CN101638369A - Method and system using carbon dioxide generated in industrial process to produce dimethyl carbonate - Google Patents
Method and system using carbon dioxide generated in industrial process to produce dimethyl carbonate Download PDFInfo
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- CN101638369A CN101638369A CN200910140291A CN200910140291A CN101638369A CN 101638369 A CN101638369 A CN 101638369A CN 200910140291 A CN200910140291 A CN 200910140291A CN 200910140291 A CN200910140291 A CN 200910140291A CN 101638369 A CN101638369 A CN 101638369A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/04—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from carbon dioxide and ammonia
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a mixture containing dimethyl carbonate, in which carbon atoms of at least two thirds of the dimethyl carbonate come from a side product of carbon dioxide generated in at leastone industrial process. The invention also provides a method for producing dimethyl carbonate. In the method, coal is converted into a liquid product under hydrogen atmosphere to obtain side productsof ammonia and carbon dioxide; at least one part of the carbon dioxide is synthesized with the ammonia to produce carbamide, and a part of carbon dioxide is led into a biomass cultivating area to obtain syngas from the cultivated biomass; and at least one part of the syngas is catalytically converted to methanol which is synthesized with the carbamide to produce the dimethyl carbonate.
Description
[technical field]
An aspect of of the present present invention relates to the method and system that utilizes the carbon dioxide production methylcarbonate that produces in the commercial run.
[background technology]
Many scientists think, comprise that the aggravation of Greenhouse effect that a large amount of discharging causes of the greenhouse gases of carbonic acid gas may be the fundamental cause of Global warming.Since the Industrial Revolution, the mankind coal combustion, oil, Sweet natural gas and trees in communications and transportation and industrial production produce and make earth intensification after great amount of carbon dioxide and methane enter atmospheric layer, make carbon cycle unbalance, have changed the energy transformation form of global biosphere.Carbon dioxide content has increased by 25% in two a century in the past in the atmosphere, considerably beyond whole historical records in the past 160,000 years that scientist may survey out, and does not still have the sign that slows down at present.
Such as, the coal liquefaction craft that is surging forward at present can be produced miscellaneous Chemicals, such as fuel oil, methyl alcohol, acetate, dme, oxo alcohol and isocyanic ester etc., but also can produce and discharge a large amount of carbonic acid gas.The carbonic acid gas of coal liquefaction craft process discharging not only can pollute environment, also is the waste of carbon resource simultaneously.
Therefore, industry member needs to reduce emission of carbon-dioxide, can effectively utilize the commercial run and the setting of carbon resource simultaneously again.
[summary of the invention]
The application's one side provides a kind of miscellany that comprises methylcarbonate, and wherein, the carbon atom in 2/3 described methylcarbonates is from carbon dioxide by-product that at least one commercial run produced.In one embodiment, the carbon atom in 2/3 described methylcarbonates comes from the biomass (biomass) at least a environment that grows in described carbon dioxide by-product.In one embodiment, these biomass are phycophyta.The miscellany of described methylcarbonate can be the pure carbon dimethyl phthalate.
The application provides a kind of miscellany that comprises methylcarbonate on the other hand, methylcarbonate is wherein obtained by following method: the carbon dioxide by-product that at least one commercial run produced is imported the zone that at least one cultivation has biomass, and be that raw material is made described methylcarbonate with described biomass.In one embodiment, be that raw material is made described methylcarbonate and comprised described gasifying biomass obtaining synthetic gas with described biomass, and the synthetic gas that is obtained is converted into methyl alcohol, again with methyl alcohol and urea synthesis methylcarbonate.With described biomass is that raw material is made described methylcarbonate and comprised that also the by product with the by product of a coal liquefaction craft process and/or described methyl alcohol and urea synthesis methylcarbonate process is used for synthetic described urea.
The application provides a kind of method of producing methylcarbonate on the other hand, it comprises that the carbon dioxide by-product that at least one commercial run is produced imports the zone that at least one cultivation has biomass, and is that raw material is made described methylcarbonate with described biomass.
Described at least one commercial run can comprise one or more in coal gasification course, Fischer-Tropsch building-up process, DCL/Direct coal liquefaction process, natural gas conversion processes and the steel smelting procedure.
The application provides a kind of integrated molded coal liquefaction method on the other hand, comprises coal, oxygen and water are converted into first synthetic gas and the first by product carbonic acid gas; Coal is converted into liquid product under hydrogen atmosphere, and obtains the second by product carbonic acid gas; The described first and second by product carbonic acid gas of near small part import one and cultivate the zone that biomass are arranged, and obtain second synthetic gas from the biomass of being cultivated; Described first and second synthetic gas of near small part are catalytically conveted to methyl alcohol; Urea is made in described first and second by product carbonic acid gas of near small part and ammonia synthesis; And with described methyl alcohol and described urea synthesis making methylcarbonate.
In one embodiment, being used for the synthetic ammonia of making urea to small part in the above integrated molded coal liquefaction method is the by product that coal is converted into liquid product under hydrogen atmosphere.In another embodiment, be used for the synthetic ammonia of making urea to small part and be by product described methyl alcohol and described urea synthesis making methylcarbonate.
In one embodiment, the carbon monoxide that is got by described first and second synthetic gas separation to small part is used to raw coal is carried out pre-treatment to obtain through pretreated coal under carbon monoxide atmosphere, should be converted into liquid product under hydrogen atmosphere through pretreated coal again.In another embodiment, to described first and second synthetic gas of small part by the synthetic liquid product that is converted into of Fischer-Tropsch, and obtain tail gas, and be used to the pre-treatment of coal in the described tail gas to the small part carbon monoxide.
In one embodiment, described integrated molded coal liquefaction method comprises that also described first and second synthetic gas of near small part are by the synthetic liquid product that is converted into of Fischer-Tropsch, and obtaining the 3rd by product carbonic acid gas, described method comprises that also described the 3rd by product carbonic acid gas of near small part imports the zone that described cultivation has biomass.
[description of drawings]
Fig. 1 is that the carbonic acid gas that utilizes commercial run to produce among the embodiment is produced the block diagram of the system of methylcarbonate.
Fig. 2 is the block diagram of commercial run among the embodiment.
[embodiment]
At present, the development of various commercial runs makes emission amount of carbon dioxide more and more come, and the discharging of great amount of carbon dioxide not only can pollute environment, also wastes a lot of carbon resources simultaneously.Provide the by product carbonic acid gas that effectively utilizes commercial run to produce to produce the system and method for required Chemicals and the product that this method is produced in the embodiment of the invention.In one embodiment, the carbon dioxide by-product that commercial run produced is used to produce methylcarbonate, makes carbon atom in 2/3 the product methylcarbonate from carbon dioxide by-product that at least one commercial run produced.
In one embodiment, as shown in Figure 1, carbonic acid gas that utilizes commercial run/system 110 to be produced system 100 of producing methylcarbonate comprises biomass breeding apparatus 120, biomass gasification device 130, methanol synthesizer 140, apparatus for urea synthesis 150 and methylcarbonate synthesizer 160.Wherein, commercial run/system 110 produces carbonic acid gas 116, also may produce ammonia 112, waste water 114, synthetic gas (main component is the mixed gas of hydrogen and carbon monoxide) 118 and/or used heat 119, biomass breeding apparatus 120 near small part carbonic acid gas 116 and/or waste water 114 are used for cultivating biomass (biomass).Wherein, biomass (biomass) are meant the organic substance that all directly or indirectly utilize green bio matter photosynthesis to form, and comprise plant, animal and microorganism and movement thereof and metabolite.In one embodiment, described biomass are mainly plant, particularly phycophyta.Algae also can be used for wastewater treatment, handling the waste water 114 that commercial run/system 110 is produced, thereby reduces environmental pollution and cost for wastewater treatment.The biomass that biomass gasification device 130 can be cultivated biomass breeding apparatus 120 gasify under suitable condition and generate synthetic gas 132, and the hydrogen-carbon ratio of this synthetic gas 132 can be roughly 1: 1.Methanol synthesizer 140 can be with synthetic gas 132 synthesizing methanols.In addition, apparatus for urea synthesis 150 can be near small part commercial run/system 110 ammonia 112 and carbonic acid gas 116 urea synthesis that are produced.Methylcarbonate synthesizer 160 can be with synthetic urea synthesis methylcarbonate in synthetic methyl alcohol and the apparatus for urea synthesis 150 in the described methanol synthesizer 140.In addition, the synthetic gas 118 that commercial run/system 110 produces also can lead in the methanol synthesizer 140 be used for synthesizing methanol, and the used heat 119 that commercial run/system 110 produces can be used for providing energy for methylcarbonate is synthetic in the methylcarbonate synthesizer 160.In addition, carrying out the ammonia 162 that produces in the methylcarbonate synthetic process in the methylcarbonate synthesizer 160 can lead in the apparatus for urea synthesis 150 and be used for urea synthesis.
The described method and system of producing methylcarbonate with the carbon dioxide by-product that commercial run produced has lot of advantages.At first, large-scale cultivation biomass (as algae) will consume great amount of carbon dioxide, can reduce the Carbon emission of total system, thereby significantly reduced processing cost (because the Environmental policy restriction Carbon emission of carbonic acid gas, therefore, need handle carbonic acid gas by compression and the means of imbedding the inferior costliness in ground); Secondly, the biomass of cultivating can be converted into synthetic gas, by technologies such as synthesising gas systeming carbinols, can further be converted into methylcarbonate, have further improved economic benefit, thereby form benign cycle; In addition, Wood Adhesives from Biomass is also can change into high additive value products such as fuel oil by technologies such as Fischer-Tropsch synthesize behind the synthetic gas.
Commercial run/system shown in Figure 1 can be a certain independent commercial run/system, it also can be integrated commercial run/system that two or more commercial runs that are mutually related/System integration forms, this association can be parallel, also can be that front and back are placed in-line.In one embodiment, as shown in Figure 2, described commercial run/system 110 can be a kind of integrated molded coal liquefaction process/system, and this system comprises coal gasification apparatus 210, Sweet natural gas preparing synthetic gas device 220, Fischer-Tropsch synthesizer 230, DCL/Direct coal liquefaction device 240 and other industrial systems 250.Can also comprise that before DCL/Direct coal liquefaction device 240 pretreatment unit 245 is used for the coal that enters DCL/Direct coal liquefaction device 240 is carried out pre-treatment.
Wherein, coal gasification apparatus 210 is used for gasification to obtain synthetic gas 212 and by product carbonic acid gas, and utilizing business-like gasification installation can obtain hydrogen-carbon ratio is 0.5: 1 to 1: 1 synthetic gas; Sweet natural gas preparing synthetic gas device 220 is used for Sweet natural gas and water or/and carbonic acid gas or/and oxygen conversion is a synthetic gas 222, may also contain a certain amount of carbonic acid gas in the air-flow of its output; Fischer-Tropsch synthesizer 230 can be used to described synthetic gas 212 and 222 is catalytically conveted to hydrocarbon products, may be rich in carbonic acid gas in its tail gas, and this building-up process also can produce waste water; The pretreatment unit 245 of DCL/Direct coal liquefaction device 240, be used under carbon monoxide atmosphere, coal being carried out pre-treatment, to improve the efficient of DCL/Direct coal liquefaction, and DCL/Direct coal liquefaction device 240, raw materials such as coal, water and the hydrogen supply dissolvent direct liquefaction under hydrogen atmosphere that is used for handling through coal pretreatment unit 245 obtains synthetic thick oil, residue, little ammonia and carbonic acid gas; Other industrial systems 250 can be any other can produce carbonic acid gas, used heat and (or) industrial system of waste water, such as smelting iron and steel system and power system etc.Wherein, the gas that is rich in carbon monoxide in the described system 110 can feed the pre-treatment that is used for coal in the pretreatment unit 245, comprise that the synthetic tail gas that produces of Fischer-Tropsch in synthetic gas and the Fischer-Tropsch synthesizer 230 etc. is (if the hydrogen-carbon ratio of Fischer-Tropsch synthetic material synthesis gas was less than 1: 1.9, and the carbon monoxide that water-gas shift was consumed during Fischer-Tropsch was synthetic seldom, such as less than 5%, the tail gas of this Fischer-Tropsch synthesis process is rich in carbon monoxide so).
Like this, described integrated molded coal liquefaction system 110 produces ammonia 112, waste water 114, carbonic acid gas 116 and the used heat 119 that can be used for system shown in Figure 1 100, may also have partial synthesis gas 118 (still having residue after the pre-treatment of the synthetic and DCL/Direct coal liquefaction of Fischer-Tropsch if be used for).Wherein, the part in the carbonic acid gas 116 and/or waste water 114 can be used for the cultivation of biomass, and another part in the carbonic acid gas 116 and ammonia 112 can be used for urea synthesis, and used heat 119 can be used for the synthetic of methylcarbonate.If system 110 is also surplus a synthetic gas 118, this synthetic gas can be used from the synthetic of methyl alcohol with the synthetic gas one that produces behind the gasifying biomass.
The hydrogen-carbon ratio of the above-mentioned synthetic gas that is obtained by Sweet natural gas preparing synthetic gas, gasification and gasifying biomass may be different, are the utilization of optimizing synthetic gas, these synthetic gas can be mixed by a certain percentage being converted into corresponding product again.Also the part carbon monoxide in the synthetic gas can be separated obtaining the synthetic gas of suitable hydrogen-carbon ratio (such as 1: 1.9,1: 1.95,1: 2 etc.), and separate the pre-treatment that the carbon monoxide that obtains can be used for coal.
Ammonia is circulating reaction thing (cycle reagent) in the system 100, and its actual consumption is less, does not therefore need to carry out to replenish in a large number, can mend ammoniated consumption by the ammonia that DCL/Direct coal liquefaction device 240 produces.
In one embodiment, also can obtain (such as buying) a certain amount of ammonia or urea from the outside and start the synthetic of methylcarbonate.
In one embodiment, the biomass breeding apparatus 120 in the system 100, biomass gasification device 130, methanol synthesizer 140, apparatus for urea synthesis 150 and corresponding technological conditions can be respectively device and processing condition, the device of synthesising gas systeming carbinol and the device and the processing condition of processing condition and urea synthesis of device that industry biomass known cultivate and processing condition, gasifying biomass.Coal gasification apparatus 210 and corresponding technological conditions, DCL/Direct coal liquefaction device 240 and corresponding technological conditions also can be respectively the device and the processing condition of the device of the known gasification of industry and processing condition, DCL/Direct coal liquefaction.Repeat no more herein.
Replacedly, commercial run/system 110 shown in Figure 1 also can be other integrated or associative form commercial run/system or a certain independent commercial run/systems, such as, can be that certain part or certain the several part in the integrated molded coal liquefaction process/system shown in Figure 2 are united the system that forms.
In one embodiment, the described biomass breeding apparatus 120 of being used for is cultivated biomass and/or is used for apparatus for urea synthesis 150 and ammonia and carries out carbonylation reaction and produce the carbonic acid gas of urea and can reclaim in any possible source from this commercial run/system 110, includes but not limited to: the air-flow of the air-flow of coal gasification apparatus 210 outputs, 220 outputs of Sweet natural gas preparing synthetic gas device, the air-flow of Fischer-Tropsch synthesizer 230 outputs, the air-flow of DCL/Direct coal liquefaction device 240 outputs, the air-flow of other industrial systems 250 outputs and the combination in above source etc.Can adopt various traditional means to reclaim carbonic acid gas, include but not limited to: absorption (such as transformation absorption (pressure swing adsorption) and " displacement purge cycles "), low temperature separation process, membrane sepn and combination thereof etc.Reclaiming carbonic acid gas from synthetic gas and tail gas may need through once or once separating, and from reformer or contain and reclaim carbonic acid gas the byproduct gas that processing unit (plant) produced of product of 3 above carbon atoms and may not need through separating, because the content of its hydrogen and water is lower, so only need heavy hydrocarbon (hydrocarbon polymer that contains six above carbon atoms) condensation can be obtained to be rich in the gas of carbonic acid gas.
From the air-flow that is rich in carbonic acid gas that step produced that the synthetic grade of Fischer-Tropsch is by product with the carbonic acid gas, reclaim carbonic acid gas and may need to adopt membrane sepn or wet-chemical separation means (wet chemicalseparation).The air-flow that is rich in carbonic acid gas that some steps produced only also can be used for follow-up by the condensation heavy hydrocarbon and ammonia carries out oxonation to obtain urea.
In one embodiment, the catalyzer that is adopted in the processing step with urea and methyl alcohol Synthesis of dimethyl carbonate relevant with methylcarbonate synthesizer 160 is composed as follows: activeconstituents accounts for weight ratio 20-50%, and carrier accounts for weight ratio 50-80%.
The material that can be used as carrier includes but not limited to: activated carbon, αYang Hualv, gamma-alumina, silicon oxide and molecular sieve etc., the monoblock type pottery also relatively is suitable as support of the catalyst.
Activeconstituents can be the oxide compound and/or the muriate of basic metal, alkaline-earth metal and transition element.
Basic metal comprises potassium, sodium, caesium and lithium.
Alkaline-earth metal comprises calcium and magnesium.
Transition element comprises zinc, lead, manganese, cerium and lanthanum.
Preparation of catalysts can may further comprise the steps: at first, prepare the aqueous solution of described basic metal, alkaline-earth metal and transition metal salt; Adjust the pH value of aqueous solution of described salt to 0-5 with ammoniacal liquor or potassium hydroxide solution; Aqueous solution dipping (such as incipient impregnation) described carrier with the salt behind the adjustment pH value has the carrier of activeconstituents to obtain appendix; Then with described carrier under 100-250 ℃ condition dry 2-24 hour; At last with described carrier roasting 2-12 hour acquisition finished catalyst under the condition of 500-1000.
The aqueous solution of wherein said basic metal, alkaline-earth metal and transition metal salt can be nitrate solution, acetate solution, oxalate, hydroxide solution, halide solution etc.
The comparatively ideal pH value of the aqueous solution that is used for the salt of impregnated carrier is 1 to 3.
Comparatively ideal maturing temperature is 650-800.
Comparatively ideal roasting time is 4-8 hour.
Wherein, control, maturing temperature and the roasting time of the pH value of aqueous solution of the described salt that is used for impregnated carrier are particularly crucial for Preparation of catalysts.
In one embodiment, in rectifying reactor (rectification reactor), carry out at the processing step of producing methylcarbonate under the catalyst action by urea and methyl alcohol.Wherein, catalyzer can be loaded into reaction zone, thereby also can be loaded into the balance that the catalytic bed that is movable through reaction zone can be controlled reaction better.Urea methanol solution enters catalytic bed from the top, because temperature is higher in the reactor, the methyl alcohol in the solution enters the rectification zone of catalytic bed top, and the urea in the solution enters catalytic bed; Material benzenemethanol is sent into from the position than the below of catalytic bed, generates methylcarbonate with the urea reaction of being brought into catalytic bed by urea methanol solution.
In one embodiment, the weight ratio of urea is 1-99% in the urea methanol solution, the air speed of urea methanol solution is 0.01-10ml/g*cat/min, the air speed of material benzenemethanol is 0.01-20ml/g*cat/min, and temperature of reaction is 120-250, and reaction pressure is 0.1-5MPa, temperature is 70-210 at the bottom of the still, the stripping section temperature is 70-250, and the rectifying section temperature is 70-280, and reflux ratio is 1/1 to 20/1.
More optimize, the weight ratio of urea is 20-50% in the urea methanol solution.
More optimize, the air speed of urea methanol solution is 0.1-2ml/g*cat/min.
More optimize, temperature of reaction is 150-200.
More optimize, reaction pressure is 0.5-3MPa.
More optimize, temperature is 110-180 at the bottom of the still.
More optimize, the stripping section temperature is 150-190.
More optimize, the rectifying section temperature is 150-200.
More optimize, reflux ratio is 1/1 to 6/1.
Above process has the following advantages: catalyst is solid carrier catalyst, is easy to preparation, has Therefore good repeatability, is easy to suitability for industrialized production; Catalyst and reactant and product are homophase not, Therefore, the separation of catalyst is simple; Can improve by improved catalysts the selective and productive rate of reaction; Secondary Product is few.
Claims (25)
1. miscellany that comprises methylcarbonate, wherein, the carbon atom in 2/3 described methylcarbonates is from carbon dioxide by-product that at least one commercial run produced.
2. a kind of miscellany that comprises methylcarbonate as claimed in claim 1, wherein, all carbon atoms in the described methylcarbonate are all from carbon dioxide by-product that at least one commercial run produced.
3. a kind of miscellany that comprises methylcarbonate as claimed in claim 1, wherein, the carbon atom in 2/3 described methylcarbonates comes from the biomass at least a environment that grows in described carbon dioxide by-product.
4. a kind of miscellany that comprises methylcarbonate as claimed in claim 1, wherein, described biomass are phycophyta.
5. a kind of miscellany that comprises methylcarbonate as claimed in claim 1, wherein, described at least one commercial run comprises one or more in coal gasification course, Fischer-Tropsch building-up process, DCL/Direct coal liquefaction process, natural gas conversion processes and the steel smelting procedure.
6. miscellany that comprises methylcarbonate, wherein, described methylcarbonate is obtained by following method: the carbon dioxide by-product that at least one commercial run produced is imported the zone that at least one kind has biomass, and be that raw material is made described methylcarbonate with described biomass.
7. a kind of miscellany that comprises methylcarbonate as claimed in claim 6, wherein, described biomass are phycophyta.
8. a kind of miscellany that comprises methylcarbonate as claimed in claim 6, wherein, described at least one commercial run comprises one or more in coal gasification course, Fischer-Tropsch building-up process, DCL/Direct coal liquefaction process, natural gas conversion processes and the steel smelting procedure.
9. a kind of miscellany that comprises methylcarbonate as claimed in claim 6, wherein, with described biomass is that raw material is made described methylcarbonate and comprised described gasifying biomass obtaining synthetic gas, and the synthetic gas that is obtained is converted into methyl alcohol, again with methyl alcohol and urea synthesis methylcarbonate.
10. method of producing methylcarbonate, it comprises that the carbon dioxide by-product that at least one commercial run is produced imports the zone that at least one kind has biomass, and is that raw material is made described methylcarbonate with described biomass.
11. method as claimed in claim 10, wherein, described biomass are phycophyta.
12. method as claimed in claim 10 wherein, is that raw material is made described methylcarbonate and comprised that with described Wood Adhesives from Biomass be synthetic gas with described biomass, and the synthetic gas that is obtained is converted into methyl alcohol, again with methyl alcohol and urea synthesis methylcarbonate.
13. method as claimed in claim 12 wherein, is that raw material is made described methylcarbonate and comprised that also partial CO 2 by product and ammonia synthesis that described at least one commercial run is produced make described urea with described biomass.
14. method as claimed in claim 12 wherein, is that raw material is made described methylcarbonate and comprised that also the by product with methyl alcohol and urea synthesis methylcarbonate process is used for synthetic described urea with described biomass.
15. method as claimed in claim 12, wherein, described at least one commercial run comprises the DCL/Direct coal liquefaction process, is that raw material is made described methylcarbonate and comprised that also the by product with described DCL/Direct coal liquefaction process is used for synthetic described urea with described biomass.
16. method as claimed in claim 10, wherein, described at least one commercial run comprises one or more in coal gasification course, Fischer-Tropsch building-up process, DCL/Direct coal liquefaction process, natural gas conversion processes and the steel smelting procedure.
17. a method of producing methylcarbonate may further comprise the steps:
Coal is converted into liquid product under hydrogen atmosphere, and obtains by product ammonia and first by product, three carbonoxides;
Urea is made in described first by product carbonic acid gas of near small part and described by product ammonia synthesis;
The described first by product carbonic acid gas of part is imported one cultivate the zone that biomass are arranged, and obtain first synthetic gas from the biomass of being cultivated;
The described synthetic gas of near small part is catalytically conveted to methyl alcohol; And
Described methyl alcohol and described urea synthesis are made methylcarbonate.
18. method as claimed in claim 17 is characterized in that, described biomass are phycophyta.
19. method as claimed in claim 17, it is characterized in that, described method also comprise be separated to the described synthetic gas of small part and carbon monoxide, and the carbon monoxide of gained is used for the pre-treatment coal, will under hydrogen atmosphere, be converted into liquid product through pretreated coal again.
20. method as claimed in claim 17, it is characterized in that, described method comprises that also the described synthetic gas of near small part is by the synthetic liquid product that is converted into of Fischer-Tropsch, and acquisition tail gas, be separated to the described tail gas of small part and get carbon monoxide, the carbon monoxide of gained is used for the pre-treatment coal, will under hydrogen atmosphere, be converted into liquid product through pretreated coal again.
21. method as claimed in claim 17 is characterized in that, the by product ammonia that described method also includes recycling to described methyl alcohol of small part and described urea synthesis making methylcarbonate is used for the synthetic urea of making.
22. method as claimed in claim 17 is characterized in that, described method also comprises coal, oxygen and water is converted into second synthetic gas and the second by product carbonic acid gas;
The described second by product carbonic acid gas of near small part imports the zone that described cultivation has biomass;
Described second synthetic gas of near small part is catalytically conveted to methyl alcohol;
Urea is made in described second by product carbonic acid gas of near small part and ammonia synthesis; And
Described methyl alcohol and described urea synthesis are made methylcarbonate.
23. method as claimed in claim 22, it is characterized in that, described method comprises that also described second synthetic gas of near small part is by the synthetic liquid product that is converted into of Fischer-Tropsch, and obtaining the 3rd by product carbonic acid gas, described the 3rd by product carbonic acid gas of near again small part imports the zone that described cultivation has biomass.
24. method as claimed in claim 17, it is characterized in that, described method comprises that also with conversion of natural gas be the 3rd synthetic gas, and described the 3rd synthetic gas of near small part with to described first and second synthetic gas of small part together by the synthetic liquid product that is converted into of Fischer-Tropsch.
25. method as claimed in claim 17 is characterized in that, described method comprises that also with conversion of natural gas be the 3rd synthetic gas, and described the 3rd synthetic gas of near small part with together be catalytically conveted to methyl alcohol to described first and second synthetic gas of small part.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844986A (en) * | 2010-05-27 | 2010-09-29 | 浙江师范大学 | Method for preparing dimethyl carbonate by using carbon dioxide (CO2) |
| CN103288645A (en) * | 2012-02-23 | 2013-09-11 | 亚申科技研发中心（上海）有限公司 | Method for separating dimethyl ether and recovering ammonia in co-production process for dimethyl carbonate and dimethyl ether via urea alcoholysis method |
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| CN1067425A (en) * | 1992-05-30 | 1992-12-30 | 化学工业部第四设计院 | Energy-saving technology for production of urea |
| CN1537156A (en) * | 2001-07-31 | 2004-10-13 | Method of biomass gasification | |
| CN1597096A (en) * | 2004-08-27 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing dimethyl carbonate from ured and methanol and its preparation method and application |
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| US6392078B1 (en) * | 2000-06-12 | 2002-05-21 | Catalytic Distillation Technologies | Process and catalyst for making dialkyl carbonates |
| CN101182294A (en) * | 2007-11-26 | 2008-05-21 | 内蒙古金骄特种新材料有限公司 | Method for preparing dimethyl carbonate by using biological methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067425A (en) * | 1992-05-30 | 1992-12-30 | 化学工业部第四设计院 | Energy-saving technology for production of urea |
| CN1537156A (en) * | 2001-07-31 | 2004-10-13 | Method of biomass gasification | |
| CN1597096A (en) * | 2004-08-27 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing dimethyl carbonate from ured and methanol and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844986A (en) * | 2010-05-27 | 2010-09-29 | 浙江师范大学 | Method for preparing dimethyl carbonate by using carbon dioxide (CO2) |
| CN103288645A (en) * | 2012-02-23 | 2013-09-11 | 亚申科技研发中心（上海）有限公司 | Method for separating dimethyl ether and recovering ammonia in co-production process for dimethyl carbonate and dimethyl ether via urea alcoholysis method |
| CN103288645B (en) * | 2012-02-23 | 2016-03-16 | 亚申科技研发中心（上海）有限公司 | Separation of dimethyl ether in the technique of alcoholysis of urea co-producing dimethyl carbonate and dme also reclaims the method for ammonia |
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