CN110105168B - Equipment and method for producing low-carbon mixed alcohol by using synthesis gas in high selectivity manner - Google Patents
Equipment and method for producing low-carbon mixed alcohol by using synthesis gas in high selectivity manner Download PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 65
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 62
- 239000007791 liquid phase Substances 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 18
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 150000001336 alkenes Chemical class 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 150000001721 carbon Chemical group 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 70
- 239000007789 gas Substances 0.000 description 67
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000011068 loading method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910017816 Cu—Co Inorganic materials 0.000 description 3
- -1 L i Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910020637 Co-Cu Inorganic materials 0.000 description 1
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 229910002549 Fe–Cu Inorganic materials 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- C07C29/152—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 characterised by the reactor used
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses equipment and a method for producing low-carbon mixed alcohol by utilizing synthesis gas in a high-selectivity manner, and belongs to the technical field of synthesis gas conversion and utilization. The method is formed by connecting a Fischer-Tropsch reactor, a hydroformylation reactor and a hydrogenation reactor in series, firstly, synthesis gas is efficiently converted into low-carbon olefin through Fischer-Tropsch synthesis, unreacted synthesis gas and the low-carbon olefin are introduced into the hydroformylation reactor to be converted into aldehyde products with one more carbon atom, the unreacted synthesis gas is separated through simple condensation and enters the Fischer-Tropsch synthesis for recycling, and the aldehyde products enter the hydrogenation reactor to carry out hydrogenation reaction on the aldehydes, so that alcohol products with very high content are obtained. The method can efficiently convert the synthesis gas into the olefin and further into the low-carbon mixed alcohol with high added value, avoids a large amount of energy consumption generated by separating the low-carbon olefin from the synthesis gas, realizes the recycling of the synthesis gas, and can control the distribution of carbon number in the mixed alcohol.
Description
Technical Field
The invention belongs to the technical field of synthesis gas conversion and utilization, and relates to equipment and a method for producing low-carbon mixed alcohol by using synthesis gas in a high-selectivity manner.
Background
With the rapid consumption of global petroleum resources and the increasing prominence of environmental issues, the development and utilization of new clean fuels and fuel additives become one of the hot spots of current research. Based on the resource composition characteristics of rich coal, lean oil and little gas in China, the synthesis gas (CO and H) is prepared from carbon-containing resources such as coal, natural gas and biomass2Mixtures) have attracted great interest in academia and industry via catalytic conversion to lower alcohols.
The lower mixed alcohol is generally C2+The alcohol mixture (see the research progress of preparing low-carbon mixed alcohol Cu-Co bimetallic catalyst from synthesis gas, Anxia and the like, the chemical development, No. 10 of volume 37 in 2018, page 3843-plus 3849) has high octane number and good miscibility with gasoline, and can be used as a gasoline additive to replace tetraethyl lead with high toxicity and methyl tert-butyl ether which has been controversial; can also be directly used as clean liquid fuel, and has the advantages of sufficient combustion, little discharge amount of nitrogen oxides and the like; the ethanol, propanol, butanol, pentanol and the like separated from the low-carbon mixed alcohol can be used as basic chemical raw materials for synthesizing high-added-value commodities such as medicines, cosmetics and the like, and the economic benefit of the production of the low-carbon alcohol is improved. Many researchers are catalyzing lower alcoholsA great deal of research is carried out on the aspects of reagent development and reaction process, but the process still does not realize large-scale industrial application at present, wherein the low selectivity of the lower alcohol is one of the main reasons for limiting the industrialization of the lower alcohol, so that the further improvement of the selectivity of the lower alcohol is necessary.
At present, the reaction for synthesizing the low-carbon alcohol is mainly a modified Fischer-Tropsch synthesis reaction, and the used catalysts are generally divided into 4 types: (1) a modified Cu-based methanol catalyst; (2) modified Fischer-Tropsch (FT) synthesis catalysts, such as Cu-Co based and Cu-Fe based catalysts; (3) mo-based catalysts, including molybdenum sulfide-based, molybdenum carbide-based, and molybdenum oxide-based catalysts; (4) a noble metal Rh based catalyst. Among them, although Rh-based catalysts have high ethanol selectivity, the storage amount of Rh metal is limited and its high price is not favorable for its industrialization; the modified Cu-based methanol catalyst comprises low pressure and high pressure, and the main products are methanol and isobutanol; the Mo-based catalyst has better selectivity and sulfur resistance of low-carbon straight-chain alcohol, but the separation cost is also high due to the characteristics of harsh reaction conditions and easy introduction of sulfur element into an alcohol product; the Cu-Co-based catalyst can react under mild reaction conditions (the general reaction pressure is 3-6 MPa, and the reaction temperature is 220-330 ℃), and has relatively high low-carbon alcohol selectivity and catalytic activity. However, the method for synthesizing the low-carbon alcohol by utilizing the modified Fischer-Tropsch synthesis reaction is limited by a reaction mechanism and ASF distribution of products, the selectivity of hydrocarbons in reactants is high, the selectivity of the alcohol is low, the product mixed alcohol mainly comprises methanol and ethanol, and the content of the alcohol is sharply reduced along with the increase of carbon chains of the alcohol; in addition, the final liquid phase product contains a large amount of water, which is not favorable for subsequent separation operations.
Therefore, a new synthetic route with high selectivity for low-carbon mixed alcohol is needed to be found for subsequent industrial production.
Disclosure of Invention
Aiming at the problem of low selectivity of low-carbon alcohol in the existing reaction process for preparing low-carbon alcohol from synthesis gas, the invention provides a novel process for producing low-carbon mixed alcohol from synthesis gas with high selectivity, which adopts a mode of connecting three reactors in series to convert the synthesis gas into low-carbon olefin, aldehyde and alcohol in turn through Fischer-Tropsch reaction, hydroformylation reaction and hydrogenation reaction to obtain a low-carbon alcohol product with very high content (the content of the low-carbon mixed alcohol in the product can reach more than 80%).
Specifically, the technical scheme of the invention is as follows: a method for producing low-carbon mixed alcohol by synthesis gas comprises the following steps: firstly, carrying out Fischer-Tropsch synthesis on synthesis gas, carrying out gas-liquid separation on a product obtained by the Fischer-Tropsch synthesis, extracting a liquid-phase product as a product, carrying out hydroformylation reaction on a gas-phase product as a reaction raw material, circularly carrying out the Fischer-Tropsch reaction on the gas-phase product obtained by the hydroformylation reaction after the gas-liquid separation, and carrying out hydrogenation reaction on the liquid-phase product obtained by the hydroformylation reaction to obtain a low-carbon mixed alcohol product.
In one embodiment of the invention, the syngas comprises CO and H2In which H is2And the volume ratio of CO is 0.5-3.
In one embodiment of the invention, the fischer-tropsch reaction is carried out in a fixed bed reactor, the packed catalyst being a cobalt-based or iron-based catalyst; the hydroformylation reactor is carried out in a slurry bed reactor or a fixed bed reactor, and the filling catalyst is rhodium-based or cobalt-based; the hydrogenation reactor is carried out in a kettle type reactor, and the filling catalyst is one or more than two of palladium-based catalyst, platinum-based catalyst, nickel-based catalyst or copper-based catalyst.
In one embodiment of the invention, the cobalt-based catalyst is a supported catalyst with or without addition of an auxiliary agent, the iron-based catalyst is a supported or precipitated catalyst with or without addition of an auxiliary agent, and the auxiliary agent is one or more of Ru, Pd, Cu, Rh, Ag, Au, Pt, L i, Na, K, Mg, Mn, Fe, Co, N and S.
In one embodiment of the invention, the operating conditions of the fischer-tropsch reaction are: the reaction temperature is 180-350 ℃, and the reaction pressure is 0.1-6.0 MPa; the operating conditions for the hydroformylation reaction are: the reaction temperature is 50-250 ℃, and the reaction pressure is 0.1-6.0 MPa; the working conditions of the hydrogenation reactor are as follows: the reaction temperature is 25-200 ℃, and the reaction pressure is 0.1-3.0 MPa.
In one embodiment of the invention, the operation temperature of the gas-liquid separator is adjustable within the range of-20 to 250 ℃. Namely, the composition of the gas-phase product entering the second-stage hydroformylation reactor can be flexibly adjusted by adjusting the temperature of the gas-liquid separator for separating the Fischer-Tropsch product, so as to achieve the purpose of adjusting the carbon number distribution of the mixed alcohol in the final product.
In one embodiment of the present invention, the operation temperature of the gas-liquid separator connected after the hydroformylation reactor is preferably-20 to 0 ℃.
In one embodiment of the invention, the hydroformylation reaction is carried out in the presence of CO or H in the gas phase product of the Fischer-Tropsch synthesis2When the content is insufficient, synthetic gas is required to be introduced to carry out hydroformylation together with the gas-phase product of Fischer-Tropsch synthesis.
In one embodiment of the invention, in the fischer-tropsch synthesis reaction, the synthesis gas is firstly efficiently converted into the low-carbon olefins, and a liquid-phase product with high carbon number and high olefin content and a gas-phase product containing the unreacted synthesis gas and the low-carbon olefins are obtained through a gas-liquid separation device; the gas mixtures do not need to be separated and directly enter a second-stage reactor as feed gas to carry out hydroformylation reaction, the hydroformylation reaction can efficiently convert the olefin into aldehyde products with one more carbon atom, namely, a gas-phase product discharged from the Fischer-Tropsch reactor contains a large amount of olefin products and unreacted synthesis gas, and provides a raw material for the hydroformylation reaction, thereby avoiding a large amount of energy consumption generated by separating the low-carbon olefin and the synthesis gas; the products obtained by the hydroformylation reaction mainly comprise aldehydes and unreacted synthesis gas, the synthesis gas and the aldehyde products can be separated by simple condensation, the gas phase obtained by the gas-liquid separator is mainly the unreacted synthesis gas and can be directly circulated back to the Fischer-Tropsch reactor for continuous reaction, the liquid phase mainly comprises the aldehyde products, the alcohol products with very high content are obtained by entering a third-stage hydrogenation reaction kettle for hydrogenation reaction of the aldehydes, and the final products contain no water, thereby being convenient for subsequent separation operation.
The invention further provides equipment for producing the low-carbon mixed alcohol by using the synthesis gas, which comprises a Fischer-Tropsch reactor 1, a first gas-liquid separator 3, a hydroformylation reactor 2, a second gas-liquid separator 4 and a hydrogenation reactor 5, wherein a product outlet of the Fischer-Tropsch reactor 1 is connected with an inlet of the first gas-liquid separator 3, an air outlet of the first gas-liquid separator 3 is connected with a feed inlet of the hydroformylation reactor 2, a product outlet of the hydroformylation reactor 2 is connected with an inlet of the second gas-liquid separator 4, a liquid outlet of the second gas-liquid separator 4 is connected with a feed inlet of the hydrogenation reactor 5, the Fischer-Tropsch reactor 1 is a fixed bed reactor, the hydroformylation reactor 2 is a slurry bed reactor or a fixed bed reactor, and the hydrogenation reactor 5 is a kettle reactor.
In one embodiment of the present invention, it is preferred that the outlet of the second gas-liquid separator 4 is connected to the inlet of the fischer tropsch reactor 1.
In one embodiment of the invention, the fischer-tropsch reactor 1 is loaded with a cobalt-based or iron-based catalyst and the hydroformylation reactor 2 is loaded with a rhodium-based or cobalt-based catalyst; the hydrogenation reactor 5 is filled with one or more than two of palladium-based catalyst, platinum-based catalyst, nickel-based catalyst or copper-based catalyst.
In one embodiment of the present invention, the fischer-tropsch reactor 1, the hydroformylation reactor 2 and the hydrogenation reactor 5 represent reactors in which a fischer-tropsch reaction, a hydroformylation reaction and a hydrogenation reaction occur, respectively.
The invention has the beneficial technical effects that:
(1) the invention adopts a new reaction process, divides the original process of directly synthesizing low-carbon alcohol from synthesis gas into a process of connecting three reactors of Fischer-Tropsch reaction, hydroformylation reaction and hydrogenation reaction in series, can efficiently convert the synthesis gas into olefin and further into high-added-value low-carbon mixed alcohol, avoids a large amount of energy consumption generated by separating the low-carbon olefin and the synthesis gas, and realizes the recycling of the synthesis gas. By this process, low CH production in a Fischer-Tropsch reactor can be achieved4Low CO content2A gas phase composition with high selectivity of the low carbon olefin and a liquid phase composition with high selectivity of the high carbon olefin; simultaneously, olefins in the Fischer-Tropsch gas phase product are efficiently converted into liquid phase high-value low-carbon mixed alcohol (C)3+-OH) product to solve the problem of gas-phase low-carbon olefin andthe unreacted synthesis gas is difficult to separate and the recycling of tail gas is affected.
(2) The invention can flexibly regulate and control the composition of the second-stage hydroformylation feed gas by regulating the Fischer-Tropsch synthesis catalyst, the Fischer-Tropsch reaction condition and the temperature of the gas-liquid separator, thereby realizing the regulation and control of the carbon number distribution in the target product mixed alcohol.
(3) The liquid phase product obtained by the Fischer-Tropsch reaction can be used as a raw material for producing aromatic hydrocarbon, so that the high-efficiency utilization of the synthesis gas is realized, and each reaction is a heterogeneous reaction system, so that the product is easy to separate.
Drawings
FIG. 1 is a schematic diagram of the apparatus for producing low carbon mixed alcohol with high selectivity by using synthesis gas according to the present invention, wherein, 1-Fischer-Tropsch reactor; 2-a hydroformylation reactor; 3-a first gas-liquid separator; 4-a second gas-liquid separator; 5-a hydrogenation reactor.
Detailed Description
The technical details of the present invention are explained in detail by the following examples. The embodiments are described for further illustrating the technical features of the invention, and are not to be construed as limiting the invention. Meanwhile, the embodiments only give some conditions for achieving the purpose, and do not mean that the conditions must be met for achieving the purpose.
The fischer-tropsch reactor is a reactor for fischer-tropsch synthesis; the hydroformylation reactor is a reactor for hydroformylation reactions; the hydrogenation reactor is a reactor for hydrogenating aldehydes to produce alcohols.
Gas and liquid phase product analysis methods: 1) gas phase product analysis method. Analysis of CO, CO Using 3Ft Porapak Q, 6FtPorapak Q, and 8Ft MolSieve 5A chromatography columns and TCD Detector2、H2、N2And CH4With an injector temperature of 250 deg.C and a detector temperature of 250 deg.C. Analysis of CH with Rt-Q-BOND chromatography column and FID Detector4And hydrocarbon products in the gas phase, wherein the injector temperature is 250 ℃ and the detector temperature is 350 ℃. 2) Liquid phase product analysis method. The analysis was performed using HP-1 chromatography and FID detector, with injector temperature 320 ℃ and detector temperature 350 ℃.
Definition and calculation of the conversion:
wherein [ CO ]]inRepresents the molar concentration of CO in the reactor inlet gas, [ CO ]]outRepresenting the moles of CO in the reactor off-gas
Molar concentration. Definition and calculation of selectivity formula:
wherein [ CO ]]outRepresenting CO in the reactor off-gas2Molar concentration of [ CH ]4]outRepresenting CH in the reactor off-gas4Is/are as follows
Molar concentration.
Selectivity S of hydrocarbon with carbon number n in productCnAnd selectivity S of hydrocarbon with carbon number from n to n + k in productCn-n+k：
Wherein [ Cn]outRepresenting the molar concentration of hydrocarbons having a carbon number n in the reactor off-gas.
Normal alcohol/total alcohol calculation formula:
wherein [ n-ROH ] represents the molar concentration of normal alcohol in the product and [ i-ROH ] represents the molar concentration of isomeric alcohol in the product.
Embodiment 1 an apparatus for producing a low carbon mixed alcohol using a synthesis gas according to the present invention
Including fischer-tropsch reactor, first vapour and liquid separator 3, hydroformylation reactor, second vapour and liquid separator 4 and hydrogenation ware, the product export of fischer-tropsch reactor links to each other with the entry of first vapour and liquid separator 3, the gas outlet of first vapour and liquid separator 3 links to each other with hydroformylation reactor's feed inlet, hydroformylation reactor's product export links to each other with second vapour and liquid separator 4's entry, second vapour and liquid separator 4's liquid outlet links to each other with hydrogenation reactor's charge door, wherein, fischer-tropsch reactor is fixed bed reactor, hydroformylation reactor is slurry bed reactor or fixed bed reactor, hydrogenation ware is cauldron formula reactor.
Preferably, the gas outlet of the second gas-liquid separator 4 is connected with the feed inlet of the Fischer-Tropsch synthesis.
Preferably, the fischer-tropsch reactor is loaded with a cobalt-based or iron-based catalyst and the hydroformylation reactor is loaded with a rhodium-based or cobalt-based catalyst; the hydrogenation reactor is filled with one or more than two of palladium-based catalyst, platinum-based catalyst, nickel-based catalyst or copper-based catalyst.
In the Fischer-Tropsch synthesis reaction, firstly, the synthesis gas is efficiently converted into low-carbon olefins, and a liquid-phase product with high carbon number and high olefin content and a gas-phase product containing unreacted synthesis gas and low-carbon olefins are obtained through a first gas-liquid separation device 3; the gas mixtures do not need to be separated and directly enter a second-stage reactor as feed gas to carry out hydroformylation reaction, the hydroformylation reaction can efficiently convert the olefin into aldehyde products with one more carbon atom, namely, a gas-phase product discharged from the Fischer-Tropsch reactor contains a large amount of olefin products and unreacted synthesis gas, and provides a raw material for the hydroformylation reaction, thereby avoiding a large amount of energy consumption generated by separating the low-carbon olefin and the synthesis gas; the products obtained by the hydroformylation reaction mainly comprise aldehydes and unreacted synthesis gas, the synthesis gas and the aldehyde products can be separated by simple condensation, the gas phase obtained by the second gas-liquid separator 4 is mainly the unreacted synthesis gas and can be directly circulated back to the Fischer-Tropsch reactor for continuous reaction, the liquid phase mainly comprises the aldehyde products, the liquid phase mainly enters a third-section hydrogenation reaction kettle for hydrogenation reaction of the aldehydes, alcohol products with very high content are obtained, and the final product does not contain water, thereby being convenient for subsequent separation operation.
Example 2
The Fischer-Tropsch reactor was a fixed bed reactor, charged with 15Co3.7Mn/SiO2The catalyst (i.e. the catalyst with Co loading of 15 wt% and Mn loading of 3.7 wt%) was reduced in situ at 230 deg.C, 1.0MPa, H21.0 of/CO (raw material gas containing 3 vol% of N)2As an internal standard) and space velocity of 4L/g/h, separating the product from the Fischer-Tropsch reactor by a gas-liquid separator at 30 ℃, collecting the separated liquid product directly as a product, analyzing the composition by offline chromatography, introducing the gas product into a second stage hydroformylation reactor for reaction, analyzing the composition of the gas product by online chromatography through a bypass, and obtaining the gas and liquid analysis results shown in Table 1, wherein the hydroformylation reactor is a fixed bed reactor filled with 15Rh/Co3O4The catalyst (i.e. the loading of Rh is 15 wt%) reacts at 120 ℃ under 1.0MPa, the tail gas is separated by a-20 ℃ gas-liquid separator at the temperature, and can be directly circulated back to the fischer-tropsch reactor for continuous reaction, the liquid obtained by the hydroformylation reaction is collected after 50 hours of reaction, and is added into a hydrogenation reactor (a kettle reactor) through a constant flow pump, the reactor is filled with a commercial Pd/C catalyst, the solvent is hexadecane, the reaction is carried out for 5 hours at 100 ℃ under 2.0MPa, and the liquid phase product is analyzed by off-line chromatography after the reaction is finished, and the results are shown in table 1.
Example 3
The catalyst, reaction materials and loading mode were the same as in example 2, the operation conditions of the Fischer-Tropsch reactor were 260 ℃, 1.0MPa, H2the/CO is 0.5, the space velocity is 4.0L/g/h, the gas-liquid separator is 30 ℃, the operation conditions of the hydroformylation reactor are 120 ℃, 1.0MPa and the gas-liquid separator is-20 ℃, and the operation conditions of the hydrogenation reactor are 100 ℃, 2.0MPa and 5 h.
Example 4
The Fischer-Tropsch catalyst is 15Co5.6Mn/SiO2(i.e., Co loading of 15 wt.% and Mn loading of 5.6 wt.%), hydroformylation and hydrogenation catalysts, reaction feed and loading were as in example 2, Fischer-Tropsch reactor operating conditions 260 ℃, 2.0MPa, H2the/CO is 0.5, the space velocity is 4.0L/g/h, the gas-liquid separator is 30 ℃, the operation conditions of the hydroformylation reactor are 120 ℃, 2.0MPa and the gas-liquid separator is-20 ℃, and the operation conditions of the hydrogenation reactor are 100 ℃, 2.0MPa and 5 h.
Example 5
The catalyst, reaction materials and loading mode were the same as in example 2, the operation conditions of the Fischer-Tropsch reactor were 260 ℃, 1.0MPa, H2the/CO is 0.5, the space velocity is 4.0L/g/h, the gas-liquid separator is 30 ℃, the operation conditions of the hydroformylation reactor are 100 ℃, 1.0MPa and the gas-liquid separator is-20 ℃, and the operation conditions of the hydrogenation reactor are 100 ℃, 2.0MPa and 5 h.
Example 6
The catalyst, reaction materials and loading mode were the same as in example 2, the operation conditions of the Fischer-Tropsch reactor were 260 ℃, 1.0MPa, H2the/CO is 0.5, the space velocity is 4.0L/g/h, the gas-liquid separator is 30 ℃, the operation conditions of the hydroformylation reactor are 120 ℃, 1.0MPa and the gas-liquid separator is-20 ℃, and the operation conditions of the hydrogenation reactor are 80 ℃, 2.0MPa and 5 h.
Example 7
The catalyst, reaction materials and loading mode were the same as in example 2, the operation conditions of the Fischer-Tropsch reactor were 240 ℃, 1.0MPa, H2the/CO is 0.5, the space velocity is 4.0L/g/h, the gas-liquid separator is 90 ℃, the operation conditions of the hydroformylation reactor are 120 ℃, 1.0MPa and the gas-liquid separator is-20 ℃, and the operation conditions of the hydrogenation reactor are 80 ℃, 2.0MPa and 5 h.
Example 8
The catalyst, reaction materials and loading mode were the same as in example 2, the operation conditions of the Fischer-Tropsch reactor were 230 ℃, 1.0MPa, H20.5 of/CO, 4.0 of space velocity of 4.0L/g/h, 140 ℃ of gas-liquid separator, 120 ℃ of hydroformylation reactor operating condition, 1.0MPa of gas-liquid separator-20 ℃, 80 ℃ of hydrogenation reactor operating condition and 2.0MPa, 5 h. The results of the product analysis are shown in Table 1.
Example 9
The Fischer-Tropsch catalyst was 70Fe/GO (Fe loading 70 wt%, the same applies below), the hydroformylation and hydrogenation catalysts, the reaction materials and the loading method were the same as in example 2, the Fischer-Tropsch reactor operating conditions were 330 ℃, 1.0MPa, H2the/CO is 1.0, the space velocity is 3.0L/g/h, the gas-liquid separator is 30 ℃, the operation conditions of the hydroformylation reactor are 120 ℃, 1.0MPa and the gas-liquid separator is-20 ℃, and the operation conditions of the hydrogenation reactor are 80 ℃, 2.0MPa and 5 h.
Example 10
The Fischer-Tropsch catalyst is 70Fe/GO, the hydroformylation and hydrogenation catalysts, the reaction raw materials and the filling mode are the same as the example 2, and the operation conditions of the Fischer-Tropsch reactor are 340 ℃, 1.0MPa and H2The catalyst has the following characteristics that the/CO is 1.0, the space velocity is 3.0L/g/h, the gas-liquid separator temperature is-10 ℃, the operation conditions of the hydroformylation reactor are 120 ℃, 1.0MPa and the gas-liquid separator temperature is-20 ℃, and the operation conditions of the hydrogenation reactor are 80 ℃, 2.0MPa and 5 h.
Example 11
The Fischer-Tropsch catalyst is 70Fe/GO, the hydroformylation and hydrogenation catalysts, the reaction raw materials and the filling mode are the same as the example 1, and the operation conditions of the Fischer-Tropsch reactor are 340 ℃, 2.0MPa and H2the/CO is 0.5, the space velocity is 3.0L/g/h, the gas-liquid separator is 30 ℃, the operation conditions of the hydroformylation reactor are 120 ℃, 2.0MPa and the gas-liquid separator is-20 ℃, and the operation conditions of the hydrogenation reactor are 80 ℃, 2.0MPa and 5 h.
As can be seen from table 1, the process for preparing mixed alcohol by using synthesis gas in which three reactors are connected in series according to the present invention can maximize the conversion of synthesis gas into a target product by adjusting the reaction conditions, catalysts, and the like of each reactor to allow each stage of reaction to be operated under optimal conditions. On the whole, the ratio of the alcohols to the hydrocarbons in the products obtained by the reactors connected in series can reach 3.0, the content of the mixed alcohol in the final product can reach more than 80 percent, and the product does not contain water, so that the cost of product separation is greatly saved, and the content of the normal alcohol in the mixed alcohol can reach more than 85 percent.
In addition, the flexible regulation and control of carbon number distribution in the product can be realized by changing the Fischer-Tropsch catalyst, the Fischer-Tropsch reaction conditions, the temperature of the condenser and the like, the reaction is more flexible, and the method can be suitable for different requirements and occasions.
TABLE 1 reaction results of synthesis gas to lower alcohols in different examples
Comparative example 1
The traditional process flow for preparing the low-carbon mixed alcohol is adopted, namely, a single fixed bed Fischer-Tropsch reactor is adopted, and the specific operation is as follows: filling a traditional Co-Cu bimetallic catalyst in a Fischer-Tropsch reactor, and carrying out reaction at 230 ℃ and 2.0MPa in the presence of H2The reaction was carried out at a space velocity of 6000/h and a/CO of 1.0, and the gas and liquid phase compositions thereof were analyzed by on-line and off-line chromatography, and the results are shown in table 2.
Comparative example 2
The traditional process flow for preparing the low-carbon mixed alcohol is also adopted, namely, a single fixed bed Fischer-Tropsch reactor is adopted, and the specific operation is as follows: filling a traditional Fe-Cu bimetallic catalyst in a Fischer-Tropsch reactor, and carrying out reaction at 240 ℃, 2.0MPa and H2The reaction was carried out at a space velocity of 6000/h and a/CO of 1.0, and the gas and liquid phase compositions thereof were analyzed by on-line and off-line chromatography, and the results are shown in table 2.
TABLE 2 reaction results of synthesis gas to lower alcohols in different comparative examples
As can be seen from the results in table 2, when the mixed alcohol is prepared from syngas using a single reactor product, the ratio of alcohol to hydrocarbon in the product is much less than 1.0, and most of the product is hydrocarbon product, mainly saturated hydrocarbon, and the alcohol product is less, and mainly methanol and ethanol, which account for 51.2% of the total alcohol.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (1)
1. A method for producing low-carbon mixed alcohol by using synthesis gas is characterized in that firstly, the synthesis gas is subjected to Fischer-Tropsch synthesis, a product obtained through the Fischer-Tropsch synthesis is subjected to gas-liquid separation, a liquid-phase product is extracted as a product, a gas-phase product is used as a reaction raw material to carry out hydroformylation reaction, the gas-phase product obtained through the hydroformylation reaction is subjected to gas-liquid separation and then is subjected to circulation to carry out Fischer-Tropsch reaction, and the liquid-phase product obtained through the hydroformylation reaction is subjected to hydrogenation reaction to obtain a low-carbon mixed alcohol product; wherein,
the synthesis gas comprises CO and H2In which H is2And CO in a volume ratio of 0.5-3;
the Fischer-Tropsch reaction is carried out in a fixed bed reactor, and the filled catalyst is a cobalt-based or iron-based catalyst; the hydroformylation reactor (2) is carried out in a slurry bed reactor or a fixed bed reactor, and the filled catalyst is rhodium-based or cobalt-based; the hydrogenation reactor (5) is carried out in a kettle type reactor, and the filling catalyst is one or more than two of palladium-based catalyst, platinum-based catalyst, nickel-based catalyst or copper-based catalyst; the operation temperature of the gas-liquid separation is-20 to 250 ℃; the Fischer-Tropsch reaction operating conditions are as follows: the reaction temperature is 180-350 ℃, and the reaction pressure is 0.1-6.0 MPa; the operating conditions of the hydroformylation reaction are as follows: the reaction temperature is 50-250 ℃, and the reaction pressure is 0.1-6.0 MPa; the operation conditions of the hydrogenation reaction are as follows: the reaction temperature is 25-200 ℃, and the reaction pressure is 0.1-3.0 MPa;
the method is carried out on a device comprising a Fischer-Tropsch reactor (1), a first gas-liquid separator (3), a hydroformylation reactor (2), a second gas-liquid separator (4) and a hydrogenation reactor (5), wherein a product outlet of the Fischer-Tropsch reactor (1) is connected with an inlet of the first gas-liquid separator (3), the gas outlet of the first gas-liquid separator (3) is connected with the feed inlet of the hydroformylation reactor (2), the product outlet of the hydroformylation reactor (2) is connected with the inlet of the second gas-liquid separator (4), the liquid outlet of the second gas-liquid separator (4) is connected with the charging hole of the hydrogenation reactor (5), wherein the Fischer-Tropsch reactor (1) is a fixed bed reactor, the hydroformylation reactor (2) is a slurry bed reactor or a fixed bed reactor, and the hydrogenation reactor (5) is a kettle reactor; and the gas outlet of the second gas-liquid separator (4) is connected with the feed inlet of the Fischer-Tropsch reactor (1).
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