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Progress and competitiveness analysis of coal-to-ethanol technology
□ Guan Ying, Research Institute of PetroChina Jilin Petrochemical Company
There are four main methods of ethanol production, one is ethylene from petroleum raw material is hydrated to produce ethanol; Second, it is produced by fermentation using grain as raw materials, which is inefficient, costly, and cannot be developed on a large scale due to the impact of food security; Third, biomass cellulose and other raw materials to produce ethanol, but due to the limitation of cost and raw material supply, the capacity increase is slow
.
Fourth, coal or industrial tail gas to ethanol technology, is currently maturing, and has the advantages of flexible raw materials and low cost, will become an important source of
ethanol in China.
There are four main technical routes for coal-to-ethanol: syngas microbial fermentation; syngas is directly hydrogenated by acetic acid; Syngas is hydrogenated by acetate; Syngas is directly produced to ethanol
.
Among them, the technology development of ethanol from acetic acid rehydrogenation (including direct hydrogenation and esterification hydrogenation) produced from coal is the most active
.
.
Fourth, coal or industrial tail gas to ethanol technology, is currently maturing, and has the advantages of flexible raw materials and low cost, will become an important source of
ethanol in China.
There are four main technical routes for coal-to-ethanol: syngas microbial fermentation; syngas is directly hydrogenated by acetic acid; Syngas is hydrogenated by acetate; Syngas is directly produced to ethanol
.
Among them, the technology development of ethanol from acetic acid rehydrogenation (including direct hydrogenation and esterification hydrogenation) produced from coal is the most active
.
1.
Syngas microbial fermentation method
Syngas microbial fermentation method
Coal-based syngas bioethanol technology is the use of special microbial strains, the water gas containing carbon monoxide and hydrogen, syngas, etc.
for fermentation, at room temperature and pressure, the syngas into the liquid medium containing biological strains, under the action of microorganisms selectively generate ethanol, by rectification and other methods to separate high-purity ethanol products, to achieve the combination of
coal chemical technology and biochemical technology.
The technology is currently in the hands and patented
by Lanza Technologies New Zealand.
for fermentation, at room temperature and pressure, the syngas into the liquid medium containing biological strains, under the action of microorganisms selectively generate ethanol, by rectification and other methods to separate high-purity ethanol products, to achieve the combination of
coal chemical technology and biochemical technology.
The technology is currently in the hands and patented
by Lanza Technologies New Zealand.
In 2011, Baosteel Metal Company and Lanze Company jointly established China's first operating enterprise for waste gas reengineering, Shanghai Baosteel Lanze New Energy Co.
, Ltd.
In April 2012, the 300-ton steel mill tail gas to ethanol demonstration project was officially put into operation
.
The project uses the tail gas (mainly CO) generated by the steelmaking plant, adopts the biological fermentation process of Lanze, and combines the membrane separation technology and fermentation process of the Chinese Academy of Sciences to produce ethanol
.
Accordingly, the industrialization project of 100,000 tons of steel mill exhaust gas to ethanol began construction in 2013 and will be completed and put into operation
in 2014.
, Ltd.
In April 2012, the 300-ton steel mill tail gas to ethanol demonstration project was officially put into operation
.
The project uses the tail gas (mainly CO) generated by the steelmaking plant, adopts the biological fermentation process of Lanze, and combines the membrane separation technology and fermentation process of the Chinese Academy of Sciences to produce ethanol
.
Accordingly, the industrialization project of 100,000 tons of steel mill exhaust gas to ethanol began construction in 2013 and will be completed and put into operation
in 2014.
In addition, New Zealand Lanze Company is also cooperating with Henan Coal Chemical Industry Group, Yankuang Lunan Fertilizer Plant, Shougang and other companies to build syngas microbial fermentation engineering projects
.
.
In March 2013, Hebei Iron and Steel Group Tang Iron and Steel Company signed a cooperation framework agreement
with Hasco Group to produce ethanol project using steelmaking converter gas.
After the completion of the project, it will process 650,000 standard m3 of converter gas per day and produce 30,000 tons
of ethanol per year.
Compared with converter gas power generation, CO2 can be reduced by about 50%, increasing the efficiency by 1.
8 times
.
with Hasco Group to produce ethanol project using steelmaking converter gas.
After the completion of the project, it will process 650,000 standard m3 of converter gas per day and produce 30,000 tons
of ethanol per year.
Compared with converter gas power generation, CO2 can be reduced by about 50%, increasing the efficiency by 1.
8 times
.
2.
Syngas directly to ethanol
Syngas directly to ethanol
The technology of direct production of coal to ethanol from syngas is characterized by a short industrial process and relatively low
coal consumption, energy consumption and investment costs.
However, from the perspective of thermodynamics and kinetics, it is difficult for the reaction to stay in the stage of only generating ethanol, the product distribution is wide, the ethanol yield is low, especially the selectivity and technical indicators of the catalyst still have some shortcomings, especially the catalyst is expensive and the amount is large, making the ethanol production cost high
.
coal consumption, energy consumption and investment costs.
However, from the perspective of thermodynamics and kinetics, it is difficult for the reaction to stay in the stage of only generating ethanol, the product distribution is wide, the ethanol yield is low, especially the selectivity and technical indicators of the catalyst still have some shortcomings, especially the catalyst is expensive and the amount is large, making the ethanol production cost high
.
The Southwest Chemical Research and Design Institute and the Institute of Dahua of the Chinese Academy of Sciences are conducting research
on technologies related to the direct production of ethanol from coal to syngas.
In 2006, the Institute of Dahua of the Chinese Academy of Sciences successfully developed the process technology of syngas catalytic conversion to ethanol and other C2 oxygen-containing compounds, and successfully developed a low-noble metal catalyst
with rhodium content less than 1%.
The pilot results show that the catalyst has stable performance for 1000 hours of continuous operation, ethanol selectivity of 90%, and ethanol and ethyl acetate can be produced highly
selectively by adjusting the catalyst components and operating conditions.
In November 2011, Jiangsu Thorpe Group started construction of a 30,000-ton syngas to ethanol complete technology research and development project, which will become the world's first 10,000-ton coal-to-ethanol industrialization plant
after completion.
After the project is put into operation, a 300,000-ton process software package will be formed as soon as possible, and a 300,000-ton commercial operation plant
will be built.
on technologies related to the direct production of ethanol from coal to syngas.
In 2006, the Institute of Dahua of the Chinese Academy of Sciences successfully developed the process technology of syngas catalytic conversion to ethanol and other C2 oxygen-containing compounds, and successfully developed a low-noble metal catalyst
with rhodium content less than 1%.
The pilot results show that the catalyst has stable performance for 1000 hours of continuous operation, ethanol selectivity of 90%, and ethanol and ethyl acetate can be produced highly
selectively by adjusting the catalyst components and operating conditions.
In November 2011, Jiangsu Thorpe Group started construction of a 30,000-ton syngas to ethanol complete technology research and development project, which will become the world's first 10,000-ton coal-to-ethanol industrialization plant
after completion.
After the project is put into operation, a 300,000-ton process software package will be formed as soon as possible, and a 300,000-ton commercial operation plant
will be built.
3.
Syngas is directly hydrogenated by acetic acid
Syngas is directly hydrogenated by acetic acid
The process flow of syngas to ethanol by direct hydrogenation of acetic acid is shown in
Figure 1.
Figure 1.
A lot of research has been carried out at home and abroad, for example, BP of the United Kingdom has applied for a patent for "carboxylic acid and its anhydride catalyzed hydrogenation to generate alcohols and/or esters"; The Institute of Dahua, Chinese Academy of Sciences, invented the "method for syngas to synthesize ethanol"; The acetic acid conversion rate of 600 tons of acetic acid direct hydrogenation technology independently developed by Pujing Chemical is greater than 99%, the ethanol selectivity is greater than 92%, and the temporal and spatial yield is greater than 850g/(kg cat)·h
.
.
Celanese, Inc.
of the United States, uses platinum/tin catalysts to produce ethanol directly and selectively from acetic acid in TCX technology
.
That is, acetic acid and hydrogen selectively generate ethanol
at a temperature of 250 °C under gas phase conditions with the help of platinum/tin catalysts supported by silica, graphite, calcium silicate or aluminosilicate.
According to this technology, large-scale industrial production of ethanol directly from acetic acid can be realized, and it has high selectivity and yield
.
In 2011, Celanese used this technology to build a large-scale industrial ethanol project in Gaolan Port Economic Zone of Zhuhai, with a design capacity of 400,000 tons; In March 2012, Celanese implemented the renovation of existing facilities in the Nanjing Chemical Industry Park to produce ethanol for industrial use, with plans to increase its production capacity to 280,000 tons; Celanese also plans to work with Beijing Oriental Yuhong Waterproofing Technology Company to build a 1 million tonne coal-to-fuel ethanol plant
in Xilingolmeng, Inner Mongolia.
of the United States, uses platinum/tin catalysts to produce ethanol directly and selectively from acetic acid in TCX technology
.
That is, acetic acid and hydrogen selectively generate ethanol
at a temperature of 250 °C under gas phase conditions with the help of platinum/tin catalysts supported by silica, graphite, calcium silicate or aluminosilicate.
According to this technology, large-scale industrial production of ethanol directly from acetic acid can be realized, and it has high selectivity and yield
.
In 2011, Celanese used this technology to build a large-scale industrial ethanol project in Gaolan Port Economic Zone of Zhuhai, with a design capacity of 400,000 tons; In March 2012, Celanese implemented the renovation of existing facilities in the Nanjing Chemical Industry Park to produce ethanol for industrial use, with plans to increase its production capacity to 280,000 tons; Celanese also plans to work with Beijing Oriental Yuhong Waterproofing Technology Company to build a 1 million tonne coal-to-fuel ethanol plant
in Xilingolmeng, Inner Mongolia.
4.
Syngas is hydrogenated by acetate
Syngas is hydrogenated by acetate
Compared with the process of hydrogenation of syngas by acetic acid to ethanol, the reaction and separation of acetate hydrogenation to ethanol process are simpler, and the catalyst is a conventional copper-based composite catalyst, which is less
costly.
At the same time, due to the weak corrosivity of its raw materials and products, carbon steel can be used, and the investment amount is greatly reduced
.
It is estimated that the investment in new process equipment is only 1/3 or less
of the acetic acid hydrogenation process.
The process flow diagram is shown in Figure 2
.
costly.
At the same time, due to the weak corrosivity of its raw materials and products, carbon steel can be used, and the investment amount is greatly reduced
.
It is estimated that the investment in new process equipment is only 1/3 or less
of the acetic acid hydrogenation process.
The process flow diagram is shown in Figure 2
.
As of March 2012, Shanghai Penzheng Engineering Technology Co.
, Ltd.
applied the 60-ton pilot plant for acetate catalytic hydrogenation to ethanol catalyst and process construction independently developed by Shanghai Penzheng Engineering Technology Co.
, Ltd.
, which has been running stably for more than 6,000 hours, with the conversion rate of acetate being greater than 96% and the selectivity of ethanol being more than
98%.
, Ltd.
applied the 60-ton pilot plant for acetate catalytic hydrogenation to ethanol catalyst and process construction independently developed by Shanghai Penzheng Engineering Technology Co.
, Ltd.
, which has been running stably for more than 6,000 hours, with the conversion rate of acetate being greater than 96% and the selectivity of ethanol being more than
98%.
In July 2012, the acetate hydrogenation ethanol production technology project independently developed by Southwest Chemical Research and Design Institute passed the expert appraisal
organized by the Sichuan Provincial Science and Technology Department in Chengdu.
The development of industrial process software packages on a scale of 200,000 tons has been completed
.
organized by the Sichuan Provincial Science and Technology Department in Chengdu.
The development of industrial process software packages on a scale of 200,000 tons has been completed
.
In August 2012, the pilot test of acetate hydrogenation to ethanol technology independently developed by Jiangsu Sudan Chemical Group Co.
, Ltd.
was successful, and the process has been opened up on the 600-ton pilot plant and operated stably for 1,000 hours
.
On this basis, the preparation
of 100,000 tons and 200,000 tons of acetate hydrogenation to ethanol process packages was completed.
, Ltd.
was successful, and the process has been opened up on the 600-ton pilot plant and operated stably for 1,000 hours
.
On this basis, the preparation
of 100,000 tons and 200,000 tons of acetate hydrogenation to ethanol process packages was completed.
In addition, there is also a process method of converting coal to ethanol by dimethyl ether in coal-to-ethanol technology, but there are not many
research reports.
research reports.
5.
Competitive analysis of several routes
Competitive analysis of several routes
From the current technical route of several coal-to-ethanol products, each has its own advantages and disadvantages, and they are not perfect
.
Among them, the reaction of ethanol by biological fermentation method is relatively slow, and there will be problems when amplification; Syngas bio-processed ethanol needs to stay for a period of time due to fermentation, which is difficult to produce continuously, and the cost will not be low
.
The syngas direct ethanol production process route is long, and the catalyst has not yet passed the customs, the product comes out after the mixture, need to purify a series of subsequent processes, its advantage is easy to achieve large-scale production
.
.
Among them, the reaction of ethanol by biological fermentation method is relatively slow, and there will be problems when amplification; Syngas bio-processed ethanol needs to stay for a period of time due to fermentation, which is difficult to produce continuously, and the cost will not be low
.
The syngas direct ethanol production process route is long, and the catalyst has not yet passed the customs, the product comes out after the mixture, need to purify a series of subsequent processes, its advantage is easy to achieve large-scale production
.
At present, the route of hydrogenation of syngas to ethanol by acetic acid is the most promising and the cost may be the lowest
.
Hydrogenation of acetic acid to ethanol, each ton of ethanol theoretically consumes 1.
304 tons of acetic acid, 973m3 of hydrogen, and produces 391 kg of water
.
At present, the price of acetic acid is cheap, and the production technology of acetic acid is mature, so the hydrogenation of acetic acid to produce ethanol is expected to be large-scale and large-scale
.
However, some people believe that if acetic acid is hydrogenated to ethanol, this technical route is competitive
only when the price of acetic acid is below 4,000 yuan / ton.
This route is mainly to solve the problem of
domestic acetic acid overcapacity.
If the price of acetic acid reaches more than 6,000 yuan / ton, this route is completely uncompetitive
.
Acetic acid is synthesized from methanol and carbon monoxide carbonyls
, while methanol is synthesized from hydrogen and carbon monoxide.
Originally hydrogen and carbon monoxide synthesis can directly synthesize ethanol, if it is used to produce acetic acid and then hydrogenation to ethanol, from the production process is equivalent to going back, around more bends, energy efficiency becomes lower and becomes undesirable
.
.
Hydrogenation of acetic acid to ethanol, each ton of ethanol theoretically consumes 1.
304 tons of acetic acid, 973m3 of hydrogen, and produces 391 kg of water
.
At present, the price of acetic acid is cheap, and the production technology of acetic acid is mature, so the hydrogenation of acetic acid to produce ethanol is expected to be large-scale and large-scale
.
However, some people believe that if acetic acid is hydrogenated to ethanol, this technical route is competitive
only when the price of acetic acid is below 4,000 yuan / ton.
This route is mainly to solve the problem of
domestic acetic acid overcapacity.
If the price of acetic acid reaches more than 6,000 yuan / ton, this route is completely uncompetitive
.
Acetic acid is synthesized from methanol and carbon monoxide carbonyls
, while methanol is synthesized from hydrogen and carbon monoxide.
Originally hydrogen and carbon monoxide synthesis can directly synthesize ethanol, if it is used to produce acetic acid and then hydrogenation to ethanol, from the production process is equivalent to going back, around more bends, energy efficiency becomes lower and becomes undesirable
.
In short, these coal-to-ethanol routes have their own advantages and disadvantages and bottlenecks, indicating that the current coal-to-ethanol technology is not mature, the comparative advantages of various technologies are not obvious, and the technical reliability and stability need to be tested by time and practice, but they are undoubtedly competitive
compared to the grain ethanol process route.
compared to the grain ethanol process route.
