CN115894171B - Method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate - Google Patents
Method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate Download PDFInfo
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- CN115894171B CN115894171B CN202211441858.2A CN202211441858A CN115894171B CN 115894171 B CN115894171 B CN 115894171B CN 202211441858 A CN202211441858 A CN 202211441858A CN 115894171 B CN115894171 B CN 115894171B
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- butyl acetate
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- catalytic distillation
- hydrogen
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 230000003197 catalytic effect Effects 0.000 claims abstract description 66
- 238000004821 distillation Methods 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 239000006227 byproduct Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract 3
- 239000007921 spray Substances 0.000 claims description 57
- 239000007789 gas Substances 0.000 claims description 56
- 238000011084 recovery Methods 0.000 claims description 36
- 238000003860 storage Methods 0.000 claims description 36
- 229910052709 silver Inorganic materials 0.000 claims description 23
- 239000004332 silver Substances 0.000 claims description 23
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000498 cooling water Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000002274 desiccant Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- VPSLGSSVPWVZFG-UHFFFAOYSA-N butan-2-yl propanoate Chemical compound CCC(C)OC(=O)CC VPSLGSSVPWVZFG-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- -1 and meanwhile Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of sec-butyl alcohol preparation, in particular to a method for preparing sec-butyl alcohol by sec-butyl acetate hydrogenation, which comprises the steps of preheating hydrogen and nitrogen by a preheater, feeding the preheated hydrogen and nitrogen into a reactor, feeding the sec-butyl acetate into the reactor, catalyzing and hydrogenating the sec-butyl acetate by a catalyst to generate sec-butyl alcohol, discharging materials from the reactor, feeding the sec-butyl alcohol product into a catalytic distillation tower, discharging the sec-butyl alcohol product from an outlet at the bottom of the tower, discharging other byproducts from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 2-6 MPa, the reaction temperature in the catalytic distillation tower is 150-250 ℃, the mole ratio of hydrogen and nitrogen is 1 (0.5-3), the mole ratio of hydrogen and sec-butyl acetate is (2-5): 1, and the space velocity of the sec-butyl acetate is 0.1-10h ‑1 In the preparation method, a catalytic distillation process is adopted, the reaction and separation are synchronously carried out, the operation efficiency is effectively improved, in the reaction, the reaction temperature is low, the reaction pressure is moderate, the requirements on the device are relatively low, and the input cost of the device is effectively saved.
Description
Technical Field
The invention relates to the technical field of sec-butyl alcohol preparation, in particular to a method for preparing sec-butyl alcohol by sec-butyl acetate hydrogenation.
Background
Sec-butanol (SBA) is colorless fragrant liquid with boiling point of 99.5 deg.C, and is water soluble, and is excellent solvent, synthetic material, gasoline additive, etc. As the solvent, the coating cosolvent can be used. As a synthetic raw material, sec-butanol may be dehydrogenated to produce Methyl Ethyl Ketone (MEK), for the production of butyl acetate, sec-butyl ester, and the like; sec-butanol can also be used to produce plasticizers, dehydrating agents, beneficiating agents, emulsifiers, herbicides, and the like. The use of sec-butanol as an organic synthesis feedstock represents 90% of its total consumption. With the shortage of petroleum resources, the use of blend gasolines as vehicle drive fuels is a trend today. The sec-butyl alcohol gasoline has the following advantages over other types of blend gasoline: under the conditions of no use of additives and no need of refitting an engine, the raw material cost and the pollution condition of gasoline tail gas can be greatly reduced; high octane number; the biological degradation and environmental protection performance are good; excellent gasoline antiknock property. The production process of sec-butyl alcohol mainly comprises transesterification, catalytic hydration and ester hydrogenation according to different raw materials and preparation processes.
The sec-butyl propionate is an important fine chemical intermediate, has the characteristics of no toxicity, no corrosiveness and the like, has low-carbon fatty acid esters with fragrance, is insoluble in water, and can be mixed with ethanol and diethyl ether.
The existing method for preparing sec-butyl alcohol by hydrogenating sec-butyl propionate has relatively low conversion rate, so we propose a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a process for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate includes preheating hydrogen and nitrogen in preheater, loading sec-butyl acetate in reactor, catalytic hydrogenation of sec-butyl acetate to obtain sec-butyl alcohol, discharging sec-butyl alcohol from reactor, discharging other by-products from tower top outlet, reaction at 150-250 deg.C under 2-6 MPa, mole ratio of hydrogen to nitrogen being 1 (0.5-3), mole ratio of hydrogen to sec-butyl acetate being 2-5 to 1 and space velocity of sec-butyl acetate being 0.1-10 hr -1
Preferably, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 30-40 parts of active aluminum oxide, 0.5-2 parts of silver and 8-15 parts of nickel sulfide.
Preferably, the specific surface area of the catalyst is 60m 2 /g-120m 2 /g
Preferably, after being discharged from the top outlet of the tower, other byproducts generated by the catalytic distillation tower enter a tube side of the heat exchanger, cooling water is filled in a shell side of the heat exchanger, and the other byproducts enter a recovery storage tank after passing through the heat exchanger.
Preferably, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Preferably, a dryer is arranged between the buffer tank and the spray tower, and a drying agent is placed in the dryer and used for drying the gas discharged into the buffer tank from the spray tower.
Preferably, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Preferably, the preheating temperature of the preheater is 120-220 .
Preferably, the reaction pressure in the catalytic distillation tower is 3-5 MPa, the reaction temperature in the catalytic distillation tower is 180-230 , the molar ratio of hydrogen to nitrogen is 1 (1-2.5), the molar ratio of hydrogen to sec-butyl acetate is 2.5-4:1, and the space velocity of sec-butyl acetate is 1-8h -1
The beneficial effects of the invention are as follows:
1. in the preparation method, a catalytic distillation process is adopted, the reaction and separation are synchronously carried out, the operation efficiency is effectively improved, in the reaction, the reaction pressure in a catalytic distillation tower is 2-6 MPa, the reaction temperature in the catalytic distillation tower is 150-250 , the reaction temperature is low, the reaction pressure is moderate, the requirement on the device is relatively low, and the input cost of the device is effectively saved.
2. In the preparation method, the heat exchanger, the recovery storage tank, the spray tower, the dryer and the buffer tank are matched to recover hydrogen and nitrogen in raw materials, and meanwhile, byproducts and unreacted sec-butyl acetate are recovered to the recovery storage tank, so that the utilization rate of the raw materials is effectively improved, resources are saved to a certain extent, the economic benefit is improved, and meanwhile, the whole device has few substances discharged to the outside and is environment-friendly.
3. In the preparation method, the active components in the catalyst are silver and nickel sulfide, the catalyst has good selectivity to sec-butyl acetate, the reaction can be carried out at low temperature and low pressure, and the conversion rate of the final product is high.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate.
In the figure: 1. n-butyl acetate inlet; 2. a hydrogen inlet; 3. a nitrogen inlet; 4. a reactor (which may be a fixed bed reactor); 5. a catalytic distillation column; 6. a heat exchanger; 7. a recovery storage tank; 8. a spray tower; 9. a dryer; 10. buffer tank
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
Referring to FIG. 1
In example 1, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 2MPa, the reaction temperature in the catalytic distillation tower is 150 , the mole ratio of hydrogen to nitrogen is 1:0.5, the mole ratio of hydrogen to sec-butyl acetate is 2:1, and the space velocity of sec-butyl acetate is 0.1h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 30 parts of activated alumina, 0.5 part of silver and 8 parts of nickel sulfide.
Further, the specific surface area of the catalyst was 60m 2 /g-120m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater is 120-220 .
In example 2, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 2-6 MPa, the reaction temperature in the catalytic distillation tower is 250 , the mole ratio of hydrogen to nitrogen is 1:3, the mole ratio of hydrogen to sec-butyl acetate is 5:1, and the space velocity of sec-butyl acetate is 10h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 40 parts of activated alumina, 2 parts of silver and 15 parts of nickel sulfide.
Further, the specific surface area of the catalyst was 120m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater was 220 .
In example 3, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 4MPa, the reaction temperature in the catalytic distillation tower is 200 , the mole ratio of hydrogen to nitrogen is 1:2.2, the mole ratio of hydrogen to sec-butyl acetate is 4:1, and the space velocity of sec-butyl acetate is 5h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 35 parts of activated alumina, 1 part of silver and 12 parts of nickel sulfide.
Further, the specific surface area of the catalyst was 90m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater is 120-220 .
In example 4, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 3MPa, the reaction temperature in the catalytic distillation tower is 180 , the molar ratio of hydrogen to nitrogen is 1:1, the molar ratio of hydrogen to sec-butyl acetate is 2.5:1, and the space velocity of sec-butyl acetate is 1h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 35 parts of activated alumina, 1 part of silver and 12 parts of nickel sulfide.
Further, the specific surface area of the catalyst was 90m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater is 120-220 .
In example 5, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 5MPa, the reaction temperature in the catalytic distillation tower is 230 , the mole ratio of hydrogen to nitrogen is 1:2.5, the mole ratio of hydrogen to sec-butyl acetate is 4:1, and the space velocity of sec-butyl acetate is 8h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 35 parts of activated alumina, 1 part of silver and 12 parts of nickel sulfide.
Further, the specific surface area of the catalyst was 90m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater is 120-220 .
In comparative example 1, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 5MPa, the reaction temperature in the catalytic distillation tower is 230 , the mole ratio of hydrogen to nitrogen is 1:2.5, the mole ratio of hydrogen to sec-butyl acetate is 1.5:1, and the space velocity of sec-butyl acetate is 8h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 35 parts of activated alumina, 1 part of silver and 12 parts of nickel sulfide.
Further, the specific surface area of the catalyst was 90m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater is 120-220 .
In comparative example 2, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 5MPa, the reaction temperature in the catalytic distillation tower is 230 , the mole ratio of hydrogen to nitrogen is 1:2.5, the mole ratio of hydrogen to sec-butyl acetate is 5:1, and the space velocity of sec-butyl acetate is 8h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 35 parts of activated alumina, 1 part of silver and 12 parts of nickel sulfide.
Further, the specific surface area of the catalyst was 90m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater is 120-220 .
In comparative example 3, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 5MPa, the reaction temperature in the catalytic distillation tower is 230 , the mole ratio of hydrogen to nitrogen is 1:2.5, the mole ratio of hydrogen to sec-butyl acetate is 4:1, and the space velocity of sec-butyl acetate is 8h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 35 parts of activated alumina and 12 parts of nickel sulfide.
Further, the specific surface area of the catalyst was 90m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater is 120-220 .
In comparative example 4, a method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate, hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, then materials flow out of the reactor and enter a catalytic distillation tower, sec-butyl alcohol is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, wherein the reaction pressure in the catalytic distillation tower is 5MPa, the reaction temperature in the catalytic distillation tower is 230 , the mole ratio of hydrogen to nitrogen is 1:2.5, the mole ratio of hydrogen to sec-butyl acetate is 4:1, and the space velocity of sec-butyl acetate is 8h -1
Further, the carrier of the catalyst is active alumina, the active components are silver and nickel sulfide, and the components in the catalyst are calculated according to parts by weight: 35 parts of activated alumina and 1 part of silver.
Further, the specific surface area of the catalyst was 90m 2 /g
Further, other byproducts generated by the catalytic distillation tower are discharged from the tower top outlet and then enter the tube side of the heat exchanger, cooling water is filled in the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
Further, the upper end of the recovery storage tank is also communicated with the gas phase inlet end of the spray tower, the gas phase outlet end of the spray tower is communicated with the buffer tank, the gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into the nitrogen inlet and is mixed with hydrogen to enter the catalytic distillation tower to participate in the reaction.
Further, be provided with the desicator between buffer tank and the spray column, the drier has been placed to the inside of desicator, and the drier is used for drying the gas that the spray column was discharged into the buffer tank.
Further, the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
Further, the preheating temperature of the preheater is 120-220 .
The following results are shown in Table 1, in which the conversion and selectivity of sec-butyl acetate are counted in examples 1 to 5 and comparative examples 1 to 4.
TABLE 1
As can be seen from Table 1, in examples 1 to 5, the conversion rate of sec-butyl acetate was 92.2% or more, the selectivity was 99.1% or more, the conversion rate and the selectivity were both high, the sec-butyl acetate was excessive, the conversion rate was decreased, the selectivity was not greatly changed, the hydrogen gas was excessive, the conversion rate and the selectivity were both decreased slightly, the catalyst was not added with silver in comparative example 3, the selectivity was significantly decreased, the conversion rate was also decreased, the catalyst was not added with nickel sulfide in comparative example 4, the conversion rate was significantly decreased, and the selectivity was decreased.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. A method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate is characterized in that hydrogen and nitrogen are preheated by a preheater and then enter a reactor, sec-butyl acetate enters the reactor, sec-butyl acetate is catalyzed and hydrogenated by a catalyst to generate sec-butyl alcohol, materials flow out of the reactor and then enter a catalytic distillation tower, the sec-butyl alcohol product is discharged from an outlet at the bottom of the tower, other byproducts are discharged from an outlet at the top of the tower, the reaction pressure in the catalytic distillation tower is 2-6 MPa, the reaction temperature in the catalytic distillation tower is 150-250 , and the mol of hydrogen and nitrogen are the same as that in the catalytic distillation towerThe ratio is 1 (0.5-3), the mole ratio of hydrogen to sec-butyl acetate is (2-4), 1, the space velocity of sec-butyl acetate is 0.1-10h -1
The catalyst is characterized in that the carrier of the catalyst is active alumina, active components are silver and nickel sulfide, and the catalyst comprises the following components in parts by weight: 30-40 parts of active aluminum oxide, 0.5-2 parts of silver and 8-15 parts of nickel sulfide.
2. The method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate according to claim 1, wherein the specific surface area of the catalyst is 60m 2 /g-120m 2 /g
3. The method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate according to claim 1, wherein other byproducts generated by the catalytic distillation tower are discharged from the top outlet and then enter the tube side of the heat exchanger, cooling water is introduced into the shell side of the heat exchanger, and the other byproducts enter the recovery storage tank after passing through the heat exchanger.
4. The method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate according to claim 3, wherein the upper end of the recovery storage tank is further communicated with a gas phase inlet end of a spray tower, a gas phase outlet end of the spray tower is communicated with a buffer tank, gas discharged from the recovery storage tank is sprayed by the spray tower and then discharged into the buffer tank, and the gas collected in the buffer tank is used for converging into a nitrogen inlet and mixing with hydrogen to enter the catalytic distillation tower to participate in the reaction.
5. The method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate according to claim 4, wherein a dryer is arranged between the buffer tank and the spray tower, and a drying agent is placed in the dryer and used for drying the gas discharged into the buffer tank from the spray tower.
6. The method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate according to claim 1, wherein the mass fraction of water in the sec-butyl acetate raw material is less than 0.1%.
7. The method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate according to claim 1, wherein the preheating temperature of the preheater is 120-220 .
8. The method for preparing sec-butyl alcohol by hydrogenating sec-butyl acetate according to claim 1, wherein the reaction pressure in the catalytic distillation column is 3-5 MPa, the reaction temperature in the catalytic distillation column is 180-230 , the molar ratio of hydrogen to nitrogen is 1 (1-2.5), the molar ratio of hydrogen to sec-butyl acetate is 2.5-4:1, and the space velocity of sec-butyl acetate is 1-8h -1
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