CN112745227B - Method for preparing tert-butylamine from isobutene and ammonia - Google Patents
Method for preparing tert-butylamine from isobutene and ammonia Download PDFInfo
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- CN112745227B CN112745227B CN201911048999.6A CN201911048999A CN112745227B CN 112745227 B CN112745227 B CN 112745227B CN 201911048999 A CN201911048999 A CN 201911048999A CN 112745227 B CN112745227 B CN 112745227B
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 116
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 32
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000005576 amination reaction Methods 0.000 claims abstract description 44
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 230000002860 competitive effect Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 239000011964 heteropoly acid Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000002699 waste material Chemical group 0.000 description 2
- SDYMYAFSQACTQP-UHFFFAOYSA-N 1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)N)=NC2=C1 SDYMYAFSQACTQP-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005586 Nicosulfuron Substances 0.000 description 1
- 229940100389 Sulfonylurea Drugs 0.000 description 1
- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- ANZXOIAKUNOVQU-UHFFFAOYSA-N bambuterol Chemical compound CN(C)C(=O)OC1=CC(OC(=O)N(C)C)=CC(C(O)CNC(C)(C)C)=C1 ANZXOIAKUNOVQU-UHFFFAOYSA-N 0.000 description 1
- 229960003060 bambuterol Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- JQXXHWHPUNPDRT-WLSIYKJHSA-N rifampicin Chemical compound O([C@](C1=O)(C)O/C=C/[C@@H]([C@H]([C@@H](OC(C)=O)[C@H](C)[C@H](O)[C@H](C)[C@@H](O)[C@@H](C)\C=C\C=C(C)/C(=O)NC=2C(O)=C3C([O-])=C4C)C)OC)C4=C1C3=C(O)C=2\C=N\N1CC[NH+](C)CC1 JQXXHWHPUNPDRT-WLSIYKJHSA-N 0.000 description 1
- 229960001225 rifampicin Drugs 0.000 description 1
- 229960002052 salbutamol Drugs 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 1
- JLEHSYHLHLHPAL-UHFFFAOYSA-N tert-butylurea Chemical compound CC(C)(C)NC(N)=O JLEHSYHLHLHPAL-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
Abstract
A method for preparing tert-butylamine by isobutene and ammonia, regard water as the auxiliary agent, or regard water and mixed solution of tert-butanol as the auxiliary agent, inject isobutene, liquid ammonia and auxiliary agent into the reactor equipped with isobutene amination catalyst separately, wherein the addition amount of auxiliary agent is calculated as the proportion of the substance and isobutene is 0.01-0.40. Compared with direct amination reaction of isobutene, amination reaction adopting water or a mixture of water and tert-butyl alcohol as a reaction auxiliary agent in the invention has advantages in thermodynamics and kinetics, and energy barrier of direct amination reaction is reduced. Meanwhile, water and tert-butyl alcohol are used as polar solvents, so that competitive adsorption of acid sites of the catalyst can be realized in the reaction process, separation from the wall surface after tert-butylamine is generated is strengthened, carbon deposition is avoided to a certain extent, and the service life and stability of the catalyst are prolonged.
Description
Technical Field
The invention relates to the technical field of amination reaction, in particular to a method for preparing tert-butylamine from isobutene and ammonia.
Background
tert-Butylamine, british name terriar-butyl amine, molecular formula C 4 H 11 N, molecular weight 76, colorless, transparent, liquid with ammonia odor. The tert-butylamine molecule contains two special groups of tert-butyl and primary amino, which also becomes an important organic synthesis intermediate in chemical production and is widely applied to the synthesis of chemical products, particularly rubber accelerators.
In the rubber field, tert-butylamine is an important raw material for preparing high-quality rubber accelerators NS (N-tert-butyl-2-benzothiazole sulfonamide) and TBSI (N-tert-butyl-2-bis benzothiazole sulfonamide). Compared with auxiliary agents such as secondary amine accelerators NOBS and the like, the rubber accelerator NS does not generate nitrosamine toxic substances in the vulcanization process, and has the characteristics of safety, environmental protection and no pollution. The NS auxiliary agent has excellent performance, can be used in different rubber varieties such as natural rubber, styrene-butadiene rubber, isoprene rubber and the like, is called as a standard accelerator, and has increasing demand, so that the demand of tert-butylamine is continuously increased.
In other aspects, the tert-butylamine also has a plurality of applications, for example, in the field of medicine, the tert-butylamine can be used for preparing drugs such as rifampicin which is an antibiotic for treating tuberculosis, salbutamol and bambuterol which are quick-acting drugs for treating bronchitis and asthma, and the like; in the field of pesticides, the tert-butylamine can be used for preparing sulfonylurea herbicides nicosulfuron, pesticide diafenthiuron and other pesticide products; in addition, the tert-butylamine has application in a variety of fields such as dyes, coatings, bactericides and lubricating oil additives. With the development of the rubber industry and the increasing need of people for producing high-quality products in the safety and environmental protection industry, the study on the production process and application of tert-butylamine as an important intermediate in the fine chemical industry, particularly in the production of rubber additives, is increasingly emphasized by researchers.
The preparation method of tert-butylamine comprises dozens of methods, and currently, the following methods are mainly applied industrially: hydrolysis synthesis of tert-butyl urea, hydrocyanic acid method, chlorination amination of tert-butyl alcohol, catalytic amination of methyl tert-butyl ether and direct amination of isobutene. The direct isobutene amination process has the advantages that isobutene and ammonia gas are directly subjected to catalytic reaction to generate tert-butylamine, the direct isobutene amination process is most consistent with atom economy compared with other processes, the reaction route is short, the selectivity is high, byproducts are few, and the separation mode is simple. The solid acid catalyst is adopted for reaction, and no hydrocyanic acid, waste residue and other pollution wastes are generated in other reaction routes, so that the method has obvious competitive advantages under the current situation that environmental protection policies are stricter.
In the book of amino of olyfms by zeolites published by Deeba et al 1988, the reaction pressure is 5.2MPa, the reaction temperature is 220 ℃ to 300 ℃, the amino-to-olefin ratio is 4 andthe gas space velocity is 1000 hr -1 Under the condition of (3), the conversion rate of isobutene reaches more than 8 percent.
The research result of the direct amination reaction of isobutene catalyzed by HZSM-5 molecular sieve reported in volume 35 and 8 of 2006 suggests that ammonia is more easily adsorbed by the catalyst at high temperature than isobutene, ammonia is adsorbed on the surface of the catalyst and then reacts with isobutene in the gas phase to form tert-butyl positive ion, and tert-butyl positive ion reacts with ammonia to form tert-butylamine. The articles in the journal of Petroleum processing, volume 34 and 4 in 2018 and the journal of catalysis, volume 38 in 2017 indicate that the conversion rate of isobutene is in linear positive correlation with the amount of strong acid in a sample catalyst and is in smaller relation with weak acid in the catalyst.
Chestnut celebration and Zhang Ge utilized IBA-01, fe in their 2012 and 2014 major papers 2 N/fumedSiO 2 The ITQ-2, TS-1 and HZSM-5 molecular sieves carry out experimental analysis on the reaction, and the strong adsorption of excessive strong acid centers on tert-butylamine is found to easily cause the reduction of catalytic activity and even the surface carbon deposition, so that the efficiency of the catalyst is reduced.
Based on other studies by Lequitte et al, in the paper "amino of butteres over Protonic Zeolites" published in Journal of Catalysis in 1996, volume 163, 1996, experiments were conducted on the catalytic performance of a series of acidic Zeolites on the Amination of isobutene under a pressure range of 1 to 6 MPa. Analysis of the catalyst deactivation studies showed that the catalyst surface was not only covered with coke, but also a nitrogen-containing species was present, which indicated that isobutene could also undergo secondary reactions during the amination process to form dihydrocarbylamine. The dihydrocarbylamine is strongly basic and tends to cause catalyst deactivation. The dihydrocarbylamine formed by the secondary reaction of isobutylene is suggested to be the primary cause of catalyst deactivation. Experiments show that the yield of the tert-butylamine can reach 5% under the conditions of pressure of 4MPa, ammonia-olefin ratio of 1 and high-aperture beta molecular sieve catalysis at 320 ℃. Experiments also show that the adoption of the large-aperture catalyst is an important way for strengthening tert-butylamine desorption to maintain efficient and stable operation of the catalyst.
Basf uses the direct amination of isobutylene for commercial production and patents such as EP0786449a and EP0778259a mention the direct reaction of olefins with ammonia over a zeolite catalyst at high temperature (above 200 ℃) and high pressure (30 MPa) to produce tert-butylamine.
The above literature indicates that the direct amination of isobutene is an acid-catalyzed reaction. However, ammonia and isobutylene are both electron rich species and direct reaction between the two is very difficult. Meanwhile, the direct amination reaction of isobutene is an exothermic reaction, and the thermodynamic conditions and the reaction kinetics of the reaction are inconsistent, so that the reaction is difficult to carry out. The increased acid content of the catalyst has obvious promotion effect on improving the conversion rate of isobutene, however, the increased acid content easily causes carbon deposition, and the generated tert-butylamine is not easy to separate from the surface of the catalyst, so that the catalyst is inactivated. At present, the reaction is carried out under the conditions of high temperature and high pressure, but under the conditions of high temperature and high pressure, the direct amination reaction of isobutene has the problems that the diffusion and removal of reaction products are difficult, the reaction heat is not easy to take away, the reaction efficiency is easy to reduce, byproducts are increased, the catalyst is inactivated and the like.
Patent CN101321723A suggests that higher reaction temperature is detrimental to the reaction since the isobutylene amination reaction is an exothermic process. The indirect heat exchange is carried out between the reaction mixture containing high concentration after the reaction in the isobutene amination reactor and the reaction mixture in the front end area of the reactor, so that the reaction heat preheats the raw materials in the reaction process, the internal temperature equalization of the reactor in the reaction process is realized, the reaction temperature of partial positions is reduced, and the effects of reducing the reaction inlet temperature and improving the conversion rate are achieved.
Guo Yufeng 2010 in the 2010 thesis of research on the preparation of tertiary butanol by catalytic hydration of heteropoly acid in isobutylene, the method for preparing tertiary butanol by hydration of isobutylene by using heteropoly acid is provided, heteropoly acid is used as a catalyst, isobutylene and water are used as reaction raw materials, the preparation of tertiary butanol by hydration of isobutylene is realized, and the conversion rate of isobutylene is more than or equal to 99.5%.
In patent CN108610260a, it is considered that it is difficult to directly react isobutylene with ammonia, tert-butyl alcohol is used as a main reaction raw material, and the reaction principle that tert-butyl alcohol and ammonia are easy to perform in reaction kinetics is utilized, so that high tert-butyl amine selectivity and yield are realized, and catalyst and raw material costs are reduced.
Disclosure of Invention
In order to solve the problems that the reaction energy barrier for preparing tert-butylamine from isobutene and ammonia is difficult to perform and carbon deposition is caused by increase of acid amount of an acidic catalyst in the prior art, the invention provides a method for preparing tert-butylamine from isobutene and ammonia.
The technical purpose of the invention is realized by adopting the following technical scheme:
a method for preparing tert-butylamine from isobutene and ammonia, water is used as an auxiliary agent, or a mixed solution of water and tert-butanol is used as an auxiliary agent, isobutene, liquid ammonia and the auxiliary agent are respectively fed into a reactor filled with an isobutene amination reaction catalyst, wherein the addition amount of the auxiliary agent is, by mass, that the ratio of the auxiliary agent to isobutene is 0.01-0.40.
Further, the molar ratio of the auxiliary agent to the isobutylene is 0.02 to 0.30, more preferably 0.05 to 1 to 0.15.
Further, when the auxiliary agent is a mixed solution of water and tert-butyl alcohol, the tert-butyl alcohol and water are mixed in any proportion, and as a preferred technical scheme, the molar ratio of water to tert-butyl alcohol is 1.
Further, the reaction temperature is 150-350 ℃, preferably 150-300 ℃, and most preferably 180-250 ℃; the pressure is 2.0MPa to 6.0MPa, preferably 2.0MPa to 5MPa, and most preferably 2.5MPa to 4MPa; the molar ratio of ammonia to isobutylene is 1 to 20, preferably 2:1 to 15, most preferably 3:1 to 10; liquid hourly space velocity of isobutene feeding of 0.1h -1 ～5.0h -1 Preferably 0.5h -1 ～2.5.0h -1 Most preferably 0.5h -1 ～1.5h -1 。
Further, the isobutene amination catalyst is a catalyst which is disclosed in the prior art and can be used for isobutene amination, such as a molecular sieve acidic catalyst, and preferably a heteropoly acid catalyst prepared by adopting the method disclosed in patent CN 1101265C.
In the technical scheme of the invention, the following reaction equilibrium exists in the isobutene amination process:
C 4 H 8 +H 2 O
C 4 H 9 OH
C 4 H 9 OH+NH 3 
C 4 H 9 NH 2 +H 2 O
in the reaction process, a mixture of water and tert-butyl alcohol is added as a reaction auxiliary agent, and the hydration catalysis of an acidic catalyst and the direct amination catalysis of isobutene are utilized to mutually cooperate to promote the generation of tert-butylamine.
Further, the amination reaction is carried out in a continuous fixed bed reactor.
Further, as a more specific embodiment, isobutene, liquid ammonia and an auxiliary agent are fed into a fixed bed reactor filled with an amination catalyst according to a preset proportion, reactants are subjected to amination reaction under the action of the catalyst, a product is discharged from the bottom of the reactor, is subjected to reduced pressure cooling and then is separated, and unreacted olefin and ammonia are discharged from the top.
Compared with the prior art, the invention has the following advantages:
(1) Compared with direct amination reaction of isobutene, amination reaction adopting water or a mixture of water and tert-butyl alcohol as a reaction auxiliary agent in the invention has advantages in thermodynamics and kinetics, and energy barrier of direct amination reaction is reduced. Meanwhile, water and tert-butyl alcohol are used as polar solvents, so that competitive adsorption of acid sites of the catalyst can be realized in the reaction process, separation from the wall surface after tert-butylamine is generated is strengthened, carbon deposition is avoided to a certain extent, and the service life and stability of the catalyst are prolonged.
(2) According to the invention, the dilution effect of the auxiliary agent is added into the system, the gas flow linear velocity in the reactor is increased, the addition of the auxiliary agent is also beneficial to improving the fluid linear velocity under the same reaction molar quantity, the rapid removal of reaction heat is accelerated, the adsorption, reaction and desorption of isobutene on the surface of the catalyst are enhanced, the generation possibility of dialkyl amine is reduced, the catalytic reaction efficiency is improved, and the service life of the catalyst is effectively prolonged.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
An amination catalyst A is prepared, and the technical scheme of the invention is utilized to carry out amination reaction:
mixing 32g of ZSM-5 zeolite with 26gSB powder, adding 56g of 15% diluted phosphoric acid, kneading on a bar extruder, extruding and molding to obtain a catalyst bar with the diameter of 1.5mm, drying at 120 ℃ for 12 hours, roasting in a muffle furnace at 550 ℃ for 6 hours, soaking in 40g of 5% silicotungstic acid aqueous solution, drying at 100 ℃ for 10 hours, and roasting at 600 ℃ for 4 hours to obtain the catalyst A, wherein the physical properties of the catalyst A are 1% of heteropolyacid content and gamma-Al 2 O 3 The content is 34 percent, and the content of ZSM-5 zeolite is 65 percent.
The direct amination reaction of isobutene adopts a fixed bed reactor, the size of the fixed bed reactor is phi 20mm multiplied by 1000mm, and the fixed bed reactor is made of a stainless steel single tube. The reactor is filled in three sections, a certain amount of quartz sand is filled at the bottom, 30mL of catalyst A is filled at the middle section, and the quartz sand is filled at the top until the catalyst A is filled. Replacing air in a fixed bed reactor with a mixed gas of nitrogen and ammonia gas for 24 hours before reaction, preheating isobutene, liquid ammonia and auxiliary water, feeding the preheated reaction materials into the fixed bed reactor for amination reaction, wherein the proportion and reaction conditions of the reaction materials are shown in table 1, feeding the reaction products into a product tank for separation after pressure reduction and cooling, discharging unreacted olefin and ammonia from the top, weighing the liquid phase materials at the bottom, and analyzing and calculating the isobutene conversion rate and the tert-butylamine selectivity by using a gas chromatography. The reaction results are shown in Table 2, and the results of the continuous operation lifetime operation are shown in Table 3.
Examples 2 to 5
The catalyst A prepared in example 1 is adopted, the added reaction auxiliary agent is changed into a mixed solution of water and tert-butyl alcohol, the proportion and the reaction conditions are shown in Table 1, and the reaction results are shown in Table 2; in which a 1500h continuous run was carried out using the reaction conditions of example 3, the results are shown in table 3.
Example 6:
an amination catalyst B is prepared, and the technical scheme of the invention is utilized to carry out amination reaction:
mixing 30g of beta zeolite and 20gSB powder, adding 30g of 14% nitric acid aqueous solution, kneading on a strip extruding machine, extruding and molding to obtain a catalyst strip with the diameter of 1.5mm, drying at 120 ℃ for 12 hours, roasting in a muffle furnace at 550 ℃ for 6 hours, soaking in 5% phosphotungstic acid aqueous solution, drying at 120 ℃ for 10 hours, and roasting at 550 ℃ for 8 hours to obtain the catalyst B before modification, wherein the physical properties of the catalyst B are that the content of heteropoly acid is 3%, and the content of gamma-Al is 3% 2 O 3 The content is 35 percent, and the content of beta zeolite is 62 percent. The evaluation was carried out in accordance with the method of example 1, and the reaction results are also shown in Table 1.
Examples 7 to 10:
the catalyst B of example 6 was used, and a mixture of water and t-butanol was used as the reaction auxiliary, and the proportions and reaction conditions thereof are shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 1
The catalyst A in example 1 is adopted, no auxiliary agent is added, isobutene and liquid ammonia are used as raw materials for reaction, the specific reaction conditions are the same as those of example 3, and the reaction results and the results of 1500-hour continuous operation are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3
Claims (12)
1. A method for preparing tert-butylamine by isobutene and ammonia is characterized in that water is used as an auxiliary agent, or a mixed solution of water and tert-butyl alcohol is used as an auxiliary agent, isobutene, liquid ammonia and the auxiliary agent are respectively introduced into a reactor filled with an isobutene amination reaction catalyst, wherein the addition amount of the auxiliary agent is 0.01-0.40;
the method comprises the steps of introducing isobutene, liquid ammonia and an auxiliary agent into a fixed bed reactor filled with an amination catalyst according to a preset proportion, carrying out amination reaction on reactants under the action of the catalyst, discharging products from the bottom of the reactor, carrying out reduced pressure cooling, then separating, and discharging unreacted olefin and ammonia from the top;
the amination catalyst is an amination catalyst A or an amination catalyst B;
the preparation method of the amination catalyst A comprises the following steps: mixing 32g of ZSM-5 zeolite with 26gSB powder, adding 56g of 15% diluted phosphoric acid, kneading on a bar extruder, extruding and molding to obtain a catalyst bar with the diameter of 1.5mm, drying at 120 ℃ for 12 hours, roasting in a muffle furnace at 550 ℃ for 6 hours, impregnating with 40g of 5% silicotungstic acid aqueous solution, drying at 100 ℃ for 10 hours, and roasting at 600 ℃ for 4 hours to obtain the catalyst bar;
the preparation method of the amination catalyst B comprises the following steps: mixing 30g of beta zeolite and 20gSB powder, adding 30g of 14% nitric acid aqueous solution, kneading on a strip extruding machine, extruding and molding to obtain a catalyst strip with the diameter of 1.5mm, drying at 120 ℃ for 12 hours, roasting in a muffle furnace at 550 ℃ for 6 hours, dipping in 5% phosphotungstic acid aqueous solution, drying at 120 ℃ for 10 hours, and roasting at 550 ℃ for 8 hours to obtain the catalyst.
2. The process according to claim 1, wherein the molar ratio of the auxiliary agent to the isobutene is from 0.02 to 0.30.
3. The process according to claim 2, wherein the molar ratio of auxiliary agent to isobutene is from 0.05.
4. The method of claim 1, wherein when the auxiliary agent is a mixture of water and t-butanol, the t-butanol is mixed with water in any ratio.
5. The method according to claim 4, wherein when the auxiliary agent is a mixed solution of water and tert-butanol, the molar ratio of water to tert-butanol is 1.
6. The method according to claim 1, wherein when the auxiliary agent is a mixed solution of water and tert-butyl alcohol, the molar ratio of water to tert-butyl alcohol is 1.
7. The process according to claim 1, wherein the molar ratio of ammonia to isobutene is controlled in the reaction feed to be 1 to 20, and the liquid hourly space velocity of isobutene feed is 0.1h -1 ～5.0h -1 。
8. The process of claim 7 wherein the reaction feed is controlled to provide a molar ratio of ammonia to isobutylene of 2:1 to 15.
9. The process of claim 8 wherein the reaction feed is controlled to provide a molar ratio of ammonia to isobutylene of 3:1 to 10.
10. The method of claim 1, wherein the reaction temperature is 150 ℃ to 350 ℃ and the pressure is 2.0MPa to 6.0MPa.
11. The process of claim 10, wherein the reaction temperature is from 150 ℃ to 300 ℃, the pressure is from 2.0mpa to 5mpa, and the molar ratio of ammonia to isobutylene is 2:1 to 15.
12. The process of claim 11, wherein the reaction temperature is from 180 ℃ to 250 ℃, the pressure is from 2.5mpa to 4mpa, and the molar ratio of ammonia to isobutylene is 3:1-10.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4937383A (en) * | 1987-10-02 | 1990-06-26 | Atochem | Process for manufacturing amines from olefins |
| JPH0820562A (en) * | 1994-07-07 | 1996-01-23 | Mitsui Toatsu Chem Inc | Production of tertiary butyl amine |
| CN1289641A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Solid acid catalyst containing heteropoly acid and its preparing process |
| CN104418754A (en) * | 2013-08-26 | 2015-03-18 | 王荣发 | Method for producing tert-butylamine by direct catalytic amination of isobutene |
| CN108610260A (en) * | 2018-06-08 | 2018-10-02 | 浙江建业化工股份有限公司 | A kind of technique preparing tert-butylamine in raw material dynamic equilibrium |
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2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4937383A (en) * | 1987-10-02 | 1990-06-26 | Atochem | Process for manufacturing amines from olefins |
| JPH0820562A (en) * | 1994-07-07 | 1996-01-23 | Mitsui Toatsu Chem Inc | Production of tertiary butyl amine |
| CN1289641A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Solid acid catalyst containing heteropoly acid and its preparing process |
| CN104418754A (en) * | 2013-08-26 | 2015-03-18 | 王荣发 | Method for producing tert-butylamine by direct catalytic amination of isobutene |
| CN108610260A (en) * | 2018-06-08 | 2018-10-02 | 浙江建业化工股份有限公司 | A kind of technique preparing tert-butylamine in raw material dynamic equilibrium |
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