CN110981694A - Environment-friendly method for preparing isopropanol by catalytic distillation - Google Patents
Environment-friendly method for preparing isopropanol by catalytic distillation Download PDFInfo
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- CN110981694A CN110981694A CN201911354988.0A CN201911354988A CN110981694A CN 110981694 A CN110981694 A CN 110981694A CN 201911354988 A CN201911354988 A CN 201911354988A CN 110981694 A CN110981694 A CN 110981694A
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- isopropanol
- fluidized bed
- bed reactor
- catalytic distillation
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 61
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- 238000004821 distillation Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 22
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 21
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 17
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 241000219782 Sesbania Species 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 2
- 235000011837 pasties Nutrition 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 50
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 239000007787 solid Substances 0.000 abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 description 21
- 238000011049 filling Methods 0.000 description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- -1 isopropyl fatty acid isopropyl ester Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UOJYYXATTMQQNA-UHFFFAOYSA-N Proxan Chemical compound CC(C)OC(S)=S UOJYYXATTMQQNA-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GAPFWGOSHOCNBM-UHFFFAOYSA-N isopropyl nitrate Chemical compound CC(C)O[N+]([O-])=O GAPFWGOSHOCNBM-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- IVNFTPCOZIGNAE-UHFFFAOYSA-N propan-2-yl hydrogen sulfate Chemical compound CC(C)OS(O)(=O)=O IVNFTPCOZIGNAE-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004208 shellac 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
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
Classifications
-
- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing isopropanol, in particular to a green method for preparing isopropanol by catalytic distillation. Acetone and hydrogen are used as raw materials, a mesoporous framework metal hybrid catalyst is filled in a bed layer of a fluidized bed reactor, the raw materials are mixed and preheated and then enter the fluidized bed reactor for catalytic reaction, reaction products are extracted and then enter a rectifying tower, and the refined isopropanol is obtained after rectification. Dissolving nickel nitrate in a hydrochloric acid solution, continuously stirring, adding a carrier into the system, continuously stirring, drying and roasting to obtain the mesoporous framework metal hybrid catalyst. The gas-liquid-solid three-phase reaction is more sufficient by utilizing a fluidized bed reactor and adopting optimized and reasonable process conditions, the reaction liquid is extracted and further rectified to obtain the high-purity isopropanol, the product purity is more than or equal to 99.2 percent, and the single yield is more than or equal to 96.5 percent.
Description
Technical Field
The invention relates to a method for preparing isopropanol, in particular to a green method for preparing isopropanol by catalytic distillation.
Background
The isopropanol can be used as chemical raw material to produce acetone, hydrogen peroxide, methyl isobutyl ketone, diisobutyl ketone, isopropylamine, isopropyl ether, isopropoxide ether, isopropyl chloride, isopropyl fatty acid isopropyl ester, isopropyl chloro fatty acid isopropyl ester and the like. In the aspect of fine chemical engineering, the method can be used for producing isopropyl nitrate, isopropyl xanthate, triisopropyl phosphite, triisoaluminum propoxide, medicines, pesticides and the like. As a solvent, the product can be used for producing coatings, printing ink, extracting agents, aerosol and the like. It can also be used as antifreezing agent, cleaning agent, additive for blending gasoline, dispersing agent for pigment production, fixing agent for printing and dyeing industry, and antifogging agent for glass and transparent plastics. Used as diluent of adhesive, anti-freezing agent, dehydrating agent, etc. Isopropanol can also be used as a reagent for measuring barium, calcium, copper, magnesium, nickel, potassium, sodium, strontium, nitrous acid, cobalt, and the like, as a chromatographic standard.
The isopropanol is used as a defoaming agent of the oil well water-based fracturing fluid, and air forms an explosive mixture which can cause combustion and explosion when meeting open fire and high heat. Can react with oxidant strongly. The vapor is heavier than air and can be diffused to a far distance at a lower position and is ignited back when meeting a fire source. If high heat is encountered, the internal pressure of the container is increased, and the danger of cracking and explosion is caused.
Isopropanol is used as a cleaning degreaser, MOS grade is mainly used for discrete devices and medium and large scale integrated circuits, BV-III grade is mainly used for super large scale integrated circuit technology; used in the electronic industry, and can be used as cleaning degreaser; the adhesive is used as a diluent of an adhesive, an extractant of cottonseed oil, and a solvent of nitrocellulose, rubber, paint, shellac, alkaloid, grease and the like. Also used for anti-freezing agent, dehydrating agent, antiseptic, antifogging agent, medicine, pesticide, perfume, printing industry, cosmetics and organic synthesis; the solvent is cheaper in industry, has wide application, can be freely mixed with water, and has stronger dissolubility than ethanol on lipophilic substances; for the production of diisopropyl ketone, isopropyl acetate and thymol as well as gasoline additives; can be used for degreasing animal origin tissue membrane.
The synthesis method of isopropanol comprises an indirect synthesis method and a direct hydration method. The indirect synthesis process of synthesizing isopropanol includes the first reaction of propylene and sulfuric acid to obtain isopropyl bisulfate, and the latter hydrolysis to prepare isopropanol. The method is characterized in that the requirement on the purity of the propylene is not high, the conversion rate of the propylene can reach 50-60 percent, and the refining cost can be reduced. But the consumption of sulfuric acid is large, and the problems of equipment corrosion and 40 percent of waste concentrated sulfuric acid exist. The direct hydration method is that propylene and water are heated and pressurized in the presence of catalyst to carry out hydration reaction. Compared with the indirect hydration method of propylene, the method does not use sulfuric acid, does not have the problem of equipment corrosion and has simple process flow; but the conversion per pass of propylene is low, the circulating quantity of propylene is too large, and the purity of the raw material propylene is required to reach 99.5%. In order to overcome the defects of the direct hydration method of propylene, 95 percent of propylene is taken as a raw material, the reaction temperature is 240-270 ℃, the reaction pressure is 14.7-19.6MPa, and the mol of water and propylene is water excess. The conversion rate of propylene is 60-70%, the selectivity of isopropanol is 99%, the purity of the rectified isopropanol can reach more than 99.9%, and the byproduct is diisopropyl ether. In addition, the molecular sieve catalysis of propylene hydration to prepare isopropanol is a very promising improved process method. However, the method adopts the reaction and the rectification separately, which increases the production cost to a certain extent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a green method for preparing isopropanol by catalytic distillation, which utilizes a fluidized bed reactor to react, optimizes process conditions and prepares a proper catalyst, so that gas-liquid-solid three-phase reaction is more sufficient, high-purity isopropanol is obtained by further rectifying reaction liquid after extraction, the product purity is high, and the single yield is high.
The invention relates to a green method for preparing isopropanol by catalytic distillation, which takes acetone and hydrogen as raw materials, fills a mesoporous framework metal hybrid catalyst in a bed layer of a fluidized bed reactor, mixes and preheats the raw materials, then enters the fluidized bed reactor for catalytic reaction, extracts reaction products, then enters a rectifying tower, and rectifies the reaction products to obtain the refined isopropanol.
Wherein:
the preheating temperature is preferably 50-60 ℃.
The preparation method of the mesoporous framework metal hybrid catalyst comprises the following steps: the preparation method is characterized by utilizing an isometric impregnation method, dissolving nickel nitrate in a hydrochloric acid solution, continuously stirring, adding a carrier into a system, then continuously stirring, drying and roasting to obtain the nickel nitrate.
As a preferred technical scheme, the preparation method of the mesoporous framework metal hybrid catalyst comprises the following steps: adding nickel nitrate into hydrochloric acid solution, ultrasonic stirring in ultrasonic instrument to dissolve it completely, and adding gamma-Al2O3A carrier, wherein the solution is pasty fluid, and the carrier is placed in an ultrasonic cleaning instrument for ultrasonic treatment to be fully dissolved; then drying and roasting to obtain the mesoporous framework metal hybrid catalyst; wherein: support gamma-Al2O3The molar ratio of the nickel nitrate to the hydrochloric acid solution is 1-1.02: 0.3-0.5: 1.05; the concentration of the hydrochloric acid solution is 15-30%.
The time of ultrasonic stirring in an ultrasonic instrument is 14-16 minutes, the time of ultrasonic cleaning in an ultrasonic cleaning instrument is 14-16 minutes, the roasting temperature is 400-500 ℃, and the roasting time is 4-5 hours.
γ-Al2O3The preparation method of the carrier comprises the following steps: pseudo-boehmite is taken as a raw material, sesbania powder is taken as an extrusion aid, and concentrated nitric acid is taken as a binder; mixing the above raw materials, dissolving in deionized water, ultrasonic dispersing in ultrasonic cleaning machine, mixing well, kneading into paste, extruding in F-26(III) twin-screw extruder, oven drying, and roasting; wherein: the mass ratio of the pseudo-boehmite to the sesbania powder to the concentrated nitric acid to the deionized water is 50-100: 1.2-2: 1-3: 55-95.
Support gamma-Al2O3The roasting temperature in the preparation method is 500-600 ℃, and the roasting time is 5-6 h.
The molar ratio of acetone to hydrogen is 1: 1-2, the amount of the mesoporous framework metal hybrid catalyst is 0.001-10% of the total mass of all raw materials.
The fluidized bed reactor is of the type of a turbulent fluidized bed. The reflux ratio of the fluidized bed reactor is 0.5-1.0.
The inlet temperature of the fluidized bed reactor is 30-60 ℃, the bed temperature is 120-160 ℃, the bottom temperature is 50-65 ℃, and the top temperature is 30-40 ℃; the absolute pressure of the top is 0.06-1.0MPa, preferably 0.1-0.8 MPa; the absolute pressure at the bottom is 0.1 to 1.2MPa, preferably 0.6 to 1.2 MPa.
The bottom temperature of the rectifying tower is 50-90 ℃, and the preferred temperature is 70-90 ℃; the top temperature of the rectification column is 30 to 80 ℃, preferably 50 to 80 ℃.
The fluidized bed and the rectifying tower adopt the conditions of reflux ratio, temperature, pressure and the like, so that the purity and the yield of the separated product are high.
Compared with the prior art, the invention has the following advantages:
(1) the invention adopts a catalytic rectification process, is substantially a heterogeneous catalytic reaction rectification process, utilizes the principle of pneumatic conveying of a fluidized bed to enable solid particles to continuously flow, achieves the aim of complete gas-liquid-solid reaction, improves the conversion rate of acetone, and obtains high-purity isopropanol through further rectification.
(2) The method for preparing isopropanol by catalytic distillation provided by the invention avoids the problems of complicated process route, low yield, low purity, complex post-treatment and the like in the traditional isopropanol synthesis method, also overcomes the problems of unstable catalyst and the like in the direct hydrogenation reduction of other raw materials, and realizes the reaction and separation simultaneously by utilizing the catalytic distillation technology.
(3) The invention relates to a green method for directly preparing isopropanol from carbonyl compounds, which utilizes a catalytic rectification method to optimize reasonable reaction conditions, the reaction is complete in a fluidized bed reactor, and reaction liquid is further rectified to obtain high-purity isopropanol, wherein the purity of the product is more than or equal to 99.2 percent, and the single yield is more than or equal to 96.5 percent.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The preparation method of the mesoporous framework metal hybrid catalyst comprises the following steps: preparing a mesoporous framework metal hybrid catalyst by using an isometric impregnation method, dissolving nickel nitrate in a certain amount of hydrochloric acid solution, wherein the concentration of the hydrochloric acid solution is 30%, and fully stirring in an ultrasonic instrument for 15min to completely dissolve the nickel nitrate. With gamma-Al2O3As a carrier, gamma-Al is added2O3Directly adding the obtained product into the dissolved solution, placing the obtained product in an ultrasonic cleaning instrument for ultrasonic treatment for 15min to fully dissolve the product, drying the product overnight, and then roasting the product at the roasting temperature of 450 ℃ for 4.5h to obtain the mesoporous framework metal hybrid catalyst; wherein: support gamma-Al2O3And the molar ratio of the nickel nitrate to the hydrochloric acid solution is 1: 0.3: 1.05.
γ-Al2O3the preparation method comprises using pseudo-boehmite as raw material, sesbania powder as extrusion aid, and concentrated nitric acid as binder. Dissolving the above raw materials in deionized water, placing in ultrasonic cleaning machine, ultrasonic dispersing for 15min, mixing well, and kneading into paste. Extruding and molding in a F-26(III) twin-screw extruder, drying overnight, and then roasting for 5.5h at the roasting temperature of 550 ℃. The mass ratio of the pseudo-boehmite to the sesbania powder to the concentrated nitric acid to the deionized water is 50: 1.2: 1: 55.
a green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 2, preheating to 60 ℃, then feeding the mixture into a fluidized bed reactor, and filling the mesoporous framework metal hybrid catalyst into a bed layer of the fluidized bed, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.5 percent of the total mass of all raw materials, the inlet temperature of the reactor is 60 ℃, the bottom temperature of the reactor is 50 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.2MPa, the reflux ratio is 0.5, the temperature of a bed layer is 130 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 70 ℃, the temperature of the tower top is 60 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 97.5%, and the purity is 99.6%.
Example 2
The preparation method of the mesoporous framework metal hybrid catalyst comprises the following steps: preparing a mesoporous framework metal hybrid catalyst by using an isometric impregnation method, dissolving nickel nitrate in a certain amount of hydrochloric acid solution, wherein the concentration of the hydrochloric acid solution is 15%, and fully stirring in an ultrasonic instrument for 16min to completely dissolve the nickel nitrate. With gamma-Al2O3As a carrier, gamma-Al is added2O3Adding the solution into the dissolved solution, placing the solution in an ultrasonic cleaning instrument for ultrasonic treatment for 16min to fully dissolve the solution, drying the solution overnight, and then roasting the solution at the roasting temperature of 400 ℃ for 5h to obtain the mesoporous framework metal hybrid catalyst; wherein: support gamma-Al2O3And the molar ratio of the nickel nitrate to the hydrochloric acid solution is 1.01: 0.35: 1.05.
γ-Al2O3the preparation method comprises using pseudo-boehmite as raw material, sesbania powder as extrusion aid, and concentrated nitric acid as binder. Dissolving the above raw materials in deionized water, placing in ultrasonic cleaning machine, ultrasonic dispersing for 15min, mixing well, and kneading into paste. Extruding and molding in a F-26(III) double-screw extruder, drying overnight, and then roasting for 5h at 600 ℃. The mass ratio of the pseudo-boehmite to the sesbania powder to the concentrated nitric acid to the deionized water is 60: 1.2: 3: 65.
a green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.5, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, filling the mesoporous framework metal hybrid catalyst in a rectifying section of the fluidized bed reactor, wherein the amount of the mesoporous framework metal hybrid catalyst is 1.0 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 0.5 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.10MPa, the reflux ratio is 0.5, the temperature of a bed layer is 130 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 80 ℃, the temperature of the tower top is 70 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 97.4%, and the purity is 99.4%.
Example 3
Method for preparing mesoporous framework metal hybrid catalystThe preparation method comprises the following steps: dissolving nickel nitrate in a certain amount of hydrochloric acid solution with a concentration of 25%, and stirring in an ultrasonic instrument for 14min to completely dissolve the nickel nitrate. With gamma-Al2O3As a carrier, gamma-Al is added2O3Adding the solution into the dissolved solution, placing the solution in an ultrasonic cleaning instrument for ultrasonic treatment for 14min to fully dissolve the solution, drying the solution overnight, and then roasting the solution at the roasting temperature of 500 ℃ for 4h to obtain the mesoporous framework metal hybrid catalyst; wherein: support gamma-Al2O3And the molar ratio of the nickel nitrate to the hydrochloric acid solution is 1.01: 0.4: 1.05.
γ-Al2O3the preparation method comprises using pseudo-boehmite as raw material, sesbania powder as extrusion aid, and concentrated nitric acid as binder. Dissolving the above raw materials in deionized water, placing in ultrasonic cleaning machine, ultrasonic dispersing for 15min, mixing well, and kneading into paste. Extruding and molding in a F-26(III) twin-screw extruder, drying overnight, and then roasting for 6h at the roasting temperature of 500 ℃. The mass ratio of the pseudo-boehmite to the sesbania powder to the concentrated nitric acid to the deionized water is 65: 1.2: 3: 65.
a green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.7, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, filling the mesoporous framework metal hybrid catalyst in a rectifying section of the fluidized bed reactor, wherein the amount of the mesoporous framework metal hybrid catalyst is 2.0 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 60 ℃, and the absolute pressure of the bottom is 0.8 MPa; the top temperature was 40 ℃, the absolute pressure was 0.2MPa, and the reflux ratio was 0.6. The temperature of the bed layer is 140 ℃, after the reaction is finished, the reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 70 ℃, the temperature of the tower top of the rectifying tower is 50 ℃, the target product isopropanol is obtained after the separation is finished, the product yield is 97.1%, and the purity is 99.5%.
Example 4
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.7, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.2% of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 60 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.4MPa, the reflux ratio is 0.6, the temperature of a bed layer is 150 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 50 ℃, the temperature of the tower top is 40 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 96.8%, and the purity is 99.4%.
Example 5
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.9, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, filling the mesoporous framework metal hybrid catalyst in a rectifying section of the fluidized bed reactor, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.2 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 0.5 MPa; the top temperature is 35 ℃, the absolute pressure at the top is 0.3MPa, the reflux ratio is 0.5, the temperature of a bed layer is 150 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 70 ℃, the temperature of the tower top is 60 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 97.2%, and the purity is 99.3%.
Example 6
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.65 to 60 ℃, then feeding the mixture into a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the example 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.3 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 55 ℃, and the absolute pressure of the bottom is 0.8 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.06MPa, the reflux ratio is 0.9, and the bed temperature is 130 ℃. After the reaction is finished, the reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the tower kettle temperature of the rectifying tower is 70 ℃, the tower top temperature of the rectifying tower is 55 ℃, and the target product isopropanol is obtained after the separation is finished, wherein the product yield is 97.3%, and the purity is 99.2%.
Example 7
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.75, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 1.0 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 0.1 MPa; the top temperature was 30 ℃, the absolute top pressure was 0.1MPa, the reflux ratio was 0.8, and the bed temperature was 120 ℃. After the reaction is finished, the reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the tower kettle temperature of the rectifying tower is 60 ℃, the tower top temperature of the rectifying tower is 50 ℃, and the target product isopropanol is obtained after the separation is finished, wherein the product yield is 97.1%, and the purity is 99.3%.
Example 8
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 2, preheating to 60 ℃, feeding in a feeding system in the middle of the fluidized bed reactor, and filling the rectification section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.5 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.4MPa, the reflux ratio is 0.9, the temperature of a bed layer is 140 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 90 ℃, the temperature of the tower top is 80 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 96.9%, and the purity is 99.3%.
Example 9
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.9, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.8 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 60 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature is 40 ℃, the absolute pressure is 0.1MPa, the reflux ratio is 0.6, the bed temperature is 130 ℃, after the reaction is finished, the reaction product enters a stripping section, is extracted by a tower kettle and then enters a rectifying tower, the tower kettle temperature of the rectifying tower is 80 ℃, the tower top temperature of the rectifying tower is 70 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 96.8%, and the purity is 99.4%.
Example 10
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.8, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.3 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 1.0 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.4MPa, the reflux ratio is 0.5, the temperature of a bed layer is 140 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 70 ℃, the temperature of the tower top is 60 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 97.1%, and the purity is 99.5%.
Example 11
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.6, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.3 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 0.8 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.7MPa, the reflux ratio is 1.0, the temperature of a bed layer is 150 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 90 ℃, the temperature of the tower top is 80 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 97.0%, and the purity is 99.3%.
Example 12
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.4, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 3.0 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature was 30 ℃, the absolute top pressure was 0.1MPa, the reflux ratio was 0.9, and the bed temperature was 160 ℃. After the reaction is finished, the reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the tower kettle temperature of the rectifying tower is 70 ℃, the tower top temperature of the rectifying tower is 60 ℃, and the target product isopropanol is obtained after the separation is finished, wherein the product yield is 97.1%, and the purity is 99.4%.
Example 13
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.35 to 60 ℃, then feeding the mixture into a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the example 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.05 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.2MPa, the reflux ratio is 0.5, the temperature of a bed layer is 130 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 50 ℃, the temperature of the tower top is 40 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 96.6%, and the purity is 99.3%.
Example 14
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.2, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.1 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 65 ℃, and the absolute pressure is 0.6 MPa; the top temperature is 30 ℃, the absolute pressure is 0.4MPa, the reflux ratio is 0.7, the bed temperature is 140 ℃, after the reaction is finished, the reaction product enters a stripping section, is extracted by a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 50 ℃, the temperature of the tower top is 40 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 96.5%, and the purity is 99.5%.
Example 15
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.5, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.1 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 50 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.1MPa, the reflux ratio is 0.7, the temperature of a bed layer is 150 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 80 ℃, the temperature of the tower top is 70 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 96.8%, and the purity is 99.3%.
Example 16
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.7, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.2% of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 60 ℃, and the absolute pressure of the bottom is 0.5 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.4MPa, the reflux ratio is 0.8, the temperature of a bed layer is 150 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 60 ℃, the temperature of the tower top is 50 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 97.4%, and the purity is 99.3%.
Example 17
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.4, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.2% of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 55 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.1MPa, the reflux ratio is 0.5, the temperature of a bed layer is 120 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 60 ℃, the temperature of the tower top is 50 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 97.4%, and the purity is 99.2%.
Example 18
A green method for preparing isopropanol by catalytic distillation is characterized in that acetone and hydrogen are mixed according to a molar ratio of 1: 1.7, preheating to 60 ℃, feeding in a feeding system in the middle of a fluidized bed reactor, and filling the rectifying section of the fluidized bed reactor with the mesoporous framework metal hybrid catalyst prepared in the embodiment 1, wherein the amount of the mesoporous framework metal hybrid catalyst is 0.3 percent of the total mass of all raw materials, the bottom temperature of the fluidized bed reactor is 60 ℃, and the absolute pressure of the bottom is 0.6 MPa; the top temperature is 30 ℃, the absolute pressure at the top is 0.2MPa, the reflux ratio is 0.5, the temperature of a bed layer is 140 ℃, after the reaction is finished, a reaction product enters a stripping section, is extracted from a tower kettle and then enters a rectifying tower, the temperature of the tower kettle of the rectifying tower is 70 ℃, the temperature of the tower top is 60 ℃, after the separation is finished, the target product isopropanol is obtained, the product yield is 97.0%, and the purity is 99.5%.
Comparative example 1
Comparative example 1 is the same as example 1 in raw materials and preparation method, except that a fluidized bed reactor is replaced by a common reactor, the common reactor is a normal pressure reaction, the temperature is 80 +/-5 ℃, after the reaction is finished, the target product isopropanol is obtained by rectification separation, the product yield is 91.5%, and the purity is 93.8%.
Comparative example 2
Comparative example 2 is the same as example 2 in raw materials and preparation method, except that a common reactor is used to replace a fluidized bed reactor, the common reactor is a normal pressure reaction, the temperature is 70 +/-5 ℃, after the reaction is finished, the target product isopropanol is obtained by rectification separation, the product yield is 91.0%, and the purity is 93.2%.
Claims (10)
1. A green method for preparing isopropanol by catalytic distillation is characterized by comprising the following steps: acetone and hydrogen are used as raw materials, a mesoporous framework metal hybrid catalyst is filled in a bed layer of a fluidized bed reactor, the raw materials are mixed and preheated and then enter the fluidized bed reactor for catalytic reaction, reaction products are extracted and then enter a rectifying tower, and the refined isopropanol is obtained after rectification.
2. The green process for the catalytic distillation preparation of isopropanol according to claim 1, characterized in that: the preparation method of the mesoporous framework metal hybrid catalyst comprises the following steps: the preparation method is characterized by utilizing an isometric impregnation method, dissolving nickel nitrate in a hydrochloric acid solution, continuously stirring, adding a carrier into a system, then continuously stirring, drying and roasting to obtain the nickel nitrate.
3. The green process for the catalytic distillation preparation of isopropanol according to claim 2, characterized in that: the preparation method of the mesoporous framework metal hybrid catalyst comprises the following steps: adding nickel nitrate into hydrochloric acid solution, ultrasonic stirring in ultrasonic instrument to dissolve it completely, and adding carrier gamma-Al2O3Placing the solution which is pasty fluid in an ultrasonic cleaning instrument for ultrasonic treatment to fully dissolve the solution; then drying and roasting to obtain the mesoporous framework metal hybrid catalyst; wherein: support gamma-Al2O3The molar ratio of the nickel nitrate to the hydrochloric acid solution is 1-1.02: 0.3-0.5: 1.05; the concentration of the hydrochloric acid solution is 15-30%.
4. The green process for the catalytic distillation preparation of isopropanol according to claim 3, characterized in that: the time of ultrasonic stirring in an ultrasonic instrument is 14-16 minutes, the time of ultrasonic cleaning in an ultrasonic cleaning instrument is 14-16 minutes, the roasting temperature is 400-500 ℃, and the roasting time is 4-5 hours.
5. The green process for the catalytic distillation preparation of isopropanol according to claim 3, characterized in that: support gamma-Al2O3The preparation method comprises the following steps: pseudo-boehmite is taken as a raw material, sesbania powder is taken as an extrusion aid, and concentrated nitric acid is taken as a binder; mixing the above raw materials, dissolving in deionized water, ultrasonic dispersing in ultrasonic cleaning machine, mixing well, kneading into paste, extruding into strips in twin-screw extruder, oven drying, and roasting; wherein: the mass ratio of the pseudo-boehmite to the sesbania powder to the concentrated nitric acid to the deionized water is 50-100: 1.2-2: 1-3: 55-95.
6. The green process for the catalytic distillation preparation of isopropanol according to claim 5, characterized in that: support gamma-Al2O3The roasting temperature in the preparation method is 500-600 ℃, and the roasting time is 5-6 h.
7. The green process for the catalytic distillation preparation of isopropanol according to any of claims 1 to 6, characterized in that: the molar ratio of acetone to hydrogen is 1: 1-2, the amount of the mesoporous framework metal hybrid catalyst is 0.001-10% of the total mass of all raw materials.
8. The green process for the catalytic distillation preparation of isopropanol according to claim 7, characterized in that: the fluidized bed reactor is a turbulent fluidized bed; the reflux ratio of the fluidized bed reactor is 0.5-1.0.
9. The green process for the catalytic distillation preparation of isopropanol according to any of claims 1 to 6, characterized in that: the inlet temperature of the fluidized bed reactor is 30-60 ℃, the bed temperature is 120-160 ℃, the bottom temperature is 50-65 ℃, and the top temperature is 30-40 ℃; the absolute pressure of the top is 0.06-1.0 MPa; the absolute pressure at the bottom is 0.10-1.2 MPa.
10. The green process for the catalytic distillation preparation of isopropanol according to any of claims 1 to 6, characterized in that: the bottom temperature of the rectifying tower is 50-90 ℃; the top temperature of the rectifying tower is 30-80 ℃.
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| CN1487911A (en) * | 2000-12-23 | 2004-04-07 | �������¹ɷ�����˾ | Method for producing alcohols by hydrogenating carbong/compounds |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102728361A (en) * | 2011-04-02 | 2012-10-17 | 中国石油化工股份有限公司 | Catalyst for isopropyl alcohol preparation through acetone hydrogenation and application thereof |
| CN102806085A (en) * | 2012-08-13 | 2012-12-05 | 中国海洋石油总公司 | Preparation method of catalyst for co-generating of isopropanol and diisobutyl ketone through acetone hydrogenation and application |
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