CN116003218A - Method for preparing isopropanol by synthesis gas one-step method - Google Patents
Method for preparing isopropanol by synthesis gas one-step method Download PDFInfo
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- CN116003218A CN116003218A CN202310081759.6A CN202310081759A CN116003218A CN 116003218 A CN116003218 A CN 116003218A CN 202310081759 A CN202310081759 A CN 202310081759A CN 116003218 A CN116003218 A CN 116003218A
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 67
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000006315 carbonylation Effects 0.000 claims abstract description 10
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 69
- 239000006260 foam Substances 0.000 claims description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000010926 purge Methods 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910018054 Ni-Cu Inorganic materials 0.000 description 4
- 229910018481 Ni—Cu Inorganic materials 0.000 description 4
- 229910007565 Zn—Cu Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910003271 Ni-Fe Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- -1 acetic acid ketone Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A one-step process for preparing isopropanol from synthetic gas (CO/H) 2 ) As reaction raw materials, realizing C-C accurate coupling on a multifunctional composite catalyst to obtain C 3 The product is isopropanol. Wherein the multifunctional composite catalyst consists of a catalyst with the functions of methanol synthesis, methanol carbonylation, ketonization of acetic acid and hydrogenation of acetone. The method for preparing isopropanol by the synthesis gas one-step method comprises the following steps: step 1, each component catalyst is sequentially filled in a reactor for pretreatment; and step 2, introducing synthesis gas, and carrying out catalytic reaction to prepare the target product isopropanol. Through the high-efficiency combination of the functional catalyst components, the catalytic conversion of the synthesis gas is implemented, and the selectivity of the isopropanol reaches more than 80 percent. The method is a one-step method route, and has the advantages of simple process, less equipment investment, low separation energy consumption and cost and good application prospect compared with the traditional multi-step method.
Description
Technical Field
The invention relates to a method for synthesizing isopropanol, in particular to a method for preparing isopropanol by a one-step method of synthesis gas, in particular to a method for preparing isopropanol by a one-step method of CO hydrogenation on a multifunctional composite catalyst.
Background
At present, the resources of China are rich in coal, lean in oil and less in gas, and the development of non-petroleum-based carbon-based resources for preparing high-added-value chemicals and liquid fuels is urgent. Coal, natural gas, biomass, carbon dioxide can be gasified, reformed, or reduced to produce synthesis gas, which can be directly converted to high value-added chemicals as a platform compound. However, besides methane and methanol synthesis, the carbon number distribution of target products generated by catalytic conversion of the synthesis gas is wide, so that great attention is paid to how to regulate and control products in a specific carbon number range to realize selective synthesis of a single product.
Isopropanol as an extremely important C 3 The chemical and the basic chemical raw materials are widely applied to industries such as pharmacy, plastics, cosmetics, perfume, paint and the like, can be used as chromatographic analysis standard substances for measuring metal, and can be used as solvent for mass production of rubber, paint, shellac, alkaloid, nitrocellulose and the like. At present, isopropanol can be produced by grain fermentation, but the method consumes a large amount of sulfuric acid, which can cause equipment corrosion. The method can also adopt a propylene direct hydration method, but the process has low propylene single pass conversion rate, low isopropanol selectivity, large quantity of circulation of propylene raw materials, large power consumption and high cost (CN 203417661U). Thus, the development of new methods and processes for highly selective synthesis of isopropanol has attracted considerable attention from researchers.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a method for preparing isopropanol by a one-step method by using synthesis gas, so that the high-selectivity synthesis of the target product isopropanol is realized.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing isopropanol by a one-step method from synthesis gas, which comprises the following steps:
1) Sequentially filling the catalyst into a reactor in a multi-bed mode, and introducing gas to pretreat the catalyst; wherein, the methanol synthesis catalyst is arranged in a first bed layer, the methanol carbonylation catalyst is arranged in a second bed layer, the acetic acid ketonization catalyst is arranged in a third bed layer, and the acetone hydrogenation catalyst is arranged in a fourth bed layer; the mass ratio of the methanol synthesis catalyst to the methanol carbonylation catalyst to the acetic acid ketonization catalyst to the acetone hydrogenation catalyst is (1.0-2.0) (0.5-4.0);
2) And (3) introducing synthesis gas to perform catalytic reaction to obtain a product mainly comprising isopropanol.
In the step 1), the pretreatment method of the catalyst comprises the following steps: introducing hydrogen or the mixed gas of hydrogen and inert gas, heating to 200-600 ℃ at the speed of 1.0-10 ℃/min, maintaining for 1.0-10 h, and then switching to inert gas purging for 0.1-5.0 h.
In the step 2), the specific method of the catalytic reaction is as follows: after the catalyst is pretreated, the temperature is reduced to 30-300 ℃, and the synthesis gas is introduced, wherein H 2 The volume ratio of the catalyst to CO is (0.25-5.0) 1, the reaction temperature is controlled to be 200-500 ℃, the reaction pressure is controlled to be 0.5-7.0 MPa, and the space velocity of the synthetic gas is controlled to be 500-20000 h -1 The synthesis gas is reacted by a catalyst bed layer to obtain the target product isopropanol.
The methanol synthesis catalyst is selected from Cu-ZnO-Al 2 O 3 、Pd-ZnO-Al 2 O 3 、ZnO-Cr 2 O 3 -Al 2 O 3 、ZnO-Cr 2 O 3 、ZnO-ZrO 2 、ZnO-Al 2 O 3 、CeO 2 -ZrO 2 、In 2 O 3 At least one of ZnO.
Said methanol carbonylationThe catalyst is at least one selected from zeolite molecular sieves with MOR, FER, ZSM-5 and EU-12 types; the molecular sieve has a micropore structure, wherein the pore diameter of micropores is 0.1-1.0 nm, and the pore volume of micropores is 0.01-1.0 cm 3 /g。
The methanol carbonylation catalyst can be treated by at least one method of metal modification, pyridine vapor adsorption and water vapor selective dealumination.
The ketonization catalyst is recorded as x wt.% MO n Y, where MO is n Is a metal oxide, x wt.% is MO n At MO n The mass ratio of/Y is 5.0-50%, M is at least one of Ce, mn, zr, la, pr, nd, Y is H-MOR, H-ZSM-5, al 2 O 3 、SiO 2 、TiO 2 、MgO、CaCO 3 At least one of them.
The acetone hydrogenation catalyst is at least one of foam copper, foam nickel and foam iron.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the process is a new process route, the synthesis gas is used as a raw material to prepare the isopropanol in one step, the process is simple as a whole, the catalytic efficiency is improved, intermediate products are not required to be separated in the reaction, the equipment use is greatly reduced, and the energy consumption and the cost are reduced;
2. the synthesis method is characterized in that methanol is prepared from synthesis gas, acetic acid is prepared from methanol through multiphase carbonylation, acetone is prepared from acetic acid ketone, isopropanol is prepared from acetone through hydrogenation, wherein CO is activated and hydrogenated to prepare methanol through metal/metal oxide responsible for synthesizing the methanol, the methanol is further catalyzed by zeolite molecular sieve with methanol carbonylation active site to prepare acetic acid, the acetic acid is converted into acetone on the supported metal oxide, then the acetone is further hydrogenated on the supported foam metal material to prepare the target product isopropanol, thereby realizing accurate coupling of C-C and high-selectivity preparation of C 3 A product;
3. the catalyst system has excellent reaction performance, and under proper catalyst and reaction conditions, the selectivity of isopropanol can reach more than 80%;
4. the preparation process of the multifunctional catalyst is simple and controllable, the preparation method is simple, the further amplified preparation is easy, the catalyst cost is low, the added value of the product is high, and the preparation method has good economic benefit and industrial application prospect.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and apparent, the invention is further described in detail below with reference to the embodiments.
Example 1
0.5g ZnO-Cr is weighed 2 O 3 -Al 2 O 3 (Zn/Cr/Al molar ratio of 4.0:3.0:1.0), 1.0g ZSM-5 (Si/al=12), 0.5g 30wt.% MnO 2 /TiO 2 And 0.5g of foam Fe, filled into a quartz tube, wherein ZnO-Cr 2 O 3 -Al 2 O 3 In the top layer, ZSM-5 in the second layer, 30wt.% MnO 2 /TiO 2 In the third layer, foam Fe is in the bottom layer. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 2
0.5g of Cu-ZnO-Al is weighed 2 O 3 (Cu/Zn/Al molar ratio 5.0:2.0:1.0), 1.0g H-MOR (Si/al=18), 0.5g 20wt.% La 2 O 3 A quartz tube was filled with/H-MOR and 0.5g of foamed Ni-Cu, wherein Cu-ZnO-Al 2 O 3 In the top layer, H-MOR in the second layer, 20wt.% La 2 O 3 The third layer, the foam Ni-Cu layer, is the H-MOR layer. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: reactionThe temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 3
Weigh 0.5g In 2 O 3 ZnO (In/Zn molar ratio 3.0:1.0), 1.0g H-MOR (Si/Al=12), 0.5g 30wt.% CeO 2 H-MOR and 0.5g of foam Zn-Cu were packed In quartz tubes, in which 2 O 3 -ZnO on top layer, H-MOR on second layer, 30wt.% CeO 2 The third layer is the H-MOR layer, and the bottom layer is the foam Zn-Cu layer. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 4
0.5g ZnO-Cr is weighed 2 O 3 (Zn/Cr molar ratio of 1.0:1.0), 1.0g of H-MOR (Si/Al=18) from which the 12-membered ring was selectively dealuminated was designated H-MOR-DA-12MR, 0.5g of 25wt.% CeO 2 A quartz tube was filled with/H-MOR-DA-12 MR and 0.5g of foamed Ni, wherein ZnO-Cr 2 O 3 In the top layer, H-MOR-DA-12MR in the second layer, 25wt.% CeO 2 The third layer is/H-MOR-DA-12 MR, and the bottom layer is foam Ni. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 5
0.5g ZnO-Al was weighed 2 O 3 (Zn/Al molar ratio of 1.0:1.0), 1.0g of pyridine modified H-MOR (Si/Al=13) was noted as Py-H-MOR, 0.5g of 35wt.% MnO 2 A quartz tube was filled with/Py-H-MOR and 0.5g of foamed Ni-Cu, wherein ZnO-Al 2 O 3 In the top layer, py-H-MOR in the second layer, 35wt.% MnO 2 The third layer is/Py-H-MOR, and the bottom layer is foam Ni-Cu. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 6
0.5g ZnO-Cr is weighed 2 O 3 -Al 2 O 3 (molar ratio of Zn/Cr/Al is 1.0:2.0:1.0), 1.0g H-MOR modified by metallic Cu modified pyridine (Si/Al=18) is recorded as 1.0wt.% Cu/Py-H-MOR, 0.5g 25wt.% CeO) 2 /SiO 2 And 0.5g of foamed Zn-Cu, in which ZnO-Cr is contained in a quartz tube 2 O 3 -Al 2 O 3 On top of this, 1wt.% Cu/Py-H-MOR on the second layer, 25wt.% CeO 2 /SiO 2 In the third layer, the foam Zn-Cu is at the bottom layer. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 7
Weigh 0.5g In 2 O 3 ZnO (In/Zn molar ratio of 3.0:1.0), 1.0g of pyridine modified H-MOR (Si/Al=16) was designated Py-H-MOR,0.5g of 20wt.% MnO/Py-H-MOR and 0.5g of foam Fe, into a quartz tube, wherein In 2 O 3 -ZnO on top layer, py-H-MOR on the second layer, 20wt.% MnO/Py-H-MOR on the third layer, foam Fe on bottom layer. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 8
0.5g of ZnO-ZrO was weighed 2 (Zn/Zr molar ratio of 1.0:5.0), 1.0g of metal Mn-modified pyridine-modified H-MOR (Si/Al=12) was recorded as 1.0wt.% Mn/Py-H-MOR, 0.5g of 20wt.% MnO 2 Per Py-H-MOR and 0.5g of foamed Ni, were packed into quartz tubes, wherein ZnO-ZrO 2 In the top layer, 1wt.% Mn/Py-H-MOR in the second layer, 20wt.% MnO 2 The third layer is/Py-H-MOR, and the bottom layer is foam Ni. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 9
0.5g of Cu-ZnO-Al is weighed 2 O 3 (Cu/Zn/Al molar ratio of 5.0:2.0:1.0), 1.0g of metallic Cu modified pyridine modified H-MOR (Si/al=18) was recorded as 1.0wt.% Cu/Py-H-MOR, 0.5g 30wt.% MnO 2 Per Py-H-MOR and 0.5g of foam Cu, in a quartz tube, wherein Cu-ZnO-Al 2 O 3 In the top layer, 1wt.% Cu/Py-H-MOR in the second layer, 30wt.% MnO 2 The layer/Py-H-MOR is on the third layer, and the foam Cu is on the bottom layer. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
Example 10
0.5g CeO was weighed 2 -ZrO 2 (molar ratio of Ce/Zr is 1.0:1.0), 1.0g of ZSM-5 modified with metallic Cu (Si/Al=12) is recorded as 1.0wt.% Cu/ZSM-5, 0.5g 30wt.% MnO 2 H-MOR and 0.5g of foam Ni-Fe, in which CeO was contained in a quartz tube 2 -ZrO 2 In the top layer, 1wt.% Cu/ZSM-5 in the second layer, 30wt.% MnO 2 The third layer, the foam Ni-Fe layer, is the bottom layer. 15% H is introduced 2 Ar mixed gas is heated to 300 ℃ at the speed of 5 ℃/min for 3 hours, and then is switched into N 2 Purging for 0.5h, cooling to 250 ℃, and then introducing synthesis gas to perform catalytic reaction under the following catalytic reaction conditions: the reaction temperature is 250 ℃, the reaction pressure is 3.0MPa, and the space velocity of the synthesis gas is 5000h -1 H in synthesis gas 2 The volume ratio to CO was 2.0. The reaction materials and products are subjected to gas chromatography on-line analysis through pipeline heat preservation, and specific catalytic reaction performances are shown in table 1.
TABLE 1
Note that: c (C) 2-4 Is C 2 -C 4 Hydrocarbons, C 5+ Is aliphatic hydrocarbon with carbon number more than or equal to 5, DME is dimethyl ether, meOH is methanol, etOH is ethanol, MA is methyl acetate, IPA is isopropanol, EA is ethyl acetate, and AA is acetic acid.
Claims (8)
1. A method for preparing isopropanol by a one-step method from synthesis gas, which is characterized by comprising the following steps:
1) Sequentially filling the catalyst into a reactor in a multi-bed mode, and introducing gas to pretreat the catalyst; wherein, the methanol synthesis catalyst is arranged in a first bed layer, the methanol carbonylation catalyst is arranged in a second bed layer, the acetic acid ketonization catalyst is arranged in a third bed layer, and the acetone hydrogenation catalyst is arranged in a fourth bed layer; the mass ratio of the methanol synthesis catalyst to the methanol carbonylation catalyst to the acetic acid ketonization catalyst to the acetone hydrogenation catalyst is (1.0-2.0) (0.5-4.0);
2) And (3) introducing synthesis gas to perform catalytic reaction to obtain a product mainly comprising isopropanol.
2. A process for the one-step preparation of isopropanol from synthesis gas according to claim 1, wherein in step 1), the catalyst is pretreated by: introducing hydrogen or the mixed gas of hydrogen and inert gas, heating to 200-600 ℃ at the speed of 1.0-10 ℃/min, maintaining for 1.0-10 h, and then switching to inert gas purging for 0.1-5.0 h.
3. A method for preparing isopropanol by a one-step synthesis gas process according to claim 1, wherein in step 2), the specific method of the catalytic reaction is as follows: after the catalyst is pretreated, the temperature is reduced to 30-300 ℃, and the synthesis gas is introduced, wherein H 2 The volume ratio of the catalyst to CO is (0.25-5.0) 1, the reaction temperature is controlled to be 200-500 ℃, the reaction pressure is controlled to be 0.5-7.0 MPa, and the space velocity of the synthetic gas is controlled to be 500-20000 h -1 The synthesis gas is reacted by a catalyst bed layer to obtain the target product isopropanol.
4. A method for preparing isopropanol by a one-step synthesis gas process as claimed in claim 1, wherein: the methanol synthesis catalyst is selected from Cu-ZnO-Al 2 O 3 、Pd-ZnO-Al 2 O 3 、ZnO-Cr 2 O 3 -Al 2 O 3 、ZnO-Cr 2 O 3 、ZnO-ZrO 2 、ZnO-Al 2 O 3 、CeO 2 -ZrO 2 、In 2 O 3 At least one of ZnO.
5. A method for preparing isopropanol by a one-step synthesis gas process as claimed in claim 1, wherein: the methanol carbonylation catalyst is at least one selected from zeolite molecular sieves with MOR, FER, ZSM-5 and EU-12 types.
6. A method for preparing isopropanol by a one-step synthesis gas process as claimed in claim 1, wherein: the methanol carbonylation catalyst can be treated by at least one method of metal modification, pyridine vapor adsorption and water vapor selective dealumination.
7. A method for preparing isopropanol by a one-step synthesis gas process as claimed in claim 1, wherein: the ketonization catalyst is recorded as x wt.% MO n Y, where MO is n Is a metal oxide, x wt.% is MO n At MO n The mass ratio of/Y is 5.0-50%, M is at least one of Ce, mn, zr, la, pr, nd, Y is H-MOR, H-ZSM-5, al 2 O 3 、SiO 2 、TiO 2 、MgO、CaCO 3 At least one of them.
8. A method for preparing isopropanol by a one-step synthesis gas process as claimed in claim 1, wherein: the acetone hydrogenation catalyst is at least one of foam copper, foam nickel and foam iron.
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| US4751248A (en) * | 1987-07-02 | 1988-06-14 | Phillips Petroleum Company | Preparation of alcohols from synthesis gas |
| US7041857B1 (en) * | 2005-09-07 | 2006-05-09 | Air Products And Chemicals, Inc. | Hydrogenation of acetone |
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| US4751248A (en) * | 1987-07-02 | 1988-06-14 | Phillips Petroleum Company | Preparation of alcohols from synthesis gas |
| US7041857B1 (en) * | 2005-09-07 | 2006-05-09 | Air Products And Chemicals, Inc. | Hydrogenation of acetone |
| CN103153930A (en) * | 2010-09-23 | 2013-06-12 | 国际人造丝公司 | Production of alcohols |
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