CN102757371A - Synthetic method of higher mercaptan - Google Patents
Synthetic method of higher mercaptan Download PDFInfo
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- CN102757371A CN102757371A CN2012102726409A CN201210272640A CN102757371A CN 102757371 A CN102757371 A CN 102757371A CN 2012102726409 A CN2012102726409 A CN 2012102726409A CN 201210272640 A CN201210272640 A CN 201210272640A CN 102757371 A CN102757371 A CN 102757371A
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Abstract
The invention discloses a synthetic method of higher mercaptan. The method mainly includes the steps of evaporating liquid olefin in an evaporator, fully mixing the olefin with hydrogen sulfide gas in a static mixer, enabling the mixed gas to enter a plasma reaction bin, powering on a plasma, reacting the mixed gas at a low temperature and under a normal pressure under the action of the plasma and a catalyst, and subjecting the gas to separation and purification to obtain the target product. The synthetic method is reacted at the low temperature and under the normal pressure, the reaction condition is mild, the safety is high, the cost is low, and the product yield is high.
Description
Technical field
The present invention relates to a kind of compound method of mercaptan, be specifically related to a kind of compound method of senior mercaptan.
Background technology
Senior mercaptan is agricultural chemicals, medicine, spices, tensio-active agent, vulcanizer, promotor midbody, can be used for producing alkyl sulfonamide etc.The main addition reaction under the HTHP of adopting is gone up in industry at present, and the shortcoming of this method is that this is reflected at reaction under the HTHP, and energy consumption is big; Catalyzer be prone to be poisoned, and selectivity, reactivity are poor, and this method yield is low, and product cost is higher relatively.
Summary of the invention
To prior art for preparing mercaptan all is under HTHP, to carry out, and causes energy consumption big, and catalyst selectivity and reactivity are poor; And product yield is low; The deficiency that production cost is high, the present invention provides a kind of compound method of senior mercaptan, and liquefied olefines is converted into gaseous olefin; Low-temperature atmosphere-pressure reacts under the synergy of plasma body and catalyzer with hydrogen sulfide down; Make that catalyst selectivity is high, long service life, the products obtained therefrom yield is high, production cost is low, and production process is safe.
The compound method of senior mercaptan provided by the present invention, concrete steps comprise:
(1) liquid olefin is evaporated in vaporizer, make that through the steam regulation flow alkene and hydrogen sulfide are thorough mixing in 150 ℃-180 ℃ the static mixer with the ratio of mol ratio 1.0-2.0:1.0-2.0 in temperature, mixed gas is with 1-80min
-1Air speed feed the plasma reaction storehouse of loading catalyst, the open plasma power supply reacts;
(2) liquid that step (1) reaction back is generated gets into thick product storage tank, and unreacted gas is through recovery, compression cycle utilization;
(3) cut under the differing temps is collected in the thick product process distillation that step (2) is obtained, and obtains target product mercaptan.
Wherein, Step (1) flashes to gaseous olefin with liquid olefin earlier in vaporizer; Get into the reaction of plasma reaction storehouse so that mix the back with hydrogen sulfide, the temperature of whole process is controlled at 150 ℃-180 ℃, can guarantee that under this temperature the alkene described in the present invention is gaseous state; Employed static mixer is the tubular reactor that need not to stir, and is existing installation, not only makes alkene and the hydrogen sulfide can thorough mixing, and is convenient to install and realize serialization production.
Liquefied olefines described in the step (1) is a kind of in 1-amylene and isomer, 1-hexene and isomer thereof, 1-heptene and isomer thereof, 1-octene and the isomer thereof.
Because moisture is conducting material, and the existence of conducting material can not be arranged in plasma environment, is the mixed gas of 60-100% so said hydrogen sulfide is the hydrogen sulfide massfraction, wherein also contains a spot of CO, CO
2And CH
4, the sub product that is petrochemical industry can form the comprehensive cyclic utilization of resource through purification exsiccant hydrogen sulfide, makes production cost reduce, and has economy.
Catalyzer described in the step (1) is one or more in silica gel, alchlor, gac, molecular sieve carried transition metal oxide, sulfide, the ionic liquid at room temperature.
Said catalyzer is to obtain according to prior art for preparing, is filled in the plasma reaction storehouse, both is full of the entire reaction storehouse as filling medium; Be again alkene and hydrogen sulfide catalyst for reaction; For the present invention, these catalyzer costs of being selected for use are low, and selectivity is good; Can reduce reaction energy barrier, improve the transformation efficiency of title product.
Catalyzer is under action of plasma, and activation energy reduces, and reduces the required energy of reaction, different carbon atoms of simultaneous excitation and the effect of sulphur hydrogen activity species, thus improve reaction preference.
Plasma power supply is one or more of medium barrier plasma, glow plasma, microwave plasma, radio-frequency plasma or jet plasma described in the step (1), can obtain by prior art.The high-energy state electronics that under the plasma body electric field action, produces directly acts on catalyzer; Reduce the activation energy of catalyzer; Improve the catalytic efficiency (and the selectivity of catalyzer, plasma body has clean-up performance to catalyzer simultaneously, has avoided catalyst carbon deposit or sulfur poisoning to lose activity; Prolong catalyzer and reach about 2000h work-ing life, reduced the use cost of catalyzer; Act on hydrogen sulfide, produce high reactivity hydrogen and sulphur hydrogen species, active specy acts on the alkene of excited state, generates title product with the alkene effect.
Among the present invention because the participation of high-energy state electronics; Making the temperature of reaction and the reaction pressure of system is the low-temperature atmosphere-pressure state, and the temperature of reaction of system is 150 ℃-180 ℃, and reaction pressure is-0.02-0.08MPa; Reaction system adopts such condition, makes that the selectivity of title product and transformation efficiency are the highest.
Alkene and hydrogen sulfide carry out thorough mixing with the ratio of mol ratio 1.0-2.0:1.0-2.0 in the said step (1) in static mixer; Make alkene steam and hydrogen sulfide with certain molar ratio thorough mixing in static mixer through regulating flow, to realize serialization production; Said plasma reaction storehouse is the pipe reaction storehouse, can make hydrogen sulfide and gaseous olefin fully reaction in reaction warehouse behind the thorough mixing like this, and can guarantee that two kinds of materials react according to the requirement to title product in reaction warehouse.
Used evaporation equipment is a stripping apparatus or high-gravity rotating bed in the said step (1), and distillation is normal pressure or underpressure distillation in the said step (3).
The present invention is according to the difference of said liquefied olefines, and the senior mercaptan of corresponding generation has 1-pentan-thiol, 1-hexylmercaptan, 1-heptanthiol, 1-spicy thioalcohol etc.
The present invention compared with prior art, its beneficial effect has:
(1) plasma body has clean-up performance to catalyzer, has avoided catalyst carbon deposit or sulfur poisoning to lose activity, and prolongs catalyzer and reaches about 2000h work-ing life, reduces Catalyst Production or regeneration cost;
(2) compared with prior art, the present invention utilizes the synergy of plasma body and catalyzer to accomplish addition reaction to generate title product mercaptan, and its product yield is compared the prior art height, reaches more than 90%;
(3) the high-energy state electronics that under the plasma body electric field action, produces of the present invention makes the temperature of reaction of system and reaction pressure be converted into the low-temperature atmosphere-pressure state, and than the high-temperature high-voltage reaction of prior art, operational condition is gentle, and is not only safe, and reduced energy consumption;
(4) for unreacted gas among the present invention through reclaiming, compress, recycling, help cleaner production control and resource circulation utilization in the commercial run, make production cost reduce;
(5) technological operation of the present invention is simple, has alleviated labour intensity, has reduced equipment requirements, makes production cost further reduce.
Embodiment
Embodiment 1
A kind of compound method of senior mercaptan is a raw material with liquefied olefines and hydrogen sulfide, and concrete steps comprise:
(1) the 1-amylene is joined in the vaporizer, the steam regulation flow be passed into temperature be in 150 ℃ the static mixer with hydrogen sulfide with mol ratio 1:1 thorough mixing, mixed gas is with 10min
-1Air speed get into to fill with the silica gel load ionic liquid be the plasma reaction storehouse of catalyzer, 150 ℃ of temperature of reaction, reaction pressure-0.02 MPa is a plasma electrical source with the medium barrier plasma, the open plasma power supply reacts;
(2) liquid that step (1) reaction back is generated gets into thick product storage tank, and unreacted gas is through recovery, compression cycle utilization;
(3) cut under the 126-127 ℃ of temperature is collected in the thick product distillation that step (2) is obtained, and obtains the target product n-amyl mercaptan, calculates purity 99.75%, yield 90.85% with the 1-amylene.
Embodiment 2
A kind of compound method of senior mercaptan is a raw material with liquefied olefines and hydrogen sulfide, and concrete steps comprise:
(1) the 1-octene is joined in the vaporizer, the steam regulation flow be passed into temperature be in 180 ℃ the static mixer with hydrogen sulfide with mol ratio 2:1 thorough mixing, mixed gas is with 40min
-1Air speed get into to fill with activated carbon supported sulfide be the plasma reaction storehouse of catalyzer, 180 ℃ of temperature of reaction, reaction pressure 0.03 MPa is a plasma electrical source with the glow plasma, the open plasma power supply reacts;
(2) liquid that step (1) reaction back is generated gets into thick product storage tank, and unreacted gas is through recovery, compression cycle utilization;
(3) cut under the 197-200 ℃ of temperature is collected in the thick product distillation that step (2) is obtained, and obtains target product 1-spicy thioalcohol, calculates purity 99.45%, yield 91.15% with the 1-octene.
Embodiment 3
A kind of compound method of senior mercaptan is a raw material with liquefied olefines and hydrogen sulfide, and concrete steps comprise:
(1) the 1-hexene is joined in the vaporizer, the steam regulation flow be passed into temperature be in 160 ℃ the static mixer with hydrogen sulfide with mol ratio 1:2 thorough mixing, mixed gas is with 80min
-1The flow velocity air speed get into to fill with molecular sieve carried transition metal oxide be the plasma reaction storehouse of catalyzer, 160 ℃ of temperature of reaction, reaction pressure 0 MPa is a plasma electrical source with the microwave plasma, the open plasma power supply reacts;
(2) liquid that step (1) reaction back is generated gets into thick product storage tank, and unreacted gas is through recovery, compression cycle utilization;
(3) cut under the 150-154 ℃ of temperature is collected in the thick product distillation that step (2) is obtained, and obtains target product 1-hexylmercaptan, calculates purity 97%, yield 92.07% with the 1-hexene.
Embodiment 4
A kind of compound method of senior mercaptan is a raw material with liquefied olefines and hydrogen sulfide, and concrete steps comprise:
(1) the 1-heptene is joined in the vaporizer, the steam regulation flow be passed into temperature be in 170 ℃ the static mixer with hydrogen sulfide with mol ratio 1:1.8 thorough mixing, mixed gas is with 60min
-1Air speed get into to fill with alchlor carrying transition metal oxide compound be the plasma reaction storehouse of catalyzer, 170 ℃ of temperature of reaction, reaction pressure 0 .08MPa is a plasma electrical source with the radio-frequency plasma, the open plasma power supply reacts;
(2) liquid that step (1) reaction back is generated gets into thick product storage tank, and unreacted gas is through recovery, compression cycle utilization;
(3) cut under the 173-176 ℃ of temperature is collected in the thick product distillation that step (2) is obtained, and obtains the target product n-heptanthiol, calculates purity 98%, yield 91.17% with the 1-heptene.
Embodiment 5
A kind of compound method of senior mercaptan is a raw material with liquefied olefines and hydrogen sulfide, and concrete steps comprise:
(1) isopentene is joined in the vaporizer, the steam regulation flow be passed into temperature be in 155 ℃ the static mixer with hydrogen sulfide with mol ratio 1:1.5 thorough mixing, mixed gas is with 20min
-1Air speed get into to fill with alchlor load sulfide be the plasma reaction storehouse of catalyzer, 155 ℃ of temperature of reaction, reaction pressure 0 .05MPa is a plasma electrical source with the jet plasma, the open plasma power supply reacts;
(2) liquid that step (1) reaction back is generated gets into thick product storage tank, and unreacted gas is through recovery, compression cycle utilization;
(3) cut under the 115-119 ℃ of temperature is collected in the thick product distillation that step (2) is obtained, and obtains the target product isopentyl mercaptan, calculates purity 97.8%, yield 90.95% with isopentene.
Embodiment 6
A kind of compound method of senior mercaptan is a raw material with liquefied olefines and hydrogen sulfide, and concrete steps comprise:
(1) isooctene is joined in the vaporizer, the steam regulation flow be passed into temperature be in 176 ℃ the static mixer with hydrogen sulfide with mol ratio 1.5:1 thorough mixing, mixed gas is with 50min
-1Air speed get into to fill with molecular sieve carried ionic liquid and silica gel load sulfide be the plasma reaction storehouse of catalyzer; 176 ℃ of temperature of reaction; Reaction pressure 0 .06MPa is a plasma electrical source with radio-frequency plasma and jet plasma, and the open plasma power supply reacts;
(2) liquid that step (1) reaction back is generated gets into thick product storage tank, and unreacted gas is through recovery, compression cycle utilization;
(3) cut under the 187-189 ℃ of temperature is collected in the thick product distillation that step (2) is obtained, and obtains the different spicy thioalcohol of target product, calculates purity 98.1%, yield 90.86% with isooctene.
Hydrogen sulfide is through petrochemical industry sub product dry, that purify in raw materials used; Liquefied olefines is the petrochemical industry sub product; Can find out through embodiment 1-6; Unreacted gas helps cleaner production control and resource circulation utilization in the commercial run through compression, recycling use, makes production cost reduce; Technological operation is simple, and the yield of resulting title product is all more than 90%, and the products obtained therefrom yield is high, production cost is low, and reaction conditions is gentle, and production process is safe.
Claims (9)
1. the compound method of a senior mercaptan is a raw material with liquefied olefines and hydrogen sulfide, and it is characterized in that: concrete steps comprise:
(1) liquid olefin is evaporated in vaporizer, make that through the steam regulation flow alkene and hydrogen sulfide are thorough mixing in 150 ℃-180 ℃ the static mixer with the ratio of mol ratio 1.0-2.0:1.0-2.0 in temperature, mixed gas is with 1-80min
-1Air speed feed the plasma reaction storehouse of loading catalyst, the open plasma power supply reacts;
(2) liquid that step (1) reaction back is generated gets into thick product storage tank, and unreacted gas is through recovery, compression cycle utilization;
(3) cut under the differing temps is collected in the thick product process distillation that step (2) is obtained, and obtains target product mercaptan.
2. the compound method of senior mercaptan according to claim 1 is characterized in that: the liquid olefin in the said step (1) is a kind of in 1-amylene and isomer, 1-hexene and isomer thereof, 1-heptene and isomer thereof, 1-octene and the isomer thereof.
3. the compound method of senior mercaptan according to claim 1, it is characterized in that: said hydrogen sulfide is that the hydrogen sulfide massfraction is the mixed gas of 60-100%.
4. the compound method of senior mercaptan according to claim 1 is characterized in that: the catalyzer in the said step (1) is one or more in silica gel, alchlor, gac, molecular sieve carried ionic liquid, transition metal oxide, the sulfide.
5. the compound method of senior mercaptan according to claim 1 is characterized in that: the plasma power supply in the said step (1) is a kind of of medium barrier plasma, glow plasma, microwave plasma, radio-frequency plasma or jet plasma or appoints several kinds.
6. the compound method of senior mercaptan according to claim 1 is characterized in that: in the said step (3) the used equipment of distillation be stripping apparatus or high-gravity rotating bed in one or both.
7. the compound method of senior mercaptan according to claim 1 is characterized in that: the vaporizer in the said step (1) be normal pressure equipment, pressure regulating equipment or high-gravity rotating bed in a kind of or any several kinds.
8. the compound method of senior mercaptan according to claim 1 is characterized in that: the temperature of reaction of system is 150 ℃-180 ℃ in the said step (1).
9. the compound method of senior mercaptan according to claim 1 is characterized in that: the reaction pressure of system is-0.02-0.08MPa in the said step (1).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496869A (en) * | 2014-12-18 | 2015-04-08 | 黄河三角洲京博化工研究院有限公司 | Method for preparing isopropyl mercaptan |
| CN112745252A (en) * | 2020-01-07 | 2021-05-04 | 南京大学 | H catalysis with ionic liquid as catalyst2Green method for synthesizing high-added-value mercaptoacid by addition reaction of S and olefine acid |
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| CN1701053A (en) * | 2002-09-25 | 2005-11-23 | 阿肯马公司 | Catalytic method of producing alkyl mercaptans by adding hydrogen sulphide to an olefin |
| JP2008055020A (en) * | 2006-09-01 | 2008-03-13 | Gunma Prefecture | Deodorizing apparatus for odor containing oil droplets and fine particles, and deodorizing method |
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| CN1701053A (en) * | 2002-09-25 | 2005-11-23 | 阿肯马公司 | Catalytic method of producing alkyl mercaptans by adding hydrogen sulphide to an olefin |
| JP2008055020A (en) * | 2006-09-01 | 2008-03-13 | Gunma Prefecture | Deodorizing apparatus for odor containing oil droplets and fine particles, and deodorizing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496869A (en) * | 2014-12-18 | 2015-04-08 | 黄河三角洲京博化工研究院有限公司 | Method for preparing isopropyl mercaptan |
| CN104496869B (en) * | 2014-12-18 | 2016-07-20 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of isopropyl mercaptan |
| CN112745252A (en) * | 2020-01-07 | 2021-05-04 | 南京大学 | H catalysis with ionic liquid as catalyst2Green method for synthesizing high-added-value mercaptoacid by addition reaction of S and olefine acid |
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| CN102757371B (en) | 2014-01-08 |
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Effective date of registration: 20200715 Address after: 256500 Boxing Economic Development Zone, Binzhou, Shandong Patentee after: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Binzhou, Shandong Patentee before: YELLOW RIVER DELTA JINGBO RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Co.,Ltd. |
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Address after: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee after: Yifeng New Material Co.,Ltd. Address before: 256500 Boxing Economic Development Zone, Shandong, Binzhou Patentee before: SHANDONG EFIRM BIOCHEMISTRY AND ENVIRONMENTAL PROTECTION Co.,Ltd. |