CN115850132A - Preparation method of tert-dodecyl mercaptan - Google Patents
Preparation method of tert-dodecyl mercaptan Download PDFInfo
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- CN115850132A CN115850132A CN202211562913.3A CN202211562913A CN115850132A CN 115850132 A CN115850132 A CN 115850132A CN 202211562913 A CN202211562913 A CN 202211562913A CN 115850132 A CN115850132 A CN 115850132A
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- molecular sieve
- fluorosilane
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- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims description 64
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 8
- -1 polyoxyethylene lauryl ether Polymers 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- DXODQEHVNYHGGW-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DXODQEHVNYHGGW-UHFFFAOYSA-N 0.000 claims description 5
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims description 5
- VBGGLSWSRVDWHB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBGGLSWSRVDWHB-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 5
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 31
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 1
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Abstract
The invention relates to a preparation method of tert-dodecyl mercaptan, which comprises the steps of taking triisobutene and hydrogen sulfide as raw materials, adding organic amine as an auxiliary agent, and using a modified molecular sieve to perform catalytic reaction to prepare tert-dodecyl mercaptan. The method has the advantages of high product selectivity, low reaction energy consumption, long catalyst service life and obvious economic advantages.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of tert-dodecyl mercaptan.
Background
Tertiary dodecyl mercaptan is used as a chain transfer agent for regulating the molecular weight in the polymerization process, is a typical polymer molecular weight regulator, and is mainly applied to the production process of products such as ABS, styrene butadiene rubber, nitrile butadiene rubber, polystyrene and the like at the downstream.
The tert-dodecyl mercaptan can be prepared by reacting triisobutene with hydrogen sulfide, the resin A-15 is adopted as a catalyst in US4891445, the tert-dodecyl mercaptan is prepared at the reaction temperature of below 20 ℃, the product selectivity is rapidly reduced once the reaction temperature is increased, but the low-temperature reaction and the refrigeration energy consumption are high, and the cost is greatly increased if the tert-dodecyl mercaptan is used for industrial production. KR20060113045A adopts a Y molecular sieve as a catalyst, and also adopts a reaction temperature lower than 20 ℃, so that tert-butyl mercaptan and tert-octyl mercaptan generated by cracking Triisobutene (TIB) are avoided, and the selectivity of the product is improved. Meanwhile, when the method is used for synthesizing the tert-dodecyl mercaptan, the catalyst is very easy to deactivate, and the main reasons are trace moisture in the raw material triisobutene and carbon deposition of a product.
Therefore, there is still a need for improvement of the catalytic system to improve the catalytic activity and stability of the catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of tert-dodecyl mercaptan, which is beneficial to improving the reaction temperature, reducing the reaction energy consumption and realizing long-period stable operation by improving a catalyst and adding an auxiliary agent.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the preparation method of tert-dodecyl mercaptan comprises the steps of taking triisobutene and hydrogen sulfide as raw materials, adding organic amine as an auxiliary agent, and using a modified molecular sieve as a catalyst to catalyze the reaction of triisobutene and hydrogen sulfide to prepare tert-dodecyl mercaptan.
In a specific embodiment, the modified molecular sieve is a molecular sieve modified with a fluorosilane solution.
In a specific embodiment, the molecular sieve is selected from any one of Y-type molecular sieve, beta-type molecular sieve, MCM-type molecular sieve; preferably, the Y-type molecular sieve is selected from at least any one of HY molecular sieve, USY molecular sieve, mesoporous Y molecular sieve and rare earth Y molecular sieve; the MCM type molecular sieve is selected from any one or two of HMCM molecular sieve and Al-MCM molecular sieve.
In a specific embodiment, the method of modifying the modified molecular sieve is as follows: and (3) soaking the molecular sieve in a fluorosilane solution for a period of time, and drying the molecular sieve after the soaking is finished to obtain the modified molecular sieve.
In a specific embodiment, the impregnation time is 0.5-4h, the volume ratio of the molecular sieve to the fluorosilane solution is 1-1; preferably, the drying temperature is 40-200 ℃ and the drying time is 4-48h.
In a specific embodiment, the fluorosilane of the fluorosilane solution has the following structure:
wherein x and y are each an integer of 0 to 12; r is selected from any one of methyl and ethyl; preferably, the fluorosilane is selected from at least any one of perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane.
In a specific embodiment, the fluorosilane solution is prepared as follows: water, fluorosilane and polyoxyethylene lauryl ether are mixed according to the mass ratio of 1: (0.01-0.1): (0.01-0.05) to prepare a solution, and adding glacial acetic acid dropwise to the solution to adjust the pH value to 2-5 to obtain the fluorosilane solution.
In a specific embodiment, the organic amine auxiliary agent is selected from C1-C20 aliphatic amine or aromatic amine; preferably a monoamine or polyamine; preferably, the organic amine is selected from methylamine or ethylenediamine; more preferably, the organic amine is added in an amount of 0.1-5%, preferably 0.5-2% by mass of triisobutene.
In a particular embodiment, the catalytic reaction is carried out in a stirred tank or in a fixed bed, preferably a fixed bed.
In a specific embodiment, a mixture of triisobutene, an organic amine and hydrogen sulfide is fed into a fixed bed reactor filled with a catalyst in an upper feeding mode, and the space velocity of the triisobutene is 0.1-2h -1 Preferably 0.2 to 0.8h -1 The molar ratio of hydrogen sulfide to olefin is 1 to 1, preferably 2; the reaction temperature is 50-150 deg.C, preferably 60-100 deg.C, and the reaction pressure is 1-10MPa, preferably 1.2-3MPa.
Compared with the prior art, the invention has the following advantages:
(1) Compared with the prior art that the reaction is carried out at a low temperature of about 10 ℃, the preparation method can be carried out at a higher reaction temperature, so that the refrigeration energy consumption of the reaction system is reduced.
(2) The preparation method of the invention has the advantages of improved catalyst stability and service life, and stable long-period operation.
The specific implementation mode is as follows:
the following examples further illustrate the method provided by the present invention for better understanding of the technical solutions of the present invention, but the present invention is not limited to the listed examples and also includes any other known modifications within the scope of the claims of the present invention.
The preparation method of tert-dodecyl mercaptan is characterized by adopting triisobutene and hydrogen sulfide as raw materials, adding organic amine as an auxiliary agent, using a modified molecular sieve as a catalyst, and carrying out catalytic reaction to prepare the tert-dodecyl mercaptan.
The molecular sieve type of the modified molecular sieve comprises a Y-type molecular sieve, a beta-type molecular sieve, an MCM-type molecular sieve and the like, and specifically, the Y-type molecular sieve comprises an HY molecular sieve, an USY molecular sieve, a mesoporous Y molecular sieve or a rare earth Y molecular sieve (ReY), but is not limited thereto; the MCM molecular sieve comprises an HMCM molecular sieve or an Al-MCM molecular sieve.
The specific modification method of the modified molecular sieve comprises the following steps: immersing the molecular sieve in a fluorosilane solution for 0.5 to 4 hours (e.g., 1 hour, 2 hours, 2.5 hours, 3 hours, 3.5 hours, etc.), wherein the volume ratio of the molecular sieve to the fluorosilane solution is 1 to 1 (e.g., including but not limited to 1.
Wherein, the general formula of the fluorosilane is as follows:
wherein x and y are each selected from integers of 0 to 12, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12; r is selected from any one of methyl and ethyl. Specifically, the fluorosilane may be, for example, at least any one of perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyltrimethoxysilane, and perfluorooctyltriethoxysilane.
The method for preparing the fluorosilane solution by adopting the fluorosilane comprises the following steps: water, fluorosilane and polyoxyethylene lauryl ether are mixed according to the mass ratio of 1:0.1:0.05 to 1:0.01:0.01 to make a solution, e.g. 1:0.05:0.03 to prepare a solution, and dripping glacial acetic acid into the solution to adjust the pH value to 2-5 to obtain the fluorosilane solution.
In the modification step, fluorosilane can react with hydroxyl on the surface of the molecular sieve to load a long chain containing fluorocarbon on the surface of the molecular sieve, the surface of the molecular sieve has excellent hydrophobicity after being modified by fluorosilane, and trace moisture in the raw material TIB is difficult to adsorb on the surface of the molecular sieve, so that the catalyst is difficult to inactivate due to moisture accumulation. In addition, fluorosilane can react with a strong acid center on the surface of the molecular sieve, a strong acid site is covered, the side reaction of the TIB cracking is obviously reduced, the selectivity of tert-dodecyl mercaptan is improved, and the temperature of reactants can be greatly improved due to the improvement of the acidity, so that the reactants do not need to react at low temperature.
The organic amine auxiliary in the present invention is C1 to C20 aliphatic or aromatic amine, including mono-or polyamines, and is not particularly limited, and for example, at least any one of methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, tert-butylamine, cyclohexylamine, aniline, trimethylamine, triethylamine, ethylenediamine, p-phenylenediamine, m-phenylenediamine, and the like, preferably methylamine and ethylenediamine. Wherein, the adding amount of the organic amine is 0.1-5% of the mass of the triisobutene, such as but not limited to 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, and preferably 0.5-2%.
In the catalytic system, the organic amine is added to adjust the acidity of the surface of the molecular sieve, inhibit cracking side reaction caused by a strong acid center, further assist in improving the selectivity of the product, reduce carbon deposition and improve the stability of the catalyst.
The catalytic reaction of the present invention may employ a stirred tank or a fixed bed, preferably a fixed bed. Specifically, a mixture of triisobutene, organic amine and hydrogen sulfide is fed into a fixed bed reactor filled with a catalyst in an upper feeding mode, and the space velocity of the triisobutene is 0.1-2h -1 For example, 0.5h -1 、1h -1 、1.5h -1 Preferably 0.2-0.8h -1 The molar ratio of hydrogen sulfide to olefin is 1 to 10, including for example but not limited to 1.5: 1. 2: 1. 2.5: 1. 3: 1. 3.5: 1. 4: 1. 4.5: 1.5: 1. 5.5: 1. 6: 1. 6.5: 1. 7: 1. 7.5: 1. 8: 1. 8.5: 1. 9: 1. 9.5:1, preferably 2. The reaction temperature is 50 to 150 ℃ such as, but not limited to, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, preferably 60 to 100 ℃, and the pressure is 1 to 10MPa (gauge pressure), such as, but not limited to, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, preferably 1.2 to 3MPa.
The present invention is further illustrated by the following more specific examples, but is not to be construed as being limited thereto.
The main raw material sources for the following examples are as follows:
perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane all purchased from Fujiu Simplex chemical Co., ltd. Molecular sieve catalysts were purchased from southern catalyst factories. Other unexplained agents are commercially available.
The analytical instruments and methods used in the examples were as follows:
a gas chromatograph: agilent-7820;
gas chromatographic column: 0.25mm 30m DB-5 capillary column, detector FID, vaporizer temperature 280 deg.C, column box temperature 280 deg.C, FID detector temperature 300 deg.C, argon carrying capacity 2.1mL/min, hydrogen flow 30mL/min, air flow 400mL/min, and sample injection 1.0 μ L. The conversion of the alkene and the selectivity of the product were calculated using area normalization. Temperature rising procedure: preheating to 40 ℃ of column temperature, keeping for 5min, raising the speed of 15 ℃/min from 40 ℃ to 280 ℃, and keeping for 2min.
All conversion and selectivity statistics below are from the chromatographic results.
Example 1
(1) Preparing a catalyst: water, perfluorodecyl trimethoxy silane and polyoxyethylene lauryl ether are mixed according to the mass ratio of 1:0.1:0.05 is prepared into solution, and glacial acetic acid is dripped into the solution to adjust the pH value to 2, thus obtaining 500mL of fluorosilane solution. Soaking 500mL of HY molecular sieve in fluorosilane solution at 20 deg.C for 0.5h, and drying the molecular sieve catalyst at 40 deg.C for 4h.
(2) 100mL of the modified molecular sieve catalyst prepared above is taken and filled in a fixed bed, and the feeding airspeed of triisobutene is 0.1h -1 The feeding amount of methylamine is 0.1 percent of the mass of triisobutene, the molar ratio of hydrogen sulfide to olefin is 1, the reaction temperature is 50 ℃, the pressure is 1Mpa, the TIB conversion rate is 78 percent, the TDM selectivity is more than 99 percent, the continuous operation is 3000 hours, the conversion rate is 72 percent, and the selectivity is more than 99 percent.
Example 2
(1) Preparing a catalyst: water, perfluorodecyl triethoxysilane and polyoxyethylene lauryl ether are mixed according to a mass ratio of 1:0.01:0.01 to prepare a solution, and dropwise adding glacial acetic acid to adjust the pH value to 5 to obtain 1000mL of fluorosilane solution. 100mL of USY molecular sieve is soaked in fluorosilane solution for 4h at the soaking temperature of 80 ℃, and after the soaking is finished, the molecular sieve catalyst is dried at the drying temperature of 200 ℃ for 48h.
(2) 100mL of the modified molecular sieve catalyst prepared above is taken and filled in a fixed bed, and the feeding airspeed of triisobutene is 2h -1 The feeding amount of methylamine is 5% of the mass of triisobutene, the molar ratio of hydrogen sulfide to olefin is 10.
Example 3
(1) Preparing a catalyst: water, perfluorooctyl triethoxysilane and polyoxyethylene lauryl ether are mixed according to the mass ratio of 1:0.05:0.03 is prepared into solution, and glacial acetic acid is dripped into the solution to adjust the pH value to 4, so that 500mL of fluorosilane solution is obtained. Soaking 100mL of ReY molecular sieve in fluorosilane solution for 2h at 60 ℃, drying the molecular sieve catalyst after soaking, wherein the drying temperature is 120 ℃, and the drying time is 24h.
(2) 100mL of the modified molecular sieve catalyst prepared above is taken and filled in a fixed bed, and the feeding airspeed of triisobutene is 0.2h -1 The feeding amount of the ethylenediamine is 0.5 percent of the mass of the triisobutene, the molar ratio of the hydrogen sulfide to the olefin is 2, the reaction temperature is 60 ℃, the pressure is 1.2Mpa, the TIB conversion rate is 85 percent, the TDM selectivity is more than 99 percent, the continuous operation is 3000 hours, the conversion rate is 83 percent, and the selectivity is more than 99 percent.
Example 4
(1) Preparing a catalyst: water, perfluorooctyl trimethoxy silane and polyoxyethylene lauryl ether are mixed according to the mass ratio of 1:0.07:0.04 to prepare a solution, and dripping glacial acetic acid into the solution to adjust the pH value to 3 to obtain 500mL of fluorosilane solution. And (2) soaking 200mL of the HMCM molecular sieve in a fluorosilane solution for 3h at 50 ℃, and drying the molecular sieve catalyst after the soaking is finished, wherein the drying temperature is 150 ℃, and the drying time is 24h.
(2) 100mL of the modified molecular sieve catalyst prepared above is taken and filled in a fixed bed, and the feeding airspeed of triisobutene is 0.8h -1 The feeding amount of trimethylamine is 2 percent of the mass of triisobutene, the molar ratio of hydrogen sulfide to olefin is 5The rate is 79%, and the selectivity is more than 99%.
Comparative example 1
The reaction of example 1 was repeated using a resin catalyst of US 4891445A-15, without addition of auxiliary, with a TIB conversion of 68% and a TDM selectivity of 78%, with continuous operation of 3000h, with a TIB conversion reduced to 21% and a TDM selectivity of 95%.
Comparative example 2
The Y molecular sieve catalyst in KR20060113045A is adopted, the reaction conditions in the example 3 are repeated, no auxiliary agent is added, the TIB conversion rate is 55%, the TDM selectivity is 74%, the continuous operation is carried out for 3000h, the TIB conversion rate is reduced to 17%, and the TDM selectivity is 97%.
Comparative example 3
The catalyst was prepared by the same method as in example 1, the only difference being that the fluorosilane modification was cancelled, but the HY molecular sieve was directly used, and the reaction conditions in example 1 were repeated, with a TIB conversion of 68% and a TDM selectivity of 85%, with a conversion of 41% and a selectivity of 82% after 3000h continuous operation.
Comparative example 4
The catalyst was prepared by the same method as in example 1, and the reaction conditions in example 1 were repeated, with the only difference that the addition of amine auxiliary methylamine was eliminated, the TIB conversion 72%, TDM selectivity 91%, continuous operation 3000h, conversion 65%, and selectivity 88%.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. The preparation method of tert-dodecyl mercaptan is characterized by comprising the step of preparing tert-dodecyl mercaptan by catalyzing the reaction of triisobutene and hydrogen sulfide by taking triisobutene and hydrogen sulfide as raw materials, adding organic amine as an auxiliary agent and using a modified molecular sieve as a catalyst.
2. The method of claim 1, wherein the modified molecular sieve is a molecular sieve modified with a fluorosilane solution.
3. The method according to claim 2, wherein the molecular sieve is selected from any one of a Y-type molecular sieve, a β -type molecular sieve, and an MCM-type molecular sieve; preferably, the Y-type molecular sieve is selected from at least any one of HY molecular sieve, USY molecular sieve, mesoporous Y molecular sieve and rare earth Y molecular sieve; the MCM type molecular sieve is selected from any one or two of HMCM molecular sieve and Al-MCM molecular sieve.
4. The method of claim 2, wherein the modified molecular sieve is modified by the following steps: and (3) soaking the molecular sieve in a fluorosilane solution for a period of time, and drying the molecular sieve after the soaking is finished to obtain the modified molecular sieve.
5. The preparation method according to claim 4, wherein the dipping time is 0.5-4h, the volume ratio of the molecular sieve to the fluorosilane solution is 1-1; preferably, the drying temperature is 40-200 ℃ and the drying time is 4-48h.
6. The production method according to any one of claims 2 to 5, wherein the fluorosilane of the fluorosilane solution has the following structure:
wherein x and y are each an integer of 0 to 12; r is selected from any one of methyl and ethyl; preferably, the fluorosilane is selected from at least any one of perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane.
7. The method according to any one of claims 2 to 6, wherein the fluorosilane solution is prepared as follows: water, fluorosilane and polyoxyethylene lauryl ether are mixed according to the mass ratio of 1: (0.01-0.1): (0.01-0.05) to prepare a solution, and dripping glacial acetic acid into the solution to adjust the pH value to 2-5 to obtain the fluorosilane solution.
8. The method according to any one of claims 1 to 7, wherein the organic amine assistant is selected from the group consisting of C1-C20 aliphatic or aromatic amines; preferably a monoamine or polyamine; preferably, the organic amine is selected from methylamine or ethylenediamine; more preferably, the organic amine is added in an amount of 0.1-5%, preferably 0.5-2% by mass of triisobutene.
9. The process according to any one of claims 1 to 8, wherein the catalytic reaction is carried out in a stirred tank or in a fixed bed, preferably a fixed bed.
10. The process according to any one of claims 1 to 9, wherein a mixture of triisobutene, an organic amine and hydrogen sulfide is fed into a fixed bed reactor filled with a catalyst in an upper feeding manner and at a space velocity of triisobutene of 0.1 to 2 hours -1 Preferably 0.2 to 0.8h -1 The molar ratio of hydrogen sulfide to olefin is 1 to 1, preferably 2; the reaction temperature is 50-150 deg.C, preferably 60-100 deg.C, and the reaction pressure is 1-10MPa, preferably 1.2-3MPa.
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| CN117603726A (en) * | 2024-01-17 | 2024-02-27 | 江阴盛源科技有限公司 | Coking inhibitor for ethylene unit cracking furnace and preparation method thereof |
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