CN114805023A - Zero-emission method for preparing olefins from coal - Google Patents
Zero-emission method for preparing olefins from coal Download PDFInfo
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- CN114805023A CN114805023A CN202210314624.5A CN202210314624A CN114805023A CN 114805023 A CN114805023 A CN 114805023A CN 202210314624 A CN202210314624 A CN 202210314624A CN 114805023 A CN114805023 A CN 114805023A
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 125
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 75
- 239000000047 product Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 239000003034 coal gas Substances 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 96
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 88
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- 239000003054 catalyst Substances 0.000 claims description 56
- 238000000926 separation method Methods 0.000 claims description 35
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 22
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- 239000007795 chemical reaction product Substances 0.000 claims description 2
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- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 111
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 13
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- 229910052720 vanadium Inorganic materials 0.000 description 4
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
Abstract
The invention relates to the technical field of coal processing and conversion, and discloses a zero-emission method for preparing olefin from coal. The method provided by the invention introduces a step of reforming treatment to produce byproducts and CO in the production process 2 Reforming is carried out, thereby achieving the purpose of producing CO in the process of preparing high carbon (alkene) hydrocarbon from coal 2 Comprehensive utilization, realizes the diversification of products prepared from the synthesis gas, and expands the technical route of coal-based clean energy chemical industry. Meanwhile, the method has the advantages of simple process flow, making the best use of all components in the coal gas, reducing the emission of greenhouse gases and the like, and realizes the coordinated development of economy, environment and energy.
Description
Technical Field
The invention relates to the technical field of coal processing and conversion, in particular to a zero-emission method for preparing olefin from coal.
Background
The high-carbon alpha-olefin is used as an important organic raw material, and has the advantages of high added value, harm reduction, easiness in transportation and storage and the like, and the application range is wide, so that the technical development value of the high-carbon alpha-olefin is high. In recent years, along with the rapid development of the synthetic resin industry in China, the production capacity of hexene-1 and octene-1 is obviously insufficient, so that the development of high-carbon alpha-energy olefin is an important research direction in the petrochemical industry in China. The production method of the high-carbon alpha-hydrocarbon olefin is more, and mainly comprises a wax cracking process, an aliphatic alcohol dehydrogenation method, an ethylene oligomerization process, an alkane catalytic cracking process, a Fischer-Tropsch synthesis process and the like, wherein the ethylene oligomerization process takes triethylaluminum as a catalyst, and the high-carbon alpha-hydrogen olefin product is finally obtained through processing flows of ethylene such as compression, preheating, growth, replacement, separation and the like. The ethylene oligomerization process produces high-carbon alpha hydrocarbon olefin with narrow polymerization degree distribution and high product quality, and is the most common process. The Fischer-Tropsch synthesis reaction has the characteristic of easily generating linear alpha olefin or primary alcohol, and the product contains alpha hydrocarbon olefin with various carbon numbers (odd number and even number), so that the defect that only even number alpha hydrocarbon olefin can be produced by an ethylene method can be overcome, the product is more widely applied, and the added value is higher. At present, the global petroleum resources are increasingly consumed, the problem of energy safety is more serious, and the research and development of a new energy system are imminent. The synthesis gas chemical industry is a hot spot in the field of energy chemical industry at present, wherein the synthesis gas prepared by coal gasification and then the synthesis of low carbon alcohol by catalytic hydrogenation of the synthesis gas are one of the more studied subjects. However, these processes all involve the presence of syngas, especially CO produced in the process 2 The problem of insufficient utilization results in excessive CO 2 Is discharged, and causes great damage to the environment.
Therefore, how to improve the yield of the high carbon hydrocarbon prepared from coal on the one hand, improve the utilization efficiency of the Fischer-Tropsch synthesis tail gas on the other hand, achieve low carbon emission and seek CO 2 The method and the process for comprehensively utilizing the resources have important environmental significance and industrial application value.
Disclosure of Invention
The invention aims to overcome the defects that the high-efficiency utilization of the synthesis gas cannot be realized in the process of preparing the olefin from the coal in the prior art, and CO generated in the process 2 The method has the advantages of simple process, low cost and CO reduction 2 The comprehensive utilization degree of the method is high, and zero emission is basically realized.
In order to achieve the above object, the present invention provides a zero-emission coal-to-olefin method, comprising the steps of: synthesis gas preparation and purification, high-carbon hydrocarbon Fischer-Tropsch synthesis, methane and carbon dioxide reforming and low-carbon alcohol synthesis;
wherein, the raw material coal is subjected to the synthesis gas preparation and purification steps to obtain pure synthesis gas and methane, and the pure synthesis gas is subjected to the high-carbon hydrocarbon Fischer-Tropsch synthesis step to obtain a liquid-phase product containing high-carbon hydrocarbons and a product containing unreacted synthesis gas and CO 2 Of the gas-phase product of (a), CO in the gas-phase product 2 And the methane obtained in the step of preparing and purifying the synthesis gas enters a methane and carbon dioxide reforming step to obtain a reformed product, then the reformed product is used as a raw material gas to enter a low carbon alcohol synthesis step, and purge gas generated in the low carbon alcohol synthesis step is recycled in the low carbon alcohol synthesis step.
Through the technical scheme, the invention can obtain the following beneficial effects:
(1) the invention makes full use of the methane in the synthesis gas produced by the pressurized gasification of the pulverized coal, the methane and CO produced in the Fischer-Tropsch synthesis 2 To prepare reformed synthesis gas (hydrogen-rich synthesis gas) and realize CO 2 The full utilization of the carbon resources is increased, and the carbon emission is reduced.
(2) Compared with the prior art for preparing hydrocarbon by using synthesis gas, the method provided by the inventionNot only can produce high carbon (alkene) hydrocarbon and utilize methane in the synthetic gas to prepare synthetic gas through reforming, but also can convert CO 2 The synthesis gas prepared by reforming the Fischer-Tropsch byproduct methane is used for producing low-carbon (alkene) hydrocarbon, the emission of greenhouse gas is avoided, and the purpose of CO production is achieved 2 Comprehensive utilization, realizes the diversification of products prepared from the synthesis gas, and expands the technical route of coal-based clean energy chemical industry.
(3) The method provided by the invention makes the best use of each component in the coal gas, has no greenhouse gas emission, saves energy, water and investment, has simple process flow and stable operation, and realizes the coordinated development of economy, environment and energy.
Drawings
FIG. 1 is a schematic diagram of a process flow for producing olefins from zero-emission coal according to the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The inventors of the present invention found in the course of research that in the production of olefins, especially higher olefins, from coal, by introducing a reforming treatment apparatus/step, methane and CO produced in the production process can be CO-produced 2 Reforming is carried out, and the reformate is used for the production of lower alcohols. Thereby realizing the recycling of by-products and wastes in the process of preparing high-carbon olefin from coal, reducing carbon emission, in particular CO 2 The emission of the process improves the environmental protection value of the process and realizes zero emission of the production.
Based on the discovery, the invention provides a zero-emission coal-to-olefin method, which comprises the following steps: synthesis gas preparation and purification, high-carbon hydrocarbon Fischer-Tropsch synthesis, methane and carbon dioxide reforming and low-carbon alcohol synthesis;
wherein, the raw material coal is subjected to the synthesis gas preparation and purification steps to obtain pure synthesis gas and methane, and the pure synthesis gas is subjected to the high-carbon hydrocarbon Fischer-Tropsch synthesis step to obtain a liquid-phase product containing high-carbon hydrocarbons and a product containing unreacted synthesis gas and CO 2 Of the gas-phase product of (a), CO in the gas-phase product 2 And the methane obtained in the step of preparing and purifying the synthesis gas enters a step of reforming methane and carbon dioxide to obtain a reformed product, then the reformed product is used as a raw material gas and enters a step of synthesizing low-carbon alcohol, and purge gas generated in the step of synthesizing low-carbon alcohol is used in the step of synthesizing low-carbon alcohol.
In the present invention, the purge gas generated in the low carbon alcohol synthesis step mainly comprises H 2 、CO、CO 2 、CH 4 、N 2 The components are subjected to carbon dioxide reforming and purge gas recycling by the method provided by the invention, N2 in the purge gas is directly discharged, and other components (such as H) are recycled 2 、CO、CO 2 、CH 4 Etc.) are recycled in the system (where "recycling" includes recycling directly or recycling after reforming). Preferably, the purge gas comprises: h 2 65-70 vol%, CO 5-10 vol%, CO 2 1-5 vol.%, CH 4 1-3 vol%, N 2 15-30% by volume.
In the present invention, there is no particular limitation on the specific operation and method in the synthesis gas preparation and purification steps. According to a preferred embodiment of the invention, wherein the synthesis gas preparation and purification step comprises feeding coal and O 2 Mixing and gasifying coal, carrying out sulfur-tolerant shift on the obtained crude gas, and then sequentially carrying out alcohol washing and methane separation to obtain pure synthesis gas and methane.
The inventor of the invention also finds that the method provided by the invention can be used for gasifying inferior coal with high water content and high ash content as a raw material, and further processing the obtained gas product to realize multi-stage co-production and graded utilization of the coal.
Preferably, the raw material coal is selected from low-grade coal powder with the moisture content of 15-30 wt%, the ash content of 9-25 wt%, the volatile content of 25-40 wt% and the carbon content of 49-61 wt%, and the particle size of the raw material coal is preferably 5-50 mm;
more preferably, the raw material coal has a moisture content of 15 to 21 wt%, an ash content of 20 to 25 wt%, a volatile content of 32 to 37 wt%, a carbon content of 50 to 55 wt%, and a particle diameter of 25 to 50 mm.
Preferably, said O is 2 Is supplied by air.
Preferably, the coal gasification is carried out by adopting a fixed bed gasification mode, a fluidized bed gasification mode, an entrained flow gasification mode and the like;
more preferably, the coal gasification conditions comprise a temperature of 1000- 2 In a volume ratio of 1:1 to 5, preferably 1:2 to 3.
Due to the complex composition of low-quality coal, the coal gas which is pressurized and gasified by the coal powder has low tapping temperature, and the composition of crude coal gas is complex. In general, possible components in the raw gas include CO and H 2 、CO 2 、CH 4 、H 2 S, organic sulfur, C 2 H 4 、C 2 H 6 、C 3 H 8 、C 4 H 10 、HCN、N 2 Ar and tar, fatty acids, monophenols, polyphenols, naphtha, oils and the like. Preferably, the raw gas contains 0.05-0.1 vol% of CH 4 55-65% by volume of CO, 21-31% by volume of H 2 3-8% by volume of CO 2 ；
Preferably, the sulfur tolerant shift employs a Co — Mo catalyst. Preferably, a Co-Mo catalyst with at least one of active alumina, magnesium aluminate spinel and aluminum titanium magnesium composite carrier as a carrier is adopted.
The catalyst for sulfur tolerance shift in the present invention may be a commercially available catalyst having the above-mentioned characteristics, for example, a catalyst of SSK type of Topusol, Denmark, BASF, Germany, K8-11 type, C113 type of Nippon corporation, QDB-04 series of sulfur tolerance shift catalysts produced by Qingdao Union chemical industries, Inc., a sulfur tolerance shift catalyst of QCS-04 series produced by Chikuwa petrochemical institute, Keli chemical industries, EB series developed by Hubei chemical institute, and the like. It is also possible to use catalysts having the above-mentioned characteristics which are prepared by themselves according to the prior art.
More preferably, the sulfur-tolerant shift reaction conditions comprise a temperature of 220-450 ℃, a pressure of 2-5MPa and a volume space velocity measured by dry gas of 1000-3000h -1 。
The inventor of the present invention has also found in research that sulfur tolerance shift conversion of part of raw gas and mixing of the shifted raw gas with unchanged raw gas can greatly reduce CO generated in shift conversion 2 Amount of, and capable of feeding the synthesis gas H to the Fischer-Tropsch synthesis reactor 2 The adjustment range of CO is enlarged, the production process is more convenient to adjust, and CO is reduced 2 And (5) discharging.
According to a preferred embodiment of the present invention, the step of shift conversion with sulfur tolerance comprises subjecting a part of the raw gas to shift conversion with sulfur tolerance, and subjecting the mixture of the remaining part of the raw gas which is not subjected to shift conversion with sulfur to alcohol washing.
Preferably, the raw gas subjected to sulfur tolerant shift represents 25 to 50% by volume, preferably 30 to 40% by volume, of the total amount of raw gas.
Removing CO, H from raw gas components (e.g. possible components as described above) 2 An active ingredient and CH 4 、N 2 Ar and hydrocarbons other than inert gas, all other components including CO 2 And sulfide are harmful impurities to be removed, and various harmful components such as CO can be completely and cleanly removed in the same device by adopting (low-temperature) alcohol washing purification 2 、H 2 S、COS、C 4 H 4 S、HCN、NH 3 、H 2 O、C 2 The above hydrocarbons (including light oil, aromatic hydrocarbons, naphtha, olefins, and colloidal substances) and other carbonyl compounds.
In order to prevent harm to the environment, equipment and personnel and improve green production of factories, the alcohol washing step is preferably carried out in a low-temperature methanol washing mode and/or a polyglycol dimethyl ether washing mode; .
More preferably, the conditions of the alcohol wash include a temperature of-33 ℃ to-55 ℃ and a pressure of 2 to 6MPa, preferably the alcohol wash is such that after the alcohol washH in raw gas 2 The S (volume fraction) content is less than 0.1ppm, and CO 2 Below 20 ppm.
Preferably, the step of alcohol washing further comprises washing out H 2 And (4) recovering the S concentrated gas. For example, the Claus sulfur recovery process can be used on H 2 And (4) recovering the S concentrated gas.
Preferably, the methane separation is performed by means of cryogenic separation and/or adsorption separation.
According to a preferred embodiment of the invention, the conditions of the cryogenic separation comprise a temperature of-145 ℃ to-175 ℃ and a pressure of 3-8 MPa.
Preferably, the conditions of the cryogenic separation comprise a temperature of-150 ℃ to-160 ℃ and a pressure of 4-5.5MPa
According to a preferred embodiment of the present invention, the step of Fischer-Tropsch synthesis of higher hydrocarbons comprises performing Fischer-Tropsch reaction on the purified synthesis gas obtained from the synthesis gas preparation and purification steps as raw material, preferably the Fischer-Tropsch reaction conditions comprise a pressure of 2-4MPa, a temperature of 220-350 ℃, and H- 2 The mol ratio of the catalyst to CO is 2-5:1, and the gas phase volume space velocity is 5000- -1 。
In the present invention, the Fischer-Tropsch reaction may employ any catalyst known in the art for use in Fischer-Tropsch reactions. In order to further improve the reaction efficiency and the carbon conversion rate, preferably, the catalyst used in the fischer-tropsch reaction is a Fe-Mn-Cu-K catalyst or a Fe-Mn-Cu-K-M catalyst, wherein M is at least one of B, C, N, Zn, Ga, and Sn. The Fe-Mn-Cu-K series catalyst is a catalyst taking Fe, Mn, Cu and K as active components of the catalyst, and the carrier of the catalyst can adopt a carrier with the characteristic of large specific surface area, such as nano flaky Al 2 O 3 And the like. The Fe-Mn-Cu-K-M catalyst is a catalyst taking Fe, Mn, Cu, K and M (the specific selection of M is as described above) as the active components of the catalyst, and the carrier can adopt a carrier with large specific surface area and slightly basic characteristics, such as nanosheet Al 2 O 3 、MgO、TiO 2 And the like.
In order to further improve the catalytic activity of the catalyst, further improve the efficiency of the fischer-tropsch reaction, and improve the conversion rate of carbon, more preferably, the weight ratio of Fe, Mn, Cu, and K in the Fe-Mn-Cu-K based catalyst may be 100: 0.2-12: 0.2-12: 0.1-10. In the Fe-Mn-Cu-K-M catalyst, the weight ratio of Fe, Mn, Cu, K and M can be 100: 0.2-12: 0.2-12: 0.1-10:3-40.
Preferably, the step of Fischer-Tropsch synthesis of high carbon hydrocarbon further comprises the step of carrying out gas-liquid separation on the reaction products to obtain liquid phase products and gas phase products.
According to a preferred embodiment of the invention, the liquid phase product comprises C8-C12 alpha-olefins and naphtha, preferably wherein the alpha-olefin content is 35-75 mole% (preferably the remainder being naphtha).
According to a preferred embodiment of the invention, wherein the gas phase product comprises CH 4 And/or CO 2 。
Preferably, the method further comprises subjecting the gas-phase product to a decarbonation treatment obtaining a recovered syngas and CO 2 Preferably the recovered synthesis gas is recycled to the fischer-tropsch reaction.
In the present invention, the purpose of the decarburization treatment is to remove CO from the gaseous product 2 And the specific decarburization treatment method and conditions are not particularly limited as long as the object can be achieved. Preferably, the decarbonization treatment comprises liquid absorption and/or molecular sieve adsorption, preferably liquid absorption, more preferably K 2 CO 3 Aqueous solution and/or Na 2 CO 3 Absorbing the water solution for decarbonization. The concentration of solute in the aqueous solution may be in the range of 240g/L to 290g/L, preferably 245g/L to 280 g/L. For better control of CO 2 An outlet content, V can be added into the aqueous solution 2 O 5 Preferably V 2 O 5 Is added in an amount such that the total vanadium concentration in the solution is greater than 20g/L, wherein the concentration of vanadium having a valence of 5 is greater than 20 g/L.
According to a preferred embodiment of the present invention, wherein the methane and carbon dioxide reforming step comprises subjecting the CO obtained in the higher hydrocarbon Fischer-Tropsch synthesis step 2 And carrying out reforming treatment on the methane separated in the synthesis gas preparation and purification steps to obtain a reformed product.
Preferably, the catalyst used in the reforming treatment comprises a main active component, a secondary active component and a carrier, wherein the main active component is Co, the main active component preferably accounts for 0.05-30 wt% of the total mass of the catalyst, the secondary active component comprises at least one of Th, Ni, Ce, Mo, Mg, Pa, Pt, Ru, Rh and Ir, the secondary active component preferably accounts for 0.01-20 wt% of the total mass of the catalyst, and the carrier comprises at least one of a carbon carrier, an inorganic oxide and a molecular sieve.
More preferably, the weight ratio of the main active component to the secondary active component is 0.1-2: 1. preferably 1-2: 1.
Preferably, the reforming treatment conditions include a pressure of 0-5MPa, a temperature of 450- -1 。
More preferably, the reforming treatment conditions include reactor pressure of 1-4MPa, temperature of 600- -1 。
According to a preferred embodiment of the present invention, wherein the reformate comprises CO, H 2 、CO 2 、CH 4 And H 2 At least one of O.
Preferably, the method further comprises subjecting the reformate to a dehydration treatment to obtain a dehydrated reformate, preferably to a cooling dehydration treatment.
More preferably, in the dehydrated reformate, H is 2 The content of O is not more than 0.01 mol%, preferably 0.001-0.005 mol%, CH 4 The content of (A) is not more than 8 mol%, CO 2 The content of (A) is not more than 12 mol%.
More preferably, in the dehydrated reformate, CO and H 2 The molar ratio of (A) to (B) is 1: 0.5-1.5. CO and H in the reformate after dehydration 2 When the molar ratio is outside this range, CO or H may be introduced from an external source 2 Adjusting the ratio to be within the above ratio range, and then introducing the mixture into a low-carbon alcohol synthesis unit to synthesize the low-carbon alcohol.
According to a preferred embodiment of the present invention, whereinThe lower alcohol synthesis step comprises reforming at least part of the methane with the reformate obtained from the carbon dioxide reforming step (mainly CO and H in the reformate) 2 I.e. reformed synthesis gas) and separating the synthesis product to obtain a crude product of the lower alcohol and a separated synthesis gas. The "lower alcohol" refers to an alcohol having not more than 4 carbon atoms, such as methanol, ethanol, propanol, n-butanol, etc.
In the invention, when partial reformed synthesis gas is adopted to enter the low carbon alcohol synthesis step, the rest reformed synthesis gas can be returned to the Fischer-Tropsch synthesis step to be used as raw material gas. The present invention is not particularly limited with respect to the proportion of lower alcohols going to the lower alcohol synthesis and fischer-tropsch synthesis steps. The person skilled in the art can adjust and select the material according to the actual needs and production conditions. For example, may be adjusted according to the market price of the product. At most the total reformed synthesis gas may be passed to the lower alcohol synthesis or fischer-tropsch synthesis step.
Preferably, the conditions for the synthesis of the lower alcohol comprise: the temperature is 250 ℃ and 290 ℃, the pressure is 2-6MPa, and the space velocity is 10000 ℃ and 30000h -1 。
In the present invention, there is no particular limitation on the specific catalyst used for the synthesis of the lower alcohol. The skilled person can select a suitable catalyst by himself or herself in consideration of the kind of the desired lower alcohol, the limitation of the equipment and conditions, and the like. The catalyst may be a catalyst prepared by itself according to the prior art or may be a related product commercially available.
According to a preferred embodiment of the present invention, when the lower alcohol is methanol, a Zn-Cr-K catalyst from Snam corporation, Italy, or a MoS2-M-K catalyst from DOW chemical corporation, USA, or a modified Cu-Zn-Al based catalyst from TOPSOE corporation, Denmark, may be selected and used as the lower alcohol synthesis catalyst.
Preferably, the separation mode comprises atmospheric distillation or vacuum distillation, preferably, the conditions of the atmospheric distillation comprise the temperature of 80-150 ℃, and preferably, the conditions of the vacuum distillation comprise the temperature of 80-150 ℃ and the pressure of-0.5-0.7 MPa.
More preferably, the atmospheric distillation conditions include a temperature of 90-130 ℃ and a pressure of 0.1-0.5 MPa.
More preferably, the conditions for the reduced pressure rectification include a temperature of 80-145 ℃ and a pressure of-0.5 to 0.2 MPa.
According to the preferred embodiment of the invention, the crude low carbon alcohol comprises at least one of C1-C6 low carbon alcohol, C1-C6 low carbon aldehyde, C1-C3 organic acid and water. Preferably wherein the lower alcohol content is 65-95 mole%. More preferably, the lower alcohol is contained in an amount of 85 to 92 mol%.
Preferably, the method further comprises an operation of refining the crude lower alcohol to obtain refined lower alcohol, and the content of the lower alcohol in the refined lower alcohol is preferably more than 99 mol%. The refining mode can be any mode for refining the alcohol product existing in the field, and the invention has no particular limitation on the specific operation and conditions thereof as long as the content of the lower alcohol in the obtained refined lower alcohol meets the requirement.
More preferably, the process further comprises recycling the separated synthesis gas (as feed gas) to the step of lower alcohol synthesis.
The present invention will be described in detail below by way of examples. It should be understood that the following examples are only intended to further illustrate and explain the contents of the present invention by way of example, and are not intended to limit the present invention.
The bituminous coal used in the following examples was from the Nindon mine and had a moisture content of about 17.81. + -. 0.5 wt%, an ash content of about 23.28. + -. 0.1 wt%, a volatiles content of about 36.14. + -. 0.5 wt%, a carbon content of about 51.06. + -. 0.5 wt% and a particle size of about 40 mm. + -. 5 mm. Unless otherwise specified, all reagents used were purchased from a normal chemical supplier and were of analytical purity.
In the following examples, ppm is a volume fraction unit unless otherwise specified, and for example, 1ppm means "parts per million by volume fraction".
Example 1
Referring to the process flow in fig. 1, bituminous coal is used as a raw material to perform the cascade production of high-carbon olefins and low-carbon olefins:
(1) clean syngas production and purification
Introducing oxygen into bituminous coal, and performing pulverized coal pressure gasification (gasification pressure 4.5MPa, gasification temperature 1200 ℃) to obtain crude gas, wherein the crude gas comprises CO and H in percentage by volume 2 :CO 2 :CH 4 :H 2 S is 48.29:24.31:14.26:12.96:0.18, 67 volume percent of raw gas is subjected to sulfur-tolerant shift under the catalysis of a Qingdao communication QDB-04 type catalyst at 250 ℃ and 3.5MPa, and the volume space velocity calculated by dry gas is 4000h -1 The shifted water/gas molar ratio was 0.35 and the shifted raw gas was mixed with another 33 vol% of the unshifted raw gas and fed to the low temperature methanol wash unit.
After the crude gas enters a low-temperature methanol washing unit, the crude gas is absorbed by low-temperature methanol at the temperature of minus 40 ℃ and the pressure of 3.5MPa to ensure that H is absorbed 2 S is reduced to 0.1ppm, CO 2 <20ppm of H washed with low temperature methanol 2 S, sending the concentrated gas to remove sulfur for recovery;
the crude gas after low-temperature methanol washing is subjected to cryogenic separation of methane, mixed refrigerant of American Comte and Bocleavazier is adopted to separate the methane in the crude gas at the temperature of-161 ℃ and the pressure of 4.4MPa, and the purity of the methane is as follows: methane volume fraction is more than or equal to 98%, sulfur content is less than or equal to 0.1ppm, CO 2 The volume fraction is less than or equal to 1.0 percent, and the pure synthesis gas meeting the synthesis of low-carbon alcohol is prepared after the crude gas is subjected to cryogenic separation of methane.
(2) Fischer-Tropsch synthesis, product separation and tail gas decarburization
The synthesis gas generates Fischer-Tropsch synthesis reaction in a slurry bed reactor, and the adopted catalyst is Fe-Mn-Cu-K series catalyst (the carrier is SiO) 2 The weight ratio of active components is Fe, Cu, K, Mn and SiO 2 100:5:3:8: 25). The reaction conditions include: the reaction pressure is 2.6MPa, the reaction temperature is 280 ℃, and the hydrogen-carbon molar ratio (as H) is 2 /CO meter) of 3.0 and a volume space velocity of 30000h -1 . After the product is cooled and separated, the heavy hydrocarbon is sent to an olefin separation unit to separate high-carbon alpha-olefin, and the mass ratio of the high-carbon alpha-olefin to the heavy hydrocarbon is 43.7%. Light hydrocarbon is subjected to low-temperature oil washing unit to remove organic matters and then is subjected to CO separation by a decarburization unit 2 The decarbonization unit adopts a liquid absorption mode to carry out decarbonizationSpecifically, the absorption liquid is potassium carbonate aqueous solution (containing V) with the concentration of 245g/L 2 O 5 And the content of pentavalent vanadium is 22 g/L). The rest of CO and H 2 Recycle to the Fischer-Tropsch reactor, CO 2 The demethanization reforming reactor produces a hydrogen-rich syngas.
(3) Methane, CO 2 Reforming
Methane separated from crude gas and CO separated from Fischer-Tropsch synthesis process 2 Mixing and then entering a reforming reactor, wherein the reforming treatment conditions comprise: CH (CH) 4 /CO 2 The volume ratio is 1.5, the pressure of the reactor is 1MPa, and the temperature is 600 ℃. The catalyst used is a Co-based catalyst (the carrier is Al obtained by roasting pseudo-boehmite with the grain diameter of 10-120 mu m for 4 hours at 400 DEG C 2 O 3 The main active component is Co, the secondary active component is Ce, and the weight ratio of the main active component to the secondary active component is 1.5: 1). The mol components of the product at the outlet of the reactor after cooling and dehydration are CO and H 2 :CO 2 :CH 4 And (3) performing cryogenic further separation on the synthesis gas to obtain water, wherein 70% of the water is removed from the synthesis gas to a methanol synthesis unit, and 30% of the water is removed from the synthesis gas to a Fischer-Tropsch synthesis unit, wherein the ratio of the water to the synthesis gas is 50.3:44.8:4.8: 0.07.
(4) Methanol synthesis
The synthesis gas after cryogenic separation enters a methanol synthesizer, adopts a Zn-Cr-K catalyst of the company Snam Italy at the reaction pressure of 4.0MPa, the reaction temperature of 300 ℃ and the hydrogen-carbon molar ratio (in terms of H) 2 a/CO meter) is 3.0, and the volume space velocity is 25000h -1 Synthesizing methanol under the condition;
CO and H obtained by PSA separation of purge gas of synthetic low-carbon alcohol 2 The product is circulated back to the methanol synthesis reactor, the product passing through the methanol synthesis reactor enters a normal pressure methanol rectifying tower, and is separated under the conditions that the temperature at the top of the tower is 75 ℃, the temperature at the bottom of the tower is 150 ℃, the pressure is normal pressure (1.01MPa) and the reflux ratio is 2.3, the molar ratio of the separated product is 85 percent of methanol, 13.5 percent of water and 0.5 percent of fusel (the fusel mainly comprises ethanol, propanol and n-butyl alcohol).
Example 2
Referring to the process flow in fig. 1, bituminous coal is used as a raw material to perform the cascade production of high-carbon olefins and low-carbon olefins:
(1) clean syngas production and purification
Using bituminous coal as raw material, introducing oxygen, and making it pass through pulverized coal pressure gasification technology (gasification pressure is 4.5MPa, gasification temperature is 1200 deg.C) to obtain crude coal gas whose composition is CO: H 2 :CO 2 :CH 4 :H 2 S is 48.29:24.31:14.26:12.96:0.18, crude gas is subjected to sulfur-resistant conversion at 250 ℃ and 3.5MPa under the action of Qingdao communication QDB-04 type catalyst, and the volume space velocity calculated by dry gas is 4000h -1 The water/gas molar ratio after conversion is 0.35, and the gas is mixed with the other 33 percent of unconverted crude gas and then sent to a low-temperature methanol washing unit.
The mixed crude gas enters a low-temperature methanol washing unit, and H is washed by low-temperature methanol at the temperature of-40 ℃ and the pressure of 3.5MPa 2 S is reduced to 0.1ppm, CO 2 <20ppm of H washed with low temperature methanol 2 And (4) sending the S concentrated gas to remove sulfur for recovery.
(2) Methane separation
The crude gas after low-temperature methanol washing is subjected to cryogenic separation of methane, mixed refrigerant of American Comte and Bocleavazier is adopted to separate the methane in the crude gas at the temperature of-161 ℃ and the pressure of 4.4MPa, and the purity of the methane is as follows: methane volume fraction is more than or equal to 98%, sulfur content is less than or equal to 0.1ppm, CO 2 The volume fraction is less than or equal to 1.0 percent, and the pure synthesis gas meeting the synthesis of the low-carbon alcohol is prepared after the crude gas is subjected to cryogenic separation of methane.
(3) Fischer-Tropsch synthesis, product separation and tail gas decarburization
The synthesis gas generates Fischer-Tropsch synthesis reaction in a slurry bed reactor, and the adopted catalyst is Fe-Mn-Cu-K-B catalyst (the carrier is Al) 2 O 3 The weight ratio of active components is Fe, Mn, Cu, K, B and Al 2 O 3 100:5:6:2:1.5: 25). The reaction conditions include: the reaction pressure is 2.7MPa, the reaction temperature is 270 ℃, and the hydrogen-carbon molar ratio is expressed by H 2 a/CO meter) is 2.5, and the volume space velocity is 25000h -1 . And cooling and separating the product, and separating high-carbon alpha-olefin from the heavy hydrocarbon by using an olefin separation unit, wherein the mass ratio of the high-carbon alpha-olefin to the heavy hydrocarbon is 45.6%. Light hydrocarbon is subjected to low-temperature oil washing unit to remove organic matters and then is subjected to CO separation by a decarburization unit 2 The decarbonization unit adopts liquid absorptionThe decarburization is carried out in such a manner that the absorption liquid used is an aqueous potassium carbonate solution (containing V) having a concentration of 245g/L 2 O 5 And the content of pentavalent vanadium is 22 g/L). The rest of CO and H 2 Recycle to the Fischer-Tropsch reactor, CO 2 The demethanization reforming reactor produces a hydrogen-rich syngas.
(4) Methane, CO 2 Reforming
Methane separated from crude gas and CO separated from Fischer-Tropsch synthesis process 2 Mixing and then entering a reforming reactor, wherein the reforming treatment conditions comprise: CH (CH) 4 /CO 2 The volume ratio is 1, the pressure of the reactor is 0.5MPa, and the temperature is 650 ℃. The catalyst used was a Co-based catalyst (the carrier was SiO obtained by calcining silica powder having a particle size of 10 to 120 μm at 600 ℃ for 4 hours) 2 The main active component is Co, the secondary active component is Mg, and the weight ratio of the main active component to the secondary active component is 1: 1). The mol components of the product at the outlet of the reactor after cooling and dehydration are CO and H 2 :CO 2 :CH 4 And (4) carrying out cryogenic further separation on the synthesis gas, wherein 70% of the synthesis gas is sent to a methanol synthesis unit, and 30% of the synthesis gas is sent to a Fischer-Tropsch synthesis unit after further moisture separation.
(5) Synthesis of methanol
The synthesis gas after cryogenic separation enters a methanol synthesizer, adopts a modified Zn-Zn-Al catalyst of the Danish TOPSOE company, and has the hydrogen-carbon molar ratio (in terms of H) at the reaction pressure of 5.0MPa and the reaction pressure of 260 DEG C 2 /CO meter) is 2.2, and the volume space velocity is 30000h -1 Synthesizing methanol under the condition;
CO and H obtained by PSA separation of purge gas of synthetic low-carbon alcohol 2 The product is circulated back to the methanol synthesis reactor, the product which passes through the methanol synthesis reactor enters a normal pressure methanol rectifying tower, the separation is carried out under the conditions that the temperature at the top of the tower is 75 ℃, the temperature at the bottom of the tower is 150 ℃, the pressure is normal pressure and the reflux ratio is 2.0, the molar ratio of the main components in the separated methanol crude product is 88.9 percent of methanol, 10.5 percent of water and 0.6 percent of fusel (the fusel mainly comprises ethanol, propanol and n-butyl alcohol).
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A zero-emission coal-to-olefin method is characterized by comprising the following steps: synthesis gas preparation and purification, high-carbon hydrocarbon Fischer-Tropsch synthesis, methane and carbon dioxide reforming and low-carbon alcohol synthesis;
wherein, the raw material coal is subjected to the synthesis gas preparation and purification steps to obtain pure synthesis gas and methane, and the pure synthesis gas is subjected to the high-carbon hydrocarbon Fischer-Tropsch synthesis step to obtain a liquid-phase product containing high-carbon hydrocarbons and a product containing unreacted synthesis gas and CO 2 Of the gas-phase product of (a), CO in the gas-phase product 2 And the methane obtained in the step of preparing and purifying the synthesis gas enters a methane and carbon dioxide reforming step to obtain a reformed product, then the reformed product is used as a raw material gas to enter a low carbon alcohol synthesis step, and purge gas generated in the low carbon alcohol synthesis step is recycled in the low carbon alcohol synthesis step.
2. The method of claim 1, wherein the syngas production and purification step comprises feeding coal and O 2 Mixing and gasifying coal, and sequentially carrying out alcohol washing and methane separation on the obtained crude coal gas after sulfur-tolerant shift to obtain pure synthesis gas and methane;
preferably, the raw material coal is selected from low-grade coal powder with the moisture content of 15-30 wt%, the ash content of 9-25 wt%, the volatile content of 28-37 wt% and the carbon content of 49-61 wt%, and the particle size of the raw material coal is preferably 5-50 μm;
preferably, said O is 2 Is provided by air;
preferably, the coal gasification is carried out by at least one of fixed bed gasification, fluidized bed gasification and fluidized bed gasification;
preferably, the sulfur-tolerant shift adopts a Co-Mo catalyst, preferably a Co-Mo catalyst with at least one of active alumina, magnesium aluminate spinel and aluminum titanium magnesium composite carrier as a carrier;
preferably, the step of alcohol washing is carried out by adopting a low-temperature methanol washing mode and/or a polyethylene glycol dimethyl ether washing mode, and the temperature of the low-temperature methanol washing is preferably-30 ℃ to-50 ℃;
preferably, the methane separation is performed by means of cryogenic separation and/or adsorption separation.
3. The method as claimed in claim 2, wherein the coal gasification conditions include a temperature of 1000- 2 In a volume ratio of 1:1 to 5, preferably 1:2 to 3;
and/or the raw gas contains 0.05-0.1 volume percent of CH 4 55-65% by volume of CO, 21-31% by volume of H 2 3-8% by volume of CO 2 ；
And/or the sulfur-resistant shift conditions comprise a temperature of 220-450 ℃, a pressure of 2-5MPa and a volume space velocity measured by crude gas of 1000-3000h -1 ；
And/or the conditions of the alcohol washing comprise the temperature of-33 ℃ to-55 ℃ and the pressure of 2-6MPa, and the alcohol washing is preferably carried out so that H in the crude gas after the alcohol washing is H 2 S content of less than 0.1ppm, CO 2 Below 20 ppm;
and/or, the conditions of the cryogenic separation comprise a temperature of-145 ℃ to-175 ℃ and a pressure of 3-8 MPa.
4. The method of claim 2 or 3, wherein the step of sulfur shift conversion comprises subjecting a portion of the raw gas to sulfur shift conversion and subjecting a mixture of the remaining portion of the raw gas that has not been subjected to sulfur shift conversion and the shifted raw gas to alcohol washing;
preferably, the raw gas subjected to sulfur tolerant shift accounts for 25-50% by volume of the total amount of the raw gas;
preferably, the step of alcohol washing further comprises washing out H 2 And (4) recovering the S concentrated gas.
5. The process of claim 1, wherein the higher hydrocarbon is fischer-tropsch derivedThe synthesis step comprises the step of taking the pure synthesis gas prepared in the synthesis gas preparation and purification steps as a raw material to carry out Fischer-Tropsch reaction, and the preferable conditions of the Fischer-Tropsch reaction comprise the pressure of 2-4MPa, the temperature of 220- 2 The mol ratio of the catalyst to CO is 2-5:1, and the gas phase volume space velocity is 5000- -1 ；
Preferably, the catalyst adopted by the Fischer-Tropsch reaction is a Fe-Mn-Cu-K series catalyst or a Fe-Mn-Cu-K-M series catalyst, wherein M is at least one of B, C, N, Zn, Ga and Sn;
preferably, the step of Fischer-Tropsch synthesis of high carbon hydrocarbon further comprises the step of carrying out gas-liquid separation on the reaction products to obtain liquid phase products and gas phase products.
6. The process of claim 5, wherein the liquid phase product comprises C8-C12 alpha olefins and naphtha, preferably wherein the alpha olefin content is 35-75 mole%;
and/or the gas phase product comprises CH 4 And/or CO 2 ；
Preferably, the method further comprises subjecting the gas-phase product to a decarbonation treatment obtaining a recovered syngas and CO 2 Preferably recycling said recovered synthesis gas to the fischer-tropsch reaction;
more preferably, the decarbonization treatment comprises liquid absorption and/or molecular sieve adsorption, preferably liquid absorption, more preferably K 2 CO 3 Aqueous solution and/or Na 2 CO 3 Absorbing the water solution for decarbonization.
7. The process of claim 1, wherein the methane and carbon dioxide reforming step comprises Fischer-Tropsch synthesis of CO from the higher hydrocarbon step 2 Reforming the methane separated in the synthesis gas preparation and purification steps to obtain a reformed product;
preferably, the catalyst used in the reforming treatment comprises a main active component, a secondary active component and a carrier, wherein the main active component is Co, the content of the main active component is 0.05-30 wt% of the total mass of the catalyst, the secondary active component comprises at least one of Th, Ni, Ce, Mo, Mg, Pa, Pt, Ru, Rh and Ir, the content of the secondary active component is 0.01-20 wt% of the total mass of the catalyst, and the carrier comprises at least one of a carbon carrier, an inorganic oxide and a molecular sieve;
preferably, the reforming treatment conditions include a pressure of 0-5MPa, a temperature of 450- -1 。
8. The method of claim 7, wherein the reformate comprises CO, H 2 、CO 2 、CH 4 And H 2 At least one of O;
preferably, the method further comprises subjecting the reformate to a dehydration treatment to obtain a dehydrated reformate, preferably to a cooling dehydration treatment;
more preferably, in the dehydrated reformate, H is 2 The content of O is not more than 0.01 mol%, preferably 0.001-0.005 mol%, CH 4 The content of (A) is not more than 8 mol%, CO 2 The content of (A) is not more than 12 mol%;
more preferably, in the dehydrated reformate, CO and H 2 The molar ratio of (A) to (B) is 1: 0.5-1.5.
9. The method of claim 1, wherein the lower alcohol synthesis step comprises the steps of carrying out lower alcohol synthesis on at least part of methane and a reformate obtained in the carbon dioxide reforming step, and separating the synthesized product to obtain a crude lower alcohol and a separated synthesis gas;
preferably, the conditions for the synthesis of the lower alcohol comprise: the temperature is 250 ℃ and 290 ℃, the pressure is 2-6MPa, and the space velocity is 10000 ℃ and 30000h -1 ；
Preferably, the separation mode comprises atmospheric distillation or vacuum distillation, preferably, the conditions of the atmospheric distillation comprise the temperature of 80-150 ℃, and preferably, the conditions of the vacuum distillation comprise the temperature of 80-150 ℃ and the pressure of-0.5-0.7 MPa.
10. The method as claimed in claim 9, wherein the crude lower alcohol comprises at least one of lower alcohol of C1-C6, lower aldehyde of C1-C6, organic acid of C1-C3 and water, preferably wherein the content of lower alcohol is 65-95 mol%;
preferably, the method further comprises an operation of refining the crude lower alcohol to obtain refined lower alcohol, wherein the content of the lower alcohol in the refined lower alcohol is preferably more than 99 mol%;
more preferably, the method further comprises the step of recycling the separated syngas to the synthesis of lower alcohols.
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| CN110055106A (en) * | 2019-04-03 | 2019-07-26 | 浙江天禄环境科技有限公司 | A kind of method that low-order coal sub-prime prepares methanol and oil using Poly-generation |
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| US20070004809A1 (en) * | 2005-06-29 | 2007-01-04 | Lattner James R | Production of synthesis gas blends for conversion to methanol or fischer-tropsch liquids |
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| CN104628508A (en) * | 2015-01-30 | 2015-05-20 | 华南理工大学 | System and process for preparing alkene from raw materials of coal and natural gas by virtue of synthesis |
| CN110055106A (en) * | 2019-04-03 | 2019-07-26 | 浙江天禄环境科技有限公司 | A kind of method that low-order coal sub-prime prepares methanol and oil using Poly-generation |
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