CN111100013B - Method for preparing tert-butylamine - Google Patents
Method for preparing tert-butylamine Download PDFInfo
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- CN111100013B CN111100013B CN201811262166.5A CN201811262166A CN111100013B CN 111100013 B CN111100013 B CN 111100013B CN 201811262166 A CN201811262166 A CN 201811262166A CN 111100013 B CN111100013 B CN 111100013B
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- 238000000034 method Methods 0.000 title claims abstract description 61
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 95
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 50
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 43
- 239000007787 solid Substances 0.000 claims description 43
- 238000005192 partition Methods 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 21
- 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 20
- 238000005406 washing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 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 15
- 239000006004 Quartz sand Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- 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
- 238000002360 preparation method Methods 0.000 claims description 11
- 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
- 230000006837 decompression Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims 2
- 238000011068 loading method Methods 0.000 claims 1
- 229910001961 silver nitrate Inorganic materials 0.000 claims 1
- 238000007598 dipping method Methods 0.000 description 23
- 238000001291 vacuum drying Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009471 action Effects 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
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003930 superacid Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CNWSQCLBDWYLAN-UHFFFAOYSA-N butylurea Chemical group CCCCNC(N)=O CNWSQCLBDWYLAN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JLEHSYHLHLHPAL-UHFFFAOYSA-N tert-butylurea Chemical compound CC(C)(C)NC(N)=O JLEHSYHLHLHPAL-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 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
- 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
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J37/024—Multiple impregnation or coating
-
- 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
-
- 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
- B01J8/0278—Feeding reactive fluids
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- 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
- B01J8/0292—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 with stationary packing material in the bed, e.g. bricks, wire rings, baffles
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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
- Y02P20/50—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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A method for preparing tert-butylamine adopts a fixed bed tubular reactor, the middle part is a catalyst bed layer, the upper part is provided with a clapboard along the axial direction, the lower end of the clapboard extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts, the two sides of the clapboard are an upper feeding section and a discharging section, and the lower part of a catalyst filling layer is a lower feeding section; isobutene and liquid ammonia enter from a raw material inlet of an upper feeding section as feeding I, liquid ammonia and nitrogen enter from a raw material inlet of a lower feeding section as feeding II, the feeding I is subjected to ammoniation reaction on a catalyst bed layer, the reacted material is mixed with the feeding II from bottom to top for further reaction, and a product is discharged from a discharge hole of a discharging section. The reaction mode of the method ensures that the materials react more fully, improves the conversion rate of the ammoniation reaction, feeds at the upper end pass through the catalyst bed layer repeatedly, reacts more fully, and improves the conversion rate of the isobutene per pass.
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 is a colorless, flammable liquid that is miscible with water and ethanol. The product is mainly used as an organic synthesis intermediate of rubber additives, insecticides, bactericides, dyes, medicines and the like. In recent years, with the enhancement of global environmental protection consciousness and the improvement of environmental protection requirements of various countries, a plurality of green and environment-friendly chemical product production technologies and production processes appear, and the technical development and application of subsequent products of tert-butylamine are further developed. Such as the synthesis of folipine, the synthesis of hindered amine serving as a desulfurization and decarbonization agent, IV-tertiary butyl 2-benzothiazole amide (rubber accelerator NS) and IV-tertiary butyl 2-benzothiazole sulfonamide and the like. The market demand of the tert-butylamine is continuously increased, and the market application prospect is good, so that the economic and efficient preparation method of the tert-butylamine gradually becomes a focus of wide attention of domestic and foreign scientific research personnel.
The synthesis method of tert-butylamine mainly includes the tert-butylurea method, the isobutylene-HCN method, the MTBE-HCN method, the isobutylene ammoniation method and the like. The tertiary butyl urea method process needs to use a large amount of strong acid and strong base as a catalyst, and has the problems of serious corrosion of equipment and environmental pollution. The preparation of tert-butylamine by the MTBE-HCN method also needs concentrated sulfuric acid as a catalyst, HCN has high toxicity, and the generation of a byproduct methyl formate causes great difficulty in subsequent separation. The tert-butylamine is synthesized by an isobutene ammoniation method, isobutene and liquid ammonia are used as raw materials, the tert-butylamine is synthesized under the action of a catalyst, the process flow is simple, no toxicity exists, the problems of equipment corrosion and environmental pollution do not exist, and the method for preparing the tert-butylamine is relatively efficient, green and environment-friendly.
MTBE is recently gaining favor as a high octane additive and an antiknock agent for gasoline. However, with the development of substitutes such as alkylate and ethanol gasoline, the market demand of MTBE is greatly influenced. In addition, there are studies that indicate that MTBE has potential threats to the environment and human health. After the environmental protection agency of the united states lists MTBE as a carcinogen, several countries in north america and europe have developed a series of policies that prohibit or limit the use of MTBE in gasoline. China will gradually limit the application of MTBE in gasoline, so that the MTBE capacity is excessive, the raw material isobutene is also necessary to be excessive, and other utilization ways are urgently needed to be found.
Patent US5648546 discloses a method for preparing tert-butylamine, the reaction temperature is 300 ℃, the reaction pressure is 20MPa, and the yield of tert-butylamine can reach 11.95%. The method adopts one or more than two of Ru, os, pb or Pt of noble metal to modify Y-type zeolite. The catalyst is modified in the reaction, so that the reaction conditions are improved, but the catalyst uses a large amount of noble metal, so that the production cost is high, and the industrial production is not facilitated. Patent US43072561 discloses a method for preparing tert-butylamine by direct ammonification of isobutylene, which comprises adopting rare earth metal La or H ion exchanged artificially synthesized alumino-silicate, taking Y zeolite as catalyst, reacting at 270-310 ℃, the conversion rate is 6.19%, and the selectivity can reach 100%. The method has the problems of harsh reaction conditions and low single-pass conversion rate of isobutene.
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, a fixed bed tubular reactor with a partition plate in the middle is adopted as the reactor, an ammoniation reaction is carried out under the action of a metal-doped solid super acidic catalyst, and the feeding mode adopts a mode of feeding materials from top to bottom simultaneously. The method can effectively improve the conversion per pass of the isobutene, and has the advantages of simple process, high efficiency, mild conditions, stable catalyst activity and long-period operation.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a method for preparing tert-butylamine adopts a fixed bed tubular reactor, wherein a catalyst bed layer is arranged in the middle of the fixed bed tubular reactor, a partition plate is arranged on the upper part of the fixed bed tubular reactor along the axial direction, the lower end of the partition plate extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts by the partition plate and the catalyst bed layer, an upper feeding section and a discharging section are arranged above two sides of the partition plate, and a lower feeding section is arranged below the catalyst bed layer; isobutene and liquid ammonia enter the reactor from a raw material inlet of an upper feeding section as feeding I, liquid ammonia and nitrogen enter the reactor from a raw material inlet of a lower feeding section as feeding II, the feeding I is subjected to ammoniation reaction on a catalyst bed layer in the middle of the reactor, the reacted material is mixed with the feeding II from bottom to top for further reaction, and a reaction product is discharged from a discharge port of a discharge section.
In the method, the length of the partition plate is 1/2-2/3 of the length of the reactor, and the top of the partition plate and two side edges of the partition plate are hermetically connected with the wall of the reactor.
In the method, the molar ratio of liquid ammonia to isobutene in the feed I is 1:1 to 10:1, preferably 4:1 to 8:1, the total liquid hourly space velocity is 0.5 to 5h -1 Preferably 1 to 3 hours -1 。
In the method, the liquid hourly space velocity of the liquid ammonia in the feed II to the catalyst is 0.1-2 h -1 Preferably 0.2 to 1 hour -1 The molar ratio of nitrogen to liquid ammonia is 100 to 150:1.
in the process of the present invention, the total liquid hourly space velocity of feed I is greater than the total liquid hourly space velocity of feed II.
In the method, quartz sand is filled at two ends of a reactor, and a mixture of the catalyst and the quartz sand is filled in a catalyst bed section, wherein the granularity range of the quartz sand is 1.5-2.0 mm, and the catalyst accounts for 50-70 v% of the total filling amount.
In the method of the present invention, the reaction conditions of the amination reaction are as follows: the reaction temperature is 180-220 ℃, and preferably 190-200 ℃; the reaction pressure is 3 to 10MPa, preferably 5 to 8MPa.
In the process of the present invention, the catalyst used for the amination is preferably a metal-doped solid superacid catalyst. The catalyst is prepared by the following method:
(1) Reacting ZrOCl 2 Dissolving in ethanol to obtain ZrOCl 2 Titrating with ammonia water 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;
(2) And (2) respectively soaking the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, drying and roasting after each step of soaking, and finally obtaining the metal-doped solid super acidic catalyst.
In the preparation method of the catalyst, the ZrOCl in the step (1) 2 The mass concentration of the ethanol solution is 30-50%.
The drying temperature in the step (1) is 70-90 ℃, the drying time is 4-6 hours, the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
The white solid particles obtained in the step (1) are cylindrical particles with the diameter of 1.0-1.5 mm.
The preparation process of the nitrate sulfuric acid solution in the step (2) is as follows: 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 5-10 mol/L, and the concentration of the palladium nitrate sulfuric acid solution is 0.1-0.3 mol/L.
The impregnation process of the step (2) is carried out under the conditions of decompression and ultrasound; the decompression is vacuum degree of 15000-20000 Pa; the ultrasonic wave has a vibration frequency of 50-60 kHz. The dipping temperature is 55-60 ℃, and the dipping time is 4-6 h.
The drying conditions in the step (2) are as follows: the drying temperature is 80 to 100 ℃, and the drying time is 6 to 8 hours; the roasting conditions are as follows: the baking temperature is 450-550 ℃, and the baking time is 4-6 hours.
Compared with the prior art, the invention has the following advantages:
(1) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the materials are fed in an upper and lower simultaneous feeding mode, the reaction materials fed in the upper mode enter the reactor and pass through a catalyst bed layer under a certain airspeed condition, part of the reactants firstly react to a certain degree and move downwards, the reaction materials fed in the lower mode enter the reactor under a certain airspeed condition, are mixed with the materials moving downwards and then pass through the catalyst bed layer and move upwards, the reaction is further carried out after the materials are mixed, and the conversion rate of the ammoniation reaction is improved.
(2) The upper feeding and the lower feeding have an airspeed difference (the upper feeding airspeed is larger than the lower feeding airspeed), so that the feeding at the upper end of the reactor passes through the catalyst bed layer in a reciprocating manner, the reaction is more sufficient, and the one-way conversion rate of the isobutene is improved.
(3) The catalyst filling section is filled by mixing with quartz sand, the lower feeding material is mixed by liquid ammonia and nitrogen, and the catalyst is continuously boiled in a gap formed by the quartz sand under the driving action of the nitrogen with certain air flow and air speed, so that the contact probability and mass transfer efficiency of reaction materials and catalyst active centers are increased, and the reaction efficiency and the conversion rate are improved.
(4) The reactor is additionally provided with the axial partition plate, so that the moving path of the feeding material at the inlet I is limited, the process that the feeding material at the inlet I is partially reacted firstly and then is further reacted with the feeding material at the inlet II is realized, the reaction is more sufficient, and the once-through conversion rate of isobutene is higher.
(5) In the preparation process of the solid super acidic catalyst, different metal solutions are adopted to be respectively impregnated according to a certain sequence, the impregnation is carried out under the conditions of reduced pressure, ultrasonic vibration and a certain impregnation temperature, and the impregnation 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. 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.
Drawings
FIG. 1 is a schematic diagram of the process for preparing tert-butylamine according to the present invention.
Wherein: 1-an upper feeding section; 2-a lower feeding section; 3-discharging section; 4-a separator; 5-catalyst bed layer.
Detailed Description
The preparation process of the solid super acidic catalyst of the present invention is specifically described as follows: 1. 50 to 100g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with the mass concentration of 30-50 percent 2 The ethanol solution is titrated by 20 to 25 percent ammonia water until no white precipitate exists, the ethanol solution is washed by deionized water for several times, each time for 5 to 10 minutes, the washing temperature is 40 to 50 ℃, the ethanol solution is washed until no chloride ion exists, then the ethanol solution is placed in a vacuum drying oven to be dried for 4 to 6 hours under the condition of 80 to 90 ℃, and after extrusion molding, the ethanol solution is roasted for 8 hours under the condition of 500 ℃ to obtain white solid particles for later use. 2. Dipping the white particles obtained in the first step by using 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; reducingThe vacuum degree is 15000-20000 Pa; the ultrasonic vibration frequency is 50-60 kHz, then the solid particles are placed in a vacuum drying oven to be dried for 4-6 hours at the temperature of 80-90 ℃, and then are roasted for 8 hours at the temperature of 500 ℃ to obtain the particles I. 3. And (5) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution to obtain particles II. 4. And (4) repeating the process of the second step by using a palladium nitrate sulfuric acid solution to obtain the metal-doped solid super acidic catalyst.
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 solid superacid catalyst is KQ-550B, the model of a circulating water type multi-purpose vacuum pump is SHB-B95T, and the ultrasonic vibrator is purchased from Zheng Changcheng Kongmao Co.
The preparation of tert-butylamine in the invention is carried out according to the process flow diagram shown in figure 1: the method comprises the steps of carrying out reaction on a fixed bed continuous reactor with a partition plate, wherein a catalyst bed layer 5 is arranged in the middle of the fixed bed continuous reactor, a partition plate 4 is arranged on the upper portion of the fixed bed continuous reactor along the axial direction, the length of the partition plate is 1/2 of the length of the reactor, the lower end of the partition plate 4 extends into the catalyst bed layer 5 and does not completely penetrate through the catalyst bed layer 5, the reactor is divided into three parts by the partition plate 4 and the catalyst bed layer 5, an upper feeding section 1 and a discharging section 3 are arranged on two sides of the partition plate, and a lower feeding section 2 is arranged below the catalyst bed layer 5; isobutene and liquid ammonia are used as a feeding material I and are respectively pumped into the reactor from a raw material inlet of the feeding section 1 by a lining tile micro-metering pump and a lining tile metal diaphragm pump, liquid ammonia is used as a feeding material II and is pumped into the reactor from a raw material inlet of the feeding section 2 by the lining tile metal diaphragm pump, nitrogen is fed according to a certain flow rate, the feeding material I is reacted on a catalyst bed layer 5 in the middle of the reactor, the reacted material is mixed with the feeding material II from bottom to top and is further reacted, and a reaction product is discharged from a discharge hole of the discharging section 3.
Example 1
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 30% 2 Titrating with 20% ammonia water to obtain an ethanol solution without white precipitate, washing with deionized water for 5 times (10 min each time) at 40 deg.CWashing until no chloride ion exists, drying in a vacuum drying oven at 90 ℃ for 6 hours, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step 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 15000Pa; the ultrasonic vibration frequency was 55kHz, 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 (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (4) repeating the process of the second step 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) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 180 ℃, the reaction pressure is 5MPa, and the hourly space velocity of the total upper feeding 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 0.3 h -1 The molar ratio of nitrogen to liquid ammonia was 150, and 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 30% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 3mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 15000Pa; 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 (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 8mol/L to obtain particles II. d:and (4) repeating the process of the second step 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) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 190 ℃, the reaction pressure is 5MPa, and the upper feeding total liquid hourly space velocity is 2h -1 The molar ratio of liquid ammonia to isobutene is 5:1; the liquid hourly space velocity of the liquid ammonia to the catalyst in the lower feeding is 0.4 h -1 The molar ratio of nitrogen to liquid ammonia was 150, and 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 30% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 3mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 17000Pa; the ultrasonic vibration frequency was 55kHz, 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 (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 7mol/L to obtain particles II. d: and (4) repeating the process of the second step 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) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 200 ℃, the reaction pressure is 6MPa, and the upper feeding total liquid hourly space velocity is 2h -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 0.3 h -1 The molar ratio of nitrogen to liquid ammonia was 150, and 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 40% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 4mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is 18000Pa; 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 (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 8mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a palladium nitrate sulfuric acid solution with the concentration of 0.3mol/L to obtain the metal-doped solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 210 ℃, the reaction pressure is 8MPa, and the hourly space velocity of the total feed liquid 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 0.3 h -1 The molar ratio of nitrogen to liquid ammonia was 150, and 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 45% 2 Titrating the ethanol solution by using 25% ammonia water until no white precipitate exists, washing the solution by using deionized water for 5 times, washing the solution for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, then drying the solution in a vacuum drying oven for 6 hours at the temperature of 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. b: dipping the white particles obtained in the step one by using a silver nitrate sulfuric acid solution with the concentration of 3mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is6h; the vacuum degree is reduced to 16000Pa; 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 (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (4) repeating the process of the second step 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) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 210 ℃, the reaction pressure is 8MPa, 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 0.3 h -1 The molar ratio of nitrogen to liquid ammonia was 150, and 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 40% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step 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 18000Pa; the ultrasonic vibration frequency was 59kHz, 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 (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (4) repeating the process of the second step 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) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1:1; the reaction temperature is 180 DEG CReaction pressure of 6MPa and upper feeding total liquid hourly space velocity of 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 0.3 h -1 The molar ratio of nitrogen to liquid ammonia was 150, and the reaction results are shown in Table 1.
Example 7
In the reaction process, the catalyst used is the existing palladium carbon catalyst, the catalyst takes active carbon as a carrier, supported metal palladium as an active component, other conditions are the same as those of the example 4, and the reaction result is shown in the table 1.
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 partition plate in the middle, other conditions are the same as example 4, and the reaction results are shown in Table 1.
Example 10
During the reaction, only liquid ammonia was fed as the lower feed, and nitrogen gas was not fed, the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
Example 11
The preparation process of the used catalyst does not have ultrasonic vibration and decompression processes, the catalyst is modified only by adopting a conventional supersaturated impregnation method, the impregnation sequence is that a silver nitrate sulfuric acid solution is placed at the end, other conditions are the same as those of the example 4, and the reaction result is shown in a table 1.
TABLE 1 reaction results (conversion in moles) of examples and comparative examples
Claims (6)
1. A method for preparing tert-butylamine adopts a fixed bed tubular reactor, and is characterized in that a catalyst bed layer is arranged in the middle of the fixed bed tubular reactor, a partition plate is axially arranged on the upper part of the fixed bed tubular reactor, the lower end of the partition plate extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts by the partition plate and the catalyst bed layer, an upper feeding section and a discharging section are arranged above two sides of the partition plate, and a lower feeding section is arranged below the catalyst bed layer; isobutene and liquid ammonia are used as a feed I and enter a reactor from a raw material inlet of an upper feeding section, liquid ammonia and nitrogen are used as a feed II and enter the reactor from a raw material inlet of a lower feeding section, the feed I is subjected to an ammoniation reaction on a catalyst bed layer in the middle of the reactor, the reacted material is mixed with the feed II from bottom to top for further reaction, and a reaction product is discharged from a discharge hole of a discharging section;
the total liquid hourly space velocity of feed I is greater than the total liquid hourly space velocity of feed II;
the molar ratio of liquid ammonia to isobutene in the feed I is 1:1 to 10:1;
the total liquid hourly space velocity of the feeding material I is 0.5-5 h -1 ；
The liquid hourly space velocity of the liquid ammonia in the feed material II to the catalyst is 0.5-2 h -1 ；
The molar ratio of nitrogen to liquid ammonia in the feed II is 100-150: 1;
the reaction conditions for the amination reaction are as follows: the reaction temperature is 180-220 ℃, and the reaction pressure is 3-10 Mpa;
the catalyst used for ammoniation reaction is a metal-doped solid super acidic catalyst, and the preparation method of the solid super acidic catalyst comprises the following steps:
(1) ZrOCl 2 Dissolving in ethanol to obtain ZrOCl 2 Titrating with ammonia water until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, molding, drying, and roasting to obtain white solid particles;
(2) And (2) respectively soaking the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, drying and roasting after each step of soaking, and finally obtaining the metal-doped solid super acidic catalyst.
2. The method of claim 1, wherein the length of the partition is 1/2-2/3 of the length of the reactor, and the top of the partition and the two sides of the partition are hermetically connected with the reactor wall.
3. The method as claimed in claim 1, wherein the catalyst is loaded by filling quartz sand at both ends of the reactor, and the catalyst bed section is filled with a mixture of catalyst and quartz sand, wherein the particle size of the quartz sand is 1.5-2.0 mm, and the catalyst accounts for 50-70 v% of the total loading of the catalyst bed.
4. The method of claim 1, wherein said ZrOCl of step (1) 2 The mass concentration of the ethanol solution is 30-50%.
5. The method according to claim 1, wherein the silver nitrate sulfuric acid solution in the step (2) is prepared by: dissolving silver nitrate in dilute sulfuric acid to obtain a silver nitrate sulfuric acid solution; the preparation processes of the nickel nitrate sulfuric acid solution and the palladium nitrate sulfuric acid solution are the same as those of the silver 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 5-10 mol/L, and the concentration of the palladium nitrate sulfuric acid solution is 0.1-0.3 mol/L.
6. The method according to claim 1, wherein the impregnation process of step (2) is performed under reduced pressure and ultrasonic conditions; the decompression is vacuum degree of 15000-20000 Pa; the ultrasonic wave has the vibration frequency of 50-60 kHz.
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Citations (6)
| 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 |
| CN102260010A (en) * | 2011-05-16 | 2011-11-30 | 苏州苏净环保工程有限公司 | Integrated natural circulating and baffling reactor |
| 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 |
-
2018
- 2018-10-27 CN CN201811262166.5A patent/CN111100013B/en active Active
Patent Citations (6)
| 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 |
| CN102260010A (en) * | 2011-05-16 | 2011-11-30 | 苏州苏净环保工程有限公司 | Integrated natural circulating and baffling reactor |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 《异丁烯直接胺化制叔丁胺》;金杏妹等;《化学世界》;20221231(第10期);第514-515页 * |
| 《异丁烯直接胺化制备叔丁胺的研究》;马皓等;《石油化工》;20051231;第34卷(第8期);第766-69页 * |
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