CN116082162A - Production process for synthesizing tert-butylamine by direct catalytic amination of isobutene - Google Patents
Production process for synthesizing tert-butylamine by direct catalytic amination of isobutene Download PDFInfo
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- CN116082162A CN116082162A CN202310036507.1A CN202310036507A CN116082162A CN 116082162 A CN116082162 A CN 116082162A CN 202310036507 A CN202310036507 A CN 202310036507A CN 116082162 A CN116082162 A CN 116082162A
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- catalyst
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- isobutene
- butylamine
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 168
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000005576 amination reaction Methods 0.000 title claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 210
- 238000006243 chemical reaction Methods 0.000 claims abstract description 171
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052751 metal Inorganic materials 0.000 claims abstract description 66
- 239000002808 molecular sieve Substances 0.000 claims abstract description 61
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000010457 zeolite Substances 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 238000003860 storage Methods 0.000 claims description 73
- 239000000463 material Substances 0.000 claims description 60
- 239000002245 particle Substances 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000007667 floating Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 18
- 238000007670 refining Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011344 liquid material Substances 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 10
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 229940044658 gallium nitrate Drugs 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- 239000011810 insulating material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- FJDAAUABGSPSKH-UHFFFAOYSA-N s-(4-tert-butyl-1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound CC(C)(C)C1=CC=CC2=C1N=C(SN)S2 FJDAAUABGSPSKH-UHFFFAOYSA-N 0.000 description 2
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a production process for synthesizing tert-butylamine by direct catalytic amination of isobutene. The production process of the invention comprises the following steps: mixing ZSM-5 zeolite with water solution of soluble metal salt, and regulating pH to 3-6; after reflux adsorption and water washing to neutrality, drying to obtain catalyst powder; uniformly mixing catalyst powder, a binder and a nitric acid aqueous solution to obtain a mixture, and crystallizing, forming, drying and calcining to obtain a metal element doped molecular sieve catalyst; liquid ammonia and isobutene are subjected to amination reaction under the catalysis of a molecular sieve catalyst doped with metal elements, and then tertiary butylamine is obtained through purification. The invention adopts a molecular sieve acidic catalyst doped with metal elements to directly aminate isobutene and liquid ammonia in a liquid phase state to generate tert-butylamine; the catalyst of the method has high catalytic efficiency, long service life, low reaction temperature, high isobutene conversion rate and high tert-butylamine selectivity.
Description
Technical Field
The invention relates to a production process for synthesizing tert-butylamine by direct catalytic amination of isobutene, and belongs to the technical field of petrochemical industry.
Background
Tert-butylamine is used as an important organic chemical raw material and is mainly used for synthesizing rubber accelerator tert-butylbenzothiazole sulfenamide (NS) and tert-butylbisbenzothiazole sulfenamide (NOBS). Meanwhile, tert-butylamine is also an important medical and agricultural chemical intermediate; it can also be used for producing dyes, lubricating oil additives, dyes, etc. With the increasingly strict environmental protection requirements of the country on the rubber auxiliary agent, the main downstream product rubber accelerator NS of the tert-butylamine is used as an environmentally friendly green rubber auxiliary agent, the market demand is continuously rising, and the demand of the tert-butylamine with excellent quality and low price is also gradually rising.
Since the industrialization of tert-butylamine in the 50 th century of 20 th century, the process routes of tert-Ding Niaoshui method, tert-butylamide hydrolysis method, isobutylene-HCN method and the like were successively applied to the synthesis of tert-butylamine. The technological route for preparing tert-butylamine by direct amination of isobutene has clean technological process and high atomic economy, meets the requirements of green chemical industry and sustainable development, and is the development direction of the development and industrial production of tert-butylamine in the future.
The use of molecular sieve catalysts having the NES structure for the direct amination of isobutene is reported in US 5840988A; the reaction temperature is 200-300 ℃, the reaction pressure is 10-30 MPa, and the airspeed is 0.38-3 h -1 . But the methodThe reaction temperature is higher, and the service life of the catalyst is lower.
The preparation of tert-butylamine from isobutene and ammonia is reported in CN112745227 a. In order to avoid carbon deposition of the catalyst and prolong the service life of the catalyst, water or tertiary butanol is introduced into the reactor to realize competitive affinity to the acid point of the catalyst. However, after the reaction, water or tertiary butanol in the material needs to be removed, the steps are complicated, and the removal of the water or tertiary butanol involves higher energy consumption and more material loss; and the conversion of isobutene is poor.
According to the prior art, the isobutene raw material in the isobutene amination reaction is easy to polymerize to generate polymer carbide such as diisobutene, and the service life of the catalyst is reduced due to the blockage of a catalyst pore channel caused by easy carbonization of the polymer due to higher reaction temperature; the existing device adopts a fixed bed adiabatic reactor to carry out catalytic amination reaction at high temperature and high pressure, and the single-pass conversion rate of the amination reaction is low; and the existing method has higher reaction temperature, which is unfavorable for equilibrium conversion of isobutene in thermodynamics.
The present invention has been made to solve the above-described problems.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a production process for synthesizing tert-butylamine by directly catalyzing and aminating isobutene. The invention adopts a molecular sieve acidic catalyst doped with metal elements to directly aminate isobutene and liquid ammonia in a liquid phase state to generate tert-butylamine; the catalyst of the method has high catalytic efficiency, long service life, low reaction temperature, high isobutene conversion rate and high tert-butylamine selectivity.
The technical scheme of the invention is as follows:
a production process for synthesizing tert-butylamine by direct catalytic amination of isobutene comprises the following steps:
(1) Mixing ZSM-5 zeolite with water solution of soluble metal salt, and regulating pH to 3-6; after reflux adsorption and water washing to neutrality, drying to obtain catalyst powder; uniformly mixing catalyst powder, a binder and a nitric acid aqueous solution to obtain a mixture, and crystallizing, forming, drying and calcining to obtain a metal element doped molecular sieve catalyst;
(2) Liquid ammonia and isobutene are subjected to amination reaction under the catalysis of a molecular sieve catalyst doped with metal elements, and then tertiary butylamine is obtained through purification.
According to the invention, in the step (1), the soluble metal salt is one or more of gallium nitrate, ferric sulfate, nickel nitrate or copper nitrate; the mass concentration of the aqueous solution of the soluble metal salt is 7% -56%.
According to the preferred invention, in step (1), the mass ratio of ZSM-5 zeolite to soluble metal salt is from 1 to 15:1, preferably 4-7:1.
according to the invention, in the step (1), the pH is adjusted by using a phosphoric acid aqueous solution with a mass concentration of 10% -40%.
According to the invention, in the step (1), the reflux adsorption temperature is 50-100 ℃ and the reflux adsorption time is 1-3 h.
According to the invention, in the step (1), the binder is pseudo-boehmite, gamma-Al 2 O 3 One or a mixture of more than two of aluminum sol and silicon aluminum sol.
According to the invention, in the step (1), the mass ratio of the catalyst powder to the binder is 1:0.1-0.2; the mass of the catalyst powder and the volume ratio of the nitric acid aqueous solution are 30-80:1g/mL; the mass concentration of the aqueous solution of nitric acid is 2% -10%.
According to a preferred embodiment of the present invention, in the step (1), the crystallization treatment method is as follows: dispersing the mixture into a mixed solution of tetrapropylammonium bromide (TPABr), sodium hydroxide and water, and treating for 20-30h at 150-250 ℃; siO in the mixture 2 The molar ratio of sodium hydroxide, tetrapropylammonium bromide and water is 1:0.02 to 0.1:0.05 to 0.2:50 to 70.
According to the invention, in the step (1), the molding method is engaged extrusion.
According to the invention, in the step (1), the drying temperature after molding is 100-200 ℃ and the drying time is 2-5 h.
According to the invention, in the step (1), the calcination temperature is 300-600 ℃ and the calcination time is 2-5 h.
According to the present invention, preferably, in the step (1), the molecular sieve catalyst doped with the metal element is a cylindrical long bar having a height of 2 to 4 mm.
According to the present invention, preferably, in the step (2), the amination reaction of liquid ammonia and isobutylene is carried out in a floating bed adiabatic reactor, an autoclave reactor or a fixed bed reactor; preferably, the amination of liquid ammonia and isobutene is carried out in a floating bed adiabatic reactor.
Preferably, the floating bed adiabatic reactor includes: a catalyst storage distributor 2, a reaction chamber 8, a catalyst particle settler 6 and a solid-liquid separator 4;
the catalyst storage distributor 2 is fixed at the top in the reaction chamber 8; the catalyst storage distributor 2 consists of a storage tank 9 and a vibrating screen 10; the storage tank 9 is used for storing the catalyst; the storage tank 9 is positioned right above the vibrating screen 10, and a valve is arranged at the bottom of the storage tank 9 to control the release of the catalyst to the vibrating screen 10; the upper part of the storage tank 9 is provided with a liquid ammonia inlet which is connected with a liquid ammonia feeding tank through a pipeline so as to input or output liquid ammonia; the storage tank 9 is movably connected with the vibrating screen 10; the vibrating screen 10 is of a conventional structure; the shape and size of the holes on the screen of the vibrating screen 10 are as per the prior art, so long as the catalyst can enter the reaction system through the screen;
a reaction material inlet 1 is arranged on the side wall of the lower part of the reaction chamber 8; a reaction material distributor 3 is arranged in the reaction chamber 8; the reaction material distributor 3 is formed by connecting a plurality of vertical pipelines in parallel, and small holes are distributed on the side walls and the tops of the vertical pipelines so that the reaction material enters the reaction chamber 8 through the small holes, and meanwhile, the catalyst is prevented from entering the reaction material distributor 3; the reactant inlet 1 is connected with the reactant distributor 3 through a pipeline;
the catalyst particle settler 6 is funnel-shaped, a settler outlet is arranged at the bottom of the catalyst particle settler 6, and a valve is arranged at the settler outlet; the side wall of the catalyst particle settler 6 is directly connected with the lower end of the side wall of the reaction chamber 8, and the catalyst particle settler 6 is communicated with the reaction chamber 8;
the solid-liquid separator 4 is provided with a reaction material outlet 5, a reaction material inlet and a catalyst outlet; the reaction material inlet of the solid-liquid separator 4 is connected with the top of the side wall of the reaction chamber 8 through a pipeline; a valve is arranged between the solid-liquid separator 4 and the reaction chamber 8;
the outlet of the catalyst particle settler 6 and the outlet of the solid-liquid separator 4 are connected with the storage tank 9 of the catalyst storage distributor 2 through a catalyst pipe chain circulation conveying system 7; the conveying mode of the pipe chain circulating conveying system 7 is pipe chain conveying, and the pipe chain circulating conveying system is just according to the existing structure.
According to the invention, the reaction chamber 8 is made of heat insulating material or the reaction chamber 8 is coated with heat insulating material. The heat insulating material is an existing material. The top of the reaction chamber 8 is provided with a door, and the upper part of the storage tank 9 can be disassembled to be filled with catalyst; the structure is just as the prior art.
According to the invention, in step (2), the catalyst amount is obtained according to the existing method according to the size of the adiabatic reactor of the floating bed and the capacity of the device.
According to a preferred embodiment of the invention, in step (2), the molar ratio of liquid ammonia to isobutene is from 1 to 2:1, preferably from 1.5 to 2:1.
According to the invention, the step (2) further comprises an activation step of a molecular sieve catalyst doped with a metal element before the amination reaction, and the activation step is specifically as follows: soaking a molecular sieve catalyst doped with metal elements in liquid ammonia at room temperature for 3-13 h; preferably, the soaking time is 5-10 hours. Through the treatment, ammonia occupies the reactive sites of the catalyst in advance.
According to the invention, in the step (2), the amination reaction temperature is 100-130 ℃, the amination reaction pressure is 15-25 MPa, and the amination reaction residence time is 0.5-10 min; preferably, the amination reaction pressure is 18-22 MPa.
According to the invention, in the step (2), the amination reaction is a catalytic reaction of a heterogeneous catalyst, namely, a reaction material is in a liquid state, a molecular sieve catalyst doped with metal elements is in a solid state, and the reaction is carried out at a solid-liquid interface.
According to the invention, in the step (2), after the amination reaction is finished, the obtained metal element doped molecular sieve catalyst is recovered through solid-liquid separation and is recycled; the liquid material obtained was purified.
According to a preferred embodiment of the present invention, in step (2), the purification comprises the steps of: treating the liquid material by a light component removing tower, obtaining a crude tert-butylamine product at the bottom of the tower, separating unreacted isobutene and liquid ammonia from the top of the tower, and recycling the unreacted isobutene and the liquid ammonia as raw materials; the pressure of the light component removing tower is 1-3 MPa, the temperature of the tower top is 50-70 ℃, and the temperature of the tower bottom is 160-180 ℃; the crude product of tert-butylamine is conveyed to a refining tower, the tert-butylamine is obtained from the tower top, and the byproduct diisobutylene and other heavy components are obtained from the tower bottom; the pressure of the refining tower is 0.05Mpa-0.2Mpa, the temperature of the top of the tower is 50 ℃ -100 ℃, and the temperature of the bottom of the tower is 90 ℃ -110 ℃.
According to a preferred embodiment of the present invention, in the step (2), the method for producing tert-butylamine using a floating bed adiabatic reactor comprises the steps of:
a. loading a molecular sieve catalyst doped with a metal element into a storage tank 9 of a catalyst storage distributor 2 of the floating bed adiabatic reactor; liquid ammonia is input through a liquid ammonia inlet of the storage tank 9, and the catalyst is soaked for 3-13 h at room temperature; liquid ammonia is output and recovered to a liquid ammonia feeding tank through a liquid ammonia inlet of the storage tank 9 to be used as a raw material;
b. fully mixing liquid ammonia and isobutene, heating to 100-130 ℃, and pressurizing to 15-25 MPa; then continuously introducing the reaction material into the reaction chamber 8 and the catalyst particle settler 6 through the reaction material inlet 1 and the reaction material distributor 3 of the floating bed adiabatic reactor, filling the reaction chamber 8 and the catalyst particle settler 6 with the reaction material, and keeping the pressure in the reaction chamber 8 and the catalyst particle settler 6 at 15-25 MPa; simultaneously starting a catalyst storage distributor 2, opening a bottom valve of a storage tank 9, enabling the molecular sieve catalyst doped with the metal elements to enter a vibrating screen 10, and starting the vibrating screen 10 to enable the molecular sieve catalyst doped with the metal elements to uniformly enter a reaction system; under the catalysis of a molecular sieve catalyst doped with metal elements, carrying out amination reaction on liquid ammonia and isobutene, wherein the reaction residence time is 0.5-10 min; continuously conveying the reaction liquid after the amination reaction to a solid-liquid separator 4, and obtaining a liquid material and a metal element doped molecular sieve catalyst through solid-liquid separation; continuously feeding the obtained liquid material into a light component removing tower, obtaining crude tert-butylamine at the bottom of the tower, separating unreacted isobutene and liquid ammonia from the top of the tower, and recycling the unreacted isobutene and the liquid ammonia as raw materials; continuously conveying the crude tert-butylamine product to a refining tower, refining to obtain tert-butylamine at the top of the tower and obtaining heavy components such as diisobutylene as a byproduct at the bottom of the tower; the molecular sieve catalyst doped with metal elements obtained by solid-liquid separation is continuously conveyed to the catalyst storage distributor 2 through the catalyst pipe chain circulating conveying system 7 and reenters the reaction system.
Preferably, during the reaction, a small part of the molecular sieve catalyst doped with metal elements in the reaction system is settled to the bottom of the catalyst particle settler 6, so that a valve at the outlet of the catalyst particle settler 6 is periodically opened during the reaction, the molecular sieve catalyst doped with metal elements is collected, and then is conveyed to the storage tank 9 of the catalyst storage distributor 2 through the catalyst pipe chain circulation conveying system 7, and reenters the reaction system.
Preferably, the heat source used for heating is one or a combination of more than two of steam, an electric heater and a floating bed adiabatic reactor.
The purpose of the catalyst storage distributor according to the invention is to distribute the catalyst uniformly in order to obtain a uniform reaction system.
The invention has the technical characteristics and beneficial effects that:
1. the invention adopts the molecular sieve acid catalyst doped with metal elements, and has the characteristics of proper reaction pore canal, high reaction activity, high mechanical strength and the like. The raw materials used by the catalyst are simple and easy to obtain, the obtained catalyst has long service life, does not need regeneration after reaction, and can be used in a reactor continuously for 2-3 years.
2. In the preparation process of the catalyst, a crystallization treatment, namely a liquid phase crystal transformation method is adopted, the molecular sieve has richer intragranular mesopores through the crystallization process, and the mesoporous volume is improved, so that better reaction efficiency is obtained, and meanwhile, the service life of the catalyst is prolonged. The catalyst is processed by a forming mode of meshing extrusion strips (meshing of a meshing machine and extrusion of thin strips), has good mechanical strength, and is more suitable for industrial production.
3. Before the catalyst for synthesizing tert-butylamine by directly catalyzing and aminating isobutene is used, liquid ammonia which is one of reaction raw materials is used for soaking, so that ammonia can occupy the reaction active site of the catalyst in advance, and the reaction is carried out after the adsorption and desorption equilibrium is reached, olefin polymerization in a catalyst pore canal can be prevented, and the service life of the catalyst is prolonged.
4. The invention adopts the floating bed adiabatic reactor, and the upper part of the reactor is provided with the catalyst storage distributor, so that the catalyst can be effectively dispersed in the reactor, and the catalytic efficiency of the catalyst is increased. Meanwhile, the reactor is provided with a catalyst circulating system, so that the catalyst can be collected and recycled, and the catalyst is uniformly distributed through a distributor.
5. The isobutene and the liquid ammonia are directly aminated under the action of the catalyst to generate the tert-butylamine in a liquid phase state, and the specific catalyst is combined with specific reaction pressure, so that the reaction temperature is lower compared with the prior art. Under the temperature condition of 100-130 ℃, the olefin polymerization can be effectively reduced, and the carbon deposition of the catalyst in the reaction process is reduced, so that the service life of the catalyst is greatly prolonged; the reaction is exothermic, and the reaction is forward carried out at a relatively low reaction temperature.
6. The technological method of the invention is taken as a whole, and the excellent effect of the invention can be realized only by the combined action of each step and each condition. The invention provides a continuous production process, which is used for carrying out light component removal and refining on the reacted material to obtain a tert-butylamine product. The process is simple and the product purity is high. The once-through conversion rate of isobutene can reach 21%, the selectivity reaches 98.5%, and the purity of the refined tert-butylamine reaches more than 99.9%.
Drawings
FIG. 1 is a schematic diagram of a floating bed reactor for the direct catalytic amination of isobutene to tert-butylamine according to the invention;
wherein: 1-reaction material inlet, 2-catalyst storage distributor, 3-reaction material distributor, 4-solid-liquid separator, 5-reaction material outlet, 6-catalyst particle settler, 7-catalyst pipe chain circulation conveying system, 8-reaction chamber, 9-storage tank and 10-vibrating screen.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The raw materials, compounds, methods and devices not described in detail in the present invention are all prior art, and are not described in detail.
In order to further understand the present invention, the following examples are provided to illustrate in detail a process for synthesizing tert-butylamine by direct catalytic amination of isobutene.
Example 1
A floating bed adiabatic reactor comprising: a catalyst storage distributor 2, a reaction chamber 8, a catalyst particle settler 6 and a solid-liquid separator 4;
the catalyst storage distributor 2 is fixed at the top in the reaction chamber 8; the catalyst storage distributor 2 consists of a storage tank 9 and a vibrating screen 10; the storage tank 9 is used for storing the catalyst; the storage tank 9 is positioned right above the vibrating screen 10, and a valve is arranged at the bottom of the storage tank 9 to control the release of the catalyst to the vibrating screen 10; the upper part of the storage tank 9 is provided with a liquid ammonia inlet which is connected with a liquid ammonia feeding tank through a pipeline so as to input or output liquid ammonia; the storage tank 9 is movably connected with the vibrating screen 10; the vibrating screen 10 is of a conventional structure; the shape and size of the holes on the screen of the vibrating screen 10 are as per the prior art, so long as the catalyst can enter the reaction system through the screen;
a reaction material inlet 1 is arranged on the side wall of the lower part of the reaction chamber 8; a reaction material distributor 3 is arranged in the reaction chamber 8; the reaction material distributor 3 is formed by connecting a plurality of vertical pipelines in parallel, and small holes are distributed on the side walls and the tops of the vertical pipelines so that the reaction material enters the reaction chamber 8 through the small holes, and meanwhile, the catalyst is prevented from entering the reaction material distributor 3; the reactant inlet 1 is connected with the reactant distributor 3 through a pipeline;
the catalyst particle settler 6 is funnel-shaped, a settler outlet is arranged at the bottom of the catalyst particle settler 6, and a valve is arranged at the settler outlet; the side wall of the catalyst particle settler 6 is directly connected with the lower end of the side wall of the reaction chamber 8, and the catalyst particle settler 6 is communicated with the reaction chamber 8;
the solid-liquid separator 4 is provided with a reaction material outlet 5, a reaction material inlet and a catalyst outlet; the reaction material inlet of the solid-liquid separator 4 is connected with the bottom of the side wall of the reaction chamber 8 through a pipeline; a valve is arranged between the solid-liquid separator 4 and the reaction chamber 8;
the outlet of the catalyst particle settler 6 and the outlet of the solid-liquid separator 4 are connected with the storage tank 9 of the catalyst storage distributor 2 through a catalyst pipe chain circulation conveying system 7; the conveying mode of the pipe chain circulating conveying system 7 is pipe chain conveying, and the pipe chain circulating conveying system is just according to the existing structure.
The reaction chamber 8 is covered with a heat insulating material. The heat insulating material is an existing material. The top of the reaction chamber 8 is provided with a door, and the upper part of the storage tank 9 can be disassembled to be filled with catalyst; the structure is just as the prior art.
Example 2
A production process for synthesizing tert-butylamine by direct catalytic amination of isobutene comprises the following steps:
(1) 120g Cu (NO) 3 ) 2 ·3H 2 O was dissolved in 880mL of pure water to prepare a copper nitrate aqueous solution having a concentration of 12 wt%. 210g Ga (NO) 3 ) 2 ·9H 2 O was dissolved in 790mL of pure water to prepare an aqueous gallium nitrate solution having a concentration of 21 wt%. 600mL of copper nitrate aqueous solution, 700mL of gallium nitrate aqueous solution and 1000g of ZSM-5 zeolite were thoroughly stirred and mixed. Dropping a dilute phosphoric acid aqueous solution with the mass concentration of 20% to adjust the pH to be=3, refluxing and adsorbing for 2 hours at 50 ℃, immersing and washing the solid powder with pure water to be pH to be=7, and then filtering and drying to obtain the catalyst powder.
Mixing the obtained 1000g catalyst powder with 105g pseudo-boehmite and 20mL nitric acid aqueous solution with mass concentration of 5% uniformly to obtain a mixture, dispersing the mixture in an aqueous solution containing TPABr and sodium hydroxide, and controllingSiO in the mixture 2 The molar ratio of sodium hydroxide, tetrapropylammonium bromide and water is 1:0.1:0.15:50. the system was left to crystallize at 200℃for 24h. And (3) performing meshing extrusion molding, drying at 120 ℃ for 5h, and calcining at 500 ℃ for 5h to obtain the metal element doped molecular sieve catalyst, namely cylindrical long-strip particles with the height of 3 mm.
(2) 800g of the above metal element-doped molecular sieve catalyst was charged into the storage tank 9 of the catalyst storage distributor 2 of the floating bed adiabatic reactor described in example 1; liquid ammonia is input through a liquid ammonia inlet of the storage tank 9, and the catalyst is soaked for 10 hours at room temperature; liquid ammonia is recycled to the liquid ammonia feed tank through the liquid ammonia inlet output of the storage tank 9.
Mixing raw material isobutene and liquid ammonia in a feed tank according to the mol ratio of liquid ammonia to isobutene of 1.6:1; pressurizing to 20MPa by a feed pump, and heating the material to 130 ℃ by using steam; then continuously introducing the reaction material into the reaction chamber 8 and the catalyst particle precipitator 6 through the reaction material inlet 1 and the reaction material distributor 3 of the floating bed adiabatic reactor, filling the reaction chamber 8 and the catalyst particle precipitator 6 with the reaction material, and keeping the pressure in the reaction chamber 8 and the catalyst particle precipitator 6 at 20MPa. Simultaneously starting a catalyst storage distributor 2, opening a bottom valve of a storage tank 9, enabling the molecular sieve catalyst doped with the metal elements to enter a vibrating screen 10, and starting the vibrating screen 10 to enable the molecular sieve catalyst doped with the metal elements to uniformly enter a reaction system; the liquid ammonia and isobutene are subjected to amination reaction under the catalysis of a molecular sieve catalyst doped with metal elements, and the reaction residence time is 3min. Continuously conveying the reaction liquid after the amination reaction to a solid-liquid separator 4, and obtaining a liquid material and a metal element doped molecular sieve catalyst through solid-liquid separation; continuously feeding the obtained liquid material into a light component removing tower, wherein the pressure of the light component removing tower is 1.9MPa, the temperature of the tower top is 50 ℃, the temperature of the tower bottom is 169 ℃, crude tert-butylamine is obtained at the tower bottom, unreacted isobutene and liquid ammonia are separated from the tower top and recycled into a feed tank to be used as raw materials; continuously conveying the crude tert-butylamine to a refining tower, wherein the pressure of the refining tower is 0.07MPa, the temperature of the tower top is 59 ℃, the temperature of the tower bottom is 98 ℃, refining the crude tert-butylamine to obtain tert-butylamine at the tower top, and obtaining heavy components such as diisobutylene as a byproduct at the tower bottom; the molecular sieve catalyst doped with metal elements obtained by solid-liquid separation is continuously conveyed to a catalyst storage distributor 2 through a catalyst pipe chain circulating conveying system 7 and reenters a reaction system;
and in the reaction process, periodically opening a valve at the outlet of a catalyst particle settler 6, collecting the molecular sieve catalyst doped with metal elements, and then conveying the molecular sieve catalyst to a storage tank 9 of a catalyst storage distributor 2 through a catalyst pipe chain circulation conveying system 7, and re-entering the reaction system.
In the continuous reaction system, the reaction material (reactor discharge) obtained from the reaction material outlet 5 and the tert-butylamine product obtained by refining are sampled and subjected to gas chromatographic analysis at intervals of 1h, and the operation is carried out for 240h. The results of partial chromatographic analysis of the reactor discharge and tert-butylamine product are shown in Table 1;
table 1 example 1 reactor discharge and tert-butylamine product portion gas chromatography analysis data
According to the mass ratio of each component analyzed by gas chromatography, the average single pass conversion rate of isobutene can reach 21%, and the selectivity of converting isobutene into tert-butylamine is over 98.5%. After the process of the invention is operated stably, the purity of the refined tert-butylamine product can reach more than 99.95 percent.
In conclusion, the production process for synthesizing tert-butylamine by directly catalyzing and aminating isobutene has the advantages of simplicity, high single-pass conversion, good product selectivity, few reaction byproducts and mild reaction conditions. The floating bed reactor is adopted for reaction, the reactor has simple structure, can realize continuous operation, and has good product stability and high product purity. After long-time continuous reaction, the catalytic activity of the catalyst is not reduced, which indicates that the catalyst produced by the process has good stability and long service life.
Example 3
A production process for synthesizing tert-butylamine by direct catalytic amination of isobutene comprises the following steps:
(1) 240g Cu (NO) 3 ) 2 ·3H 2 O was dissolved in 760mL of pure water to prepare a copper nitrate aqueous solution having a concentration of 24 wt%. 760mL of copper nitrate aqueous solution was thoroughly mixed with 1000g of ZSM-5 zeolite. After the ph=3 was adjusted by dropping a diluted phosphoric acid aqueous solution having a mass concentration of 20% and reflux-adsorbing at 50 ℃ for 2 hours, the solid powder was immersed in pure water to ph=7. Then filtering and drying to obtain the catalyst powder.
Uniformly mixing 1000g of the obtained catalyst powder with 105g of pseudo-boehmite and 20mL of 5% nitric acid aqueous solution by mass concentration to obtain a mixture, dispersing the mixture into an aqueous solution containing TPABr and sodium hydroxide, and controlling SiO in the mixture 2 The molar ratio of sodium hydroxide, tetrapropylammonium bromide and water is 1:0.1:0.15:50. the system was left to crystallize at 200℃for 24h. And (3) performing meshing extrusion molding, drying at 120 ℃ for 5h, and calcining at 500 ℃ for 5h to obtain the metal element doped molecular sieve catalyst, namely cylindrical long-strip particles with the height of 3 mm.
(2) Step (2) is the same as in example 2.
In the continuous reaction system, the reaction materials (reactor discharge) obtained from the reaction material outlet 5 were sampled every 1 hour for gas chromatographic analysis.
Of the main components of the reactor output (reactor run 120 h), NH 3 29.26% of C 4 H 8 The mass ratio is 53.86 percent, C 4 H 11 The mass ratio of N is 16.58%, C 8 H 16 The mass ratio is 0.18%, and the mass ratio of other heavy components is 0.12%. The single pass conversion of isobutene was calculated to be 19.97% and the selectivity of isobutene to tert-butylamine was 94.65%.
Example 4
A production process for synthesizing tert-butylamine by direct catalytic amination of isobutene comprises the following steps:
(1) A molecular sieve catalyst doped with a metal element was prepared as in example 2.
(2) Step (2) as described in example 2, except that: the activation step of the molecular sieve catalyst doped with the metal element is omitted. Other steps and conditions were consistent with example 2.
Namely: 800g of the above metal element-doped molecular sieve catalyst was charged into the storage tank 9 of the catalyst storage distributor 2 of the floating bed adiabatic reactor described in example 1. Mixing raw material isobutene and liquid ammonia in a feed tank according to the mol ratio of liquid ammonia to isobutene of 1.6:1; pressurizing to 20MPa by a feed pump, and heating the material to 130 ℃ by using steam; then continuously introducing the reaction material into the reaction chamber 8 and the catalyst particle precipitator 6 through the reaction material inlet 1 and the reaction material distributor 3 of the floating bed adiabatic reactor, filling the reaction chamber 8 and the catalyst particle precipitator 6 with the reaction material, and keeping the pressure in the reaction chamber 8 and the catalyst particle precipitator 6 at 20MPa. Simultaneously starting a catalyst storage distributor 2, opening a bottom valve of a storage tank 9, enabling the molecular sieve catalyst doped with the metal elements to enter a vibrating screen 10, and starting the vibrating screen 10 to enable the molecular sieve catalyst doped with the metal elements to uniformly enter a reaction system; the liquid ammonia and isobutene are subjected to amination reaction under the catalysis of a molecular sieve catalyst doped with metal elements, and the reaction residence time is 3min. Continuously conveying the reaction liquid after the amination reaction to a solid-liquid separator 4, and obtaining a liquid material and a metal element doped molecular sieve catalyst through solid-liquid separation; continuously feeding the obtained liquid material into a light component removing tower, wherein the pressure of the light component removing tower is 1.9MPa, the temperature of the tower top is 50 ℃, the temperature of the tower bottom is 169 ℃, crude tert-butylamine is obtained at the tower bottom, unreacted isobutene and liquid ammonia are separated from the tower top and recycled into a feed tank to be used as raw materials; continuously conveying the crude tert-butylamine to a refining tower, wherein the pressure of the refining tower is 0.07MPa, the temperature of the tower top is 59 ℃, the temperature of the tower bottom is 98 ℃, refining the crude tert-butylamine to obtain tert-butylamine at the tower top, and obtaining heavy components such as diisobutylene as a byproduct at the tower bottom; the molecular sieve catalyst doped with metal elements obtained by solid-liquid separation is continuously conveyed to a catalyst storage distributor 2 through a catalyst pipe chain circulating conveying system 7 and reenters a reaction system;
and in the reaction process, periodically opening a valve at the outlet of a catalyst particle settler 6, collecting the molecular sieve catalyst doped with metal elements, and then conveying the molecular sieve catalyst to a storage tank 9 of a catalyst storage distributor 2 through a catalyst pipe chain circulation conveying system 7, and re-entering the reaction system.
In the continuous reaction system, the reaction materials (reactor discharge) obtained from the reaction material outlet 5 were sampled every 1 hour for gas chromatography analysis.
Of the main components of the reactor output (reactor run 120 h), NH 3 The mass ratio is 29.64 percent, C 4 H 8 The mass ratio is 53.97 percent, C 4 H 11 N mass ratio is 15.23%, C 8 H 16 The mass ratio is 0.85%, and the mass ratio of other heavy components is 0.31%. The single pass conversion of isobutene was calculated to be 19.80% and the selectivity of isobutene to tert-butylamine was calculated to be 87.66%.
Example 5
A production process for synthesizing tert-butylamine by direct catalytic amination of isobutene comprises the following steps:
(1) A molecular sieve catalyst doped with a metal element was prepared as in example 2.
(2) 10g of the catalyst particles obtained in the above steps were placed in an autoclave reactor (existing commercially available apparatus), 27.2g of liquid ammonia was introduced into the reactor, and after immersing at room temperature for 10 hours, 56.1g of isobutylene was introduced. After mixing uniformly, the reactor was warmed to 130℃and maintained at a pressure of 20MPa for 1h.
The sample was analyzed by gas chromatography, and the conversion of isobutene was calculated to be 11.2% and the selectivity 91.6%. Approximately 0.5g of isobutene was polymerized to give diisobutene.
Example 6
A production process for synthesizing tert-butylamine by direct catalytic amination of isobutene comprises the following steps:
(1) A molecular sieve catalyst doped with a metal element was prepared as in example 2.
(2) 800g of a metal element-doped molecular sieve catalyst was charged into the catalyst packing layer in the middle of a fixed bed reactor (existing commercial apparatus). Liquid ammonia is input, and the catalyst is soaked for 10 hours at room temperature; outputting and recycling liquid ammonia to a liquid ammonia feeding tank.
Mixing raw materials of isobutene and liquid ammonia in a feed tank according to the mol ratio of the liquid ammonia to the isobutene of 1.6:1, pressurizing to 20MPa by a feed pump, heating the materials to 130 ℃ by using steam, continuously entering a reactor, and keeping the pressure in the reactor at 20MPa. The liquid ammonia and isobutene are subjected to amination reaction under the catalysis of a molecular sieve catalyst doped with metal elements, and the reaction residence time is 3min. The reaction liquid after amination reaction continuously enters a light component removal tower, the pressure of the light component removal tower is 1.9MPa, the temperature of the tower top is 50 ℃, the temperature of the tower bottom is 169 ℃, crude tert-butylamine is obtained at the tower bottom, unreacted isobutene and liquid ammonia are separated from the tower top and recycled into a feed tank to be used as raw materials.
In the continuous reaction system, discharging the reactor at intervals of 1h, sampling crude tert-butylamine at the bottom of the light ends removal tower, and performing gas chromatographic analysis for 72h. The results of chromatographic analysis of the reactor discharge are shown in Table 1:
table 2 comparative example 2 reactor discharge gas chromatography analysis data
The average single pass conversion of isobutene was calculated to be 19.98% and the tert-butylamine selectivity was calculated to be 96.92% based on the mass fractions of the components analyzed by gas chromatography.
Comparative example 1
A process for the direct catalytic amination of isobutene to tert-butylamine, as described in example 2, with the difference: in the preparation process of the catalyst in the step (1), omitting the crystallization treatment step; other steps and conditions were consistent with example 2.
Namely, the catalyst preparation method is as follows:
120g Cu (NO) 3 ) 2 ·3H 2 O was dissolved in 880mL of pure water to prepare a copper nitrate aqueous solution having a concentration of 12 wt%. 210g Ga (NO) 3 ) 2 ·9H 2 O was dissolved in 790mL of pure water to prepare an aqueous gallium nitrate solution having a concentration of 21 wt%. 600mL of copper nitrate aqueous solution, 700mL of gallium nitrate aqueous solution and 1000g of ZSM-5 zeolite were thoroughly stirred and mixed. Dropping a dilute phosphoric acid aqueous solution with the mass concentration of 20% to adjust the pH to be=3, refluxing and adsorbing for 2 hours at 50 ℃, immersing and washing the solid powder with pure water to be pH to be=7, and then filtering and drying to obtain the catalyst powder.
The 1000g of the obtained catalyst powder is evenly mixed with 105g of pseudo-boehmite and 20mL of nitric acid aqueous solution with mass concentration of 5%, the mixture is subjected to meshing extrusion molding, the mixture is dried at 120 ℃ for 5h, and calcined at 500 ℃ for 5h, so that the metal element doped molecular sieve catalyst, namely the cylindrical long-strip particles with the height of 3mm, is obtained.
In the continuous reaction system, the reaction material (reactor discharge) obtained from the reaction material outlet 5 and the tert-butylamine product obtained by refining are respectively sampled every 1h for gas chromatographic analysis, and the total operation is 240h.
The average single pass conversion of isobutene was 20.21% and the selectivity of isobutene to tert-butylamine was 98.51% over 160h of reaction run; after running to 160h, the single pass conversion of isobutene gradually decreased, with an average of 18.45%.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (10)
1. A production process for synthesizing tert-butylamine by direct catalytic amination of isobutene comprises the following steps:
(1) Mixing ZSM-5 zeolite with water solution of soluble metal salt, and regulating pH to 3-6; after reflux adsorption and water washing to neutrality, drying to obtain catalyst powder; uniformly mixing catalyst powder, a binder and a nitric acid aqueous solution to obtain a mixture, and crystallizing, forming, drying and calcining to obtain a metal element doped molecular sieve catalyst;
(2) Liquid ammonia and isobutene are subjected to amination reaction under the catalysis of a molecular sieve catalyst doped with metal elements, and then tertiary butylamine is obtained through purification.
2. The process for the direct catalytic amination of isobutene to tert-butylamine according to claim 1, wherein in step (1) one or more of the following conditions are included:
i. the soluble metal salt is one or more of gallium nitrate, ferric sulfate, nickel nitrate or copper nitrate; the mass concentration of the water solution of the soluble metal salt is 7% -56%;
ii. The mass ratio of ZSM-5 zeolite to soluble metal salt is 1-15:1, preferably 4-7:1, a step of;
iii, adjusting the pH value by using a phosphoric acid aqueous solution with the mass concentration of 10-40%;
iv, the reflux adsorption temperature is 50-100 ℃, and the reflux adsorption time is 1-3 h;
v, the adhesive is pseudo-boehmite, gamma-Al 2 O 3 One or more of aluminum sol and silicon aluminum sol;
vi, the mass ratio of the catalyst powder to the binder is 1:0.1-0.2; the mass of the catalyst powder and the volume ratio of the nitric acid aqueous solution are 30-80:1g/mL; the mass concentration of the aqueous solution of nitric acid is 2% -10%.
3. The process for synthesizing tert-butylamine by direct catalytic amination of isobutene according to claim 1, wherein in step (1), the crystallization treatment method is as follows: dispersing the mixture into a mixed solution of tetrapropylammonium bromide (TPABr), sodium hydroxide and water, and treating for 20-30h at 150-250 ℃; siO in the mixture 2 The molar ratio of sodium hydroxide, tetrapropylammonium bromide and water is 1:0.02 to 0.1:0.05 to 0.2:50 to 70.
4. The process for the direct catalytic amination of isobutene to tert-butylamine according to claim 1, wherein in step (1) one or more of the following conditions are included:
i. the forming method is engaged extrusion;
ii. The drying temperature after molding is 100-200 ℃ and the drying time is 2-5 h;
iii, the calcination temperature is 300-600 ℃, and the calcination time is 2-5 h;
the molecular sieve catalyst doped with metal elements is cylindrical long strips with the height of 2-4 mm.
5. The process for the direct catalytic amination of isobutene to tert-butylamine according to claim 1, wherein in step (2) the amination of liquid ammonia and isobutene is carried out in a floating bed adiabatic reactor, autoclave reactor or fixed bed reactor; preferably, the amination of liquid ammonia and isobutene is carried out in a floating bed adiabatic reactor.
6. The process for the direct catalytic amination of isobutene to tert-butylamine according to claim 5, wherein the floating bed adiabatic reactor comprises: a catalyst storage distributor 2, a reaction chamber 8, a catalyst particle settler 6 and a solid-liquid separator 4;
the catalyst storage distributor 2 is fixed at the top in the reaction chamber 8; the catalyst storage distributor 2 consists of a storage tank 9 and a vibrating screen 10; the storage tank 9 is used for storing the catalyst; the storage tank 9 is positioned right above the vibrating screen 10, and a valve is arranged at the bottom of the storage tank 9 to control the release of the catalyst to the vibrating screen 10; the upper part of the storage tank 9 is provided with a liquid ammonia inlet which is connected with a liquid ammonia feeding tank through a pipeline so as to input or output liquid ammonia; the storage tank 9 is movably connected with the vibrating screen 10;
a reaction material inlet 1 is arranged on the side wall of the lower part of the reaction chamber 8; a reaction material distributor 3 is arranged in the reaction chamber 8; the reaction material distributor 3 is formed by connecting a plurality of vertical pipelines in parallel, and small holes are distributed on the side walls and the tops of the vertical pipelines so that the reaction material enters the reaction chamber 8 through the small holes, and meanwhile, the catalyst is prevented from entering the reaction material distributor 3; the reactant inlet 1 is connected with the reactant distributor 3 through a pipeline;
the catalyst particle settler 6 is funnel-shaped, a settler outlet is arranged at the bottom of the catalyst particle settler 6, and a valve is arranged at the settler outlet; the side wall of the catalyst particle settler 6 is directly connected with the lower end of the side wall of the reaction chamber 8, and the catalyst particle settler 6 is communicated with the reaction chamber 8;
the solid-liquid separator 4 is provided with a reaction material outlet 5, a reaction material inlet and a catalyst outlet; the reaction material inlet of the solid-liquid separator 4 is connected with the top of the side wall of the reaction chamber 8 through a pipeline; a valve is arranged between the solid-liquid separator 4 and the reaction chamber 8;
the outlet of the catalyst particle settler 6 and the outlet of the solid-liquid separator 4 are connected with the storage tank 9 of the catalyst storage distributor 2 through the catalyst pipe chain circulation conveying system 7.
7. The process for the direct catalytic amination of isobutene to tert-butylamine according to claim 1, characterized in that in step (2) one or more of the following conditions are included:
i. the molar ratio of liquid ammonia to isobutene is 1-2:1, preferably 1.5-2:1;
ii. After the amination reaction is finished, carrying out solid-liquid separation, and recovering and recycling the obtained molecular sieve catalyst doped with the metal element; purifying the obtained liquid material;
iii, purification comprises the steps of: treating the liquid material by a light component removing tower, obtaining a crude tert-butylamine product at the bottom of the tower, separating unreacted isobutene and liquid ammonia from the top of the tower, and recycling the unreacted isobutene and the liquid ammonia as raw materials; the pressure of the light component removing tower is 1-3 MPa, the temperature of the tower top is 50-70 ℃, and the temperature of the tower bottom is 160-180 ℃; the crude product of tert-butylamine is conveyed to a refining tower, the tert-butylamine is obtained from the tower top, and the byproduct diisobutylene and other heavy components are obtained from the tower bottom; the pressure of the refining tower is 0.05Mpa-0.2Mpa, the temperature of the top of the tower is 50 ℃ -100 ℃, and the temperature of the bottom of the tower is 90 ℃ -110 ℃.
8. The process for synthesizing tert-butylamine by direct catalytic amination of isobutene according to claim 1, wherein the step (2) further comprises a step of activating a molecular sieve catalyst doped with a metal element before the amination reaction, specifically comprising the following steps: soaking a molecular sieve catalyst doped with metal elements in liquid ammonia at room temperature for 3-13 h; preferably, the soaking time is 5-10 hours.
9. The process for synthesizing tert-butylamine by direct catalytic amination of isobutene according to claim 1, wherein in the step (2), the amination reaction temperature is 100-130 ℃, the amination reaction pressure is 15-25 MPa, and the amination reaction residence time is 0.5-10 min; preferably, the amination reaction pressure is 18-22 MPa.
10. The process for the direct catalytic amination of isobutene to tert-butylamine according to claim 1, wherein in step (2) the method for preparing tert-butylamine using a floating bed adiabatic reactor comprises the steps of:
a. loading a molecular sieve catalyst doped with a metal element into a storage tank 9 of a catalyst storage distributor 2 of the floating bed adiabatic reactor; liquid ammonia is input through a liquid ammonia inlet of the storage tank 9, and the catalyst is soaked for 3-13 h at room temperature; liquid ammonia is output and recovered to a liquid ammonia feeding tank through a liquid ammonia inlet of the storage tank 9 to be used as a raw material;
b. fully mixing liquid ammonia and isobutene, heating to 100-130 ℃, and pressurizing to 15-25 MPa; then continuously introducing the reaction material into the reaction chamber 8 and the catalyst particle settler 6 through the reaction material inlet 1 and the reaction material distributor 3 of the floating bed adiabatic reactor, filling the reaction chamber 8 and the catalyst particle settler 6 with the reaction material, and keeping the pressure in the reaction chamber 8 and the catalyst particle settler 6 at 15-25 MPa; simultaneously starting a catalyst storage distributor 2, opening a bottom valve of a storage tank 9, enabling the molecular sieve catalyst doped with the metal elements to enter a vibrating screen 10, and starting the vibrating screen 10 to enable the molecular sieve catalyst doped with the metal elements to uniformly enter a reaction system; under the catalysis of a molecular sieve catalyst doped with metal elements, carrying out amination reaction on liquid ammonia and isobutene, wherein the reaction residence time is 0.5-10 min; continuously conveying the reaction liquid after the amination reaction to a solid-liquid separator 4, and obtaining a liquid material and a metal element doped molecular sieve catalyst through solid-liquid separation; continuously feeding the obtained liquid material into a light component removing tower, obtaining crude tert-butylamine at the bottom of the tower, separating unreacted isobutene and liquid ammonia from the top of the tower, and recycling the unreacted isobutene and the liquid ammonia as raw materials; continuously conveying the crude tert-butylamine product to a refining tower, refining to obtain tert-butylamine at the top of the tower and obtaining heavy components such as diisobutylene as a byproduct at the bottom of the tower; the molecular sieve catalyst doped with metal elements obtained by solid-liquid separation is continuously conveyed to a catalyst storage distributor 2 through a catalyst pipe chain circulating conveying system 7 and reenters a reaction system;
preferably, during the reaction, a small part of the molecular sieve catalyst doped with metal elements in the reaction system is settled to the bottom of the catalyst particle settler 6, so that a valve at the outlet of the catalyst particle settler 6 is periodically opened during the reaction, the molecular sieve catalyst doped with metal elements is collected, and then is conveyed to the storage tank 9 of the catalyst storage distributor 2 through the catalyst pipe chain circulation conveying system 7, and reenters the reaction system.
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| CN117463556A (en) * | 2023-12-27 | 2024-01-30 | 福建省德旭新材料有限公司 | Preparation facilities of solid super acidic catalyst for preparation of ethylene sulfate |
| CN117463556B (en) * | 2023-12-27 | 2024-03-12 | 福建省德旭新材料有限公司 | Preparation facilities of solid super acidic catalyst for preparation of ethylene sulfate |
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