CN106673955A - Method for preparing isopropanol - Google Patents
Method for preparing isopropanol Download PDFInfo
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- CN106673955A CN106673955A CN201510740295.0A CN201510740295A CN106673955A CN 106673955 A CN106673955 A CN 106673955A CN 201510740295 A CN201510740295 A CN 201510740295A CN 106673955 A CN106673955 A CN 106673955A
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- Prior art keywords
- reaction
- exchange resin
- accordance
- catalyst
- acetic acid
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- 238000000034 method Methods 0.000 title claims abstract description 53
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 20
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000007259 addition reaction Methods 0.000 claims abstract description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 5
- 239000000413 hydrolysate Substances 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 14
- 150000003751 zinc Chemical class 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 239000003729 cation exchange resin Substances 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 238000004448 titration Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- ONJMNXFNTYIEEA-UHFFFAOYSA-N benzene ethene Chemical compound C1=CC=CC=C1.C=C.C=C.C=C ONJMNXFNTYIEEA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 229960000583 acetic acid Drugs 0.000 description 31
- 238000001291 vacuum drying Methods 0.000 description 14
- 238000006703 hydration reaction Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000036571 hydration Effects 0.000 description 11
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 10
- 229940011051 isopropyl acetate Drugs 0.000 description 9
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007921 spray Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229940023913 cation exchange resins Drugs 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- -1 electronics industry Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 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
- 239000004208 shellac Substances 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
-
- 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
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing isopropanol. The method comprises the following contents: acetic acid and propylene serve as reaction raw materials, an addition reaction is carried out in a stationary bed continuous reaction device filled with an ion exchange resin catalyst, the materials and water after the reaction enter a reboiler of a catalytic distillation column, azeotropic steam goes up to a reaction zone of the catalytic distillation column filled with a modified ion exchange resin catalyst for hydrolysis reaction, a small amount of water is added into the top of the reaction zone in the reaction process, and hydrolysate is distilled off from the top of the column and is purified, so as to obtain an isopropanol product. The method disclosed by the invention is simple in reaction process and mild in conditions; the catalysts are stable in activity and can be operated for a long term.
Description
Technical field
The present invention relates to a kind of method for preparing isopropanol, especially prepares the side of isopropanol as raw material with acetic acid and propylene
Method.
Background technology
Isopropanol, molecular formula (CH3)2CHOH, water white transparency volatile liquid has the smell mixed like ethanol and acetone,
Can with ethanol, ether, chloroform and water it is miscible.Isopropanol is a kind of organic solvent of function admirable, is widely used as shellac, nitro
The solvent of cellulose, alkaloid, rubber and grease etc..Isopropanol still produces the important intermediate of various organic compounds,
Can be used as the raw material of synthetic glycerine, isopropyl acetate and acetone etc., be also widely used as oil-fired antifreeze additive, be used for
The aspect such as automobile and aviation fuel.Additionally, isopropanol can also be used to manufacture bactericide, insecticide, cleaning agent and disinfection preservative
Deng it can be used alone, it is also possible to and other alcohol, surfactant are used in combination, in agricultural chemicals, electronics industry, medicine, coating, day
Have been widely used with the fields such as chemical industry and organic synthesis tool, exploitation prospect is wide.
The main method of production isopropanol is propylene hydration method, including two methods of direct hydration and indirect hydration.Wherein,
Propylene indirect hydration method be by propylene be dissolved in sulfuric acid solution occur esterification generate isopropyl acid sulphate and sulfuric acid two it is different
Propyl ester, then Jing hydrolysis be obtained thick isopropanol, most after Jing be refining to obtain highly purified isopropanol product.Due to " three wastes " pollution, if
The problems such as standby seriously corroded and high production cost, the method is gradually eliminated after the eighties in 20th century.
Propylene direct hydration method is to make propylene that hydration reaction directly to occur in the presence of a catalyst to generate isopropanol, is divided into gas
Phase direct hydration method, liquid phase direct hydration method and solution-air mixed phase hydration method.Gas phase direct hydration method is using phosphoric acid/kieselguhr
Catalyst, the method is employed to balancing unfavorable high-temperature low-pressure reaction bar to prevent phosphoric acid dissolution, needs from water is switched to gaseous state
Part, makes propylene conversion per pass low, and a large amount of unreacted propylene need to recycle, and energy consumption is big, and density of propylene has high demands；Liquid phase
Direct hydration method water alkene causes containing a large amount of water in crude product than big, and distillation heat consumption amount is big, and reaction pressure is too high, and equipment is thrown
Money is big；Solution-air mixed phase hydration method adopts strongly acidic ion-exchange resin catalyst, resin catalyst non-refractory, and temperature can not
More than 175 DEG C, and there is losing issue in resin catalyst, and the life-span is shorter.
CN103880591A discloses a kind of method that acetic acid and propylene prepare isopropanol and ethanol, and the method passes through vinegar
Acid and propylene addition reaction generate isopropyl acetate, it is purified after, then be hydrogenated to isopropanol in the presence of Cu series catalysts
And ethanol, the method flow process is complicated, and hydrogenation conditions are harsh, and running cost and energy consumption are higher.CN103980089A is described
For isopropanol and the technique of ethanol, using copper-based catalysts, crome metal, nickel etc. are helped isopropyl acetate Hydrogenation as catalyst
Agent, 150～300 DEG C of reaction temperature, there are severe reaction conditions in 4.0～10.0MPa of reaction pressure and catalyst environmental pollution is asked
Topic.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of method for preparing isopropanol.The method is with acetic acid and propylene
For raw material, isopropyl acetate is generated by addition reaction, then in the presence of modified resin catalyst, reacted by catalytic distillation
Device hydrolysis generates isopropanol, and reaction process is simple, and mild condition and catalyst activity are stably and being capable of long-term operation.
The method for preparing isopropanol of the present invention, including following content：With acetic acid and propylene as reaction raw materials, it is being filled with
The continuous fixed bed reaction or continuous device of ion-exchange resin catalyst carries out addition reaction, and reacted material and water enter catalysis essence
Tower reboiler is evaporated, azeotropic vaporization rises to the catalytic rectifying tower conversion zone equipped with modified ion-exchange resin catalyst and is hydrolyzed
Reaction, adds a small amount of water, hydrolysate to be distillated by tower top in course of reaction to conversion zone top, it is purified after obtain isopropanol product
Product.
In the inventive method, the ion-exchange resin catalyst that addition reaction is used is the friendship of polystyrene highly acidic cation
Resin is changed, exchange capacity is 4.4～5.3mol/kg, and the mass content of water is 49%～53%, and wet apparent density is 0.75～0.95g/
Ml, wet true density is 1.1～1.3g/ml.
In the inventive method, the reaction condition of addition reaction is as follows：80～130 DEG C of reaction temperature, preferably 90～100
℃；Reaction pressure is 1～6MPa, preferably 3～5MPa；Olefin(e) acid mol ratio is 1：1～10：1, preferably 2：1～5：1；Acetic acid
It is 0.2～2h to the volume space velocity of catalyst-1, preferably 0.4～1h-1。
In the inventive method, the inflow of reboiler is 0.2 with the volume ratio of acetic acid inlet amount：1～1：1, preferably
0.4：1～0.8：1.
In the inventive method, catalytic distillation hydrolysis reaction condition is as follows：80～100 DEG C of reboiler temperature, preferably 85～
95 DEG C, 90～140 DEG C of conversion zone temperature, preferably 120～130 DEG C；Reaction pressure is normal pressure；Reflux ratio is 20%～50%, excellent
Elect 30%～40% as.
In the inventive method, the inflow at the top of conversion zone is 0.01 with the volume ratio of acetic acid inlet amount：1～0.1：1, it is excellent
Elect 0.05 as：1～0.08：1.
In the inventive method, described modified ion-exchange resin catalyst, preparation method is as follows：
（1）Ion exchange resin is washed with deionized into 3～5 times, every time 5～10 minutes；
（2）Put the resin after washing into capable vacuum drying；
（3）Then the aqueous solution of the resin soluble zinc salt for obtaining is processed, then with ammonia water titration to neutrality, it is scrubbed, dry
Modified ion-exchange resin catalyst is obtained after dry, roasting.
Said method, step（1）Described ion exchange resin is polystyrene storng-acid cation exchange resin, is exchanged
Capacity is 5.0～5.5mol/kg, and the mass content of water is 48%～51%, and wet apparent density is 0.77～0.91g/ml, wet true density
For 1.1～1.2g/ml.
Step（2）In baking temperature be 70～90 DEG C, drying time be 4～8h；Step（3）Middle soluble zinc salt is nitre
Sour zinc, zinc sulfate or zinc chloride, the mass percent concentration of the aqueous solution of soluble zinc salt is 10%～40%, preferably 15%～
30%；The aqueous solution processing procedure of soluble zinc salt is：A, resin being fitted in fine and closely woven steel wire mesh bag, mesh bag thickness is 1～
5mm, preferably 2～3mm, in being laid in ultrasonic vibrator；B, ultrasonic frequency vibratory be 50～60kHz under conditions of,
By the gas-liquid mixture of the aqueous solution of soluble zinc salt and nitrogen by atomizer sprayed resin, jet length is 0～2cm,
Preferably 0.5～1cm, injection pressure be 0.02～0.2MPa, preferably 0.05～0.1MPa, 1～4h of injecting time, preferably
2～3h；C and then again by the aqueous solution of resin soluble zinc salt supersaturation 0.5～1h of dipping.
Step（3）Described baking temperature is 70～90 DEG C, and drying time is 6～8h；Sintering temperature is 200～230 DEG C,
Roasting time is 6～8h.
The present invention has the advantage that compared with prior art：
（1）Catalytic distillation bottoms material is acetic acid, isopropyl acetate and water, and using the characteristic of its three-phase azeotropic acetic acid isopropyl is caused
Ester and water azeotropic rise to conversion zone, and hydrolyze in the presence of modified resin catalyst, and now isopropyl acetate is both azeotropic
Agent, is again reactant.The present inventor has found under study for action, in hydrolysis reaction, at the top of conversion zone plus such as a small amount of water simultaneously
Controlling its addition can break the azeotropic composition of water and isopropyl acetate so that hydrolysis is more abundant, improves reaction
Conversion ratio.
（2）Under Ultrasonic Conditions, with nitrogen and modified solution spray treatment catalyst, make small poly- in catalyst duct
Compound is blown, while inside the more uniform solid load duct of modified material, make catalyst have preferably activity and
Stability.
Specific embodiment
Lower mask body introduces the modifying process of ion-exchange resin catalyst of the present invention：First, by 50～100g highly acids sun
Ion exchange resin is washed with deionized 3～5 times, washes every time 5～10 minutes, and wash temperature is 50～70 DEG C, then 70
It is placed under conditions of～90 DEG C in vacuum drying chamber and is dried 6～8 hours.2nd, by dried storng-acid cation exchange resin
In being fitted into steel wire mesh bag, in being laid in ultrasonic vibrator, thickness is 2mm, with atomizer by certain density Zn (NO3)2·
6H2The O aqueous solution and nitrogen spray immersion resin under conditions of ultrasonic activation, jet length is 1～2cm, and injection pressure is
0.05～0.1MPa, injecting time is 1～2h.Three and then identical modified solution supersaturation impregnating resin, dip time is
1h, then with ammonia water titration to neutrality.4th, the condition after is washed resin according to step one is dried, then by dry tree
Fat roasting under conditions of 200～230 DEG C obtains modified ion-exchange resin catalyst in 6～8 hours.
The specific embodiment of the present invention is described in detail with reference to embodiment.In following examples and comparative example
If no special instructions, % is mass percent.Wave agitator model used in resin catalyst is modified, atomizer
Model JLN-G type high pressure micro-atomizing nozzle, purchases in Jining Jun Dou spraying apparatus Co., Ltd.It is ion-exchange resin catalyzed
Agent is purchased in Dandong Mingzhu Special Type Resin Co., Ltd..
The specific embodiment of the present invention is as follows：Addition reaction is carried out using continuous fixed-bed reactor, acetic acid is by inner
Watt micrometering pump is squeezed into, and propylene is squeezed into by high-pressure plunger pump, is reacted by beds after the mixing of two liquid phases, reaction life
Mixture into isopropyl acetate enters catalytic rectifying tower reboiler, and isopropyl acetate is hydrolyzed in catalytic rectifying tower conversion zone
Reaction generates isopropanol and distillates from tower top.
Embodiment 1
1st, modified ion-exchange resin catalyst is prepared：a：By 100 grams of polystyrene storng-acid cation exchange resins spend from
Sub- water washing 5 times, 10 minutes every time, is dried 4 hours in transferring vacuum drying chamber at 90 DEG C；b：By dried highly acid sun from
Sub-exchange resin is fitted in the thick steel wire mesh bags of 2mm, and in being laid in ultrasonic vibrator, vibration frequency is 59kHz, by quality hundred
Fraction is 20% Zn (NO3)2The aqueous solution and nitrogen atomizer spray immersion 2 hours, jet length 1cm, injection pressure
0.05MPa；c：Resin is impregnated into 1h with 200ml modified solutions, then with ammonia water titration to neutrality；d：In 90 DEG C of decentralizations after washing
In vacuum drying chamber be dried 6 hours, by dried ion exchange resin under conditions of 210 DEG C roasting 8 hours, that is, changed
Property ion-exchange resin catalyst.
2nd, addition reaction is carried out on continuous fixed bed reaction or continuous device, loads 30ml D005 type resin catalysts, reaction temperature
120 DEG C of degree, reaction pressure 3.0MPa, acetic acid volume space velocity 1.0h-1, olefin(e) acid mol ratio is 3：1；Hydrolysis is in catalytic distillation
Carry out in tower, load 200ml modified resin catalysts, 95 DEG C of tower bottom reboiler temperature, 110 DEG C of conversion zone temperature, reflux ratio
30%, reboiler inflow and acetic acid input material volume ratio 0.5：1, inflow and acetic acid input material volume ratio 0.05 at the top of conversion zone：1,
Reaction result is shown in Table 1.
Embodiment 2
1st, modified ion-exchange resin catalyst is prepared：a：By 100 grams of polystyrene storng-acid cation exchange resins spend from
Sub- water washing 5 times, 10 minutes every time, is dried 6 hours in transferring vacuum drying chamber at 90 DEG C；b：By dried highly acid sun from
Sub-exchange resin is fitted in the thick steel wire mesh bags of 3mm, in being laid in ultrasonic vibrator, by the Zn that mass percent is 25%
(NO3)2The aqueous solution and nitrogen atomizer spray immersion 2 hours, jet length 2cm, injection pressure 0.08MPa；c：With
Resin is impregnated 1h by 200ml modified solutions, then with ammonia water titration to neutrality；d：Transfer in vacuum drying chamber at 90 DEG C after washing
Be dried 6 hours, by dried ion exchange resin under conditions of 220 DEG C roasting 8 hours, that is, obtain modified ion exchange tree
Fat catalyst.
2nd, addition reaction is carried out on continuous fixed bed reaction or continuous device, loads 30ml D005 type resin catalysts, reaction temperature
120 DEG C of degree, reaction pressure 3.0MPa, acetic acid volume space velocity 1.0h-1, olefin(e) acid mol ratio is 3：1；Hydrolysis is in catalytic rectifying tower
In carry out, load 200ml modified resin catalysts, 95 DEG C of tower bottom reboiler temperature, 120 DEG C of conversion zone temperature, reflux ratio 35%,
Reboiler inflow and acetic acid input material volume ratio 0.5：1, inflow and acetic acid input material volume ratio 0.06 at the top of conversion zone：1, reaction
The results are shown in Table 1.
Embodiment 3
1st, modified ion-exchange resin catalyst is prepared：a：By 100 grams of polystyrene storng-acid cation exchange resins spend from
Sub- water washing 5 times, 10 minutes every time, is dried 6 hours in transferring vacuum drying chamber at 90 DEG C；b：By dried highly acid sun from
Sub-exchange resin is fitted in the thick steel wire mesh bags of 2mm, in being laid in ultrasonic vibrator, by the Zn that mass percent is 30%
(NO3)2The aqueous solution and nitrogen atomizer spray immersion 2 hours, jet length 1cm, injection pressure 0.05MPa；c：With
Resin is impregnated 1h by 200ml modified solutions, then with ammonia water titration to neutrality；d：Transfer in vacuum drying chamber at 90 DEG C after washing
Be dried 6 hours, by dried ion exchange resin under conditions of 220 DEG C roasting 8 hours, that is, obtain modified ion exchange tree
Fat catalyst.
2nd, addition reaction is carried out on continuous fixed bed reaction or continuous device, loads 30mlD005 type resin catalysts, reaction temperature
120 DEG C of degree, reaction pressure 3.0MPa, acetic acid volume space velocity 1.0h-1, olefin(e) acid mol ratio is 3：1；Hydrolysis is in catalytic rectifying tower
In carry out, load 200ml modified resin catalysts, 95 DEG C of tower bottom reboiler temperature, 120 DEG C of conversion zone temperature, reflux ratio 35%,
Reboiler inflow and acetic acid input material volume ratio 0.8：1, inflow and acetic acid input material volume ratio 0.05 at the top of conversion zone：1, reaction
The results are shown in Table 1.
Embodiment 4
1st, modified ion-exchange resin catalyst is prepared：a：By 100 grams of polystyrene storng-acid cation exchange resins spend from
Sub- water washing 5 times, 10 minutes every time, is dried 6 hours in transferring vacuum drying chamber at 90 DEG C；b：By dried highly acid sun from
Sub-exchange resin is fitted in the thick steel wire mesh bags of 2mm, in being laid in ultrasonic vibrator, by the Zn that mass percent is 35%
(NO3)2The aqueous solution and nitrogen atomizer spray immersion 2 hours, jet length 2cm, injection pressure 0.08MPa；c：With
Resin is impregnated 1h by 200ml modified solutions, then with ammonia water titration to neutrality；d：Transfer in vacuum drying chamber at 90 DEG C after washing
Be dried 6 hours, by dried ion exchange resin under conditions of 220 DEG C roasting 8 hours, that is, obtain modified ion exchange tree
Fat catalyst.
2nd, addition reaction is carried out on continuous fixed bed reaction or continuous device, loads 30mlD005 type resin catalysts, reaction temperature
120 DEG C of degree, reaction pressure 3.0MPa, acetic acid volume space velocity 1.0h-1, olefin(e) acid mol ratio is 3：1；Hydrolysis is in catalytic rectifying tower
In carry out, load 200ml modified resin catalysts, 95 DEG C of tower bottom reboiler temperature, 130 DEG C of conversion zone temperature, reflux ratio 35%,
Reboiler inflow and acetic acid input material volume ratio 0.8：1, inflow and acetic acid input material volume ratio 0.08 at the top of conversion zone：1, reaction
The results are shown in Table 1.
Embodiment 5
1st, modified ion-exchange resin catalyst is prepared：a：By 100 grams of polystyrene storng-acid cation exchange resins spend from
Sub- water washing 5 times, 10 minutes every time, is dried 6 hours in transferring vacuum drying chamber at 90 DEG C；b：By dried highly acid sun from
Sub-exchange resin is fitted in the thick steel wire mesh bags of 3mm, in being laid in ultrasonic vibrator, by the Zn that mass percent is 35%
(NO3)2The aqueous solution and nitrogen atomizer spray immersion 2 hours, jet length 1cm, injection pressure 0.08MPa；c：With
Resin is impregnated 1h by 200ml modified solutions, then with ammonia water titration to neutrality；d：Transfer in vacuum drying chamber at 90 DEG C after washing
Be dried 6 hours, by dried ion exchange resin under conditions of 230 DEG C roasting 8 hours, that is, obtain modified ion exchange tree
Fat catalyst.
2nd, addition reaction is carried out on continuous fixed bed reaction or continuous device, loads 30mlD005 type resin catalysts, reaction temperature
120 DEG C of degree, reaction pressure 3.0MPa, acetic acid volume space velocity 1.0h-1, olefin(e) acid mol ratio is 3：1；Hydrolysis is in catalytic rectifying tower
In carry out, load 200ml modified resin catalysts, 95 DEG C of tower bottom reboiler temperature, 130 DEG C of conversion zone temperature, reflux ratio 35%,
Reboiler inflow and acetic acid input material volume ratio 0.8：1, inflow and acetic acid input material volume ratio 0.08 at the top of conversion zone：1, reaction
The results are shown in Table 1.
Embodiment 6
1st, modified ion-exchange resin catalyst is prepared：a：By 100 grams of polystyrene storng-acid cation exchange resins spend from
Sub- water washing 5 times, 10 minutes every time, is dried 6 hours in transferring vacuum drying chamber at 90 DEG C；b：By dried highly acid sun from
Sub-exchange resin is fitted in the thick steel wire mesh bags of 2mm, in being laid in ultrasonic vibrator, by the Zn that mass percent is 35%
(NO3)2The aqueous solution and nitrogen atomizer spray immersion 2 hours, jet length 2cm, injection pressure 0.08MPa；c：With
Resin is impregnated 1h by 200ml modified solutions, then with ammonia water titration to neutrality；d：Transfer in vacuum drying chamber at 90 DEG C after washing
Be dried 6 hours, by dried ion exchange resin under conditions of 230 DEG C roasting 8 hours, that is, obtain modified ion exchange tree
Fat catalyst.
2nd, addition reaction is carried out on continuous fixed bed reaction or continuous device, loads 30ml D005 type resin catalysts, reaction temperature
120 DEG C of degree, reaction pressure 3.0MPa, acetic acid volume space velocity 1.0h-1, olefin(e) acid mol ratio is 3：1；Hydrolysis is in catalytic rectifying tower
In carry out, load 200ml modified resin catalysts, 95 DEG C of tower bottom reboiler temperature, 130 DEG C of conversion zone temperature, reflux ratio 35%,
Reboiler inflow and acetic acid input material volume ratio 0.5：1, inflow and acetic acid input material volume ratio 0.1 at the top of conversion zone：1, reaction
The results are shown in Table 1.
Comparative example 1
The catalyst that catalytic distillation conversion zone is used is DNW type Ⅱ resin catalyst, and other conditions are same as Example 5, reaction
The results are shown in Table 1.
Comparative example 2
In course of reaction, control catalytic rectifying tower conversion zone top does not intake, and other conditions are same as Example 5, reaction result
It is shown in Table 1.
Comparative example 3
In course of reaction, inflow and acetic acid input material volume ratio 1 at the top of control catalytic rectifying tower conversion zone：1, other conditions and reality
Apply that example 5 is identical, reaction result is shown in Table 1.
Comparative example 4
The modifying process of the catalyst for using does not have vibration of ultrasonic wave and modification liquid and nitrogen mixing jetting process, only with routine
The method modified catalyst of supersaturation dipping, other conditions are same as Example 5, and reaction result is shown in Table 1.
The reaction result of the embodiment of table 1 and comparative example（Conversion ratio is calculated in mol with selective）
Note：Inflow 1 is reboiler inflow and acetic acid input material volume ratio；Inflow 2 is conversion zone top inflow and acetic acid
Input material volume ratio.
Claims (13)
1. a kind of method for preparing isopropanol, it is characterised in that including following content：With acetic acid and propylene as reaction raw materials,
Being filled with the continuous fixed bed reaction or continuous device of ion-exchange resin catalyst carries out addition reaction, and reacted material and water are entered
Catalytic rectifying tower reboiler, azeotropic vaporization rises to the catalytic rectifying tower conversion zone equipped with modified ion-exchange resin catalyst and enters
Row hydrolysis, adds a small amount of water, hydrolysate to be distillated by tower top in course of reaction to conversion zone top, it is purified after obtain different
Propyl alcohol product.
2. in accordance with the method for claim 1, it is characterised in that the ion-exchange resin catalyst that addition reaction is used is benzene
Ethene system storng-acid cation exchange resin, exchange capacity is 4.4～5.3mol/kg, and the mass content of water is 49%～53%, wet
Apparent density is 0.75～0.95g/ml, and wet true density is 1.1～1.3g/ml.
3. in accordance with the method for claim 1, it is characterised in that the reaction condition of addition reaction is as follows：Reaction temperature 80～
130 DEG C, reaction pressure is 1～6MPa, and olefin(e) acid mol ratio is 1：1～10：1, acetic acid is 0.2 to the volume space velocity of catalyst～
2h-1。
4. according to the method described in claim 1 or 3, it is characterised in that the reaction condition of addition reaction is as follows：Reaction temperature is
90～100 DEG C；Reaction pressure is 3～5MPa；Olefin(e) acid mol ratio is 2：1～5：1, acetic acid is 0.2 to the volume space velocity of catalyst
～2h-1。
5. in accordance with the method for claim 1, it is characterised in that the inflow of reboiler is with the volume ratio of acetic acid inlet amount
0.2：1～1：1.
6. in accordance with the method for claim 1, it is characterised in that catalytic distillation hydrolysis reaction condition is as follows：Reboiler temperature
80～100 DEG C, 90～140 DEG C of conversion zone temperature, reaction pressure is normal pressure, and reflux ratio is 20%～50%.
7. in accordance with the method for claim 1, it is characterised in that the volume of inflow and acetic acid inlet amount at the top of conversion zone
Than for 0.01：1～0.1：1.
8. the preparation method of the modified ion-exchange resin catalyst described in a kind of claim 1, it is characterised in that including as follows
Content：（1）Ion exchange resin is washed with deionized into 3～5 times, every time 5～10 minutes；（2）Resin after washing is put
It is vacuum dried；（3）Then the aqueous solution of the resin soluble zinc salt for obtaining is processed, then with ammonia water titration to neutrality,
Modified ion-exchange resin catalyst is obtained after scrubbed, dry, roasting.
9. in accordance with the method for claim 8, it is characterised in that step（1）Described ion exchange resin is polystyrene
Storng-acid cation exchange resin, exchange capacity is 5.0～5.5mol/kg, and the mass content of water is 48%～51%, wet apparent density
For 0.77～0.91g/ml, wet true density is 1.1～1.2g/ml.
10. in accordance with the method for claim 8, it is characterised in that step（2）In baking temperature be 70～90 DEG C, be dried
Time is 4～8h.
11. in accordance with the method for claim 8, it is characterised in that step（3）Middle soluble zinc salt is zinc nitrate, zinc sulfate
Or zinc chloride, the mass percent concentration of the aqueous solution of soluble zinc salt is 10%～40%.
12. in accordance with the method for claim 8, it is characterised in that step（3）The aqueous solution of described soluble zinc salt is processed
Process is：A, resin is fitted in fine and closely woven steel wire mesh bag, mesh bag thickness is 1～5mm, in being laid in ultrasonic vibrator；b、
Under conditions of ultrasonic frequency vibratory is 50～60kHz, the aqueous solution of soluble zinc salt is led to the gas-liquid mixture of nitrogen
Atomizer sprayed resin is crossed, jet length is 0～2cm, and injection pressure is 0.02～0.2MPa, 1～4h of injecting time；C, so
Afterwards again by the aqueous solution supersaturation 0.5～1h of dipping of resin soluble zinc salt.
13. in accordance with the method for claim 8, it is characterised in that step（3）Described baking temperature is 70～90 DEG C, is done
The dry time is 6～8h, and sintering temperature is 200～230 DEG C, and roasting time is 6～8h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112771016A (en) * | 2018-10-03 | 2021-05-07 | 株式会社德山 | High-purity isopropyl alcohol and method for producing same |
| WO2021189637A1 (en) * | 2020-03-25 | 2021-09-30 | 南京延长反应技术研究院有限公司 | Fixed bed enhanced reaction system and process for preparing isopropanol by means of hydration of propylene |
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|---|---|---|---|---|
| CN101896448A (en) * | 2007-12-10 | 2010-11-24 | 巴斯夫欧洲公司 | The method for preparing Virahol and 2-butanols by corresponding alkane |
| CN102249913A (en) * | 2011-05-17 | 2011-11-23 | 上海华谊丙烯酸有限公司 | Preparation method of butyl acrylate |
| CN103769215A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Modified cation exchange resin catalyst and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896448A (en) * | 2007-12-10 | 2010-11-24 | 巴斯夫欧洲公司 | The method for preparing Virahol and 2-butanols by corresponding alkane |
| CN102249913A (en) * | 2011-05-17 | 2011-11-23 | 上海华谊丙烯酸有限公司 | Preparation method of butyl acrylate |
| CN103769215A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Modified cation exchange resin catalyst and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112771016A (en) * | 2018-10-03 | 2021-05-07 | 株式会社德山 | High-purity isopropyl alcohol and method for producing same |
| WO2021189637A1 (en) * | 2020-03-25 | 2021-09-30 | 南京延长反应技术研究院有限公司 | Fixed bed enhanced reaction system and process for preparing isopropanol by means of hydration of propylene |
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