CN119059945B - Method for improving tertiary dodecyl mercaptan conversion rate by using catalyst - Google Patents
Method for improving tertiary dodecyl mercaptan conversion rate by using catalyst Download PDFInfo
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- dodecyl mercaptan
- hydrogen sulfide
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 80
- CTRBSQNAGYJDQX-UHFFFAOYSA-N [C].C=CCCCCCCCCCC Chemical compound [C].C=CCCCCCCCCCC CTRBSQNAGYJDQX-UHFFFAOYSA-N 0.000 claims abstract description 72
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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 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
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- 239000002808 molecular sieve Substances 0.000 claims description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 32
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 25
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 22
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- 238000002360 preparation method Methods 0.000 claims description 15
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 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 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 230000001965 increasing effect Effects 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
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- 239000002253 acid Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- VNNLHYZDXIBHKZ-UHFFFAOYSA-N thiophene-2-sulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CS1 VNNLHYZDXIBHKZ-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
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- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000000630 rising effect Effects 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
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- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000005245 sintering Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/04—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by addition of hydrogen sulfide or its salts to unsaturated compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本申请公开了一种利用催化剂提高叔十二烷基硫醇转化率的方法，涉及催化技术领域，所述方法，包括如下步骤：S1：将球形固体酸催化剂装填入反应器内，将摩尔比为4~10:1硫化氢和碳十二烯烃混合均匀，得到含有微气泡的混合液，然后将混合液转入反应器内，反应器内部压力设为1~8MPa，反应温度设为50~220℃，使之发生反应，得到反应后的合成气液；S2：将合成气液通过分离装置，硫化氢通过循环装置，进入下一轮反应，形成硫化氢气相循环，叔十二烷基硫醇被收集到产品罐。本申请采用的方法，持续运行较长时间，碳十二烯烃依然保持较好的转化率，进而提高了叔十二烷基硫醇的收率。
The present application discloses a method for improving the conversion rate of tert-dodecyl mercaptan by using a catalyst, and relates to the field of catalytic technology. The method comprises the following steps: S1: loading a spherical solid acid catalyst into a reactor, uniformly mixing hydrogen sulfide and carbon dodecene in a molar ratio of 4 to 10:1, obtaining a mixed solution containing microbubbles, and then transferring the mixed solution into a reactor, wherein the internal pressure of the reactor is set to 1 to 8 MPa, and the reaction temperature is set to 50 to 220°C, so as to react and obtain a synthetic gas liquid after the reaction; S2: passing the synthetic gas liquid through a separation device, and hydrogen sulfide through a circulation device, and entering the next round of reaction, forming a hydrogen sulfide gas phase circulation, and tert-dodecyl mercaptan is collected in a product tank. The method adopted in the present application continues to operate for a long time, and carbon dodecene still maintains a good conversion rate, thereby improving the yield of tert-dodecyl mercaptan.
Description
Technical Field
The application relates to the technical field of catalysis, in particular to a method for improving the conversion rate of tert-dodecyl mercaptan by using a catalyst.
Background
The tertiary dodecyl mercaptan is used as a molecular weight regulator and a chain transfer agent in the high molecular polymerization process, especially in the production of styrene-butadiene rubber, ABS resin and the like, and plays a vital role in optimizing the product performance, improving the production efficiency and ensuring the product quality. In addition, tertiary dodecyl mercaptan plays an important role in the fields of environment-friendly pesticides, lubricating oil industry, high-performance nano composite materials and the like. With the increasing demand of environmental protection and high performance products in various fields, the increasing market demand of tertiary dodecyl mercaptan is a necessary trend year by year.
Currently, tertiary dodecyl mercaptan is industrially synthesized by the addition reaction of carbon dodecene and hydrogen sulfide in the presence of a solid acid catalyst. The reaction is a gas-liquid-solid three-phase reaction and is carried out in a fixed bed reactor, because hydrogen sulfide gas and liquid carbon dodecene are fed from top to bottom, the solid acid catalyst activation hydrogen sulfide process is easy to be interfered by a phase interface in the fixed bed reactor, the solubility of the hydrogen sulfide gas is reduced along with the rise of temperature, a large amount of hydrogen sulfide needs to be introduced, the utilization degree of the hydrogen sulfide is not high, and the tertiary dodecyl mercaptan conversion rate is low. This is disadvantageous both with regard to the consumption of raw materials and costs and with regard to safety and stability during the reaction.
The existing solid acid catalyst is easy to accumulate carbon under certain pressure (1-8 MPa) and temperature (50-220 ℃), side reactions can be increased along with the increase of the temperature, the selectivity and conversion rate of reactants are affected, and the yield of tertiary dodecyl mercaptan is further reduced. Therefore, how to safely and efficiently produce the mercaptan and improve the service life and the stability of the solid acid catalyst are all the key points of producing the mercaptan by adding the olefin.
The patent application publication No. CN117797857A discloses the application of a Ni-S-Y hierarchical pore molecular sieve catalyst in catalyzing triisobutene to synthesize tert-dodecyl mercaptan.
The Y-type molecular sieves employed in this patent application have poor thermal stability and anti-carbon deposition capability, and when operated continuously for a longer period of time, the conversion of triisobutene decreases rapidly, resulting in lower yields of tertiary dodecyl mercaptan.
Disclosure of Invention
In order to increase the conversion of tertiary dodecyl mercaptan, the application provides a method for increasing the conversion of tertiary dodecyl mercaptan by using a catalyst.
The application provides a method for improving the conversion rate of tert-dodecyl mercaptan by using a catalyst, which adopts the following technical scheme:
a method for increasing the conversion of tertiary dodecyl mercaptan by using a catalyst, comprising the steps of:
S1, filling a spherical solid acid catalyst into a reactor, uniformly mixing hydrogen sulfide and carbon dodecene with a molar ratio of 4-10:1 to obtain a mixed solution containing microbubbles, transferring the mixed solution into the reactor, setting the internal pressure of the reactor to be 1-8 MPa, and setting the reaction temperature to be 50-220 ℃ to enable the mixed solution to react to obtain a reacted synthesis gas liquid;
and S2, enabling the synthesis gas and the liquid to pass through a separation device, enabling hydrogen sulfide to pass through a circulation device, enabling the hydrogen sulfide to enter the next round of reaction, forming hydrogen sulfide phase circulation, and collecting tertiary dodecyl mercaptan into a product tank.
Preferably, the pump type air floatation machine is adopted to fully mix the hydrogen sulfide and the carbon dodecene to form a mixed solution containing micro bubbles.
Preferably, in step S1, the rotating speed of the pump type air floatation machine is 200-800r/min.
Preferably, the reactor is a fluidized bed reactor, and the mixed liquid is fed from the bottom of the fluidized bed reactor by adopting a high-pressure feed pump, wherein the flow rate of the mixed liquid is 0.1-0.5L/min.
Preferably, the separation device is a condenser and a gas-liquid separator, the synthesis gas and liquid are condensed by the condenser, hydrogen sulfide and tertiary dodecyl mercaptan are separated by the gas-liquid separator, the hydrogen sulfide is circulated back into the pump type air floatation machine through a pipeline to form hydrogen sulfide gas-phase circulation, and the tertiary dodecyl mercaptan is collected into a product tank.
Preferably, the condensing medium in the condenser is water, and the temperature is-10-20 ℃.
By adopting the technical scheme, the pump type air flotation machine is adopted to form the mixed solution of continuous microbubbles, and the high-pressure feed pump is adopted to feed the mixed solution from the bottom of the fluidized bed, so that the possibility of back mixing of gas-liquid-solid three-phase reaction of the fluidized bed is reduced, disturbance of a phase interface is weakened, and the production cost and the consumption of raw materials are reduced through hydrogen sulfide circulation.
The spherical solid acid catalyst has higher specific surface area and stability, hydrogen sulfide and carbon dodecene molecules pass through the form of micro bubbles, on one hand, due to the characteristic of uniformity of the spherical structure of the spherical solid acid catalyst, the micro bubbles have higher surface energy, so that the micro bubbles can be adsorbed and uniformly dispersed on the surface of the spherical solid acid catalyst, and on the other hand, when the micro bubbles are close to micropores on the surface of the catalyst, substances in the bubbles are pushed to diffuse into the micropores by higher pressure inside the micro bubbles, so that permeation is realized. When hydrogen sulfide and carbon dodecene carried by micro bubbles are dispersed on the surface of the spherical solid acid catalyst and permeate into the spherical solid acid catalyst, the distance between the hydrogen sulfide and carbon dodecene molecules and the active site of the catalyst is greatly shortened, and the hydrogen sulfide and carbon dodecene molecules can reach the acid site of the catalyst more quickly, so that the reaction rate is accelerated, and the close contact enables the reaction to be more sufficient, and the conversion rate and the selectivity of the reaction can be improved.
In addition, the generated tertiary dodecyl mercaptan can be diffused from the inside to the outside of the spherical solid acid catalyst along with the movement of the micro bubbles, and new hydrogen sulfide and carbon dodecene can be timely supplemented, so that the performance of the whole reaction system is improved.
Preferably, the preparation method of the spherical solid acid catalyst comprises the following steps:
S11, uniformly mixing sodium hydroxide, water, an aluminum source, a template agent and a silicon source to obtain initial sol;
s12, performing thermal crystallization reaction on the initial sol water, and roasting to obtain a molecular sieve precursor;
And S13, uniformly mixing the heteropoly acid, the molecular sieve precursor and the solvent to form slurry, standing at room temperature for 8-12 h, drying, cooling to obtain a compound, preparing a sphere, and roasting and cooling to obtain the spherical solid acid catalyst.
Preferably, the template is tetrapropylammonium hydroxide.
Preferably, in step S11, the silicon source is calculated as SiO 2, the aluminum source is calculated as Al 2O3, the sodium hydroxide is calculated as Na 2 O, the template agent is calculated as TPAOH, and the molar ratio of each substance is:
SiO2:Al2O3:TPAOH:Na2O=40~150:1:5~20:5~30。
Preferably, the silicon source is water glass, and the aluminum source is any one of aluminum isopropoxide, aluminum sulfate and sodium metaaluminate.
Preferably, the mass ratio of the heteropolyacid to the molecular sieve precursor is 1:5-50, and the mass ratio of the solvent volume to the molecular sieve precursor is 0.8-1.2 ml:1g.
Preferably, the mass ratio of the heteropolyacid to the molecular sieve precursor is 1:10.
Preferably, the heteropolyacid is at least one of phosphotungstic acid, vanadotungstic acid and phosphomolybdic acid.
By adopting the technical scheme, some functional groups on the surface of the molecular sieve can form chemical bonds with heteropoly acid molecules to form a strong adsorption effect, so that the heteropoly acid is not easy to fall off from a carrier or generate structural change in the reaction process, and the stability of the catalyst in long-time reaction is ensured.
The molecular sieve has a regular pore structure and a larger specific surface area, so that the heteropolyacid can be highly dispersed, agglomeration of heteropolyacid particles is prevented, the heteropolyacid is uniformly dispersed on the surface or in the pore of the molecular sieve, more active sites can be provided, and the overall acidity of the catalyst is enhanced, thereby being more beneficial to activating hydrogen sulfide and carbon dodecene molecules, enhancing the reactivity of the hydrogen sulfide and carbon dodecene molecules and further improving the initial rate of the reaction.
In addition, the molecular sieve has a specific pore size, and can limit the occurrence of side reactions, so that the reaction mainly proceeds towards the direction of generating tertiary dodecyl mercaptan, thereby improving the conversion rate of the tertiary dodecyl mercaptan.
Preferably, in step S11, after sodium hydroxide is dissolved in water, an aluminum source is added, and mixed for 0.5 to 1.5 hours, after the sodium hydroxide is completely dissolved, a template agent is added, a silicon source is slowly added dropwise, and the silicon source is stirred dropwise until gel is formed, and aged for 18 to 32 hours at room temperature, thus obtaining an initial sol.
By adopting the technical scheme, the aluminum source is completely dissolved firstly, which means that aluminum is uniformly dispersed in the solution in the form of ions, and then the template agent and the silicon source are added, and the uniformity is favorable for forming a molecular sieve precursor with relatively uniform particle size, because the template agent can more effectively construct a uniform pore channel structure, the obtained pore diameter structure is more regular and orderly, the structural performance is more stable, and in the catalytic reaction, the catalytic activity and the selectivity are better, and the adsorption capacity is larger.
Preferably, in step S11, after sodium hydroxide is dissolved in water, an aluminum source is added, and mixed for 0.5 to 1.5 hours, after the sodium hydroxide is completely dissolved, a template agent and a polystyrene microsphere suspension are added, and after the sodium hydroxide is uniformly mixed, a silicon source is slowly added dropwise, and the mixture is stirred while being dropwise added until gel is formed, and aged for 18 to 32 hours at room temperature, thus obtaining an initial sol.
Preferably, the particle size of the polystyrene microsphere is 0.5-1.5 mu m, and the polystyrene microsphere accounts for 2% -4% of the mass of the silicon source.
Preferably, in step S11, the preparation method of the template agent and polystyrene microsphere suspension comprises the following steps:
dispersing polystyrene microsphere in water to form polystyrene microsphere suspension, adding template agent, and mixing to obtain template agent and polystyrene microsphere suspension.
By adopting the technical scheme, after the template agent and the polystyrene microspheres are added, the molecular sieve precursor formed in the subsequent process has a composite structure of macropores and micropores, so that the specific surface area and the number of active sites of the molecular sieve precursor are increased. The macroporous structure can allow large carbon dodecene molecules to diffuse into the molecular sieve rapidly, and for hydrogen sulfide gas, the macropores also provide a convenient channel, so that the hydrogen sulfide molecules can reach the vicinity of an active site in the molecular sieve rapidly.
Although the partial microporous structure can not contain the complete entry of the carbon dodecene molecules, the microporous structure has strong adsorption capacity on hydrogen sulfide molecules, so that the hydrogen sulfide molecules locally form higher concentration, and the microporous structure can activate the adsorbed hydrogen sulfide, so that the adsorbed hydrogen sulfide can react with the carbon dodecene more easily. The macroporous and microporous structures have synergistic effect on the adsorption of different reactants, and promote the effective progress of the reaction, thereby improving the conversion rate of tertiary dodecyl mercaptan.
Preferably, in step S12, the initial sol is placed in a reaction kettle, and then the reaction kettle is placed in an oven to perform a hydrothermal crystallization reaction, wherein the temperature of the hydrothermal crystallization reaction is 150-200 ℃, the time of the hydrothermal crystallization reaction is 36-60 h, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 h.
Preferably, after the hydrothermal crystallization reaction is completed, the hydrothermal crystallization reaction liquid is subjected to cooling, solid-liquid separation, washing and drying in sequence to obtain a hydrothermal crystallization product.
Preferably, in step S13, the composite is put into a ball mill to prepare a sphere with a diameter of 5-15 μm, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 hours.
Preferably, in step S13, after baking, the method further comprises the step of adding monomer a:
Dispersing the monomer A in a solvent, adding the roasted product after roasting, uniformly mixing, standing at room temperature for 8-12 h, and drying to obtain the solid acid catalyst, wherein the mass ratio of the monomer A to the heteropoly acid is 0.1-0.3:1.
The monomer A is any one of 4-dimethylaminopyridine and 2-thiophenesulfonyl chloride.
The volume of the solvent and the roasting the mass ratio is 0.4-0.8 ml/1 g.
By adopting the technical scheme, the monomer A is further introduced into the spherical solid acid catalyst, so that hydrogen sulfide molecules and carbon dodecene molecules can be further activated, the electron cloud density distribution of carbon dodecene double bonds is changed, the attack of hydrogen sulfide is easier to accept, meanwhile, the dissociation balance of hydrogen sulfide in an acidic environment is regulated, the hydrogen sulfide exists in a more favorable reaction form, the reaction activity of the hydrogen sulfide and the carbon dodecene is enhanced, the reaction can be guided to be carried out towards the direction of generating tertiary dodecyl mercaptan, the activation energy of the reaction is reduced, the reaction is carried out under milder conditions, the reaction rate is improved, the occurrence of side reactions is reduced, and the selectivity and the yield of the tertiary dodecyl mercaptan are improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. The application adopts the pump type air floatation machine to form continuous micro-bubble mixed liquid, and feeds from the bottom of the fluidized bed, thereby reducing the possibility of back mixing of gas-liquid-solid three-phase reaction of the fluidized bed, further weakening disturbance of a phase interface, and reducing production cost and consumption of raw materials through hydrogen sulfide circulation.
2. The solid acid catalyst with spherical supported heteropoly acid is used to raise specific surface area and stability, and when the hydrogen sulfide and carbon dodecene carried by micro bubble are dispersed homogeneously on the surface of the spherical solid acid catalyst and permeated into the inside, the distance between the hydrogen sulfide and carbon dodecene molecule and the active site of the catalyst is shortened greatly, and the hydrogen sulfide and carbon dodecene molecule may reach the acid site of the catalyst fast to raise the reaction rate.
3. The spherical solid acid catalyst adopted by the application can also reduce the occurrence of side reaction and the generation of carbon deposit, has good thermal stability and long catalytic life, and ensures that the production process is safer, more efficient and continuous.
Drawings
FIG. 1 is a process flow diagram of the present application;
wherein, the device comprises a pump type air floatation machine 1, a feeding pump 2, a fluidized bed reactor 3, a condenser 4, a gas-liquid separation device 5, a product tank 6, a circulating device 7.
Fig. 2 is an SEM image of the spherical solid acid catalyst in example 1.
Detailed Description
The present application will be described in further detail with reference to examples.
In the following examples:
1. The raw material sources are as follows:
in the water glass solution, 8.5% of SiO 2：26.2%;Na2 O, 1.374gmL ‒1 of density and 65.3% of water content, and the water glass is purchased from Nanjing road service building materials industry Co., ltd;
Sodium hydroxide, analytically pure, with a mass fraction of active ingredient exceeding 99%, purchased from sigma aldrich (Shanghai) trade company, inc;
the mass fraction of the effective components of the carbon dodecene is 99 percent, and the carbon dodecene is purchased from Nanjing Xinhua Chemie Co., ltd;
hydrogen sulfide, the mass fraction of the active ingredient is 99.9%, and the active ingredient is purchased from Shandong Huixin chemical industry Co., ltd;
Phosphotungstic acid, the mass fraction of the active ingredient is 99%, purchased from the biological technology limited company of Wuhan Ji Xinyi nation;
vanadium tungstic acid, the mass fraction of the active ingredient is 99%, purchased from the biological technology limited company of Wuhan Ji Xinyi bang;
Phosphomolybdic acid, the mass fraction of the active ingredient is 99%, purchased from Hubei Xinyu macro biological medicine technology Co.
2. The analysis method comprises the following steps:
meteorological chromatography, column temperature 50 ℃ for 5min, temperature 10 ℃/min up to 280 ℃, and FID detector for detecting sample injection amount 0.5 μl.
Examples of the method for improving the conversion rate of tertiary dodecyl mercaptan by using the catalyst of the application are as follows:
Example 1
The present example provides a process for increasing the conversion of tertiary dodecyl mercaptan using a spherical solid acid catalyst comprising the steps of:
S1, filling 150g of spherical solid acid catalyst into a fluidized bed reactor, taking hydrogen sulfide and carbon dodecene with a molar ratio of 6:1 as raw materials, uniformly mixing the hydrogen sulfide and the carbon dodecene through a pump type air floatation machine to obtain mixed liquid containing microbubbles, wherein the rotating speed of the pump type air floatation machine is set to be 500r/min, then feeding the mixed liquid from the bottom of the fluidized bed reactor through a feeding pump at a flow rate of 0.2L/min, setting the internal pressure of the fluidized bed to be 3MPa, setting the reaction temperature to be 95 ℃, and reacting the mixed liquid to obtain the reacted synthetic gas liquid;
S2, condensing the synthesis gas liquid through a condenser (0 ℃ water condensation), separating the synthesis gas liquid through a gas-liquid separator, separating hydrogen sulfide and tertiary dodecyl mercaptan through a gas-liquid separation device, and recycling the hydrogen sulfide into a pump type air floatation machine through a pipeline to form hydrogen sulfide gas phase circulation, wherein the tertiary dodecyl mercaptan is collected into a product tank.
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 79.3 percent, the tertiary dodecyl mercaptan selectivity is more than 99 percent, the tertiary dodecyl mercaptan yield is 79.3 percent, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 4.6 percent.
The preparation method of the spherical solid acid catalyst comprises the following steps:
S11, dissolving 19.2g of sodium hydroxide in 200ml of deionized water, adding 6.84g of aluminum sulfate, stirring and mixing for 1h at room temperature, adding 40.68g of tetrapropylammonium hydroxide (TPAOH) as a template agent after the sodium hydroxide is fully dissolved, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution while dropwise forming gel, and aging for 24h at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material is SiO 2:Al2O3:TPAOH:Na2 O=100:1:10:12;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 180 ℃ for 48 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 550 ℃ for 5 hours to obtain a molecular sieve precursor;
s13, dissolving 10g of phosphotungstic acid in 100ml of water, adding 100g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 10 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 10 mu m by using a ball mill, placing the sphere into a muffle furnace for roasting for 5 hours at 550 ℃, and cooling to room temperature along with the furnace at the temperature of 2 ℃ per minute to obtain the spherical solid acid catalyst, wherein the spherical solid acid catalyst is shown in figure 1.
From fig. 1, it can be inferred that the molecular sieve had obvious agglomerates on the surface and that these were sized and shaped to match the expected morphology of phosphotungstic acid, and that the heteropolyacid had been loaded onto the molecular sieve precursor.
Example 2
This embodiment differs from embodiment 1 in that:
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 75.5%, the tertiary dodecyl mercaptan selectivity is more than 99%, the tertiary dodecyl mercaptan yield is 75.2%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 4%.
The preparation method of the spherical solid acid catalyst comprises the following steps:
S11, dissolving 19.2g of sodium hydroxide in 200ml of deionized water, adding 6.84g of aluminum sulfate, stirring and mixing for 1h at room temperature, adding 40.68g of tetrapropylammonium hydroxide (TPAOH) as a template agent after the sodium hydroxide is fully dissolved, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution while dropwise forming gel, and aging for 24h at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material is SiO 2:Al2O3:TPAOH:Na2 O=100:1:10:12;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 180 ℃ for 48 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 550 ℃ for 5 hours to obtain a molecular sieve precursor;
S13, dissolving 10g of phosphomolybdic acid in 100ml of water, adding 100g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 10 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 10 mu m by using a ball mill, placing the sphere into a muffle furnace for roasting for 5 hours at 550 ℃, and cooling to room temperature along with the furnace at the temperature of 2 ℃ at the heating rate of 2 ℃ per minute to obtain the spherical solid acid catalyst.
Otherwise, the same as in example 1 was conducted.
Example 3
This embodiment differs from embodiment 1 in that:
the gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 77.6%, the tertiary dodecyl mercaptan selectivity is more than 99%, the tertiary dodecyl mercaptan yield is 77.4%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 4.3%.
The preparation method of the spherical solid acid catalyst comprises the following steps:
S11, dissolving 19.2g of sodium hydroxide in 200ml of deionized water, adding 6.84g of aluminum sulfate, stirring and mixing for 1h at room temperature, adding 40.68g of tetrapropylammonium hydroxide (TPAOH) as a template agent after the sodium hydroxide is fully dissolved, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution while dropwise forming gel, and aging for 24h at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material is SiO 2:Al2O3:TPAOH:Na2 O=100:1:10:12;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 180 ℃ for 48 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 550 ℃ for 5 hours to obtain a molecular sieve precursor;
S13, dissolving 10g of vanadium tungsten acid in 100ml of water, adding 100g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 10 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 10 mu m by using a ball mill, placing the sphere into a muffle furnace for roasting for 5 hours at 550 ℃, and cooling to the room temperature along with the furnace at the temperature of 2 ℃ per minute to obtain the spherical solid acid catalyst.
Otherwise, the same as in example 1 was conducted.
Example 4
The present example provides a process for increasing the conversion of tertiary dodecyl mercaptan using a spherical solid acid catalyst comprising the steps of:
S1, filling 82g of spherical solid acid catalyst into a fluidized bed reactor, taking hydrogen sulfide and carbon dodecene with a molar ratio of 10:1 as raw materials, uniformly mixing the hydrogen sulfide and the carbon dodecene through a pump type air floatation machine to obtain mixed liquid containing microbubbles, wherein the rotating speed of the pump type air floatation machine is set to be 200r/min, then feeding the mixed liquid from the bottom of the fluidized bed reactor through a feeding pump at a flow rate of 0.1L/min, setting the internal pressure of the fluidized bed to be 10MPa, setting the reaction temperature to be 50 ℃, and reacting the mixed liquid to obtain the reacted synthetic gas liquid;
S2, condensing the synthesis gas and liquid through a condenser (-10 ℃) water condensation, separating the synthesis gas and the liquid through a gas-liquid separator, separating hydrogen sulfide and tertiary dodecyl mercaptan through a gas-liquid separation device, and recycling the hydrogen sulfide into a pump type air floatation machine through a pipeline to form hydrogen sulfide gas phase circulation, wherein the tertiary dodecyl mercaptan is collected into a product tank.
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 80.5%, the tertiary dodecyl mercaptan selectivity is more than 90%, the tertiary dodecyl mercaptan yield is 72.2%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 8%.
The preparation method of the spherical solid acid catalyst comprises the following steps:
S11, dissolving 20g of sodium hydroxide in 180ml of deionized water, adding 8.20g of sodium metaaluminate, stirring and mixing for 0.5h at room temperature, adding 50.84g of tetrapropylammonium hydroxide (TPAOH) as a template agent after the sodium metaaluminate is fully dissolved, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution dropwise until gel is formed, and aging for 24h at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material is SiO 2:Al2O3:TPAOH:Na2 O=40:1:5:5;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 200 ℃ for 36 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 500 ℃ for 6 hours to obtain a molecular sieve precursor;
S13, dissolving 10g of phosphotungstic acid in 60ml of water, adding 50g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 12 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 15 mu m by using a ball mill, placing the sphere into a muffle furnace for roasting for 6 hours at the temperature of 500 ℃, and cooling to the room temperature along with the furnace at the temperature of 2 ℃ per minute to obtain the spherical solid acid catalyst.
Example 5
The present example provides a process for increasing the conversion of tertiary dodecyl mercaptan using a spherical solid acid catalyst comprising the steps of:
The method comprises the steps of S1, filling 694g of spherical solid acid catalyst into a fluidized bed reactor, taking hydrogen sulfide and carbon dodecene with a molar ratio of 4:1 as raw materials, uniformly mixing the hydrogen sulfide and the carbon dodecene through a pump type air floatation machine to obtain mixed liquid containing microbubbles, wherein the rotating speed of the pump type air floatation machine is set to be 200r/min, then feeding the mixed liquid from the bottom of the fluidized bed reactor through a feeding pump at a flow rate of 0.1L/min, the internal pressure of the fluidized bed is set to be 1MPa, and the reaction temperature is set to be 220 ℃ to enable the mixed liquid to react, so as to obtain reacted synthetic gas liquid;
S2, condensing the synthesis gas liquid through a condenser (20 ℃ water condensation), separating the synthesis gas liquid through a gas-liquid separator, separating hydrogen sulfide and tertiary dodecyl mercaptan through a gas-liquid separation device, and recycling the hydrogen sulfide into a pump type air floatation machine through a pipeline to form hydrogen sulfide gas phase circulation, wherein the tertiary dodecyl mercaptan is collected into a product tank.
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 73.5%, the tertiary dodecyl mercaptan selectivity is more than 99%, the tertiary dodecyl mercaptan yield is 73.2%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 3.8%.
The preparation method of the spherical solid acid catalyst comprises the following steps:
S11, dissolving 32g of sodium hydroxide in 300ml of deionized water, adding 5.45g of aluminum isopropoxide, stirring and mixing for 1h at room temperature, adding 54.30g of tetrapropylammonium hydroxide (TPAOH) as a template agent after the aluminum isopropoxide is fully dissolved, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution while dropwise forming gel, and aging for 24h at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material is SiO 2:Al2O3:TPAOH:Na2 O=150:1:20:30;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 150 ℃ for 60 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 600 ℃ for 4 hours to obtain a molecular sieve precursor;
s13, dissolving 1g of phosphotungstic acid in 40ml of water, adding 50g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 8 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 5 mu m by using a ball mill, placing the sphere into a muffle furnace for roasting for 4 hours at 600 ℃, and cooling to the room temperature along with the furnace at the temperature of 2 ℃ per minute to obtain the spherical solid acid catalyst.
Example 6
This embodiment differs from embodiment 3 in that:
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 82.5 percent, the tertiary dodecyl mercaptan selectivity is more than 99 percent, the tertiary dodecyl mercaptan yield is 82.2 percent, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 5.5 percent.
The preparation method of the spherical solid acid catalyst comprises the following steps:
S11, dissolving 20g of sodium hydroxide in 200ml of deionized water, adding 6.84g of aluminum sulfate, stirring and mixing for 1h at room temperature, adding 40.68g of tetrapropylammonium hydroxide (TPAOH) as a template agent after the sodium hydroxide is fully dissolved, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution while dropwise until gel is formed, and aging for 24h at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material is SiO 2:Al2O3:TPAOH:Na2 O=100:1:10:12;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 180 ℃ for 48 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 550 ℃ for 5 hours to obtain a molecular sieve precursor;
And S13, dissolving 5g of phosphotungstic acid and 5g of vanadium tungstic acid in 100ml of water, adding 100g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 10 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 10 mu m by using a ball mill, placing the sphere into a muffle furnace, roasting for 5 hours at 550 ℃, heating to the temperature of 2 ℃ per minute, and cooling to the room temperature along with the furnace to obtain the spherical solid acid catalyst.
Otherwise, the same as in example 3 was conducted.
Example 7
This embodiment differs from embodiment 6 in that:
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 83.5%, the tertiary dodecyl mercaptan selectivity is more than 99%, the tertiary dodecyl mercaptan yield is 83.4%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 4.8%.
The preparation method of the spherical solid acid catalyst comprises the following steps:
S11, dissolving 19.2g of sodium hydroxide in 200ml of deionized water, adding 6.84g of aluminum sulfate, stirring and mixing for 1.5 hours at room temperature, adding a template agent and polystyrene microsphere suspension after the aluminum sulfate is fully dissolved, uniformly mixing, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution while dropwise until gel is formed, and aging for 24 hours at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material SiO 2:Al2O3:TPAOH:Na2 O=100:1:10:12;
The preparation method of the template agent and polystyrene microsphere suspension comprises the steps of uniformly mixing 3.18g of polystyrene microsphere with 100ml of water, and then adding 40.68g of tetrapropylammonium hydroxide to uniformly mix to obtain the template agent and polystyrene microsphere suspension, wherein the particle size distribution of the polystyrene microsphere is 0.5-1 mu m;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 180 ℃ for 48 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 550 ℃ for 5 hours to obtain a molecular sieve precursor;
S13, dissolving 5g of phosphotungstic acid and 5g of phosphomolybdic acid in 100ml of water, adding 100g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 10 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 10 mu m by using a ball mill, placing the sphere into a muffle furnace, roasting for 5 hours at 550 ℃, heating to the temperature of 2 ℃ per minute, and cooling to the room temperature along with the furnace to obtain the spherical solid acid catalyst.
Otherwise, the same as in example 6.
Example 8
This embodiment differs from embodiment 7 in that:
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 83.0%, the tertiary dodecyl mercaptan selectivity is more than 99%, the tertiary dodecyl mercaptan yield is 82.7%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 6.5%.
In the preparation method of the spherical solid acid catalyst, the amount of the polystyrene microsphere is 6.36g.
Otherwise, the same as in example 7.
Example 9
This embodiment differs from embodiment 8 in that:
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 85.5%, the tertiary dodecyl mercaptan selectivity is more than 99%, the tertiary dodecyl mercaptan yield is 85.2%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 5%.
S13, dissolving 5g of phosphotungstic acid and 5g of phosphomolybdic acid in 100ml of water, then adding 100g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 10 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 10 mu m by using a ball mill, placing the sphere into a muffle furnace for roasting for 5 hours at 550 ℃, and cooling to the room temperature along with the furnace at a temperature rising rate of 2 ℃ per minute to obtain a roasted sphere;
3g of 4-dimethylaminopyridine and 80ml of absolute ethyl alcohol are uniformly mixed, then the roasted spheres are added, after uniform mixing, the mixture is kept stand for 12 hours at room temperature, and after being dried for 4 hours in a 100 ℃ oven, the mixture is cooled to the room temperature, so that the spherical solid acid catalyst is obtained.
Otherwise, the same as in example 8.
Example 10
This embodiment differs from embodiment 9 in that:
the gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 85.5%, the tertiary dodecyl mercaptan selectivity is more than 99%, the tertiary dodecyl mercaptan yield is 85.2%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is only reduced by 6%.
S13, dissolving 5g of phosphotungstic acid and 5g of phosphomolybdic acid in 100ml of water, then adding 100g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 10 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, preparing a sphere with the diameter of 10 mu m by using a ball mill, placing the sphere into a muffle furnace for roasting for 5 hours at 550 ℃, and cooling to the room temperature along with the furnace at a temperature rising rate of 2 ℃ per minute to obtain a roasted sphere;
1g of 2-thiophenesulfonyl chloride and 40ml of absolute ethyl alcohol are uniformly mixed, then the roasted spheres are added, after uniform mixing, the mixture is kept stand for 8 hours at room temperature, and after being dried for 4 hours in a 100 ℃ oven, the mixture is cooled to the room temperature, so that the spherical solid acid catalyst is obtained.
Otherwise, the same as in example 9.
Comparative example 1
The difference between this comparative example and example 1 is that:
this comparative example provides a process for increasing the conversion of tertiary dodecyl mercaptan using a spherical solid acid catalyst comprising the steps of:
S1, filling 150g of spherical solid acid catalyst into a fluidized bed reactor, taking hydrogen sulfide and carbon dodecene with a molar ratio of 6:1 as raw materials, uniformly mixing the hydrogen sulfide and the carbon dodecene, feeding the mixed solution from the top to the bottom of the fluidized bed reactor at a flow rate of 0.2L/min through a feed pump, setting the internal pressure of the fluidized bed reactor to be 3MPa, setting the reaction temperature to be 95 ℃, and reacting the mixed solution to obtain a reacted synthetic gas liquid;
S2, condensing the synthesis gas liquid through a condenser (0 ℃ water condensation), separating the synthesis gas liquid through a gas-liquid separator, separating hydrogen sulfide from tertiary dodecyl mercaptan, recycling the hydrogen sulfide into a fixed reactor through a pipeline to form hydrogen sulfide gas-phase circulation, and collecting the tertiary dodecyl mercaptan into a product tank.
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 68.7%, the tertiary dodecyl mercaptan selectivity is 88%, the tertiary dodecyl mercaptan yield is 60.4%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is reduced by 10.8%.
Otherwise, the same as in example 1 was conducted.
Comparative example 2
The difference between this comparative example and example 1 is that:
this comparative example provides a process for increasing the conversion of tertiary dodecyl mercaptan using a spherical solid acid catalyst comprising the steps of:
S1, filling 150g of spherical solid acid catalyst into a fixed reactor, taking hydrogen sulfide and carbon dodecene with a molar ratio of 6:1 as raw materials, uniformly mixing the hydrogen sulfide and the carbon dodecene through a pump type air floatation machine to obtain mixed liquid containing microbubbles, wherein the rotating speed of the pump type air floatation machine is set to be 500r/min, then feeding the mixed liquid from the bottom of the fixed reactor through a feeding pump at a flow rate of 0.2L/min, setting the internal pressure of the fixed reactor to be 3MPa, setting the reaction temperature to be 90 ℃, and reacting the mixed liquid to obtain reacted synthetic gas liquid;
S2, condensing the synthesis gas liquid through a condenser (0 ℃ water condensation), separating the synthesis gas liquid through a gas-liquid separator, separating hydrogen sulfide and tertiary dodecyl mercaptan through a gas-liquid separation device, and recycling the hydrogen sulfide into a pump type air floatation machine through a pipeline to form hydrogen sulfide gas phase circulation, wherein the tertiary dodecyl mercaptan is collected into a product tank.
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 70.4 percent, the tertiary dodecyl mercaptan selectivity is more than 99 percent, the tertiary dodecyl mercaptan yield is 70.1 percent, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is reduced by 15.3 percent.
Otherwise, the same as in example 1 was conducted.
Comparative example 3
The difference between this comparative example and example 1 is that:
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 69.8%, the tertiary dodecyl mercaptan selectivity is 90%, the tertiary dodecyl mercaptan yield is 62.8%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is reduced by 15.7%.
The preparation method of the solid acid catalyst comprises the following steps:
S11, dissolving 19.2g of sodium hydroxide in 200ml of deionized water, adding 6.84g of aluminum sulfate, stirring and mixing for 1h at room temperature, adding 40.68g of tetrapropylammonium hydroxide (TPAOH) as a template agent after the sodium hydroxide is fully dissolved, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution while dropwise forming gel, and aging for 24h at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material is SiO 2:Al2O3:TPAOH:Na2 O=100:1:10:12;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 180 ℃ for 48 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 550 ℃ for 5 hours to obtain a molecular sieve precursor;
And S13, dissolving 10g of phosphotungstic acid in 100ml of water, adding 100g of molecular sieve precursor, stirring and mixing for 2 hours to form slurry, standing for 10 hours at room temperature, drying for 2 hours in a 120 ℃ oven, cooling to room temperature, placing in a muffle furnace for roasting for 5 hours at 550 ℃, heating to 2 ℃ per minute, cooling to room temperature along with the furnace, and slightly grinding and dispersing to obtain the solid acid catalyst.
Otherwise, the same as in example 1 was conducted.
Comparative example 4
The difference between this comparative example and example 1 is that:
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 56.5 percent, the tertiary dodecyl mercaptan selectivity is 70 percent, the tertiary dodecyl mercaptan yield is 39.5 percent, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is reduced by 44.7 percent.
The preparation method of the solid acid catalyst comprises the following steps:
S11, dissolving 19.2g of sodium hydroxide in 200ml of deionized water, adding 6.84g of aluminum sulfate, stirring and mixing for 1h at room temperature, adding 40.68g of tetrapropylammonium hydroxide (TPAOH) as a template agent after the sodium hydroxide is fully dissolved, slowly dropwise adding 458.25g of water glass solution, stirring the water glass solution while dropwise forming gel, and aging for 24h at room temperature to obtain a mixed material, wherein at the moment, the molar ratio of the mixed material is SiO 2:Al2O3:TPAOH:Na2 O=100:1:10:12;
S12, transferring the mixed material into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven for hydrothermal crystallization at 180 ℃ for 48 hours, cooling to room temperature after the reaction is finished, filtering, washing with deionized water until the pH value of the solution is 7, carrying out suction filtration and drying, and then placing in a muffle furnace for roasting at 550 ℃ for 5 hours to obtain a molecular sieve precursor;
And S13, putting the molecular sieve precursor into a ball mill to prepare a sphere with the diameter of 10 mu m, putting the sphere into a muffle furnace to be roasted for 5 hours at the temperature of 550 ℃, and cooling to room temperature along with the furnace at the temperature of 2 ℃ per minute to obtain the spherical solid acid catalyst.
Otherwise, the same as in example 1 was conducted.
Comparative example 5
The difference between this comparative example and example 1 is that:
The gas chromatography is adopted to detect that the initial carbon dodecene conversion rate is 71.6%, the tertiary dodecyl mercaptan selectivity is 95%, the tertiary dodecyl mercaptan yield is 68.0%, the catalyst is continuously operated for 3000 hours, and the carbon dodecene conversion rate is reduced by 53.2%.
The preparation method of the solid acid catalyst comprises the following steps:
And respectively placing 15g of phosphotungstic acid and 150g of molecular sieve precursors in a 120 ℃ oven for drying for 2 hours, cooling to room temperature, respectively preparing spheres with the diameter of 10 mu m by using a ball mill, respectively placing the spheres in a muffle furnace for roasting for 5 hours at the temperature of 550 ℃, heating to the temperature of 2 ℃ per minute, cooling to the room temperature along with the furnace, and uniformly mixing the two spheres to obtain the spherical solid acid catalyst.
Otherwise, the same as in example 1 was conducted.
As can be seen from the above examples and comparative examples, the present application improves the stability and specific surface area of the catalyst by using the spherical solid acid catalyst, and improves the probability of contact of hydrogen sulfide and carbon dodecene at the active site of the spherical solid acid catalyst by combining a pump type air floatation machine and a fluidized bed, reduces the interference of different relative reactions, improves the utilization rate of hydrogen sulfide and the conversion rate of carbon dodecene, improves the stability and service life of the spherical solid acid catalyst, reduces the cost of raw materials and the catalyst, has obvious economic benefit, and is suitable for mass production.
In addition, in the process of synthesizing the spherical solid acid catalyst, polystyrene microspheres, 2-thiophenesulfonyl chloride or 4-dimethylaminopyridine are further introduced, on one hand, the polystyrene microspheres are decomposed in the sintering process, so that pore structures are formed in the spherical solid acid catalyst, and the pore structures can be used as transmission channels of carbon dodecene, hydrogen sulfide and tert-dodecyl mercaptan, so that the diffusion of substances is promoted, and the reaction rate is improved. And the pore structure can also increase the adsorption capacity of the spherical solid acid catalyst, so that the spherical solid acid catalyst can better adsorb hydrogen sulfide and carbon dodecene, and the conversion rate of the reaction is improved.
On the other hand, the further introduction of the 2-thiophenesulfonyl chloride or the 4-dimethylaminopyridine can increase the acid sites of the spherical solid acid catalyst, adjust the acid center distribution, and ensure that the acid centers are distributed more uniformly on the surface of the spherical solid acid catalyst, thereby optimizing the adsorption and catalysis of the solid acid catalyst on hydrogen sulfide and carbon dodecene.
The 2-thiophenesulfonyl chloride or 4-dimethylaminopyridine can further activate hydrogen sulfide molecules and carbon dodecene molecules, adjust dissociation balance of hydrogen sulfide in an acidic environment, enable the hydrogen sulfide to exist in a form more favorable for reaction, enhance the reactivity of the hydrogen sulfide with the carbon dodecene, guide the reaction to proceed towards the direction of generating tertiary dodecyl mercaptan, improve the reaction rate, help reduce the occurrence of side reaction, and further improve the selectivity and conversion rate of the tertiary dodecyl mercaptan.
Claims (4)
1. A method for improving the conversion rate of tertiary dodecyl mercaptan by using a catalyst, which is characterized by comprising the following steps:
S1, filling a spherical solid acid catalyst into a reactor, uniformly mixing hydrogen sulfide and carbon dodecene with a molar ratio of 4-10:1 to obtain a mixed solution containing microbubbles, transferring the mixed solution into the reactor, setting the internal pressure of the reactor to be 1-8 MPa, and setting the reaction temperature to be 50-95 ℃ to enable the mixed solution to react to obtain a reacted synthesis gas liquid;
S2, enabling the synthesis gas and the liquid to pass through a separation device, enabling hydrogen sulfide to pass through a circulation device, enabling the hydrogen sulfide to enter the next round of reaction, forming hydrogen sulfide phase circulation, and collecting tertiary dodecyl mercaptan into a product tank;
in the step S1, the reactor is a fluidized bed reactor, a high-pressure feed pump is adopted to feed the mixed solution from the bottom of the fluidized bed reactor, and the flow rate of the mixed solution is 0.1-0.5L/min;
The preparation method of the spherical solid acid catalyst comprises the following steps:
S11, uniformly mixing sodium hydroxide, water, an aluminum source, a template agent and a silicon source to obtain initial sol;
s12, performing thermal crystallization reaction on the initial sol water, and roasting to obtain a molecular sieve precursor;
S13, uniformly mixing heteropoly acid, a molecular sieve precursor and a solvent to form slurry, standing at room temperature for 8-12 h, drying, cooling to obtain a compound, preparing a sphere, roasting, and cooling to obtain a spherical solid acid catalyst;
the heteropolyacid is at least one of phosphotungstic acid, vanadotungstic acid and phosphomolybdic acid;
In the step S1, the silicon source is calculated by SiO 2, the aluminum source is calculated by Al 2O3, the sodium hydroxide is calculated by Na 2 O, the template agent is calculated by TPAOH, and the molar ratio of the substances is as follows:
SiO2 :Al2O3 :TPAOH:Na2O=40~150:1:5~20:5~30;
In the step S13, the compound is put into a ball mill to prepare a sphere with the diameter of 5-15 mu m, the roasting temperature is 500-600 ℃, and the roasting time is 4-6 hours;
in step S13, after calcination, the method further includes the step of adding monomer a:
Dispersing a monomer A in a solvent, adding the roasted spheres, uniformly mixing, standing at room temperature for 8-12 h, and drying to obtain a spherical solid acid catalyst, wherein the mass ratio of the monomer A to the heteropoly acid is 0.1-0.3:1;
the monomer A is any one of 4-dimethylaminopyridine and 2-thiophenesulfonyl chloride.
2. The method for increasing the conversion rate of tertiary dodecyl mercaptan by utilizing a catalyst according to claim 1, wherein in step S1, hydrogen sulfide and carbon dodecene are fully mixed by using a pump type air floatation machine to form a mixed solution containing micro bubbles.
3. The method for improving the conversion rate of tertiary dodecyl mercaptan by utilizing a catalyst according to claim 1, wherein the silicon source is water glass, and the aluminum source is any one of aluminum isopropoxide, aluminum sulfate and sodium metaaluminate.
4. The method for improving the conversion rate of tert-dodecyl mercaptan by using a catalyst according to claim 1, wherein in the step S11, after sodium hydroxide is dissolved in water, an aluminum source is added, and the mixture is mixed for 0.5 to 1.5 hours, after the sodium hydroxide is completely dissolved, a template agent and polystyrene microsphere suspension are added, and after the template agent and polystyrene microsphere suspension are uniformly mixed, a silicon source is slowly added dropwise, and the silicon source is stirred dropwise until gel is formed, and aged at room temperature for 18 to 32 hours, so that an initial sol is obtained.
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