CN111100013A - Method for preparing tert-butylamine - Google Patents
Method for preparing tert-butylamine Download PDFInfo
- Publication number
- CN111100013A CN111100013A CN201811262166.5A CN201811262166A CN111100013A CN 111100013 A CN111100013 A CN 111100013A CN 201811262166 A CN201811262166 A CN 201811262166A CN 111100013 A CN111100013 A CN 111100013A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sulfuric acid
- reaction
- feeding
- acid solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 68
- 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 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 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 17
- 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 7
- 239000007787 solid Substances 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000005192 partition Methods 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 239000006004 Quartz sand Substances 0.000 claims description 14
- 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 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 229910006213 ZrOCl2 Inorganic materials 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
- 238000002360 preparation method Methods 0.000 claims description 9
- 230000006837 decompression Effects 0.000 claims description 5
- 238000005576 amination reaction Methods 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000003930 superacid Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 238000007598 dipping method Methods 0.000 description 21
- 238000005470 impregnation Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 8
- 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 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000047 product 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
- 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
- 238000005516 engineering process Methods 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
- 238000002604 ultrasonography Methods 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst 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
- CNWSQCLBDWYLAN-UHFFFAOYSA-N butylurea Chemical group CCCCNC(N)=O CNWSQCLBDWYLAN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 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
- 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
- 239000008187 granular material Substances 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
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead 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
- 229910052762 osmium Inorganic materials 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- 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
Landscapes
- 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 a lower feeding section is arranged below a catalyst filling layer; 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 environmental-friendly chemical product production technologies and production processes appear, and the subsequent product technology development and application of tert-butylamine are further developed. Such as the synthesis of folipine, the synthesis of desulfurization decarbonizer hindered amine and IV-tertiary butyl-2-benzothiazole amide (rubber accelerator NS) and IV-tertiary butyl-2-benzothiazole sulfonamide, and the like. The demand of tert-butylamine on the market is increasing continuously, and the market application prospect is good, so that the economic and efficient preparation method of tert-butylamine becomes the focus of wide attention of domestic and foreign researchers.
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 MTBE-HCN method for preparing tert-butylamine also needs concentrated sulfuric acid as a catalyst, HCN has high toxicity, and the generation of a byproduct methyl formate brings great difficulty for 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.
In recent years, MTBE has been favored by regulators as a high octane additive and 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 process for preparing tert-butylamine, the reaction temperature is 300 ℃, the reaction pressure is 20MPa, 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 the steps of adopting rare earth metal La or H ion exchange to artificially synthesize alumino-silicate, using Y zeolite as a catalyst, and reacting at 270-310 ℃, wherein 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 hole 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: 1-10: 1, preferably 4: 1-8: 1, the total liquid hourly space velocity is 0.5-5 h-1Preferably 1 to 3 hours-1。
In the method, the liquid hourly space velocity of the liquid ammonia in the feed material II on the catalyst is 0.1-2 h-1Preferably 0.2 to 1 hour-1The molar ratio of nitrogen to liquid ammonia is 100-150: 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.
According to 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 3-10 MPa, preferably 5-8 MPa.
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) ZrOCl2Dissolving in ethanol to obtain ZrOCl2Ethanol solution, then titrating with ammonia water until no white precipitate is generated, and filteringWashing until no chloride ion exists, drying to obtain white solid powder, extruding the white solid powder into strips, forming the 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)2The 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 particle size 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 carried out at the vacuum degree of 15000-20000 Pa; the ultrasonic wave has the 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 80-100 ℃, 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.
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 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, 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 SO4 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 ZrO2The 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 solid state ultrasounds of the invention are described in detail belowThe preparation process of the strong acid catalyst comprises the following steps: firstly, 50-100 g ZrOCl2Dissolving in ethanol to obtain ZrOCl with the mass concentration of 30-50%2And (2) titrating the ethanol solution with 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, drying the solution in a vacuum drying oven for 4-6 hours at the temperature of 80-90 ℃, extruding the solution into 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; and (3) 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 the solid particles are roasted for 8 hours at the temperature of 500 ℃ to obtain particles I. Thirdly, repeating the impregnation process of the second step by using a nickel nitrate sulfuric acid solution to obtain particles II. Fourthly, 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 ultrasonic vibrator used in the preparation of the solid super acidic catalyst is KQ-550B, the circulating water type multipurpose vacuum pump is SHB-B95T, and the product is purchased from Zhengzhou great wall Korsao 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; isobutene and liquid ammonia are squeezed into the reactor from a raw material inlet of the feeding section 1 as a feeding I by a lining micro-metering pump and a lining metal diaphragm pump respectively, liquid ammonia is squeezed into the reactor from a raw material inlet of the feeding section 2 as a feeding II by a lining metal diaphragm pump, nitrogen is simultaneously fed according to a certain flow, the feeding I is reacted on a catalyst bed layer 5 in the middle of the reactor, the reacted material is mixed with the feeding II from bottom to top, the reaction is further carried out, and the reaction product is discharged from a discharge port of the discharging section 3.
Example 1
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 30%2And (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 reduced to 15000 Pa; 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-1The 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-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 30%2Titrating with 20% ammonia water to remove white precipitate, washing with deionized water for 5 times, each for 10 minWashing at 40 deg.C until no chloride ion exists, drying in a vacuum drying oven at 90 deg.C for 6 hr, extruding to form strips, and calcining at 500 deg.C for 8 hr to obtain white solid particles. 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 15000 Pa; 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 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-1The 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-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 30%2And (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 17000 Pa; 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: the impregnation of the second step is repeated by using a nickel nitrate sulfuric acid solution with the concentration of 7mol/LThe process yielded granule 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-1The 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-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 40%2And (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 18000 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 (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 upper feeding total liquid hourly space velocity is 1.5h-1The 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-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 45%2Titrating the ethanol solution with 25% 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 16000 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 (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-1The 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-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 40%2And (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: immersing the white particles obtained in the first step in a silver nitrate sulfuric acid solution with the concentration of 2mol/L, and immersingThe temperature is 55 ℃, and the dipping time is 6 h; the vacuum degree is 18000 Pa; 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 ℃, the reaction pressure is 6MPa, and the hourly space velocity of the total upper feeding liquid is 1.5h-1The 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-1The 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 has no ultrasonic vibration and decompression process, only adopts the conventional supersaturated impregnation method to modify the catalyst, and the impregnation sequence is that the sulfuric acid solution of silver nitrate is put at the end, other conditions are the same as the example 4, and the reaction result is shown in the table 1.
TABLE 1 reaction results (conversion in moles) of examples and comparative examples
Claims (14)
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 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 hole of a discharge section.
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 wall of the reactor.
3. The process according to claim 1, characterized in that the molar ratio of liquid ammonia to isobutene in said feed I is 1: 1-10: 1.
4. the process according to claim 3, wherein the total liquid hourly space velocity of the feed I is 0.5 to 5h-1。
5. The method of claim 1, wherein the liquid hourly space velocity of the liquid ammonia in the feed II on the catalyst is 0.5-2 h-1。
6. The process of any one of claims 1 to 5, wherein the total liquid hourly space velocity of feed I is greater than the total liquid hourly space velocity of feed II.
7. The method according to claim 5, wherein the molar ratio of nitrogen to liquid ammonia in the feed II is 100-150: 1.
8. 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 the catalyst and the 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 amount of the catalyst bed.
9. The method according to claim 1, wherein the amination reaction is carried out under the following reaction conditions: the reaction temperature is 180-220 ℃, and the reaction pressure is 3-10 Mpa.
10. The process according to claim 1, wherein the catalyst used for the amination is a metal-doped solid superacid catalyst.
11. The method of claim 10, wherein the solid super acidic catalyst is prepared by the following steps:
(1) ZrOCl2Dissolving in ethanol to obtain ZrOCl2Titrating 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.
12. According to the rightThe method of claim 11, wherein ZrOCl in step (1)2The mass concentration of the ethanol solution is 30-50%.
13. The method as claimed in claim 11, 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.
14. The method of claim 11, wherein the impregnating process of step (2) is conducted under reduced pressure and ultrasonic conditions; the decompression is carried out at the vacuum degree of 15000-20000 Pa; the ultrasonic wave has the vibration frequency of 50-60 kHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811262166.5A CN111100013B (en) | 2018-10-27 | 2018-10-27 | Method for preparing tert-butylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811262166.5A CN111100013B (en) | 2018-10-27 | 2018-10-27 | Method for preparing tert-butylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111100013A true CN111100013A (en) | 2020-05-05 |
| CN111100013B CN111100013B (en) | 2023-03-07 |
Family
ID=70418495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811262166.5A Active CN111100013B (en) | 2018-10-27 | 2018-10-27 | Method for preparing tert-butylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111100013B (en) |
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 |
|---|
| 金杏妹等: "《异丁烯直接胺化制叔丁胺》", 《化学世界》 * |
| 马皓等: "《异丁烯直接胺化制备叔丁胺的研究》", 《石油化工》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111100013B (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7090158B2 (en) | Manufacturing method of AEI structural molecular sieve | |
| CN1243718C (en) | Process for the manufacture of diethylenetriamine and higher polyethylenepolyamines | |
| CN104232140A (en) | Method for synthesizing high-density aviation fuel by using cyclopentanone as raw material | |
| CN109894144B (en) | Synthesis method of 1, 3-butadiene and preparation method of catalyst thereof | |
| CN111100013B (en) | Method for preparing tert-butylamine | |
| CN112844452B (en) | Modified molecular sieve, preparation method thereof, catalyst for preparing methyl acetate by carbonylation of dimethyl ether and method | |
| CN111099968B (en) | Method for preparing p-tert-butylphenol | |
| CN113070054A (en) | Preparation method of non-supported catalyst, product and application | |
| CN111825555B (en) | Method for preparing tert-butylamine by using MTBE as raw material | |
| CN111100009B (en) | Method for preparing tert-butylamine by using MTBE as raw material | |
| CN111825556B (en) | Preparation method of tert-butylamine | |
| CN111099966B (en) | Method for preparing tert-butyl phenol | |
| CN116162035A (en) | Preparation method of isopropanolamine | |
| CN111825837A (en) | Preparation method of polyether amine | |
| CN111099971B (en) | Method for preparing p-tert-butylphenol by using MTBE as raw material | |
| CN111099967B (en) | Preparation method of tert-butyl phenol | |
| CN111790437B (en) | Strontium-tantalum-titanium trimetal oxide catalyst for preparing 2-pentanone by liquid phase method ethanol and preparation method and application thereof | |
| CN111099972B (en) | Method for preparing p-tert-butyl catechol from MTBE (methyl tert-butyl ether) | |
| CN1566049A (en) | Solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration | |
| CN116351431B (en) | CO-CO2Catalyst for synthesizing deuterated methanol by system and method for synthesizing deuterated methanol | |
| CN108067293B (en) | Catalyst for producing 2-methyl-2-propylamine by amination of methyl propylene and preparation method thereof | |
| CN114247449B (en) | Catalyst for synthesizing piperazine by hydroxyethyl ethylenediamine, and preparation method and application thereof | |
| CN112745224B (en) | Method for preparing tert-butylamine | |
| CN111099969A (en) | Method for preparing p-tert-butyl catechol | |
| CN110937982B (en) | Method for preparing p-tert-butylphenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231109 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |