International Journal of Civil Engineering and Technology (IJCIET)
Volume 10, Issue 04, April 2019, pp. 142-151, Article ID: IJCIET_10_04_016
Available online at http://www.iaeme.com/ijciet/issues.asp?JType=IJCIET&VType=10&IType=04
ISSN Print: 0976-6308 and ISSN Online: 0976-6316
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THE MAIN ORGANIC SYNTHESIS BASED ON
COAL: GEOGRAPHY AND DEVELOPMENT
PROSPECTS
Volkov Arseniy Andreevich
Postgraduate, Department of Social – Economic Geography of foreign countries
Lomonosov Moscow State University, GSP – 1, Leninnskie gory, Moscow, 119991, Russian
Federation
ABSTRACT
The industry of basic organic synthesis is one of the most important branches of the
modern chemical industry. Its value is due to the production of chemical products
necessary for the production of polymers, chemical fibers, resins, dyes and other
compounds, without which the progress of many industries is impossible. The main raw
materials for the production of chemical products are traditionally oil and natural gas,
the problem of depletion of which is the main agenda of humankind in the 21st century.
In terms of searching for alternative energy sources, as well as raw materials for the
chemical industry, researches in the field of coal conversion are very important.
Existing modern technologies of coal processing in the future can significantly affect
the energy market. The article gives a brief description of the main organic synthesis
based on coal. The author considers the processes of chemical conversion of coal as
pyrolysis, gasification and hydrogenation. The collected materials and their analysis
allowed identifying the scale, as well as geographical and structural features of the
main organic synthesis based on coal in some countries and in the world as a whole.
Keywords: the main organic synthesis, coal, coal chemistry, gasification of coal, coke
chemistry.
Cite this Article: Volkov Arseniy Andreevich, the Main Organic Synthesis Based on
Coal: Geography and Development Prospects. International Journal of Civil
Engineering and Technology, 10(04), 2019, pp. 142-151
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1. INTRODUCTION
In the middle of the XIX century, almost all organic compounds were obtained from plant and
animal raw materials. Thanks to the development of metallurgy in the same century, and with
it the production of coke, a raw material base (coal tar, crude benzene) was created, which is
necessary for the production of organic products. [General chemical technology ..., 1955]
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At the beginning of the XIX century, coal was used to produce coal gas, and then it became
the main raw material in the development of organic synthesis. Drugs, dyes, explosives, etc.
were made from coal tar obtained during coking.
At the beginning of the 20th century a special feature in the development of chemical
processes was the introduction of methods based on the use of catalysts, high pressures and
temperatures, deep cold and continuous processes. With the help of these technologies, the
synthesis of methanol from carbon monoxide and hydrogen under pressure was started, and the
production of artificial liquid fuels was carried out. [General chemical technology ..., 1955].
Then the products of coal processing gave way to hydrocarbons obtained from the
extraction and processing of oil.
This transition, which began in the 1950s in the USA and somewhat later in Western
Europe, led to the dominant use of oil and gas. In the period from 1960 to 1975, the share of
coal in the raw material balance of benzene production decreased in the United States from 32
to 7%, and in Japan from 85 to 13.3%. The corresponding situation has developed with the
production of raw materials for the synthesis of methanol and other products [Chornii, 1983].
The basis of modern industry of organic synthesis is oil and natural gas. About 96% of all
organic products worldwide are obtained from oil and gas, the remaining 4% - from coal,
products of processing of plant and animal raw materials, as well as products of biotechnology
[Industrial production of organic ...].
Considered as a major factor in the growth of the industrial age and the development of
organic chemistry in the mid-19th century, coal may again become a key raw material in the
global chemical industry in the current century.
Thus, carbon chemistry, which originated at the end of the 19th century, now receives
additional impulses of development in connection with the development of new technologies
of the production of raw materials in order to produce synthetic hydrocarbons and their
products.
In this connection, the purpose of the article is determined as to give a general description
of the main organic synthesis based on coal and the peculiarities of its geography.
2. RESULTS
Products of modern basic organic synthesis based on coal chemistry are coke, resin, synthesis
gas, ammonia, coal pitch, dyes and plastics, as well as about 130 types of chemical
intermediates and 5 thousand types of products [10 reasons for ...].
Currently, four types of coal conversion are in industrial use in the world: they are pyrolysis
(coking), gasification, indirect hydrogenation and hydrogenation.
Pyrolysis of coals is called pyrogenic processes used to process coal by heating them
without air access to temperatures of 400 - 1200 C. The approximate yield of coking products
in terms of dry coal is in%: coke is 75-78; coke oven gas is 14 - 18, coal tar is 2.5 - 4 [Avdokhin,
2012]. Schematically, the coking products are shown in Pic.1.
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Pyrolysis
Oven coke
Calcium carbide
Coal-tar
Aromatic compounds
Crude benzol
Benzol, xylene, methyl
benzene
Ethyne
Polyvinyl chloride
Butandiol
Picture. 1 - Pyrolysis products
Applying the method of pyrolysis, about 900 mln tons of coking coal have been used for
2016, as a result about 650 million tons of metallurgical coke and about 30 million tons of coal
tar are being produced in the world. Half of the recycled coal tar is used to produce numerous
aromatic or polyaromatic compounds. The rest is coal tar pitch, which is used as a binder in
the production of anodes used in the production of aluminum. Currently, about 100 different
products have been isolated from the resin, which are raw materials for the production of
plastics, chemical fibers, the synthesis of dyes, etc. [Avdokhin, 2012; China coal tar ...].
China is the largest producer (22.13 million tons) and a processor of coal tar in the world,
with one-fourth of the world's capacity for the deep processing of coal tar in 2016 [China coal
tar ...].
The largest companies in the deep processing of coal tar are Koppers (USA), Ruetgers
(Germany), Nippon Steel & Sumikin Chemical (Japan) and Baoshun Technology (PRC).
Koppers is the world leader in the processing of coal tar (2.10 million tons per year), the
Chinese Baoshun Technology is the largest national company in China with a capacity of 1.05
million tons per year. [China coal tar ...].
In the conditions of stagnation of metallurgical production, an alternative source of demand
for metallurgical coke may be the production of calcium carbide. Technical calcium carbide is
widely used for the industrial production of acetylene and its products.
China is the dominant player in the global calcium carbide market: 96% of the world supply
and demand of it is in this country, which is also the world's largest exporter of calcium carbide.
In China, 94–97% of polyvinyl chloride is produced using calcium carbide technology. At the
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end of 2014, 12 million tons of polyvinyl chloride (30% of world production) were produced
on the basis of coal. Due to the growing domestic demand for polyvinyl chloride in China, it is
expected that consumption of calcium carbide from coal will increase by 2-3% annually.
Growth in calcium carbide consumption is also expected in Western European countries (0.6%
per year on average for the region) and the USA (1-2%) [Analysis of the prospects for
conversion ...].
Coal gasification is the process of converting its organic mass into combustible gases. For
the purpose of chemical conversion, coal gasification is carried out by its interaction with water
vapor to produce a so-called synthesis gas according to the formula: C + H2O → CO + H2. In
order to ensure the required heat balance, oxygen can be additionally used, due to which an
exothermic reaction of coal combustion takes place in parallel according to the formula C +
½O2 → CO. The ratio of CO and H2 in the raw synthesis gas, depending on the method of its
production, varies from 1: 1 to 1: 3. As a rule, the percentage of substances in it is as follows:
CO - 15-18%, H2 - 38-40%, CH4 - 9-11%, CO2 - 30-32%. The synthesis gas may contain other
substances - inert gases (N2) and sulfur containing compounds (H2S). Carbon dioxide and
sulfur are disposed from it by purification with selective solvents [Synthesis - gas: methods ...].
Synthesis gas is a structural element in the production of olefins (ethylene and propylene),
and can also be used in the production of carbamide and motor fuels (diesel and gasoline). (Pic.
2) Synthesis gas can also be modified to the quality of “artificial natural gas”, and it is used as
a substitute for natural gas at gas CHP plants and in the industry.
Synthesis gas is not a self-sufficient market product, since in terms of its basic
characteristics (calorific value), it is significantly inferior to the natural gas and it is used mainly
in several technological schemes for the profitable and environmentally friendly utilization of
low-quality coal.
The purified synthesis gas is then used to produce ammonia and methanol, liquid
hydrocarbons (by the Fischer-Tropsch reaction), in oxosynthesis, and in other chemical
processes.
A special place is occupied by the technology of underground coal gasification, allowing it
to be used without excavation to the surface. Their significance is primarily determined by the
fact that in the world coal reserves exceed the oil and gas reserves a lot.
China, South Africa, Australia, Canada, and the United States [Klimenko, 2009] have
shown the greatest interest in technologies of underground coal gasification in recent years.
Currently, coal gasification processes differ significantly from the level of the mid-20th
century, both in terms of technology, and in terms of economic and environmental indicators.
In modern coal chemistry, there are dozens of ways of coal gasification. The main factor in this
diversity is that there is no universal technology that uses different types of coal and is capable
of developing products that are suitable simultaneously for the energy, chemical and
metallurgical industries. At the present stage the distinctive feature of development of
gasification processes is the technologies of gasification with the combined production of
several chemical products, which have increased economic efficiency.
It is important to note that most of the existing hydrocarbon gasification plants in the world
are focused specifically on the use of coal gasification processes (about 60%). The following
technologies have industrial experience in obtaining chemical products from coal synthesis
gas:
- “Coal-in-liquid fuel” (international abbreviation - CTL);
- Coal-to-Methanol (CTM);
- Coal-to-Olefins (CTO);
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- Coal-to-ammonia (CTA);
- Coal-to-Synthetic Natural Gas (CTSNG);
- Coal-to-ethylene glycol (CTMEG);
- “Coal-in-benzene” (PTS, in contrast to coke-benzene, technology is more pure and new)
[Higman, 2014]
Production of “clean” electricity in a combined cycle with intra-cycle gasification and
associated products (hydrogen, artificial natural gas, synthetic ammonia, straight-run gasoline,
diesel fuel, methanol and derivatives, dimethyl)
The use of technology of such a cycle allows the commissioning of interbranch industrial
complexes in the energy and chemical industries and the combination of the output of specified
products for specific raw materials and market conditions in the required proportions.l ether).
is one of the most promising coal utilization technologies.
The technology provides a more efficient (compared to simply burning coal) production of
electricity or chemical products (in the case when electricity is not needed or cannot be
transferred to the consumer), or a whole "basket" of associated market products, the cost of
which exceeds the cost of electricity , obtained by burning coal in thermal power plants.
At the end of 2014, 41 million tons of ammonia (24%), 14 million tons of methanol (22%),
2.6 million tons of olefins (ethylene / propylene) (2%) were produced in the world by
gasification of coal [Perspective Analysis conversion ...]. In the process of producing chemical
products from coal by gasification, the base semi-product is synthesis gas. (Pic. 2)
Gasification
Synthesis-gas
Methanol
Monoethyleneglycol
Dimethyl ether
Synth. ammonia
Polyesters
Olefins
Carbamide
Sodium carbonate
Picture. 2. Products of coal gasification
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At the end of 2014, there were 272 gasification installations for carbon-containing raw
materials in the world, comprising 686 gas generators with a total capacity (for synthesis gas)
of 117 GW. More than 400 (61%) of existing gas generators use coal as raw materials,
including plants for underground gasification of coal (underground gasification of coal),
production of liquid (coal into liquid) and gaseous hydrocarbons (synthetic natural gas),
production of chemicals (coal-chemicals), etc., using coal as a raw material. At the construction
stage, there are 74 more plants comprising 238 gas gas generators with a capacity of 83 GW.
Over the past 30 years, the specific power of gas generators has increased almost 2 times.
[Gasification plant databases…, 2016].
In the countries of the Asia-Pacific region, most of the existing coal gasification plants
(excluding those under construction and designed) are operating.
China is the world leader in coal mining and processing, and is the leader in the number of
these enterprises. The PRC has the largest number of coal gas generators:
205 industrial coal gasification projects for the production of chemical products, of which
143 are operating (35% of all global gas generators), 62 will be put into service from 2015 to
2020;
9 industrial projects for the production of liquid motor fuel from coal, nine of them are
working, three will be put into service from 2015 to 2020.
Coal gasification in the country accounts for 5% of total coal consumption, and the coal
chemical industry of China for 2015 received 14 million tons of methanol and 2.6 million tons
of olefins [Analysis of the prospects for conversion ...; Zuhong, Wang, 2017].
In China, projects of production of olefins using the technology HUNDRED / MTO, got
special attention because here they are considered to be means of diversifying the raw material
base of the chemical industry, creating for the rapidly growing coal output of a new consumer
with higher profitability and releasing additional quantities of deficient (liquid) fuel for the
country's growing fleet.
According to the forecasts of the China National Energy Administration, by 2020 the
annual capacity of plants for the production of gaseous hydrocarbons from coal (“synthetic
gas”) will be 50 billion m3, and liquid hydrocarbons (“synthetic oil”) will be about 50 million.
tons and the processing of coal into olefins will be 15 million tons (42% of the national
production of olefins) [Anderson, 2014].
Apart from China, similar factories also operate in Japan, Malaysia, Singapore, South
Korea, Taiwan and India.
In Europe, due to severe environmental restrictions on carbon emissions into the
atmosphere, the expansion of coal gasification practices, in particular, the construction of plants
belonging to the “zero emissions” class, is also becoming relevant and promising.
In 2014, there were 51 coal gasification plants in the European region. Germany was the
leading country (20 plants). It was followed by Italy (7), Finland (5), the Netherlands and
Sweden (3 plants each), Portugal, Spain and the United Kingdom (2 plants each).
In the United States, there are 33 operating coal gasification plants, including with
complete separation technology and carbon dioxide separation. According to the country's
Energy Department, the cost of electricity produced using coal gasification technology is only
10% higher than a traditional coal-fired power plant. It is logical to expect that the development
and promotion of clean technologies in the country will be facilitated by the introduction of
tangible taxes on carbon dioxide emissions into the atmosphere.
About 10 factories using coal gasification technologies currently operate in Canada.
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In Africa, plants using coal gasification technology are located in South Africa and the
Republic of Mozambique. In South Africa, liquid fuel from coal (CTL) is used not only in cars,
but also in other vehicles. Thus, the national energy company Sasol has permission to use it in
commercial air travel.
Currently, about 30% of the country's needs for gasoline and diesel fuel are satisfied by
producing them from local coal. The total production capacity of liquid fuels in South Africa
is about 8 million tons per year. Since its inception in 1955, Sasol has produced more than 200
million tons of synthetic fuels and chemical products from coal. Sasol activity makes a
significant contribution to the country's economy - $ 3 billion a year or 2% of GDP [World
Coal Institute, 2006].
However, it should be noted that the high level of coal chemistry development in the
country is mainly due to political (introduction of an oil embargo), but not due to economic
reasons.
In the South American region, coal gasification technologies are used only in Brazil. Also,
one pilot project of the Portuguese Portucel is implemented in the Middle East in Qatar.
Hydrogenation of coal is its interaction with hydrogen. This technology is considered as
“direct liquefaction of coal” (“direct liquefaction process”), while the Fischer-Tropsch reaction
is considered as “indirect coal liquefaction process” (Avdokhin, 2012).
Hydrogenation, depending on the process conditions, makes it possible to convert solid
fuels into high-quality motor fuel (gasoline, diesel, boiler fuel) and feedstock for organic
synthesis (phenols, nitrogen bases, polycyclic aromatic hydrocarbons, etc.).
Currently, there is only one “direct liquefaction of coal” plant in the world, its capacity is
estimated at 1 million tons per year. It is owned by the Chinese company Shenhua CTL and is
located in the Inner Mongolia region of China [Shenhua Coal to ...].
The current scale of chemical processing of coal, with the exception of pyrolysis processes
(coke chemistry), is 119.28 million toe. (3.2% of world consumption [International Energy
Agency, 2018.]. These estimates also do not take into account coal gasification data for the
purpose of generating electricity and heat generation, since they are presented in the
corresponding coal consumption items.
Table 1 The scale of the total chemical processing of coal in the countries (million toe)1
Countries
2000 year
( %)
2010 year
(%)
2016 year
(%)
China
30,24
63,71
85,33
84,18
105,63
88,5
Japan
The USA
India
Poland
Germany
Republic of
South Africa
Turkey
2,61
7,35
2,52
1,26
0,399
5,49
15,5
5,3
2,65
0,84
3,32
4,96
2,03
1,44
0,616
3,28
4,89
2
1,42
0,6
3,92
3,26
1,47
1,12
0,98
3,28
2,73
1,2
0,93
0,82
1,05
2,21
0,98
0,96
0,77
0,64
0,07
0,14
0,41
0,4
0,56
0,46
Check Republic
1,792
3,77
0,553
0,54
0,385
0,32
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France
tbc
tbc
0,308
0,3
0,35
0,29
Other countries
World
in total
0.769
0,39
1,42
1,43
0,835
0,83
47,46
100
101,36
100
119,28
100
Source: compiled by the author on the basis of IEA data [International Energy Agency,
2018]
As of 2016, the production of chemical products from coal was carried out in 20 countries
of the world (Pic. 3). 9 countries represented in Table 1 account for just over 99% of world
consumption.
China is the undisputed leader in the chemical processing of coal over the past 40 years.
Since the 1980s, the amount of coal used in the chemical industry has increased in 3.5 times,
from 29.47 to 105.63 million toe (that is 2.9% of global coal consumption). The countries of
the Asia-Pacific region account for the bulk of total coal consumption in the chemical industry:
China (88.5%), Japan (3.92), India (1.2), Korea (0.1), Australia (0.1) ) - in aggregate it is
93.38%.
The estimates do not include coking coals used in the pyrolysis process.
Picture. 3. Volumes of chemical processing of coal in the world, mln. toe
Source: compiled by the author based on IEA data [International Energy Agency, 2018]
The main locomotives of chemical processing of coal in Europe, which accounts for just
under 5%, are the traditional “coal economies” of Poland and the Czech Republic, as well as
Germany, France, Norway and the United Kingdom.
The United States, which occupied the traditional second place after China, in the past two
decades has lost its position in the production of chemical products based on coal, preferring
cheaper hydrocarbons. The special attention of coal chemistry in the USA is paid to gasification
processes for the purpose of power generation and heat generation.
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3. CONCLUSION
In the near future, further growth of chemical processing of coal is expected at the expense of
the APR countries, primarily due to the commissioning of a large number of capacities in
China. This trend should especially attract the attention of countries with large coal reserves,
including in Russia, Indonesia, Kazakhstan and others.
Thus, in terms of the volume, scale of production and the diversity of the products obtained,
the pyrolysis processes occupy a leading role among the existing coal chemical processes.
However, the chemical products obtained in the process of the specified coal conversion, in
fact, are only related "by-products" of the metallurgical industry.
Of particular interest in the efficient use of coal, both from an economic and environmental
point of view, the main producers and consumers of coal are gasification processes that
combine the production of electricity with the production of coal products.
Despite the high cost of coal gasification technology, in contrast to the traditional use of oil
and natural gas, significant progress has been made recently in reducing the capital and
operating costs of coal gasification (from 3,500 to ~ $ 2,000 per ton) [SIBENCO Annual Report
, 2018].
The technology of converting coal into liquid fuel (CTL) seems to be particularly
significant. The figures also indicate that CTL production costs are $ 67-82 per barrel (figures
from SASOL), which in the future will allow coal to compete with traditional energy resources
[World coal institute, 2009].
In addition, modern technologies make it possible to involve illiquid coal resources — lowcalorie, oxidized and brown coal — into economic circulation massively, which makes the
construction of coal enterprises in remote and hard-to-reach regions at the expense of reducing
enormous transportation costs cost-effective.
An important market trend of recent years is a shift in the main volumes of imports,
consumption, and due to them chemical processing of coal towards the Asia-Pacific region.
South-East Asia, India, South Korea and Japan, as well as the developing coal markets of
Vietnam, Pakistan, Bangladesh, Myanmar and Taiwan are the most dynamic in this respect.
These markets need more high-calorific coal for new power plants. For example, in China,
more than half of the huge number of coal-fired plants were put into service less than 10 years
ago, and their overall efficiency has already exceeded 42%. Some countries have already begun
to build power plants with an efficiency of 50%.
It is also worth noting that in 2017, with the support of the Academy of Sciences of the
PRC, the first plant for the production of ethyl alcohol from coal was launched in this country.
Adding 10% ethanol to gasoline can reduce exhaust emissions by a third [SIBENCO Annual
Report, 2018].
The European market has now exhausted its growth potential. Due to the tightening of
environmental requirements and high competition of gas and renewable energy sources, coal
consumption in Northern Europe is being decreased, but interest in chemical processing is
remained at the same level.
Coal gasification is one of the key technologies in the efficient and environmentally
friendly processing of coal and important in the development of organic synthesis (methanol,
olefins, aromatic hydrocarbons, ethylene glycol, etc.) and power generation with full separation
and carbon dioxide separation technology.
Oil and gas reserves are inevitably depleted, according to various estimates, the peak in
their use will be in 2030, while according to forecasts of the International Energy Agency, and
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peak in coal use will be in 2040. However, taking into account the existing trends in the
development of coal chemistry, already in the middle of the XXI century coal can become No.
1 hydrocarbon in the world’s fuel and energy balance, and as the main raw material of the
world chemical industry.
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