A kind of synthetic method of senior mercaptan
Technical field
The present invention relates to a kind of synthetic method of mercaptan, be specifically related to a kind of synthetic method of senior mercaptan.
Background technology
Senior mercaptan is agricultural chemicals, medicine, spices, tensio-active agent, vulcanizer, promotor intermediate, can be used for producing alkyl sulfonamide etc.Addition reaction under industrial main employing High Temperature High Pressure at present, the shortcoming of the method is that this reaction is reacted under High Temperature High Pressure, energy consumption is large; Catalyzer is easily poisoning, and selectivity, reactivity are poor, and the method yield is low, and product cost is relatively high.
Summary of the invention
Preparing mercaptan for prior art is all to carry out under High Temperature High Pressure, cause energy consumption large, catalyst selectivity and reactivity are poor, and product yield is low, the deficiency that production cost is high, the invention provides a kind of synthetic method of senior mercaptan, liquefied olefines is converted into to gaseous olefin, under low-temperature atmosphere-pressure, with hydrogen sulfide, under the synergy of plasma body and catalyzer, react, 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 synthetic method of senior mercaptan provided by the present invention, concrete steps comprise:
(1) liquid olefin is evaporated in vaporizer, by the steam regulation flow, make alkene take the ratio of mol ratio 1.0-2.0:1.0-2.0 with hydrogen sulfide and fully mix in the static mixer of 150 ℃-180 ℃ in temperature, mixed gas is with 1-80min
-1air speed pass into the plasma reaction storehouse of loading catalyst, the open plasma power supply is reacted;
(2) liquid generated after step (1) reaction is entered to thick product storage tank, unreacted gas is through recovery, compression cycle utilization;
(3) thick product step (2) obtained, through distillation, is collected the cut under differing temps, obtains target product mercaptan.
Wherein, step (1) first flashes to liquid olefin gaseous olefin in vaporizer, so that with enter the reaction of plasma reaction storehouse after hydrogen sulfide mixes, the temperature of whole process is controlled at 150 ℃-180 ℃, can guarantee that at this temperature the alkene described in the present invention is gaseous state; The static mixer used is without the tubular reactor stirred, and is existing installation, not only makes alkene and hydrogen sulfide fully mix, and is convenient to install and realize serialization production.
Liquefied olefines described in step (1) is a kind of in 1-amylene and isomer, 1-hexene and isomer thereof, 1-heptene and isomer thereof, 1-octene and isomer thereof.
Because moisture is conducting material, the existence of conducting material can not be arranged in plasma environment, so described hydrogen sulfide is the mixed gas that the hydrogen sulfide massfraction is 60-100%, wherein also contain a small amount of CO, CO
2and CH
4, be the byproduct hydrogen sulfide dry through purification of petrochemical industry, can form the comprehensive cyclic utilization of resource, make production cost reduce, there is economy.
Catalyzer described in step (1) is one or more in silica gel, alchlor, gac, molecular sieve carried transition metal oxide, sulfide, ionic liquid at room temperature.
Described catalyzer is to prepare according to prior art, be filled in the plasma reaction storehouse, both as filled media, be full of whole reaction warehouse, it is again the catalyzer of alkene and hydrogen sulfide reaction, for the present invention, these selected catalyzer costs are low, and selectivity is good, can reduce reaction energy barrier, improve the transformation efficiency of target product.
Catalyzer is under action of plasma, and activation energy reduces, and reduces the required energy of reaction, excites different carbon atoms and the effect of sulphur hydrogen activity species simultaneously, thereby improves reaction preference.
Described in step (1), plasma power supply is one or more of medium barrier plasma, glow plasma, microwave plasma, radio-frequency plasma or jet plasma, by prior art, can obtain.The high-energy state electronics produced under the plasma body electric field action directly acts on catalyzer, reduce the activation energy of catalyzer, improve catalytic efficiency and the selectivity of catalyzer, plasma body has clean-up performance to catalyzer simultaneously, avoided catalyst carbon deposit or sulfur poisoning to lose activity, extending catalyst reaches the 2000h left and right work-ing life, has 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, with the alkene effect, generates target product.
In the present invention due to the participation of high-energy state electronics, making 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 the selectivity of target product and transformation efficiency the highest.
In described step (1), alkene fully mixes with the ratio of mol ratio 1.0-2.0:1.0-2.0 with hydrogen sulfide in static mixer, by adjust flux, make alkene steam and hydrogen sulfide fully mix in static mixer with certain mol ratio, to realize serialization production; Described plasma reaction storehouse is the pipe reaction storehouse, can make so the fully reaction in reaction warehouse of abundant mixed hydrogen sulfide and gaseous olefin, and can guarantee that two kinds of materials are reacted according to the requirement to target product in reaction warehouse.
In described step (1), evaporation equipment used is stripping apparatus or high-gravity rotating bed, and in described step (3), distillation is normal pressure or underpressure distillation.
The present invention is according to the difference of described liquefied olefines, and the senior mercaptan of corresponding generation has 1-pentan-thiol, 1-hexylmercaptan, 1-heptanthiol, 1-spicy thioalcohol etc.
Compared with prior art, its beneficial effect has in the present invention:
(1) plasma body has clean-up performance to catalyzer, has avoided catalyst carbon deposit or sulfur poisoning to lose activity, and extending catalyst reaches the 2000h left and right 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 complete addition reaction to generate target product mercaptan, and its product yield is high compared to existing technology, reaches more than 90%;
(3) the high-energy state electronics that the present invention produces under the plasma body electric field action makes the temperature of reaction of system and reaction pressure be converted into the low-temperature atmosphere-pressure state, than the high-temperature high-voltage reaction of prior art, and the operational condition gentleness, not only safe, and reduced energy consumption;
(4) for unreacted gas in the present invention through reclaiming, compress, recycling, be conducive to cleaner production control and resource circulation utilization in 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 synthetic method of senior mercaptan, take liquefied olefines and hydrogen sulfide as raw material, and concrete steps comprise:
(1) the 1-amylene is joined in vaporizer, the steam regulation flow is passed in the static mixer that temperature is 150 ℃ and fully mixes with mol ratio 1:1 with hydrogen sulfide, and mixed gas is with 10min
-1air speed enter to fill and take the plasma reaction storehouse that the silica gel load ionic liquid is catalyzer, 150 ℃ of temperature of reaction, reaction pressure-0.02 MPa, take medium barrier plasma as plasma electrical source, the open plasma power supply is reacted;
(2) liquid generated after step (1) reaction is entered to thick product storage tank, unreacted gas is through recovery, compression cycle utilization;
(3) thick product distillation step (2) obtained, collect the cut at 126-127 ℃ of temperature, obtains the target product n-amyl mercaptan, calculates purity 99.75%, yield 90.85% with the 1-amylene.
Embodiment 2
A kind of synthetic method of senior mercaptan, take liquefied olefines and hydrogen sulfide as raw material, and concrete steps comprise:
(1) the 1-octene is joined in vaporizer, the steam regulation flow is passed in the static mixer that temperature is 180 ℃ and fully mixes with mol ratio 2:1 with hydrogen sulfide, and mixed gas is with 40min
-1air speed enter to fill and take the plasma reaction storehouse that activated carbon supported sulfide is catalyzer, 180 ℃ of temperature of reaction, reaction pressure 0.03 MPa, take glow plasma as plasma electrical source, the open plasma power supply is reacted;
(2) liquid generated after step (1) reaction is entered to thick product storage tank, unreacted gas is through recovery, compression cycle utilization;
(3) thick product distillation step (2) obtained, collect the cut at 197-200 ℃ of temperature, obtains target product 1-spicy thioalcohol, calculates purity 99.45%, yield 91.15% with the 1-octene.
Embodiment 3
A kind of synthetic method of senior mercaptan, take liquefied olefines and hydrogen sulfide as raw material, and concrete steps comprise:
(1) the 1-hexene is joined in vaporizer, the steam regulation flow is passed in the static mixer that temperature is 160 ℃ and fully mixes with mol ratio 1:2 with hydrogen sulfide, and mixed gas is with 80min
-1the flow velocity air speed enter to fill and take the plasma reaction storehouse that molecular sieve carried transition metal oxide is catalyzer, 160 ℃ of temperature of reaction, reaction pressure 0 MPa, take microwave plasma as plasma electrical source, the open plasma power supply is reacted;
(2) liquid generated after step (1) reaction is entered to thick product storage tank, unreacted gas is through recovery, compression cycle utilization;
(3) thick product distillation step (2) obtained, collect the cut at 150-154 ℃ of temperature, obtains target product 1-hexylmercaptan, calculates purity 97%, yield 92.07% with the 1-hexene.
Embodiment 4
A kind of synthetic method of senior mercaptan, take liquefied olefines and hydrogen sulfide as raw material, and concrete steps comprise:
(1) the 1-heptene is joined in vaporizer, the steam regulation flow is passed in the static mixer that temperature is 170 ℃ and fully mixes with mol ratio 1:1.8 with hydrogen sulfide, and mixed gas is with 60min
-1air speed enter to fill and take the plasma reaction storehouse that alchlor carrying transition metal oxide compound is catalyzer, 170 ℃ of temperature of reaction, reaction pressure 0 .08MPa, take radio-frequency plasma as plasma electrical source, the open plasma power supply is reacted;
(2) liquid generated after step (1) reaction is entered to thick product storage tank, unreacted gas is through recovery, compression cycle utilization;
(3) thick product distillation step (2) obtained, collect the cut at 173-176 ℃ of temperature, obtains the target product n-heptanthiol, calculates purity 98%, yield 91.17% with the 1-heptene.
Embodiment 5
A kind of synthetic method of senior mercaptan, take liquefied olefines and hydrogen sulfide as raw material, and concrete steps comprise:
(1) isopentene is joined in vaporizer, the steam regulation flow is passed in the static mixer that temperature is 155 ℃ and fully mixes with mol ratio 1:1.5 with hydrogen sulfide, and mixed gas is with 20min
-1air speed enter to fill and take the plasma reaction storehouse that alchlor sulfur loaded compound is catalyzer, 155 ℃ of temperature of reaction, reaction pressure 0 .05MPa, take jet plasma as plasma electrical source, the open plasma power supply is reacted;
(2) liquid generated after step (1) reaction is entered to thick product storage tank, unreacted gas is through recovery, compression cycle utilization;
(3) thick product distillation step (2) obtained, collect the cut at 115-119 ℃ of temperature, obtains the target product isopentyl mercaptan, calculates purity 97.8%, yield 90.95% with isopentene.
Embodiment 6
A kind of synthetic method of senior mercaptan, take liquefied olefines and hydrogen sulfide as raw material, and concrete steps comprise:
(1) isooctene is joined in vaporizer, the steam regulation flow is passed in the static mixer that temperature is 176 ℃ and fully mixes with mol ratio 1.5:1 with hydrogen sulfide, and mixed gas is with 50min
-1air speed enter to fill and take the plasma reaction storehouse that molecular sieve carried ionic liquid and silica gel load sulfide is catalyzer, 176 ℃ of temperature of reaction, reaction pressure 0 .06MPa, take radio-frequency plasma and jet plasma as plasma electrical source, and the open plasma power supply is reacted;
(2) liquid generated after step (1) reaction is entered to thick product storage tank, unreacted gas is through recovery, compression cycle utilization;
(3) thick product distillation step (2) obtained, collect the cut at 187-189 ℃ of temperature, obtains the different spicy thioalcohol of target product, calculates purity 98.1%, yield 90.86% with isooctene.
The petrochemical industry byproduct that raw materials used middle hydrogen sulfide is drying, purification, liquefied olefines is Some Petrochemical Byproducts, by embodiment 1-6, can find out, unreacted gas is compressed, recycling use, be conducive to cleaner production control and resource circulation utilization in commercial run, make production cost reduce; Technological operation is simple, and the yield of resulting target product is all more than 90%, and the products obtained therefrom yield is high, production cost is low, and the reaction conditions gentleness, and production process is safe.