CN111825556B - Preparation method of tert-butylamine - Google Patents
Preparation method of tert-butylamine Download PDFInfo
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- CN111825556B CN111825556B CN201910306463.3A CN201910306463A CN111825556B CN 111825556 B CN111825556 B CN 111825556B CN 201910306463 A CN201910306463 A CN 201910306463A CN 111825556 B CN111825556 B CN 111825556B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 59
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 42
- 238000007598 dipping method Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- DDTCPFLJOHVHIM-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Ag+] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Ag+] DDTCPFLJOHVHIM-UHFFFAOYSA-N 0.000 claims description 12
- QQPGSKVIALIXNV-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] QQPGSKVIALIXNV-UHFFFAOYSA-N 0.000 claims description 12
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- OCVLFZHGBFWPKC-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] OCVLFZHGBFWPKC-UHFFFAOYSA-N 0.000 claims description 5
- ULYWVQJMDWAEFW-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] ULYWVQJMDWAEFW-UHFFFAOYSA-N 0.000 claims description 5
- NTZRHUFVUDIPGK-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Pt+2].[N+](=O)([O-])[O-] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Pt+2].[N+](=O)([O-])[O-] NTZRHUFVUDIPGK-UHFFFAOYSA-N 0.000 claims description 5
- VTZTWCMBKJCBTH-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Rh+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Rh+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] VTZTWCMBKJCBTH-UHFFFAOYSA-N 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 4
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- QRPKFJXKQPHBNN-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] QRPKFJXKQPHBNN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003930 superacid Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- JLEHSYHLHLHPAL-UHFFFAOYSA-N tert-butylurea Chemical compound CC(C)(C)NC(N)=O JLEHSYHLHLHPAL-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- TZPYMTWJXBLYOV-UHFFFAOYSA-N 4-butyl-1,3-benzothiazole-2-sulfonamide Chemical group CCCCC1=CC=CC2=C1N=C(S(N)(=O)=O)S2 TZPYMTWJXBLYOV-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- -1 butyl amino ethanol methacrylate Chemical group 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940064302 folacin Drugs 0.000 description 1
- 235000019152 folic acid Nutrition 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—Feeding reactive fluids
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00893—Feeding means for the reactants
- B01J2208/00902—Nozzle-type feeding elements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a preparation method of tert-butylamine, which comprises the steps of adopting a tubular reactor, enabling liquid ammonia and isobutene serving as a feed I to enter the reactor from the top of the reactor, enabling liquid ammonia serving as a feed II to enter the reactor from the bottom of the reactor, arranging a plurality of catalyst bed layers which are arranged in a staggered mode from top to bottom in the reactor, wherein each catalyst bed layer comprises a bed plate and a catalyst distributed on the bed plate, one end of each bed plate is hermetically connected with the wall of the reactor, the other end of each bed plate horizontally extends to the wall of the opposite reactor and keeps a certain distance with the opposite reactor, a vertical baffle is arranged at the tail end of each bed plate, and two adjacent bed plates are connected to the walls of the reactors at different sides; the bed plate is provided with a plurality of openings, the feeding I penetrates through the catalyst bed layer from top to bottom to react, and the feeding II is in reverse contact with the feeding I from bottom to top and further reacts with unreacted isobutene in the feeding I. The reactor and the feeding mode enable the reaction process to have the advantages of a trickle bed and catalytic rectification at the same time, and the reaction conversion rate is improved.
Description
Technical Field
The invention relates to a method for preparing tert-butylamine, in particular to a method for preparing tert-butylamine by using isobutene and liquid ammonia as raw materials.
Background
Tert-butylamine of formula C 4 H 11 N is a colorless flammable liquid, has special smell and is easily mixed with water and ethanol. Tert-butylamine is widely used as an organic synthesis intermediate in the fields of rubber additives, dyes, insecticides, bactericides, medicines and the like. In the united states, tert-butylamine is consumed primarily as an ethylene oxide adduct. This is achieved byThe tertiary butyl amino ethanol methacrylate derived from the adduct can be used as a raw material of a copolymer and a rubber auxiliary agent of a lubricating oil additive. In recent years, a plurality of green and environment-friendly chemical product production technologies and production processes appear, and the technical development and application of the subsequent product of tert-butylamine are further developed. Such as the synthesis of folacin, the synthesis of desulfurization decarbonizer sterically hindered amine and IV-tertiary butyl-2-benzothiazole amide (rubber accelerator NS) and IV-tertiary butyl-2-benzothiazole sulfonamide, and the like, and particularly, the synthesis also has wide application in agricultural chemicals. Therefore, the market demand of tert-butylamine is continuously increased, the market application prospect is good, and the research and development of economic and efficient synthesis methods of tert-butylamine gradually become research hotspots of domestic and foreign researchers.
The synthesis method of tert-butylamine mainly comprises the following steps: a t-butylurea method, MTBE-HCN method, isobutylene amination method, and the like. Although the tert-butylurea method has the advantages of simple process and easily obtained raw materials, the process needs to use a large amount of strong acid and strong base catalysts and high boiling point solvents, so that equipment is corroded, the environment is polluted, and the solvent is difficult to recover. The MTBE-HCN method and the isobutene-HCN method also use concentrated sulfuric acid as a catalyst for preparing tert-butylamine, and HCN has large toxicity and has large influence on environment and production. The tert-butylamine is synthesized by the isobutene ammoniation method, the tert-butylamine is directly ammoniated by taking isobutene and liquid ammonia as raw materials, the process flow is simple, no toxicity is caused, the problem of environmental pollution is solved, and the method is a high-efficiency and environment-friendly method for preparing the tert-butylamine.
The synthesis technology of methyl tert-butyl ether (MTBE) is an effective method for separating the isobutene from the mixed C4, and the rapid development is achieved in recent years, and particularly the popularization of a new gasoline formula is more concerned by the oil refining industry. However, with the development of substitutes such as alkylate and ethanol gasoline, the market demand of MTBE is greatly influenced. MTBE has been reported by the United states environmental protection agency to be a carcinogen. In addition, there are studies that have shown that MTBE has a potential threat to the environment and human health. Several countries in north america and europe have banned or restricted the use of MTBE in gasoline. China will gradually limit the addition of MTBE in gasoline, so the market demand of MTBE will be greatly reduced, and isobutene will find other utilization ways.
The patent US43072561 discloses a method for preparing tert-butylamine, rare earth metal La or H ion exchange is used for artificially synthesizing alumino-silicate, Y zeolite is used as a catalyst, the reaction temperature is 270-310 ℃, although the selectivity of tert-butylamine can reach 100%, the isobutene conversion rate is only 6.19%. The method has the advantages of harsh reaction conditions and low single-pass conversion rate of isobutene. Patent US5648546 discloses a process for the preparation of tert-butylamine using noble metal modified Y-type zeolite as catalyst, the reaction being carried out at elevated temperature and pressure. In the reaction, a large amount of noble metal is used for modifying the catalyst, so that the production cost is greatly increased, the process condition is severe, and the industrial production is difficult to realize.
Disclosure of Invention
Aiming at the problems of higher catalyst cost, harsh reaction conditions and lower single-pass conversion rate of isobutene in the method for preparing tert-butylamine by using isobutene and liquid ammonia as raw materials in the prior art, the invention provides a method for preparing tert-butylamine. The method takes isobutene and liquid ammonia as raw materials, and the isobutene and the liquid ammonia are fed into a tubular reactor through an upper part and a lower part at the same time, and are matched with a metal-doped solid super acidic catalyst, so that the conversion rate of the reaction can be effectively improved, the process is simple, no pollution is caused, the condition is mild, and the reactor can be stably operated for a long period.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of tert-butylamine adopts a tubular reactor, liquid ammonia and isobutene are used as a feed I to enter the reactor from the top of the reactor, liquid ammonia is used as a feed II to enter the reactor from the bottom of the reactor, a plurality of catalyst bed layers which are staggered are arranged in the reactor from top to bottom, each catalyst bed layer comprises a bed plate and catalysts distributed on the bed plates, one end of each bed plate is hermetically connected with the wall of the reactor, the other end of each bed plate horizontally extends to the wall of the opposite side reactor and keeps a certain distance with the wall of the opposite side reactor, the tail end of each bed plate is provided with a vertical baffle, and the two bed plates which are adjacent up and down are connected to the wall of the reactor at different sides; the bed plate is provided with a plurality of openings, the feeding material I penetrates through the catalyst bed layer from top to bottom to react, and the feeding material II reversely contacts with the feeding material I from bottom to top to further react with unreacted isobutene in the feeding material I.
In the above preparation method, further, the feed I is fed into the reactor in the form of a spray.
In the preparation method, further, an upper feed port is arranged at the top of the reactor, and an atomizing nozzle is arranged at the upper feed port.
In the preparation method, the length of the bed plate in the reactor is 2/3-3/4 of the diameter of the reactor.
In the preparation method, the diameter of the hole on the bed plate is 0.5-2 mm.
In the preparation method, further, the height of the baffle is 30-80 mm.
In the above preparation method, further, the reaction conditions in the reactor are: the reaction temperature is 180-220 ℃, and preferably 190-200 ℃; the reaction pressure is 2-6 MPa, preferably 3-4 MPa.
In the above production process, further, the molar ratio of liquid ammonia to isobutylene in the feed I is 1: 1-10: 1, preferably 4: 1-8: 1, the total volume airspeed is 0.5-5 h -1 Preferably 1 to 3 hours -1 。
In the preparation method, further, the volume space velocity of the feeding material II is 0.5-2 h -1 Preferably 1 to 1.5 hours -1 。
In the above preparation method, further, the catalyst is selected from the catalysts commonly used in the prior art for preparing tert-butylamine by reacting liquid ammonia with isobutene, and in the technical scheme of the invention, a solid super acidic catalyst is preferred.
In the preparation method, the catalyst can be in any shape, most preferably in a strip-shaped clover shape, and the length of the catalyst is 2-4 mm.
Further, the invention also provides a preparation method of the solid super acidic catalyst suitable for the reaction, which comprises the following steps:
s1 preparation of ZrOCl 2 And AlCl 3 Dissolved in BIn alcohol to obtain ZrOCl 2 And AlCl 3 Titrating with ammonia water under stirring until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, drying, and roasting to obtain white solid particles;
and S2, dipping the white solid particles obtained in the step S1 in a silver nitrate sulfuric acid solution, drying and roasting to obtain particles I, dipping the particles I in one or two of a nickel nitrate sulfuric acid solution, a cobalt nitrate sulfuric acid solution, a molybdenum nitrate sulfuric acid solution and a tungsten nitrate sulfuric acid solution, drying and roasting to obtain particles II, dipping the particles II in one of a palladium nitrate sulfuric acid solution, a platinum nitrate sulfuric acid solution and a rhodium nitrate sulfuric acid solution, drying and roasting to obtain the metal-doped solid super acid catalyst.
Further, ZrOCl in step S1 2 And AlCl 3 The mass concentration of the ethanol solution is 10-30% and 20-30% respectively.
Further, the drying temperature in the step S1 is 70 to 90 ℃, the drying time is 4 to 6 hours, the baking temperature is 450 to 550 ℃, and the baking time is 4 to 6 hours.
Further, the preparation process of the nitrate sulfuric acid solution in step S2 is: dissolving nitrate in dilute sulfuric acid to obtain a nitrate sulfuric acid solution; the concentration of the dilute sulfuric acid is 0.3-0.6 mol/L, the concentration of the silver nitrate sulfuric acid solution is 2-4 mol/L, the concentration of the nickel nitrate sulfuric acid solution is 5-15 mol/L, the concentration of the cobalt nitrate sulfuric acid solution is 5-10 mol/L, the concentration of the molybdenum nitrate sulfuric acid solution is 10-15 mol/L, the concentration of the palladium nitrate sulfuric acid solution is 0.05-0.2 mol/L, the concentration of the platinum nitrate sulfuric acid solution is 0.1-0.2 mol/L, and the concentration of the rhodium nitrate sulfuric acid solution is 0.1-0.3 mol/L.
Further, the dipping process of step S2 is performed under reduced pressure and ultrasonic vibration. The decompression condition is 15000-20000 Pa; the ultrasonic condition is that the vibration frequency is 50-60 kHz; the dipping temperature is 55-60 ℃, and the dipping time in each step is 4-6 h.
Further, the drying conditions in step S2 are: the drying temperature is 80-100 ℃, and the drying time is 6-8 hours; the roasting conditions are as follows: the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
Furthermore, the catalyst prepared by the method is preferably strip-shaped clover-shaped particles with the length of 2-4 mm.
Compared with the prior art, the invention has the following advantages:
(1) the reaction of liquid ammonia and isobutene is carried out on a tubular reactor with a bed plate, the feeding is carried out in an upper and lower simultaneous feeding mode, the reaction material fed in the upper mode is firstly contacted with the catalyst on the bed plate and reacts, the reactant flows to the next bed plate step by step through the air holes on the catalyst bed plate and reacts, the reaction material fed in the lower mode enters the reactor under the condition of certain airspeed, the reaction material is rapidly gasified under the reaction condition, the reaction material ascends step by step through the air holes on the bed plate and permeates into the space of the reactor through gaps among the catalyst bed plates, the concentration and the flow rate of the lower feeding gas in the reactor are improved, the reaction material mixed with the reactant fed in the upper mode is further reacted on the catalyst bed plate, and the reactor and the feeding mode enable the reaction process to have the advantages of a trickle bed and catalytic rectification simultaneously, and the reaction conversion rate is improved.
(2) In the preparation process of the solid super acidic catalyst, ZrO is adopted 2 -Al 2 O 3 The composite carrier and different metal solutions are respectively impregnated in a certain order under the conditions of reduced pressure, ultrasonic vibration and a certain impregnation temperature, and the impregnating solution is continuously boiled, SO that the catalyst has uniform particle size and SO 4 2- The coordination with the metal ions on the surface of the oxide is rapid and uniform, so that the catalyst has stronger acidity. ZrO (ZrO) 2 -Al 2 O 3 In the composite carrier, a new active site is formed at the interface of the carrier, and the active metal and the defect site of the carrier jointly activate a C = C bond, so that the reaction activity is increased. Ag + Is pre-doped to ZrO 2 The crystal grains tend to exist in a monoclinic type (M), and the monoclinic type (M) is a relatively stable crystal phase structure, so that the catalyst has higher activity and better stability.
(3) The reaction materials fed upwards enter the reactor through the atomizing nozzle under a certain airspeed condition, the materials passing through the atomizing nozzle exist in a mixed state of mist small droplets under the reaction condition, the mixing and the distribution are more uniform, and the reaction efficiency on a catalyst bed layer is higher.
Drawings
FIG. 1 is a schematic view of a tubular reactor for the production of tert-butylamine according to the present invention.
Wherein: wherein: 1-an upper feeding port; 2-lower feed inlet; 3-discharging port; 4-a catalyst; 5-a baffle plate; 6-bed board; 7-atomizing nozzle.
The working process of the reactor of the invention is as follows: the feeding I enters the reactor from the upper feeding port 1, after being atomized by the atomizing nozzle 7, a mist mixture is formed to contact with the catalyst 4 filled in a space formed by the bed plate 6 and the baffle plate 5, the reaction is carried out under certain reaction conditions, reactants flow to the next bed plate step by step through the air holes on the bed plate 6 and react, the feeding II enters the reactor from the lower feeding port 2, the gasification is carried out rapidly under the reaction conditions, the reactants ascend step by step through the open holes of the bed plate 6 and permeate the space of the reactor through the gaps among the catalyst bed plates, the reactants mixed with the feeding I further react on the catalyst bed plate, and the final reaction product is discharged from the discharging port 3.
Detailed Description
The preparation process of the solid super acidic catalyst of the present invention is specifically described as follows: firstly, respectively mixing 50-100 g ZrOCl 2 And AlCl 3 Dissolving in ethanol to obtain ZrOCl 2 10 to 30 percent of mass concentration and AlCl 3 Titrating an ethanol solution with the mass concentration of 20-40% by using 20-25% ammonia water until no white precipitate exists, washing the solution with deionized water for several times, wherein the washing time is 5-10 minutes each time, the washing temperature is 40-50 ℃, washing the solution until no chloride ion exists, then drying the solution in a vacuum drying oven for 4-6 hours at the temperature of 80-90 ℃, extruding the solution to form strips, and roasting the strips for 8 hours at the temperature of 500 ℃ to obtain white solid particles for later use. Secondly, dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2-4 mol/L, wherein the dipping temperature is 55-60 ℃, and the dipping time is 4-6 h; the decompression vacuum degree is 15000-20000 Pa; the ultrasonic vibration frequency is 50-60 kHz, and then the solid particles are dried in vacuum at the temperature of 80-90 DEG CDrying for 4-6 hours in a drying oven, and roasting for 8 hours at 500 ℃ to obtain particles I. And thirdly, impregnating the particles I with one or two selected from a nickel nitrate sulfuric acid solution, a cobalt nitrate sulfuric acid solution, a molybdenum nitrate sulfuric acid solution and a tungsten nitrate sulfuric acid solution, and repeating the process of the second step to obtain particles II. And fourthly, dipping the particles II by one selected from a palladium nitrate sulfuric acid solution, a platinum nitrate sulfuric acid solution and a rhodium nitrate sulfuric acid solution, and repeating the process of the second step to obtain the metal-doped solid super acidic catalyst.
The specific embodiment of the invention is as follows: reacting on a fixed bed continuous reactor with a catalyst bed plate, wherein liquid ammonia and isobutene serving as a feed I enter the reactor from the top of the reactor under reaction conditions, liquid ammonia serving as a feed II enters the reactor from the bottom of the reactor, a plurality of staggered catalyst bed layers are arranged in the reactor from top to bottom, each catalyst bed layer comprises a bed plate and a catalyst distributed on the bed plate, one end of each bed plate is hermetically connected with the wall of the reactor, the other end of each bed plate horizontally extends to the wall of the opposite reactor and keeps a certain distance with the wall of the opposite reactor, a vertical baffle is arranged at the tail end of each bed plate, and two adjacent bed plates are connected to the walls of the reactors at different sides; the bed plate is provided with a plurality of openings, the feeding I penetrates through the catalyst bed layer from top to bottom to react, and the feeding II is in reverse contact with the feeding I from bottom to top and further reacts with unreacted isobutene in the feeding I.
The following examples are provided to illustrate specific embodiments of the present invention. In the following examples and comparative examples,% represents mass% unless otherwise specified. The model of an ultrasonic vibrator used in the preparation of the metal-doped solid super acidic catalyst is KQ-550B, and the model of an upper feeding atomization nozzle is JLN-G type high-pressure fine atomization nozzle, which is purchased from Jining Jun spray equipments, Inc. The inner diameter of the reactor is 25mm, the height of the reactor is 160cm, the length of the bed plate is 2/3 of the diameter of the reactor, and the edge of the bed plate is hermetically connected with the wall of the reactor. The aperture of the air holes is 1mm, and the air holes are uniformly distributed on the bed plate; the height of the baffle at the tail end of the bed board is 40 mm.
Example 1
(1) Preparation of solid superacid catalystAgent: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 25% 2 Ethanol solution, 40 g of AlCl 3 Dissolved in ZrOCl 2 Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: b, dipping the white particles obtained in the step a by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 15000 Pa; the ultrasonic vibration frequency was 55kHz, and then the solid particles were dried in a vacuum drying oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to obtain particles I. c: and (c) repeating the impregnation process in the step (b) by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (c) repeating the process of the step (b) by using a palladium nitrate sulfuric acid solution with the concentration of 0.1mol/L to obtain the metal-doped solid super acidic catalyst.
(2) Preparation of tert-butylamine: the reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60mL of catalyst is filled and uniformly filled on the catalyst bed plates; the reaction temperature is 190 ℃, the reaction pressure is 2MPa, and the hourly space velocity of the total feed liquid is 1.5h -1 The molar ratio of liquid ammonia to isobutene is 6: 1; the liquid hourly space velocity of the liquid ammonia to the catalyst in the lower feeding is 1.3h -1 The reaction results are shown in Table 1.
Example 2
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 25% 2 Ethanol solution, and then 40 g of AlCl 3 Dissolved in ZrOCl 2 Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: dissolving with silver nitrate sulfuric acid with the concentration of 3mol/LB, soaking the white particles obtained in the step a in liquid, wherein the soaking temperature is 55 ℃, and the soaking time is 6 hours; the vacuum degree is reduced to 16000 Pa; the ultrasonic vibration frequency was 58kHz, and then the solid particles were dried in a vacuum drying oven at 90 ℃ for 6 hours and further calcined at 500 ℃ for 8 hours to obtain particles I. c: and (c) repeating the impregnation process of the step (b) by using a nickel nitrate sulfuric acid solution with the concentration of 8mol/L to obtain particles II. d: and (c) repeating the process of the step (b) by using a palladium nitrate sulfuric acid solution with the concentration of 0.1mol/L to obtain the metal-doped solid super acidic catalyst.
(2) Preparation of tert-butylamine: the reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60mL of catalyst is filled and uniformly filled on the catalyst bed plates; the reaction temperature is 180 ℃, the reaction pressure is 3MPa, and the hourly space velocity of the total upper feeding liquid is 1.5h -1 The molar ratio of liquid ammonia to isobutene is 7: 1; the liquid hourly space velocity of the liquid ammonia to the catalyst in the lower feeding is 1.0 h -1 The reaction results are shown in Table 1.
Example 3
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 25% 2 Ethanol solution, 40 g of AlCl 3 Dissolved in ZrOCl 2 Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: b, dipping the white particles obtained in the step a by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 17000 Pa; the ultrasonic vibration frequency was 56kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (c) repeating the impregnation process of the step (b) by using a nickel nitrate sulfuric acid solution with the concentration of 7mol/L to obtain particles II. d: and (c) repeating the process of the step (b) by using a palladium nitrate sulfuric acid solution with the concentration of 0.15mol/L to obtain the metal-doped solid super acidic catalyst.
(2) System for makingPreparing tert-butylamine: the reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60mL of catalyst is filled and uniformly filled on the catalyst bed plates; the reaction temperature is 190 ℃, the reaction pressure is 2MPa, and the upper feeding total liquid hourly space velocity is 1.5h -1 The molar ratio of liquid ammonia to isobutene is 8: 1; the liquid hourly space velocity of the liquid ammonia to the catalyst in the lower feeding material is 1.3h -1 The reaction results are shown in Table 1.
Example 4
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 25% 2 Ethanol solution, 40 g of AlCl 3 Dissolved in ZrOCl 2 Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: b, dipping the white particles obtained in the step a by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is 18000 Pa; the ultrasonic vibration frequency was 60kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (c) repeating the impregnation process of the step (b) by using a nickel nitrate sulfuric acid solution with the concentration of 8mol/L to obtain particles II. d: and (c) repeating the process of the step (b) by using a palladium nitrate sulfuric acid solution with the concentration of 0.2mol/L to obtain the metal-doped solid super acidic catalyst.
(2) Preparation of tert-butylamine: the reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60mL of catalyst is filled and uniformly filled on the catalyst bed plates; the reaction temperature is 190 ℃, the reaction pressure is 4MPa, and the upper feeding total liquid hourly space velocity is 1.5h -1 The molar ratio of liquid ammonia to isobutene is 8: 1; the liquid hourly space velocity of the liquid ammonia to the catalyst in the lower feeding material is 1.2h -1 The reaction results are shown in Table 1.
Example 5
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 25% 2 Ethanol solution, 40 g of AlCl 3 Dissolved in ZrOCl 2 Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, wherein the washing temperature is 40 ℃, washing for 10 minutes each time until no chloride ion exists, then drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting for 8 hours at 500 ℃ to obtain white solid particles for later use. b: b, dipping the white particles obtained in the step a by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 16000 Pa; the ultrasonic vibration frequency was 58kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (c) repeating the impregnation process of the step (b) by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (c) repeating the process of the step (b) by using a palladium nitrate sulfuric acid solution with the concentration of 0.1mol/L to obtain the metal-doped solid super acidic catalyst.
(2) Preparation of tert-butylamine: the reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60mL of catalyst is filled and uniformly filled on the catalyst bed plates; the reaction temperature is 200 ℃, the reaction pressure is 5MPa, and the upper feeding total liquid hourly space velocity is 1.5h -1 The molar ratio of liquid ammonia to isobutene is 8: 1; the liquid hourly space velocity of the liquid ammonia to the catalyst in the lower feeding material is 1.2h -1 The reaction results are shown in Table 1.
Example 6
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 25% 2 Ethanol solution, 40 g of AlCl 3 Dissolved in ZrOCl 2 Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: b, impregnating the white silver obtained in the step a with silver nitrate sulfuric acid solution with the concentration of 2mol/LThe dipping temperature of the particles is 55 ℃, and the dipping time is 6 h; the vacuum degree is reduced to 17000 Pa; the ultrasonic vibration frequency was 57kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (c) repeating the impregnation process of the step (b) by using a nickel nitrate sulfuric acid solution with the concentration of 7mol/L to obtain particles II. d: and (c) repeating the process in the step (b) by using a palladium nitrate sulfuric acid solution with the concentration of 0.15mol/L to obtain the metal-doped solid super acidic catalyst.
(2) Preparation of tert-butylamine: the reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60mL of catalyst is filled and uniformly filled on the catalyst bed plates; the reaction temperature is 190 ℃, the reaction pressure is 5MPa, and the upper feeding total liquid hourly space velocity is 1.5h -1 The molar ratio of liquid ammonia to isobutene is 8: 1; the liquid hourly space velocity of the liquid ammonia to the catalyst in the lower feeding is 1.3h -1 The reaction results are shown in Table 1.
Example 7
The catalyst used in the reaction was a DNW II type resin catalyst, the other conditions were the same as in example 4, and the reaction results are shown in Table 1. DNW II type resin catalysts are available from Special resins, Inc. of Dandeng Mingzhu.
Example 8
During the reaction, only the feeding mode is adopted, other conditions are the same as example 4, and the reaction results are shown in table 1.
Example 9
In the reaction process, the fixed bed reactor has no bed plate in the middle, other conditions are the same as example 4, and the reaction results are shown in Table 1.
Example 10
The preparation process of the used catalyst has no ultrasonic vibration and pressurization operation process, the dipping sequence of the modification solution is that firstly, nickel nitrate sulfuric acid solution is used, then palladium nitrate sulfuric acid solution is used, finally, silver nitrate sulfuric acid solution is used for dipping treatment, the catalyst is modified by adopting a conventional dipping method, other conditions are the same as the example 4, and the reaction result is shown in the table 1.
Example 11
In the reaction process, a conventional fixed bed tubular reactor was used, the catalyst prepared in example 10 was used, the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
TABLE 1 reaction results (conversion in moles) of the examples
Claims (7)
1. A preparation method of tert-butylamine is characterized in that a tubular reactor is adopted, an upper feed inlet is formed in the top of the reactor, an atomizing nozzle is arranged on the upper feed inlet, liquid ammonia and isobutene serving as a feed I enter the reactor from the top of the reactor, liquid ammonia serving as a feed II enters the reactor from the bottom of the reactor, a plurality of catalyst bed layers which are arranged in a staggered mode are arranged in the reactor from top to bottom, each catalyst bed layer comprises a bed plate and a catalyst distributed on the bed plate, one end of each bed plate is hermetically connected with the wall of the reactor, the other end of each bed plate horizontally extends to the wall of the opposite reactor and keeps a certain distance with the wall of the opposite reactor, a vertical baffle is arranged at the tail end of each bed plate, and two bed plates which are vertically adjacent are connected to the walls of the reactors at different sides; a plurality of openings are formed in the bed plate, the feeding material I penetrates through the catalyst bed layer from top to bottom to react, and the feeding material II is in reverse contact with the feeding material I from bottom to top and further reacts with unreacted isobutene in the feeding material I;
the catalyst is a solid super acidic resin catalyst, and the preparation method comprises the following steps:
s1 preparation of ZrOCl 2 And AlCl 3 Dissolving in ethanol to obtain ZrOCl 2 And AlCl 3 Titrating with ammonia water under stirring until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, drying, and roasting to obtain white solid particles;
s2, dipping the white solid particles obtained in the step S1 in a silver nitrate sulfuric acid solution, drying and roasting to obtain particles I, dipping the particles I in one or two of a nickel nitrate sulfuric acid solution, a cobalt nitrate sulfuric acid solution, a molybdenum nitrate sulfuric acid solution and a tungsten nitrate sulfuric acid solution, drying and roasting to obtain particles II, dipping the particles II in one of a palladium nitrate sulfuric acid solution, a platinum nitrate sulfuric acid solution and a rhodium nitrate sulfuric acid solution, drying and roasting to obtain a metal-doped solid super acid catalyst;
wherein the preparation process of the nitrate sulfuric acid solution comprises the following steps: dissolving nitrate in dilute sulfuric acid to obtain a nitrate sulfuric acid solution; wherein the concentration of the dilute sulfuric acid is 0.3-0.6 mol/L, the concentration of the silver nitrate sulfuric acid solution is 2-4 mol/L, the concentration of the nickel nitrate sulfuric acid solution is 5-15 mol/L, the concentration of the cobalt nitrate sulfuric acid solution is 5-10 mol/L, the concentration of the molybdenum nitrate sulfuric acid solution is 10-15 mol/L, the concentration of the palladium nitrate sulfuric acid solution is 0.05-0.2 mol/L, the concentration of the platinum nitrate sulfuric acid solution is 0.1-0.2 mol/L, and the concentration of the rhodium nitrate sulfuric acid solution is 0.1-0.3 mol/L;
the impregnation is carried out under the conditions of decompression and ultrasonic vibration, and the decompression condition is 15000-20000 Pa; the ultrasonic condition is that the vibration frequency is 50-60 kHz; the dipping temperature is 55-60 ℃, and the dipping time in each step is 4-6 h.
2. The method of claim 1, wherein the reaction conditions in the reactor are as follows: the reaction temperature is 180-220 ℃; the reaction pressure is 2-6 MPa.
3. The process of claim 1, wherein the molar ratio of liquid ammonia to isobutylene in feed I is 1: 1-10: 1.
4. the process according to claim 3, wherein the molar ratio of liquid ammonia to isobutene in feed I is 4: 1-8: 1.
5. the preparation method according to claim 1, wherein the total volume space velocity of the feed I is 0.5-5 h -1 。
6. The preparation method according to claim 1, wherein the volume space velocity of the feed II is 0.5-2 h -1 。
7. The method of claim 1, wherein ZrOCl is formed in step S1 2 And AlCl 3 The mass concentration of the ethanol solution is 10-30% and 20-30% respectively.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19526502A1 (en) * | 1995-07-20 | 1997-01-23 | Basf Ag | Process for the preparation of amines from olefins on zeolites of the type PSH-3, MCM-22, SSZ-35 or mixtures thereof |
| CN1289761A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for direct amination of olefine |
| CN101209423A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Preparation method of molecular sieve catalyst with superpower acidity |
| CN101229999A (en) * | 2008-02-04 | 2008-07-30 | 陕西科技大学 | Method for preparing oleic acid esters by using solid super acid as catalyst |
| CN108654594A (en) * | 2017-03-27 | 2018-10-16 | 万华化学集团股份有限公司 | A kind of solid acid catalyst and preparation method thereof and purposes |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19526502A1 (en) * | 1995-07-20 | 1997-01-23 | Basf Ag | Process for the preparation of amines from olefins on zeolites of the type PSH-3, MCM-22, SSZ-35 or mixtures thereof |
| CN1289761A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for direct amination of olefine |
| CN101209423A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Preparation method of molecular sieve catalyst with superpower acidity |
| CN101229999A (en) * | 2008-02-04 | 2008-07-30 | 陕西科技大学 | Method for preparing oleic acid esters by using solid super acid as catalyst |
| CN108654594A (en) * | 2017-03-27 | 2018-10-16 | 万华化学集团股份有限公司 | A kind of solid acid catalyst and preparation method thereof and purposes |
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