conditions
for refining the petroleum, may be included either in the structure of the
type LK-6u block-unit as a stage of preparing the mazut, or directly in the `
structure of the block-unit of its Tieavy refining system.
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The preliminary preparation of the mazut and catalytic processing of the
raw material refined in this way affords real prerequisites for designing
block-units for heavy refining of sour crude or high sulfur mazuts with a
unit capacity of up to 5-6 million tons, with the output of motor f uels
no lo~.~er than 65-70 percent. In the case of production of boiler fuel,
_ however, it ensures a reduction in the sulfur in it to 0.5-0.7 percent,
which is very important both for environmental protection and for the pro-
- duction of low-sulfur electrode coke. '
The principles of optimum combination also find a place for themselves in
petrochemistry. For example, on the basis of thermal pyrolysis of various
fractions of petroleum, we were able, on the staff of the Nizhnekamsk Petro-
chemical Complea, to design a powerful combined system for obtaining lower
olefins, dienes--butadiene and isoprene, and also benzene. This system is
unique with respect to its technical designs and capacities. Start-up and
adjustment ~aork has now begun at the first such combined system.
In the lOth Five-Year Plan we are planning to construct several combined
systems like this one. Some of them are already under construction at
major petroleum refining and chemistry centers. These centers will be
interconnected by ethylene pipelines, which will ensure the stable opera-
tion of the ethylene-consuming production facilities in the country,
regardless of their departmental affiliation. .
Scientific-technical progress in the petroleum refining industry and the
modern achievements of chemical science and technology have created favor-
able conditions for outstripping development ef petrochemistry in the lOth
Five-Year Plan.
Perhaps the main factor in ensuring high development rates and efficiency
in petrochemistry, along with a considerable--5-6-fold--increase in the
unit capacities of various prodt~ction facilities, is a sound improvement
in the selectivity of a number of petrochemical processes.
At present, many industrial processes for the output of the basic product,
and among them, ethylene and phenol oxides, acids of...the aliphatic series
and many others, have low selectivity, precisely in the range from 35 to
70 percent, which with large scales for the production facility leads to
huge losses of ethylene, benzene, paraffins, xylenes, dienes and other
types of expensive raw materials, now calculated by tens of thousands of
tons and, as a result, creates a shortage of it.
- Therefore, increasing the selectivity of chemical conversions is becoming
one of th e most important tasks of chemical science and, in our opinion,
- the degree of selectivity should be one of the basic criteria for evaluat-
ing the trends in scientific-technical research, developments and cnoice
of the processes for executing them in industry.
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In mentioning raising the selectivity of the processes of chemical tech-
_ nology, I should like to note that today the catalytic systems for the
production of glycols made from ethylene oxide with a selectivity of
95 percent, oxidation of isopropylbenzene into phenol with a selectivity
of 93-95 percent and the synthesis of other products with similar yields,
developed by NIIMSK [Scientific Research Institute of Monomers for Synthetic -
_ Rubber] and other insti~utes of the industry, in conjunction with~institutes
of the USSR Academy of Sciences, are putting us in a good situation.
An analysis of the state of achievements in domestic and world science and
. technology in the theory and modern methods of catalysis indicate that we
are already justified in demanding from science the invention of processes
with a selectivity of at least 90 percent of the theory.
An important means of increasing the efficiency of capital investments and
pradurtion is also a reduction in the stage-nature of the syntheses and a
transition to simpler, but more reliable industrial processes for obtaining
the specific product. Modern achievements in chemical science are increas-
in gly confirming this potential. AJong with the successful industrial
accomplishment of direct oxidation of ethylene into acetaldehyde, a true
perspective has appeared for replacing multistage processes with low- or
single-stage processes at production facilities:
For butadiene (by oxidizing~dehydrogenation of butane); aliphatic alcohols
(from paraffin); glycol (directly from ethylene); methylethylketone (f rom
butylenes); isoprene (f rom isobutylene an~' formaldehyde) and certain other
- highly promising developments of NIIMSK, VNIIPAV [not further identified],
VNIINeftekhim, VNIISK [Al1-Union Scientific Research Institute of Synthetic
Rubber imeni S. V. Lebedev] and institutes of the USSR Academy of Sciences.
On this plane, and on the plane of the problems which were mentioned above,
a great contribution to the development of scientific-technical progress in
the petroleum refining and petrochemical industry will be carrying out the
fundamental directions in the development of natural and social sciences in
1976-1980, worked out by divisions of the USSR Academy of Sciences with the
participation of scientific councils on the most important problems and
approved by the Presidium of the USSR Academy of Sciences.
Also attesting to the achievements of domestic chemical science and its
unlimited potentials is the scientific-technical progress in the field of
- producing rubbers, the output of which will increase 1.7-fold in the years
of the lOth Five-Year Plan, and of stereoregular elastomers--approximately -
2.4-fold, which will make it possible in just the years of this five-year
plan to reduce the consumption of natural rubber by over 2.5 million tons
and to retain about 1.5 billion rubles in the country's hard currency fund.
The f ruitful work of the scientists of the collectives of VNIISK, VNIIMSK
and many other institutes of the industry and institutes of the USSR Academy
of Sciences, many of whom are participants in this congress, and of the
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innovative workers, engineers and technicians of the synthetic rubber indus- ,
try has been crowned by the establishing in our country of large-scale pro-
duction of va.r.ious types of synthetic rubbers.
The chemistry research on polyisoprene showed for the first time the poten-
tial for control of the growth and structure of the molecular chain and
established the fundamental conformances to principle in the field of ion-
coordination catalysis, cahich enriched polymeric science as a whole, and
information on the nature of the active centers of polymerization of paired
dienes, obtained by the method of nuclear-magnetic resonance, and made it
possible for the first time for our scientists to propose a mechanism,
co;~unon for all dienes, for forming polymeric chains, based on the determin-
ing role of the structure of the allyl link at the end of the live chain of
polydiene. It is on this basis, by modifying the catalytic systems, that
, we have succeeded in producing polyisoprene with almost double the produc-
tivity of equipmen.t and output of rubber, and in raising its q uality to the
level of natural rubber and, what is most important, in creating the con-
ditions for an increase in the lOth Five-Year Plan of the outp ut of this
elastomer at existing plants. This program has already been put into
operation.
While noting the progress in science and technology in producing stereo-
regular elastomers, we wi11 discuss certair? tasks in this field and tYie
directions of acr_omplishing them in the near future.
First of all the search must be continued for new catalytic sys tems, as
well as for modifying agents that increase the stereospecific nature of
the catalysts studied, in order to achieve the maximum, close to 100 per-
cent, content of 1,4-cis-structure in the elastomers, especially since
VNIISK, working in this direction, has reported the latest achievement-- ~
rubber has been obtained with a content of 98 percent 1,4-cis-structure.
There are also certain problems in the field of designing new types of
elastomers and, particularly, in th e synthesis of stereoregular carbon-
chain polyme rs through polymerization of cycloolefins with the scission of
the ring and obtaining polymers of the most varied structure, including
trans-polypentanamer, since its use in a mixture with isoprene rubber
appears very promising in order to attain favorable properties of both
elastomers.
There is great importance in the polymerization with scission of the ring
of cyclical oligomers for the production of polybutadiene that does not
contain 1,2-links, as well as for obtaining the alternate copolymer of
butadiene with isoprene and a number of other new polymers.
Also reflected in this connection in the work plans of the industry's
institutes are:
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The synthesis of new types of rubbers for general purposes--alternate copoly- '
merization of dienes with olefins, especially since data have already been -
obtained on the valuable complex of properties of alternate copolymers of
butadiene with propylene;
The development of the synthesis of liquid rubbers, which opens the way to
a prcduction p rocess, new in principle, in the tire and industrial rubber
industry, namely the transition to completely automated continuous processes
for manufacturin~; items by casting methods, with a considerable reduction
in the production areas and heavy equipment, rise in productivity and
' improvement in work conditions.
At the industrial institutes and institutes of the USSR Academy of Sciences
work must be intensified in the following directions:
Designing new elastomers which should guarantee long operational life for
the items made from them, with retention at the same time of their shape
and elasticity at temperatures of 300�C and over;
Increasing th e thermal stability of polymers on the basis c,f working on the
synthesis of b lock-copolymers, the main ch ains of which a~:�e constructed from ~
flexible blocks which have a low glass transition temper.ature and from rigid
high-melting blocks;
Developing work on designing fluorine-containing elastomers with good low-
_ temperature p roperties, and on the synthesis of rubbers that have substan-
tially increased resistance to oxidation destruction, as well as designing
elastomers that combine good frost-resistance, high oil and gasoline-
resistance, acid-resistance and combustion-resistance.
It is quite understandable that creating a broad range of elastomers for
both common an d special purposes is not an end in itself, but a means to
producing a quality of structural rubber material with a given set of
properties that provide for the needs of the most varied sectors of the
national economy, culture and everyday life in man's society.
Now, with the tremendous scale of elastomer production, the main problem
- is that of providing them with the production of monomers. The point is
that a certain break has been revealed in the industry between the growth
rates of the production of elastomers on th e one hand and on the other--
the production of monomers, chiefly butadiene and isoprene.
The situation is also somewhat complicated by the fact that in the Eiiropean
part of th e country the resources of butanes and pentanes have been virtually
exhausted.
�
In a word, the problem of monomers is a key problem. We will solve it pri-
marily on the basis of accelerating construction in the homeland of D. I.
- Mendeleyev of the Tobol'sk Petrochemical Combine. At this combine, on the
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basis of huge resources of b utanes and pentanes, contained in the casing-
head gases in the extraction of petroleum in Western Siberia, an extremely
large-scale production facility for monomers--divinyl and isoprene--will
be established. The synthesis of monomers on the basis of the lower
olefins, chiefly ethylene and propylene, with the aid of the reaction of
dimerization, codimerization and disproportioning of double ~onds in the
olefin molecules occurring in the presence of inetalloorganic complexes,
will be completely new and truly modern. Carrying out these trends in
synthesis will make it possib le, by using the potentials of thermal pyroly-
sis of hydrocarbon raw material, which is available at any petroleum
refinery, to ensure accelerated development of the production of butadiene,
isoprene, the higher olefins and other monomers from a small number of
initial olefins.
There are also promising potentials here for the synthesis of linear
_ bifunctional monomers, each containing two double bonds at the ends of the
alkyl chain. These monomers, the practical value of which is obvious, are
formed with a high yield in the disproportionation of ethylene with
cycloalkenes.
The process of pyrolysis is essentially a sort of basic connecting link,
opening up the actual possibility of establishing major comprehensive pro-�
duction facilities not only for monomers for synthet.ic r:~bber, but also
for many other functional derivatives of hydrocarbons.
I should like to stress the fact that chemical science and its present-day
discoveries are a source of unlimited potentials for increasing the effi-
ciency, the road to whi~ch is being laid t~y coope ration and comprehensive
development of petroleum refining and petrochemistry.
Our country's high level of industrial development, the achievements of
science and technology and the tremendous resources of oil and gas--the ~
technical basis of the petroleum refining and petrochemical industry--
are creating truly favorable circumstances for the fulfillment of the
complex tasks of all-round development of the petroleum refining and petro-
chemical industry in our coun try in the lOth Five-Year Plan of quality and
efficien cy.
COPYRIGHT: Izdatel'stvo "Nauka", 1977
12151
CSO: 1841
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PHOSPHORUS INDUSTRY
11TH MENDELEYEV CONGRESS ON GENERAL AND APPLIED CHEMISTRY--PLENARY REPORTS
Moscow XI MENDELEYEVSKIY S"EZD PO OBSHCEiEY I PRIKLADNOY KHIMII: PLENARNYYE
DOKLADY in Russian 1977 signed to press 30 May 77 pp 82-102
[Article by S. I. Vol'fkovich: "Problems of Phosphorus"J
[Text] It is possible that among some chemists the question arises as to
why, at the plenary session of the llth Mendeleyvskiy Congress, out of the
107 elements of the Periodic Table of D. I. Mendeleyev, one chemical element
--phosphorus, which is contained in the earth's crust in an amount of about
. 0.1 percent (according to Clark) and moreover is not newly discovered, but
has a history of 300 years--is the subject of a separate report. There are
several reasons for this.
In the first place, phosphorus and its compounds play a key role in the
biology of man, plants, animals, microorganisms and other bearers of life.
"Phosphorus is the element of life and thought," wrote A. Ye. Fersman.
But elemental white phosphorus and a number of its compounds are also
poisons that have a toxic effect on the vital activity of organisms: Forty
y ears ago V. A. Engel'gardt and M. N. Lyubimova discovered the energy role
of phosphorus in living organisms. A study was made of its varying, includ-
ing its therapeutic, effect on many physiological processes.
Fertilizers containing phosphorus have been used for about 150 y.ears, and
their world production in 1973 reached 33 million tons for P205, for which
about 300 million tons of phosphate raw material was extracted from the
underground. There is a rapid growth of the production and use of fodder
agents containing phosphorus in livestock breeding, as well as the use of
compounds containing phosphorus in the production of a number of foa.d,
medicinal, pesticidal and other bioactive substances.
In the second place, phosphorus and its compounds have a broad a.nd very
varied indtis~ri.al use. Elemental phosphorus is not only a"hearer of
light" (this is the meaning of the word in Greek), but a number of its
inorganic compounds are used as fire-proofing, heat-resistance and binding
substances. Many of its compounds have complexing and polymerizing,
plasticizing, ion-exchanging, dehydrating, water-softening, lubricating,
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sur�ace-active, flocct~lating, stabilizi�g, metal-corrosion-inhibiting and
other propert~ies. From elementary textbc~oks the i~se of phosphorus is known
in defense equipment such as smoke-forming and incendiary devices, used in
compounds with sulfur and certain resins in the last few wars.
In the third place, the chemistry and technology of phosphorus, its oxides,
hydrides and lialogenides of phosphoric acids and many thousand other com-
pounds of it (particularly organic) and the study of their structure and
physical-dh.emical properties are of great theoretical scientific importance.
This interest, which does not weaken, but intensifies with each year, draws
continually growing attention and increases the flow of research of numProus
chemists, hiologists, geologists, technicians and other specialists. It is
, sufficient to recall th e works of A. Lavoisier, J. Liebi~, F. Veler,
G. Sheyele, D. I, Mendeleyev, D. N. Pryanishnikov, G. Tamman, A. Ye.
,L,~ Arbuzov, E. V. Britske, Ya. V. Samoylov, A. Ye. Fersman, V. N. Ipat'yev, _
~ A. A. Belopol'skiy, P. Bridgeman, E. Tillot, A. Mikhailis, F. Waggaman,
~ R. i~hignet, N. Vitting, J. Van Weser, Ya. Kobayashi, G. Koran and also
our domestic contemporaries N. N. Semenov, M. I. Kabachnik, A. V. Kirsanov,
V. A. Engel'~ar.dt, I. V. Tananayev, N. N, Mel'nikov, B. A. Arbuzov,
_ A. N. Pudovik, I, F. Lutser.ko, N. N. Postn~kov, M. Ye. Pozin, A. B.
Bekturov, M. I. N abiyev, Yu. N. Khodakov and many others. ~
Despite the large n umb er of research works, there is still a great deal in
the chemistry of phosphorus and its compounds that is unclear and requires
further creative study.
The 3irect proximity of phosphorus with silicon and carbon in the Periodic
5ystem of D. I. Mendeleyev gives rise to many scientific comparisons and
questions. By today the tremendous scope of synthetic, physical-chemical,
industrial and biological works on the cheinistry of phosphorus has reached
sucti a theoretical and methodological level that the American chemist
Van Weser, in his two-volume monograph, "Phosphorus and Its Compounds,"
s�ggested that the chemistry of phosphorus be singled out into a separ:~te
scientific discipline, similar to the chemistry of carbon [1].
Finally, it must be noted that in Kazakhstan, in the post-October period,
several deposits of n atural phosphates we re discovered, the largest of
which are the Middle Cambrian deposits in the Karatau Mountains. Discovered
lon~ ago, but not utilized until recent times, are deposits of phosphorites
in the regions of Aktyubinsk and certain other regions.
Here it would be appropriate to say that almost all the natural phosphates
extracted in the USSR ar~d now bein~ utilized were discovered and studied
in the Soviet period. It is impossible to discuss the multi-faceted and
exceptionally interesting history of phosphorus and its compounds, beginning -
with medieval alchemy arid continuing to our times, in this survey report,
since its task is to look into the futurc and shed light on the p rincipal
problems facing th e chemistry and technology of phosphorus and its compounds.
Given below are the :~ost important inorganic and organic phosphorus compounds:
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Most Important Inorganic Phosphorus Compounds
PH3--phosphine
P2H4--diphosphi:ne
P H--lower hydrides of phosphorus ( X,>y ) -
P4~6~p2~3~~ p4~10~P205)--phosphorus oxides '
H-P(OH)2--hypophosphorotis acid .
P(OH)3--phosphorous acid
HP03_-metaphosphoric acid
H3P04--orthophosphoric acid
H4P20~--pyrophosphoric acid
Hn+2Pn~3n+l--Polyphosphoric acid
~HSP3~10--tripolyphosphoric, HgP4Q13--tetrapolyphosphoric and other acids
PX3, PXS, POX3, PSX3--halogenidPS and ~oxy(thio)halogenides of phosphorus
(X=F, C1, Br)
P4gn--phosphorus sulfide (P4S3~ P4S5, P4S7~ P4S9~ P4~ S11~
(PNC12)n_-phosphonitryl chlorides (n=3-7)
~=P~NH2)3--orthophosphoric acid amides
PnNm -phosphorus nitrides (N:P=0.9-1.7)
Salts of phosphoric and polyphosphoric acids
Most Important Organic Phospliorus Compounds
Derivatives of hydrogen phosphide
RPFI2, R2PH, R3P---phosphines: primary, secondary, tertiary
R2P-PR2--diphosphines; phosphine, thiophosphine oxides; phosphonium cnm-
pounds; phosphazo compounds, etc.
Derivatives of trivalent phosphorus acids
R(OH)3--phosphorous acid, monoalkyl(aryl)phosphites, dialkyl(aryl)phosphites,
trialkyl(aryl)phosphites, thio ethers, anhydrides, ether halogen anhydrides,
etc.
R-P(OH) --phosphonous acid Halogen anhydrides, ethers, thio ethers,
R2-P(OH~--phosphonous acid amides, anhydrides
Derivatives of pentavalent phosphorus acids
0=P(OH)3--orthophosphoric acid, mono-, di-, trialkyl(aryl)phosphates,
thiaphosphates, ether h alogen anhydrides, ether amides, etc.
P(C6x5)S~P~(OC6H5)5--phosphoranes
R3p=N-R--iminophosphoranes, or phosphazo compounds `
HO +I !O g '-Pyrophosphoric acid, tetraalk.yl(aryl)pyrophosphates, -
thiophosphates, etc.
\
HO OH
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RP-(OH)2--phosphonic acid Halogen anhydrides, ethers, anhydrides,
amides for botii acids and ether halogen �
anhydrides, ether.amides for phosphonic
~ acid
R2p-OH--phosphonic acid
- The main directions in the use of compounds containing phosphorus are the
following: fertilizers, fodder and food agents, agents to protect plants -
- and animals (insecticides, fungicides, herbicides, etc.), medicines, cata- '
lysts, polymeric materials, plasticizers and stabilizers for polymers,
hydraulic fluids, lubricants, surfactants, fireproofing devices--fire-
_ proofing cnmpounds, corrosion inhibitors, incendiary and smoke-forming
substances, semi-conductor and laser materials, glass with special
properties, etc. ~
Raw Material Resources
Permit me to begin with a brief elucidation of the present level of study
_ of the natural resovrces of phosphorus.
Tn the ear.th's crust phosphorus is contained in over 170 minerals, varying
in their origin, concentration of phosphorus, composition of accompanying
compoim ds and thickness of the deposits. To obtain phosphorus, phosphoric
acids, fertilizers, fodder substances and commercial products, industr,~ _
mainly uses phosphorites and apatites, which constitute 95 percent of the
total amount of natural phosphorus-containing raw material extracted.
Guano, phosph al and vivianite (iron phosphate) are used in negligible
amounts. Up to the second half of the nineteenth century, industry and
agriculture used mainly animal bones. Phosphorites are known in the
deposits of almost all the geological systems--f rom the Precambrian to the
_ Pliocene. Many of them are distinguished by heightened radioactivity [2J.
T.he largest phosphorite deposits are in North Africa--their geological
resot~rces constitute 41 billion tons--in North America--14 billion tons--
and in the USSR--about 16 billion tons (see diagram) [3]. Although the
total numt~er of deposits in the world exceeds 250, many of them have
shallow or medium reserves, containing a low percentage of phosphorus and
many undesirable impurities, which makes their economic utilization dif-
ficult. In the last few years new deposits have been discovered in the
Western Sahara, Togo, Syria, China, India, Vietnam, Brazilia and a number
oF other countries. Unique magmatic deposits of apatite-nepheline ores,
- discovered in the Soviet Union in 1925 at Khibiny, on the Kol'skiy _
Peninsula, acquired worldwide renown. When these ores were concentrated,
apatite concentrate was obtained with a content of 39.4 percent P205.* [4]. ~
The exception is the concentrates of enriched phosphorites~of the Pacific
Ocean Island of Naura, which contain 42.5 percent P205.
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As a result, for several decades less attention was paid to the lean
~ phosphorites known at that time.
~ �
~ ~ ~ G~~
~ ~ o
~ ~ ~ ~ ~
~a ~ ~
� � ,
, 0~ �
, ~ b
r ~.i~ ~ ~ ~
- ~L 7.~`-w~ ~ ~ L`~_~~ o
~l_,,, ~ ' ~ ~
~ ~ ' ~~o ~
_ ~
, ~ ~ '
; ~ r' ~
I , f!~ ' ~_--y~
, ~r
~ ~ n ~7'
Distribution of Main Deposits of Phosphate Raw Material in the World
In 1936 a second large raw material base was discovered in the USSR--geo-
synclinal phosphorites of the powerful Middle Cambrian Age in Karatau
(Southern Kazakhstan). The principal phosphorite resources of Kazakhstan
(the Karatau basin and Aktyubinsk group) constitute 30 percent, and the
rest of the phosphate deposits in the European and Asian parts of the USSR
--approximately 30 percent of the all-union resources. Included among the
latter are deposits in the central regions of the USSR (Yegor'yevskoye,
Vyatsko-Kamskoye and others), in the Baltic basin (Maardu, Toolse, Kingi~epp
and others), in Siberia--in Krasnoyarskiy Kray, in Gornaya Shoriya
(Belkinskoqe), in the Aldan River basin (Solikdarskoye), in Kemerovskaya
Oblast (Tashtogol'skiy Rayon), in Buryatiya (Oshurkovskoye) and others.
The figures mentioned will of course change with progress in geological
prospecting work. Over two-thirds of the phosphates prospected in the USSR
belong to the low-percentage group.
As a result of the geological studies of the last few years in the USSR a
number of mineral deposits have been revealed, the ores of which contain
apatite. In the process of their prospecting and concen~tating, along with _
the basic mineral, apatite concentrate may be obtained that is suitable for
chemical processing and contains from 30 to 40 percent P205. Among these
deposits is the Yeno-Kovdorskoye, on the Kol'skiy Peninsula. Similar
combined deposits were also discovered in Siberia--the Beloziminskoye,
Kruchininskoye, Solikdarskoye, etc., and in the Urals--the Volkovskoye.
In view of the ever-increasing demand for phosphorus fertilizers of Siberia
and the Far East and th e still inadequate quantitative and qualitative
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provision of phosphate raw material for this huge eastern territory of the
Soviet Union, the geochemists, geologists, concentration specialists and
technologists, despite the p rogress achieved, continue to be faced with
the pressing problem of expanding, intensifying and accelerating compre-
hensive research. There must also be intensification of the study of. the
perspectives for u~ing phosphorus-containing iron ores, particularly of the
eastern regions, for simultaneous obtaining of steel and phosphate slags,
as well as comprehensive use of other ores and their associated minerals.
Indicative of the characteristics of the present-day importance of the
problem of phosphate raw material are the predictive calculations of its
world demand, made by American economists [5]. According to these calcula-
tions, the demand for phosphate raw material by the year 2000 will increase
almost 4-fold as compared with 1970, an d will be approximately 300 billion -
tons (for total weight); 93 percent of this amount is required by the.
fertilizer iadustry.
Selling prices for Florida phosphorites have almost quadrupled in three
years (from 21.28 dollars per ton in 1972 to 47.50 dollars in 1974) [6].
Export prices for a ton of phosphorites from Morocco in 1974 rose from
42 to 63 dollars (PZ05 content--34 pereent). With acidic methods of `pro-
cessing natural phosphates for fertilizer, the value of the raw material
constitutes approximately three-fourths of the total production cost,
Therefore, the problems of improving and reducing the expense of the pro-
cesses of extraction and concentration of phosphate ores are very urgent
ones. Unfortunately, in the study of the processes of concentrating phos-
phorites, until recently little use was made of chemical methods (use of
acids, organic and other reagents) and their combination with physical and
neco technical devices. This work is now being successfully~developed. o
The largest and most upsetting problem of phosphorus raw material on the
long-range plane is its limited natural resources, as well as the slow
cycle of phosphorus compounds in nature and its great dispersion in the
earth's c n~st an d waters of th e sea.
Rough summaries of the analytical data on the composition of the earth's
crust (so-called clarkes) indicate that it contains approximately 32-fold
less pho~phorus than silicon, sodium and magnesium. The phosphorus
resources detected and studied in the earth's crust up to recently are
estimated at approximately 8.7�1010 tons (not counting dispersed phosphorus)
[7]. Up until the last few years deposits of phosphate ores with a content�
of phosphorus pentoxide lower than 10-12 percent were regarded as unsuitable
for the production of superphosphate and wet-process phosphoric acid, but
now they are beginning to use ores with a content of 3-4 percent P205. In
a number of countries, including the USSR, the deposits for the most part
are lean, requiring more complex technical and consequently more expensive
_ processing method~s.
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Considering the growth of th e world population and the rapid development of
- chemization of agric~ilture--the chief consumer of phosphorus fertilizers,
fodder agents and phosphorus-containing plant protection agents--the
resources of mineral phosphates studied up to the present can provide for -
the demand for them as raw material for only 40-50 years in some countries,
and in others (a few) for 200 years and more. A niimber of ~eposits also
exist that, with the present-day scale of utilization, may be exhausted in
15-25 years. Many countries have no phosphate deposits at all. Hence a
problem of global importance arises: how to provide the next generations
of people with phosphorus, and in some regions-- our contemporaries.
In addition to the intensified development of geological prospecting, an
improvement in industrial methods of extracting phosphorus from lean ores,
from sea water and bottom deposits [8] (according to the estimates of
M. V. Fe doseyev and V. V. Mokiyevska, the total amoimt of phosphates
accumulated in the ocean waters is (67-84)�109 tons) and the use of the
wastes of industry, rural and municipal services, in the future,physicists
and chemists will probably raise the question (so far still unclear) of
obtaining phosphorus by converting elements through decomposition energy
and synthesis of atomic nuclei.
In connection with the limited nature of the natural resources of phos-
phorus, the problem becomes acute of considerably increasing the coefficient
of the useful effect of phosphorvs products, particularly fertilizers con-
taining phosphorus, and of the degree of removing phosphorus in their
extraction, concentration and chemical processing of ores. If, to the con-
siderable losses accompanying these processes, one ~adds the losses of phos-
phorus in agriculture as the result of binding phosphorus in unassimilable
compounds, as well as the losses in storage, transport and application to
the soil, the total degree of use of natural phosphorus resources is approxi-
mately 40-60 percent. Agrochemical research on methods of raising the
degree of utilizing phosphorus fertilizers is very urgent.* This problem
is a glotaal one. Finally, in the planned economy of the socialist countries
these two problems can and should be solved more quickly and efficiently
through the callective efforts of the chemists, in conjunction with the
~ technicians, biologists, economists and other specialists.
The problem of raising the degree of utilization of natural resources of
phosphates, of course, does not remove the need for widescale development
of geological exploration and prospecting of new phosphate deposits, par-
ticularly in the regions not provided with raw material, as for e~;ample in
*
At the Department of Chemical Technology of Moscow University imeni M. V.
Lomonosov and the Scientific Research. Institute of Fertilizers and
Insecto-fungicides in 1951-1954 phosphamide compounds were synthesized
that were not bound by soil (S. I. Vol'fkovich, A. M. Malets, T. I.
Sokolova); studies in this direction have'~been developed in the last few
years at the SRIFI by A. S. Lenskiy and at MTU by L. V. Kubasova and
others.
Y
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rux urrt~ttu., U~~ UNLY
Eastern Siberia, the Far East and other regions of the USSR, as well as the
expansion of geological prospecting work in regions where the extraction of
phosphates is already being carried out. The importance of these tasks is
= continually increasing because.of the rapid development in the USSR in the
last few years of the phosphorus-containing fertilizer indiistry.
Using Ph~sphates I~iso] uble and Slightly Soluble in Water
A problem of'~~,great importance for the further progress of agrochemistry and
the technolo~y c~f fertilizers is solving the question of the efficiency of
phosphorus compounds that are slightly soluble in water. Studies and dis-
cussions in regard to the efficiency of using citrate-soluble phosphates in
- farming have an almost century-old history. Citrate-soluble phosphates are
used efficiently in the agriculture of a~number of countries--Thomas slag*,
finely pulverized phosphorite meal, soluble in a 2-% citric acid solution, -
thermophosphates--products of the caking of phosphorites with soda or pro-
ducts of fusion with magnesium compounds and others, vivianite--iron phos-
phate Fe3(P04)2�3H2O, etc. Citrate-soluble phosphates are used in a number
of countries mainly in acidic soils, along with using water-soluble phos-
phates, which have the advantage, with their local application to the soil, ~
as top-dressings. In some coimtries, however, agriculture imposes a demand
on the chemical industry--to supply fertilizers mainly in water-soluble
forms. This demand is also imposed by many agrochemists in the USSR, despite
the fact that as f ar back as the nineteenth century D. I. Mendeleyev and
A. N. Engel`hardt, and in the twentieth century, D. N. Pryanishnikov,
A. N. Lebedyantsev and others in numerous field experiments showed that
finely pulverized phosphorite meal is highly effective on soddy-podzolic
and broken-down leached chernozem soils, and remains effective for a number
of years. D. I: Mendeleyev, in his time, wrote that in some experiments,
careful pulverizing of the phosphates in the presence of organic and nitro-
gen substances made it possible to do without the use of acid.
_ Modern agrochemical studies have established the fact that pulverizing
phosphorites of a certain type (mainly lumpy, sandy and clayey) are effec-
tive in acidic soils on a par with water-soluble fertilizers, and some--~
with application in doses-- 1.5-2-fold greater. The possibility of direct
application of phosphorite meal is of practical importance for ores that
are unsuitable for processing in water-soluble forms for basic application
plowing. In many cases, phosphorite meal can have an advantage as a neutral
fertilizer, not bound by the soils, and effective for several years. This
question is critical both with respect to water-soluble uniform and complex
fertil.izers containing some phosphorus in the composition af insoluble
compounds of iron, aluminum, calcium, etc.
~
Successfully used in the GDR, FRG, France, England, Belgium and other
countries.
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The Decree of the CPSU Central Committee and the USSR Council of Ministers
"On Measures for Further Development of the Agriculture of the Nonchernozem
Zone of the RSFSR,"* intensifies the importance of the problem of using
phosphates that are insoluble in water, but soluble in weak acids and are -
assimilable ir soils that have actual, potential and exchange acidity.
In the last few years, in the USSR and certain other countries, processes
have been developed to treat phosphorites and apatites with steam at a high
temperature (1250-1500�), as the result of which the fluorine is removed and
the phosphate passes into a form assi.milable by plants and animals. For this
purpose natural phosphate is subjected to ~.rocessing by gases obtained from
the combustion of natural gas. The products of this so-called hydrothermal
method of producing defluorinated phosphates have been used until recently
mainly as an efficient supplementary feeding for animals. The defluorinated
phosphate is the cheapest fodder agent, considerably increasing the gain in
milk, meat, coat, and making the animals healthier.** The production of
defluorinated phosphates does~not require considerable amounts of acids or
allcalis and electric energy. Some 400 field experiments carried out in the
- USSR in 15 years on using de�luorinated phosphates in all types of soils
and for various agricultural crops showed that this type of phosphates, con-
taining mainly tricalcium phosphate, gives a similar increase in harvest
yield per weight unit of phosphorus as superphosphate, and for some crops
improves their quality [9-13].
During the last few years various countries have been conducting experiments
with elemental phosphorus as a source of plant nutrition. In vegetation and
field experiments, noncombustible and nontoxic red phosphorus has been used
with an admixture of a catalyst (salts of copper, iodine, etc.), which
accelerates the transfer of the phosphorus into phosphoric acid compounds.
The experiments conducted in the USSR (at NIUIF) by A. V. Sokolov,
N. D. Talanov and K. F. Gladkova [14] and others, indicated that red phos-
phorus may be acidified in th e soil and serve as a plant nutrient. Its
_ expensiveness, however, caused by the length and difficulty of processing
white phosphorus into red, requires a considerable improvement in the indus-
trial processes both for obtaining elemental Fhosphorus through its reduc-
tion and sublimation from natural phosphates and for converting it into the
red (polymeric) variant.
Phosnhorus is now being obtained in the USSR and a number of other countries
in electric furnaces with a power of up to 72,000-98,000 kilowatts, and the
task is posed of achieving napacities of 150,000 kilowatts. Up to 12-14
kilowatt-hours of electric power are spent to obtain 1 ton of phosphorus
from phosphorites. The cost of one ton.of so-called thermal phospho.ric acid
obtained from elemental phosphorus, under today's economic conditions, is
considerably more expensive than 1 ton of wet-pr.ocess phosphoric acid,
* _
PRAVDA, 3 April 1974.
This process was developed at the NIUIF, MGU and Tekhnoenergokhimprom,
and was put into operation at four plants.
,
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obtained as the result of breaking down the phosphates in sulft~ric acid.
_ Thermal phosphoric acid, however, is much purer and more concentrated when
obtained than wet-process phosphoric acid. The electrothermal process makes
it possible to ubtain, relatively easily, phosphorus anhydride and poly-
_ phosphoric acids, rontaining up to 85 percent P205, as well as to process
phosphstes of any composition and concentration of phosphorus (with, of.
course, varying energy expenditure). Under today's conditions the problem
o{ reducing electric energy consumption for phosphorus sublimation is an
urgent one. With a view to this studies and production tests are being
made for partial or complete replacement of electric energy with the
_ energy f.rom burning natural or commercial gas.
The use of the heat from the phosphorus oxidation process and heat from the
exhaust gases from f.urnaces has been developed at new enterprises. There is
also the problem of chemical utilization of carbon monoxide fo-rmed in a
r.eaction furnace. Solving these industrial energy problems promises a per-
ceptible improvement in the economics of. producing phosphorus and pho~phoric
acids. A longer-range significance to these problems, being solved in
Kazakhstan, stems from the fact that the use of combined electrothermal and
gas (cyclone) units, of the so-called industrial energy method of processing
phosphates, permits easier utilization of low-quality raw material than for
the wet processes. Because of the reduction in quality of many natural
phosphates, as they become depleted, the cost of the acid processes (mainly
sul�uric- and nitric-acid) will rise and of the thermal processes--go down.
Therefore, a11 these methods must be creatively improved. The series of
experiments in thermal dissociation of phosphates in electric vacuum and
plasma reactars, with the separation of P205, conducted by R. G. Aziyev and
S. I. Vol'fkovich [15J are worthy of continuation, to solve the economic
problems.
Since the inter.esting, but uncompleted studies of processes of oxidizing
phosphor.us by water in steam and liquid f.orm under pressure, conducted
before World War II by E. V. Britske, V, N. Ipat'yev, A. V. Frost and their
associates, this work has so far not been renewed, evpn thoiigh it has long-
range interest For the simultaneous production of phosphoric acids and
hydro~en.
Because of the striving to bind phosphorus ~vith n:trogen in a maximally con-
centrated form, research was done on the conditions of synthesis, structure
and technical properties of the phosphorus nitrides PN and P2N5, and the
potentials for their use as fertilizer and new commercial material. This
work is being continued.
A substantial series.c~f studies has been devoted to methods of obtaining and -
_ to the properties of phosphides of iron, aluminum, magnesium, zinc, boron
and some transitional metals, allo}~s used in metallurgy and also for obtain-
in~ phosphorous hydrides and other compounds. Some phosphides have recently
been used at production facilities for infusible semiconductors, electro-
luminescent compounds, photocells, quantum generators (lasers), etc.
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In this field of research on the structure and properties of phosphides,
a great deal new is still expected for technology, including for three-
and higher-component phosphides.
Phosphorus hydrides, oxides, halogenides (particularly chlorides, hydroxy-
chlorides, fluorides and bromides), sulfides and compounds similar to them,
as well as oxy-acids of phosphorus and their salts, compounds of phosphorus
with aluminum, silicon, chromium and a number of rare elements, are not
discussed in this essas�, since they are being covered increasingly widely
. in the literature, by including immediate problems of scientific research
and their practical use.
Researchers are also faced with many theoretical problems of further,
intensified study of stereochemistry and the properties of phosphorus
compounds, particularly coordinational ones.
Phase transformations and the~material composition and crystal chemistry of
phosphorites and apatites merit further minute studies. To improve the -
in.dustrial processes, thermodynamic and kinetic studies of phosphorus com-
pounds and the processes of their reaction with other substances should be
continued.
When covering the subject of the various functions of phosphorus, and the
fields of use, one must not fail to mention the highly useful role of the
radioactive phosphorus 32P in compounds and preparations tagged with this
isotope in scientific and technical research [29].
Polyphosphates
In the field of the chemistry of inorganic phosphorus compounds, particular
attention should be directed toward the sharply intensified studies of the
processes of polymerization of phosphoric acids and salts. New works are
of great interest from the theoretical and technical standpoint, despite
the fact that, beginning in the nineteenth century, conderised (polymeric)
phosphate drew a great deal of attention. The great progress in the last
20- 30 years was achieved due to the progress in the chemistry of high-
~ molecular and complex compounds, their synthesis and analysis. A particu-
larly large role was played by the use of modern phy~ical-chemical methods -
of study: X-ray phase analysis, nuclear magnetic resonance, infrared
spectroscopy, chromatography, viscosimetry, cryoscopy, dialysis, isotopy
- and new methods of chemical analysis.
Although these methods made it possible to establish�the structure and
properties of numerous polyphosphates and polyphosphoric acids, many
questions still remained inadequately studied, including the series of
~ crystalline, amorphous, vitreous and oligomeric products of polycondensa-
tion and polymerization, the opti.mal conditions for obtaining and alrering
the ir properties (solubility, fusibility, decomposition, capacity for
chelation, etc.). Differences of opinion and contradictions still exist
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on questions of th e conditions for obtaining certain linear, cyclical,
ramified and combined polyphosphates, and even in their terminology.* '
These probler~s are covered in the well-known two-volume work by Van Weser
an d in the monograph by Ye. A. Prodan, and other works [16].
Polyphosphates have attained large and varied use in the production of
cleaning agents and detergents (mainly sodium and potassium tripolyphos-
phates), additives to certain food products (fusion of cheese, sausage,
etc.), to sof ten water, as flotation agents, in the production of cellu-
_ lose, paper, textile, rubber and leather materials, coxr.os~ion inhib itors,
the components of some medicinal and cosmetic preparations and many others.
This variety of the spheres of application is due to the numerous properties
of polyphosphates: cumplexing, condensing, structuring, suspending,
emulsifying, stabilizing, plasticizing, water-softening, oxidation inhibi- ~
ting, froth-forming, corrosion inhibiting, etc.
During the last few decades there has been increasing use of phosphoric
- acids, phosphates and polyphosphates as binding materials, possessing
adhesive properties and ensuring, in compositions with other inorganic and
organic substances, heat-resistance, fire-resistance, mechanical strength,
corrosion resistance and other qualities [17, 18]. As the result of the
p~lycondensation of the binders during heating, a reaction occurs with the
"fillers" (silicates, clays, chromium, zinc and many other materials), and
so-called phosphate cements, ceramic and other materials are obtained.
Phosphate glass, fiber glass and enamels with special properties are also
well-known. Phosphates are successfully used in lasers.
The group of commercial phosphates making it possible to glue and bond
various materials--metals, silicates, ceramics, wood and others--is of
advanced significance for the construction, metallurgical, electrical equip-
ment and other sectors of industry. Modern research in this field, which
utilizes the progress in physical-chemical mechanics, crystal chemistry
and solid state physics, is directed toward the further development of the
most economical compounds of phosphates and other substances.
At a n umber of scientific institutes of the USSR Academy of Sciences and
the republic academies of sciences, ministries and WZ's in the USSR, as
well as in other countries, in the past few years polyphosphates of ammonia,
potassium, sodium, magnesium, carbamide and organic compounds have been
studied an d introduced into production, as well as amide- and imidophos-
phates (as efficient fertilizers), and some of them--also as fodder supple-
ments in livesto ck breeding. Polyphosphate fertilizers are the most highly
concentrated and have a slow, but consequently longer action, higher degree ~
of phosphorus utilization, reduced quality of binding with soils (retro-
gradation), good physical-mechanical p~operties and other qualities. Their
r_omulex-forming and ion-exchange properties should also be noted.
~
So far, along with the chemical classification and terminology in the
literature, obsolete names of high-polymer salts, named after researchers,
are used, as for example, Grem, Kurrol, Madrell salts, and others.
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The polyphosphates of carbamide and compounds of ammonium phosphates with
carbamide and potassium salt (called "karbammophoska" in our country) are
of great interest for the future j19-22].
Phosphorus-containing fertilizers, alkylated derivatives of phosphorus
amides (alkylphosphates), available and only weakly retrogradive in soils,
and considerably surpassing the efficiency of orthophosphates in sierozem
soils, are very in teresting. Also of long-range importance are the pro-
cesses for producing potassium and ammonium polymetaphosphates. Potassium
polymetaphosphates are 100-percent complex, chlorine-free fertilizers, with
excellent physical properties, and may be obtained with varying solubility
- and with a varying ratio of phosphorus and potassium [23-26]. Ammonium
polyphosphates are distinguished by high efficiency as highly concentrated
fertilizers (a content of up to 75-80 percent nitrogen and phosphorus
pentoxide). Superphosphates are also of interest. _
Mention deserves to be made of the use of polyphosphates in the nuclear
- industry as additives to agents for cleaning the surface of equipment and
clothing of traces of many elements and deactivating radioactive residues
(particularly strontium, calcium, etc.) [2 7, 28].
Organophosphorus Compounds _
~
In passing to the subject of organophosphorus compounds, it should be
recalled that with respect to the number of synthesized compotm ds they
are a thousand times greater than the inorganic, and the total content by
weight of phosphorus in organic compounds is hundreds of times less.
The scientific and national economic importance of organophosphorus com-
pounds is tremendous, and is rapidly growing in the fields of biology,
medicine and agriculture. The range of their use in technology and biology
is continually expanding.
The use of organophosphorus compounds began earlier in technology than in
biolagy. Among the technologically important products are solvents,
plasticizers and condensing agents, in plastics production; flotation
agents for ore-con centration; additives for lubricants, increasing their
rheological and corrosion-inhibiting properties at various temperatures
and.pressures. A valuable property of plastics obtained from unsaturated
phosphorus-containing compounds (as well as a number of inorganic phosphorus
compounds) is their complete incombustibility ox reduced ignitability, which
makes it possible to use some of them as fireproofing compounds for fire-
proofing wooden, textile and oth.er materials. Selective organophosphorus
extractants have become very important in the technology of rare and radio-
active elements [30j.
The present-day state and protalems of science and technology in these fields
of the chemistry of organophosphorus compounds is relatively well covered in
a number of books.and journal surveys, so we will restrict our discussion .
here only to a mention of them [31, 32].
-
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Research done by physical chemists and biochemists in the last quarter of
a century achieved great progress in the field of the synthesis, analysis,
structure and physiological f~m ctions of complex organophosphorus compounds.
The synthesis of organophosphorus compounds, begun 130 years ago by L. Tenar,
was not systematically developed until the end of the nineteenth and begin-
nin g of the twentieth century. D. I. Mendeleyev, in "Fundamentals of
Chemistry" noted a number of important but unexplored theoretical problems
of the o rganic chemistry of phosphorus compounds. A. Ye. Arbuzov, in one
of his works, mentions that it was these propositions of D. I. Mendeleyev
that instigated the beginning of his systematic study of organophosphorus
compounds, to wh ich he and h is school devoted over half a century of
creative work.
Included among the fundamen tal wo rks on organophosphorus compounds are the
studies of r~emists from our country: N. A. Menshutkin, Ye. Ye. Vagner,
G. M. Kosolapov, A. Ye, and B. A. Arbuzov, V. M. Plets, T. A. Mastryukova,
A. V. Kirsanov, A. N. Pudovik, N. N. Mel'nikov, I. F. Lutsenko, E. Ye.
Nifant'yev, N. N. Godovikov, K. A. Petrov and others, and in foreign
coun tries--H. Hofman, A. Mikhailis, R. Schrader, A. Todd, A. Frank,
G. Van Weser, D. Braun, K. Suenag, A. Cotter and other scientists. These
studies laid the foundation of th e large, tall building of the chemistry
of organophosphorus compoun ds, which has grown in the last few decades in
a number of countries, and is rapidly being filled with creative scientific
and pra.ctical content. The number and variety of o rganophosphorus compounds
spn thesized and studied in laboratories are now calculated in tens of
thousands, and those produced in industry--in hundreds.
The many-faceted interest in organophosphorus compounds on the part of
, chemists and biologists is so great that at special international and
' domestic conferences and symposiuns, convened every year, hundreds of
papers and reports on new work are delivered.
In the last 30-40 years the extremely important role of organic and inorgan ic -
phospY?oric acids in the life of animals, plants and microorganisms has been
revealed and studied. Their role is diverse, particularly in the metabolic
processes--catabolism and anabolism; in the processes of glycolysis and the
- breakdown of hydrocarbons, photosynthesis and chemosynthesis in cells [33-
35]. As is knoc,m, phosphorus is included in tfi e composition of nucleinic
acids, n ucleoproteins, phosphamides, saccharophosph ates and also a number
of vitamins and enzymes. Organic compounds of phosphorus participate in
many oxidation-reduction reactions, in the processes of carboxylation and
decarboxylation, acetylation, transamination and also as coenzymes in the
transfer of phosphorus groups of adenosine triphosphoric (ATF), adenosine
diphosphoric (ADF) and adenosine monophosphoric (AMF) acids.
The revelation of the role of organophosphorus compounds in the transmissian
of neural stimuli was an important discovery in the twentieth century.
Another great event in biochemistry and physiology was the discovery by
- id. A. Engelhardt of the mechanism of oxidizing phosphorization in the
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respiratory processes of the cell, accompanied by the conversion of inorganic
phosphate into an organic phosphate derivative--adenosine triphosphoric acid.
Later on, in conjunction with M. N. Lyubimova, he established the energy
role of ATP in the functioning of human and animal muscles [36]. In the
last few years valuable research in bioenergetics--the molecular generators
of electric current--was performed by V. P. Skulachev, Ye. A. Liberman,
L. M. Tsofina and A. A. Shaytis. Many processes in organisms take place
by means of organophosphorus compounds, particularly phosphorus proteins
and nucleinic acids. As early as 1945, W. A. Engelhardt wrote [37] that
the biochemical dynamics of the cell may be characterized as the chemistry
of compounds of phosphoric acid. Scientific progress is continually giving ~
us increasingly new cases and proofs of the participation of phosphorus
compounds in the vital life processes. -
- Problems of the energetics and metabolism of organophosphorus compounds in
the life of animals and plantsteave not yet been fully disclosed, and in the
light of today's tasks of molecular biology and bionics, deserve further
tho rough and precise studies.
It is widely known that many organophosphorus compounds, such as medica*_ions,
insectofungicides,~herbicides, stimulants, mutagens, sterilants and many
other substances have a strong physiological action that affects the vital
activity of organisms, as well as their participation in the construction of
molecules of nucleinic acids, some vitamins, enzymes an d hormones. Some
phosphate coenzymes play the role of intermediary transmitters (acceptors
and donors) of certain chemical groupings, as well as of electrons and atoms
. of hydrogen. For example, nucleotide transferase, which catalyzes this
process, is among the carriers of nucleide residues containing phosphoric
acid.
It can be said without exaggeration that in metabolism, in the phenomena of
heredity and in the evolution of the development of organisms, organic and
inorganic phosphorus-containing compounds play an extremely varied role,
as yet insufficiently revealed. The further development of work in the
field of the synthesis, analysis and physical-chemical research at the
juncture of various fields of chemistry and biology is also substantial
and drawing attention.
The most general analysis of modern development and progress in the chemis-
try of organic compounds of ptiosphorus [38-40] attests to the fact that,
despite the major achievements in science and practical work, researchers
are still faced with many important tasks in broadening and deepening our
_ concepts in the sphere of physiology, toxicology, pharmacology, medicine
and agriculture, in the theoretical study of the conformances to principle _
that relate their composition, structure and properties, and also in seek-
ing new production processes an d improving the existing ones, including
the problem of raw material, labor safetp and environmental protection.
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Using Compounds Containing Phosphorus in Medicine and Chemical Protection `
of Plants anc~ Animals
Progress in synthesizing and analyzing afforded the opportunity, at the
beginning of the twentieth century, of using compounds containing phosphorus '
_ in medicine, veterinary science and chemical protection of plants and
animals. In the twentieth century there was exceptionally widescale,
comprehensive and rapid development of work in studying and using insecto-
fungicides, herbicides and other bioactive agen ts in plant growing, and,
more slowly--in livestock breeding. New medications undezwent prolonged
testing due Co the need for detailed and multifaceted evaluation of their
physiological effect and consequences for man, domesticated animals and
insects.
Some of the first preparations used in medicine were calcium, sodium and
magnesium phosphates, glycerophosphate, leucitine, products of adenile
acid and, widely used in the last few years, adenosine triphosphoric acid
(ATF). These preparations are used as tonics, vasodilators, stimulants of
cardial activity and hemopoiesis, in anemia, rickets, osteomalacia, tuber-
culosis and a number of nervous diseases. The organophosphorus preparations
used against glaucoma are widely known: phosarbine,* phosphacol, armine
and other preparations, developed by A. Ye. Arbuzov.
Clinical studies also indicated the efficiency of using a number of organo-
phosphorus nrepa.rations against mental diseases, traumatic paralysis and
intestinal atony, to accelerate the labor process, and for other purposes.
Some compounds containing phosphorus that suppress choline esterase broaden
the perspective for affecting the central nervous system and functions of
the cerebral cortex.
Comprehensive research on medicines, with respect to the nature of the
study, approximate work on chemical agents to protect plants and animals:
- insectofungicides, acoricides, herbicides, defoliants, helminthocides and
other veterinary agents. Among the many hundreds of these agents, one of the
leading roles is pla~ed by phosphorus compounds, the world assortment of
which is close to 150 p reparations, and is continually growing. Their s uc-
cess i~ due to the high efficiency in a variety of spheres of application,
- comparative economical nature, rapidity of decomposition in most organisms,
in soils and waters, with the formation of compounds that are nontoxic, or
_ only slightly toxic, to man, domestic animals and insects, as well as to
- the lack of an ability to accumulate in organisms.
Biochemical studies indicate that organophosphorus preparations that corre-
spond to Schrader's formula i.nhibit choline esterase relatively rapidly.
M,:inly used to protect plants are derivatives of phosphoric, thio- and ~
dithiophosphoric and phosphoric acids [41-44]. A good effect in the
quality of the insecticides and acaricides was shown by alkylphosphates
and amides of fluorophosphoric acids. It is interesting to note that
_ Tetraethylmonothiopyrophosphate.
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substituting one of the oxygen atoms fo-r sulfur in derivatives of phosphoric
acid considerably reduces the harmful effect of these compounds on man and
animals, while retaining the necessary pesticidal activity. Some compounds
(particularl.y ethers of phosphorous acid) are efficient weed kil.lers.
The variety and number of organophosphorus compoun ds that are important in
protecting plants and animals is so great that in the monograph by N. N.
Mel~nikov, "The Chemistry and Technology of Pesticides," the tables listing
them take up 24 pages.
_ The research and studies of new phosphorus-containing medicinal, pesticidal
_ and other bioactive agents, developed racently, are directed toward study-
ing the conformances to principle that join together their composition, -
structure and biochemical and physical-chemical properties. An example of -
- this'scientific work, uniting chemists and biologists, is the comprehensive
- study by M. I. Kabachnik, Ya. Mikhel'son and their associates, who
established th.e relationship between the composition, structure and
mechanism of the toxic effect of organophosphorus compounds on various _
physiological processes. A thorough study of the mechanism of the physio-
logical action ~f organophosphorus insecticides and acaricides makes it
possible to create new preparations with selective action, and to reveal
their structure.
The biochemical studies on the molecular level made by F. Krik, Kh. G.
Korana, A. S. Spirin and others open great perspectives in the field of
the structure and functions of organophosphorus compounds in proteins, '
nucleinic acids and other objects.
It should be hoped that empirical research and screening of new physio-
logically active substances will be increasingly substituted for theoretical
prognoses. *
When speaking of pesticides and other toxic substances, one must not fail to ~
mention ways of pratecting man and the environment. In our time these vital
questions should mainly be solved through prophylactic measures, with the
development of production processes and application, and not by rendering
poisonous products harmless after their use or with careless use of them.
Despite the high efficiency of a number of organophosphorus preparations,
shortcomings are inherent in many of them that force chemists and biologists
to seek new agents to p rotect plants and animals. Therefore, scientific
boards of experts and plans specify: intensification of work on seeking
no t only synthetic, but also microbiological agents that ar.e harmless for
man and animals; the use of integration measures, combining cl.iemical, bio-
logical, agro- and zootechnical agents, and also methods such as granulztion
and capsuli.zation of solid preparations and others. Despite the great
progress in the production and use of organophosphorus compounds, chemists,
*
- A center was recently organized in the USSR to test newly synthesized
bioactive compounds.
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technologists; toxicologists and other specialists are still faced with
many complex problems, the solution to which requi.res ~horough and precise
research. Ttie problem is being solved of thei:r syntheses with the medium
_ not only of phdsplioric chlorides and sulfides, but also of elemental phos-
phorus, phosphorus trioxide and other initial compounds of phosphorus. _
It is probably useful for toxicologists and physiologists to have a deeper "
acquaintance with the results of research in molecular biology and '
enzymology, and to make broader use of the newest physical and physical-
chemical methods of studying the structure and properties of bioactive
compounds. ~ _
Conclusion .
From the brief survey given it can be seen what a large number of various
phosphorus-containing substances are being thoroughly studied and used and
merit rurther purposeful comprehensive research. There can be no doubt -
that the br_idges being built between chemistry, k~iology and technology,
between inorganic, organic and physical chemistry of phosphorus and between
_ theory and practice will ensure new creative achievements, intensify the
feedback among various sectors of science and raise even higher the impor-
tance of phosphorus for life and for social and cultural progress. It is
good that th e chemists of the Soviet Union, in cooperation with the scien-
tists of oth er countries in the world, are taking a worthy, creative part -
in the tremendous, fruitful international work.
The first part of this survey emphasized the limited nature of the natural
resources of phosphoru~ and the low degree of their use in today's basic
chemical industry, aoriculture and other major sectors of the national
economy, which raises great, complex problems for geologists, chemists,
biologists and specialists in various sectors of technology. We are
obliged to deepen the theory purposefully, in accordance with the plan,
to intensify research and to accelerate putting the scientific achievements
into effect in the national economy an d public health, taking into con-
~ideration envi.ronmental protection, the economics of production and the
use of compounds containing phosphorus.
In concludin g the report, I feel the need to recall the fact that I975
marked the SOth anniversary of the discovery in the Soviet Union of the
extremely large deposits of apatite ores in Khibiny, which was a historic
_ landmark in establishing the powerful domestic phosphate industry. This
discovery and rapid development of these ores in the unpopulated polar
regions, which was the collective achievement of specialists in various ~
fields of science and technology--geologists, chemists, engineers, agro-
chemists, economists, etc.--inscribed bright pages in the history of the
building of socialism in our country and became the beginning of a new era
in creating the powerful phosphate industry and in chemization of agri-
_ culture in the Soviet Union. It is also appropriate to mention that 1976
marked the 40th anniversary of the discovery of the second powerful raw
materials base of the phosphate industry--the Karatau deposits.
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Recalling these significant dates and surging flow of research on the
chemistry of phosphorus, there can be no douht that the scientists and
" production workers will also in the future work on the study and optimum
use of phosphorus, so that this "light-carrier" and "life element" may
contrihute to the �_`urther rise in health and well-being of the people, -
nourish and strengthen their powers, create new materials and make a
_ creative contribution to the progress and flourishing of human society.
BIBLIOGRAPHY
1. Van Weser, in ~the collection, "Fosfor i ego soyedineniya" [Phosphorus -
and Its Compounds], Vol 1, Moscow, Mir, 1962, p 8,
2. B. M. Gimmel'farTi, IZV. AN SSSR. SERIYA GEOLOGICH., No 11, 1952, p 46.
3. "Syrevaya baza fos�atnoy promyshlennosti" [The Raw Materials Base of the
Phosphate Industry], Mosco~r, Izdatel'stvo Ministerstvo Geologii SSSR,
19 73 .
4. B. M. Gimmel'farb, IZV. AN SSSR. SERIYA GEOLOGICH., No 11, 1952, p 38.
- 5. M. C. Man derson, "Offerire Technok. Conferenz.," Houston Texas, Pt 2,
19.7.2, p 393.
_ 6. T. P. Unanyants, "Sovremennoye sostoyaniye i perspektivy primeneniya
mineral`nykh udobreniy v S ShA" [The Present State and Perspectives
in Usin$ Mineral Fertilizers in the United States], Moscow, Izdatel'stvo
Ministerstvo sel'skogo khozyaystva, 1975.
_ 7. K. M. Malin, "Zhiznennyye resursy chelovechestva" [Vital Resources For
Mankind], Izdatel'stvo AN SSSR, 1961, p 88.
8. V. N. Stepanov, "Mirovoy okean" [The World Ocean], Moscow, Znaniye, 1974.
9. "Trudy nauchno-metodicheskikh soveshchaniy Geograficheskoy seti opytov
s udobreniyami" [Works of the Scientific-Methodological Conferences of
the Geographical System of Experiments With Fertilizers], Vol 22,
Moscow, 1973.
10. A. V. Sokolov, and T. D. Koritskaya, UDOBRENIYA I UROZHAY, No 11, 1958,
p 39.
11. I. T. Kondrat'yev, and G. V. Podkolyazina, AGROKHIMIYA, No 12, 1970.
12. G. V. Podkolyazina, Author's Abstract of a Candidatorial vissertation,
Moscow, NIUIF, 1975.
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13. S. I. Vol'fkovich; V. V. Illarionov; A. A. Ionass; A. L. Malykh; and
R. Ye. Remen, "Gidrotermicheskaya pererabotka fosfatov na udobrPniya
i kormovyye sredstva" [Hydrothermal Processing of Phosphates for
Fertilizers and Fodder AgentsJ, Moscow, Khimiya, 1969.
- 14. A. V. Sokolov; K. F. Gladkova; and N. D. Talanov, AGROKHIMIYA, No 4,
1972, p 24.
15. S. I. Vol'fikovich, and R. G. Aziyev, DOKL. AN SSSR, No 162, 1965,
_ p 1310.
16. Ye. A. Prodan' L. I. Prodan; and N. F. Yermolenko, "Tripolifosfati i
ikh primeneniye" [Tripolyphosphates and Their Use], Moscow, Nauka i
Tekhnika, 1969. ~
17. S. L. Golynko-Vol'fson; M. M. Sychev; A. G. Sdukas; and L. I. Skoblo,
"Khimicheskiye osnovy tekhnologii i primeneniya fosfatnykh sbyazok .
i pokrytiy" [Chemical Fundamentals of the Technology and Use of Phos-
phate Binders and Coatings], Leningrad, IChimiya, 1968.
18. "Tekhnologiya i svoystva fosfatnykh materialov" [The Technology and �
Properties of Phosphate Materials], a~ollection edited by V. A.
KopEpkin, Moscow, Stroyizdat, 1974.
19. S. I. Vol'fkovich, ZH. PRIKL. KHIMII, No 11, 1972, p 2361.
20. S. I. Vol'fkovich, and L. V. Kubasova, in the collection, "Novyye
_ vidy kompleksnykh udobreniy" [New Types of Complex Fertilizers],
Vol 3, Izdatel'stvo MGU, 1972, p 3.
21. F. V. Yanishevskiy, and M. A. Prokosheva, AGROKHI~IIYA, No 2, 1975, p 14.
22. V. M Borisov, et al., "Mineral Fe.rtilizers and Sulfuric Acid," _
"Trudy NIUIF" [Works of the Scientific Research Institute o� Ferti-
lizers, Insecticides and Fungicides imeni Ya'. V. Samoylov], Vol 221,
1973, 3, 92, 154.
23. B. M. Beglov, Author's Abstract of a Doctoral Dissertation, Tashkent,
Institute of Chemistry of the Uzbek SSR, 1975. ~
24. S. I. Vol'fkovich, and A. S. Cherepanova, "Mineral Fertilizers and
Sulfuric Acid," "Trudy NIUIF, Val 221, 1973, p 167.
25. F. V. Yanishevskiy, and M. A. Prokosheva, AGROKHIMI`ZA, No 2, 1972, p 3.
26. K. F. Gladkova, and A. S. Cherepanova, AGROKHIMIYA, No 1, 1974, p 28.
27. Z. Peterson, and R. Uaymer, "Khiiniya i atonmaya tekhnologiya"
[Chemistry and,Nuclear Technology], Moscow, Atomizdat, 1967.
~ 53
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28: Yu. V. Kuznetsov; V. N. Shchebetkovskiy; and A. G, Trusov, "Osnovy
dezaktivatsii" [Fundamentals of Deactivation], Moscow, Atomizdat, 1968.
29. Z. I. Dykhova, and V. M. Fedorov, "Radioaktivnyy fosfor" [Radioactive
Phosphorus], Moscow, Atoinizdat, 1961.
30, A. N. Nesmeyanov, "Radiokhimiya" [Radiochemistry], Moscow, Khimiya,
1972.
31. Ye. L. Gefter, "Fosfororganicheskiye monomery i polimery" [Organo-
phosphorus Monomers and Polymers], Moscow, Izdatel'stvo AN SSSR, 1960.
32. V. M. Plets, "Organicheskiye soyedineniya fosfora" [Organic Phosphorus
Compounds], Kazan`, 1940.
33. A. N. Belozerskiy, "Molekulyarnaya biologiya--novaya stupen'
poznaniya prirody" jMolecular Biology--A New Stage in the Knowledge of
Nature], Moscow, Sovetskaya Rossiya, 1970.
34. M. S. Kulayev, "Biokhimiya vysokomolekulyarnykh polifosfatov" [The
Biochemistry of High-Molecular Polyphosphates], Izdatel'stvo MGU, 1975.
35. N. P. Lisovskaya, and N, B. Livanova, "Fosforproteiny" [Phosphorus
Proteins], Moscow, Izdatel'stvo AN SSSR, 1960..
36._ V. A. Engel'gardt, and M. N. Lyubimova, NATURE, No 168, 1939, p 144.
37. V. A. Engel'gardt, IZVESTIYA AN SSSR. SERIYA BIOLOG., No 182, 1945,p 2. ~
38. "Organophosphorus Compounds," Vols 1-6, edited by G. M. Kosolapoff and
1. Maien, New York, Intern. Publ., 1970-1973.
39. G. I. nerkach; I. N. Zhmurova; A. V. Kirsanov; V. I. Shevchenko; and
A. S. Shtepansk, "Fosfizosoyedineniya" [Phosphide CompoundsJ, Kiev,
Naukova Dumka, 1965. ~ -
40. "Uspekhi khimii fosfororganicheskikh i seroorganic soyedineniyy"
jProgress in the Chemistry of Organic Phosphorus and Orgariic Sulfur
_ Com pounds], Pts 1-3, edited by A. V. Kirsanov, I. N. Zhmurova, Kiev,
Naukova Dumka, 1969, 197Q, 1973.
41. N. N. Mel'nikov, "Khimiya i tekhnologiya pestitsidov" [Chemistry and
Technology of Pesticides], Moscow, Khimiya, 1974.
42. A. A. Shamshurin, and M. Z. Krimer, "Fiziko-khimicheskiye svoystva
organicheskikh yadokhimatov i regulyatorov rosta. Spravochnik"
[Physical-Chemical Properties of Organic Toxic Chemicals and Growth
Regulators. A Handbook), Moscow, Nauka, 1966.
~ 5~+
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43. "Kratkiy spravochnik po yadokhimikatam" jA Brief Handbook on Toxic
Chemicals], edited by P. N. Yukhtin, Moscow, Kolos, 1973. ~
44. G. Shrader, "Novyye fosfororganicheskiye insektitsidy" [New Organic
Phorphorus Insecticides], Moscow, 1965.
COPYRIGHT: Izdatel'stvo "Nauka", 1977
12151
CSO: 1841
55
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RADIATION CFIEMtSTRY
UDC: 541.1S _
CHEMICAL PROTECTION OF ORGANIC SYSTEMS AGAINST IONIZING RADIATION
Moscow KHIMICHESKAYA ZASHCHITA ORGANICHESKIKH SISTEM OT IONIZIRUYUSHCHEGO
IZLUCHENIYA (Chemical Protection of Organic Systems Against Ionizing
Radiation) in Russian 1978 signed to press 2 Aug 77 pp 2, 141
[Annotation and.table of contents from book by Mikhail Fedorovich Romantsev,
Atomizdat, 1550 copies, 144 pages]
[Text] ~nhancement of radioresistance of rubber, oils and lubricants,
organic coolan:ts and-.uther materials by means of special chemical additives
(antirads) opens up new possibilities for the use of such materials in
_ the atomic industry, in spa.ce and in cases where the materials may be exposed
to ionizing radiation. ~
This book sheds light, on the basis of published data and studies of the
author, on the current status of chemical protection of organic systems
against ionizing radiation; it discusses the mechanism and kinetic patterns
of action of antirads, suitability of different substances as protective
supplements and possible approaches to solving the problem of chemical
protection.
There is comprehensive coverage of questions of practical use of antirads to
stabilize lubricants, elastomers, polymers, coolants, fuels, dyes and other
systems.
This book is intended for specialists in the field of radiation chemistry,
radiation materials technology and different fields related to the use of
atomic energy.
There are 44 illustrations and 69 tables; bibliography lists 259 items.
Contents Page
Introduction 3
Chapter 1. Main Patterns of Radiochemical Reactions of
Chemical Compounds 6
1.1. Primary physicochemical processes with exposure of a
substance to radiation 6
56
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Contents, continued Page
1.2. Reactions of charged particles 8 -
1.3. Excited molecules and their reactions 11
1.4. Formation and reactions of free radicals 14
1.5. Distinctions of radiochemical processes in the condensed phase 17
Chapter 2. General Principles of Selection and Use of Antiradiation .
Additives 19
2.1. Relation between protective properties of compounds and
ionization potential. affinity for electron and energy of
excited state 19
2.2. Effect of molecule structure on protective properties of
substances 26
2.3. The role of compatibility of components 33
2.4. Synergistic effects in the combined action of additives 34
Chapter 3. Mechanism of Action of Protective Additives on Radiolytic
Processes 36
- 3.1. Aromatic hy3rocarbons . 36
3.2. Olefins 41
3.3. Haloid-containing compounds 45
3.4. Amines 50
3.5. Sulfur-containing compounds 57
3.6. Stable iminoxyl radicals 62
3.7. Carboranes 69
3.8. Phenols 75
3.9. Organometal compounds 78
3.10. Other compounds 82
- Chapter 4. Practical Applications of Antirads . 88
4.1. General approach to evaluation of radioresistance of materials 88
4.2. Distinctions of polymer radiolysis and possibility of
enhancing their radioresistance by means of antirads 90
4.3. Chemical protections of elastomers against radiation 99
4.4. Radioresistance of oils and chemical protection thereof 107
4.5. Lubricants [grease] 113
4.6. Enhancement of radioresistance of organic coolants 115
4.7. Other applications of antiradiation additives 124
Bibliography 128
[103--10,657]
COPYRIGHT: Atomizdat, 1978
10657 .
CSO: 1841
57
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PLANT SAFETY
UDC: (661.7/19)004.58
SAFETY RULES FOR PLANTS PRODUCING ORGANIC CHEMICAL REAGENTS
. Moscow PRAVILA BEZOPASNOSTI DLYA PROIZVODSTV ORGANICHESKIKH KHIMICHESKIKH
REAKTIVOV (Safety Rules in Organic Chemical Reagent Industries) in Russian
1978 signed to press 6 Jun 78 pp 2, 74-75
[Annotation and table of contents from book edited by Yu. N. Slesarev et
al. (Gosgortekhnadzor SSSR [State Committee of the USSR Council of Ministers
for Supervision of Industrial Safety and for Mining Inspection]),
Izdatel'stvo Nedra, 6600 copies, 76 pages]
[Text] These rules define the safety requirements for organic chemical -
reagent plants that are being designed, under construction, remodeling _
and in operation. In addition to general requirements, there are safety :
requirements for individual chemical processes. The specificationa are
spelled out for each type of production with regard to outfitting with
monitoring and measuring instruments, automatic control systems,
protective devices, blocks [interlocks], cut-offs and signal systems.
There is discussion of requirements referable to territory, buildings and
installations, transport routes and roads, arrangement of equipment and
~ work places. Attention is given to fire-control measures and personnel
protective devices for workers.
These rules are intended for all engineering and technical workers concerned
with design, assembly, remodeling and operation of organic chemical reagent
plants.
Contents Page
Foreword 3
Section 1. General Theses 5
Section 2. Territory, Buildings and Installations 8
Section 3. Sanitary and Technical Devices 9
Heating and ventilation 9
Water supply and sewer system 13
Section 4. Technological Section 16
General specifications 16
Specifications for equipment and work places 20
Shielding devices and units 25
a
58 .
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Contents, continued Page
Mechanization of laborious, deleterious and hazardous work ~ 25
~ Specifications for pipes and fittings 26
Monitoring and measuring instruments 29
Communications and signaling system 30
Automation and remote control 31
Protection against corrosion 32
Supply of inert gas 33
Specific requirements for different processes 33
Processes involving the use of inethanol 34
Chlor.ination process 36
Bromination process 38
Cyanidation process 39
Processes involving the use of inetal sodium (calcium, potassium,
lithium) 42 -
Hydration process 43
Processes involving the use of inercury and compounds thereof 45
Processes involving the use of arsenic and compounds thereof 47
Sulfonation process 48
Chlorosulfonation process 48
Nitrosation, nitration and diazotization processes 50. _
PhosUenation process 51
Methylation process 54
Amination process 55
Section S. Electrical installations 56
Section 6. Gas Safety ["Rescue"?] Service 60
Section 7. Special Fire Control Measures 61
Saction 8. Upkeep, Repair, Cleaning of Equipment, Pipelines and
Production Buildings 63
Section 9. Personnel Protection Devices and Personal Hygiene for
Workers 71
Section 10. Responsibility for Infraction of Safety Rules 73
[109-10,657] ~
COPYRIGHT: Izdatel'stvo "Nedra"
10657 _
CSO: 1841
59
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WATER TREATMENT
WATER TREATMENT BY REVERSE OSMOSIS AND ULTRAFILTRATION
Moacow OBRABOTKA VODY OBRATNOM OSMOSOM I UL'TRAFIL'TRATSIYEY in Ruseian 1978
signed to press 13 Kpril 1978 p 2, inside front cover
[Annotation and table of contents from book by A. A. Yasminov, A. K. Orlov,
F. N. Karelin and Y. D. Rapoport, Stroy3zdat, 5000 copies, 121 pp]
[Text] This book discusses problems of the preparation of natural and purified
waste waters by~means of semipermeable membranes, as well as describing the pro-
perties of the membranes and methods of preparing them. The designs and char-
acteristics of inembrane element`s and apparatus are described, they are classi-
fied and an analysis of their techr.ological parameters is given. Units using
different processes are described, and design calculation methods and operat- -
ing results ar~ given. A technical and economic evaluation of inembrane
treatment of water is given.
The book is intended for scientific and engineering-technical workers in sci- -
entific research and planning organizations.
Contents Page
J Foreword 3.
Table of Symbols � 4
Chapter 1. Fundamentals of Reverse Osmosis and Ultrafiltration
Treatment of Water..... 6
1. Reverse osmosis (hyperfiltration) 6
2. Ultraf3ltration 16
3. Semipermeable membranes 18
4. The effect of pressure, salt content and temperature on the
water treatment process 25
5. Sedimentation in membranes 31
Chapter 2. Membrane Elements and Apparatus 36 ;
1. Flat-chaihber elements and apparatus... 39
2. Coil-type apparatus..... 44
3. Elements and apparatus based on tubular membranes 47
60
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4. Apparatus with hollow ~ibers 56
S. Design and design calculations of inembrane apparatus 61
Chapter 3. Design Calculations for Reverse Osmosis and Ultrafiltra-
tio~~1 Unit Design~�.... ~ 71 -
1. Designs for desalination units 72
2. Designs for wastewater purif ication and concentration units...... 75
3. Designs for reverse filtration unita for processing electro-
lytic plant wash waters.... 77
Chapter 4. Water Treatment Installations 81
1. Desalination installations 83
2. Wastewater purification installations 95
3. Preparatory treatment of wat er in installations 102
4. Installation equipment and automation 105
~ Chapter 5. Technical and Economic Aspects of Water Treatment by
Reverse Osmosis and Ultrafiltration 110
Bibliography 119
8480
CSO: 1841 END
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61.
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