CN104829507B - Without the method that fragrant thiophenol is produced under catalyst action - Google Patents
Without the method that fragrant thiophenol is produced under catalyst action Download PDFInfo
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Abstract
The present invention relates to the synthetic method of fragrant phenyl-sulfhydrate compounds, more particularly to a kind of method without the fragrant thiophenol of production under catalyst action, using 1 halogenated aromatic compound as reaction raw materials, the hydrogen sulfide in being reclaimed with refinery exhaust reacts the fragrant thiophenol of generation at 550 700 DEG C.The hydrogen sulfide of the invention effectively utilized in refinery exhaust, excessive hydrogen sulfide can be recycled.Without using catalyst, production cost is greatlyd save.1 halogenated aromatic compound is reacted in hydrogen sulfide atmosphere, improve the conversion ratio of the reaction mass of costliness, improve product selectivity and once through yield.Can be by adjusting the ratio of reaction mass, the direction that regulation reaction occurs reaches maximization of economic benefit.
Description
Technical field
It is more particularly to a kind of without production virtue under catalyst action the present invention relates to the synthetic method of fragrant phenyl-sulfhydrate compounds
The method of fragrant thiophenol.
Background technology
Fragrant thiophenol is a kind of organosulfur compound with application value, is widely used in the row such as medicine, agricultural chemicals, dyestuff
Industry, is used to synthesize fibrin ferment polymerization inhibitor, bactericide, dermatitis medicine, herbicide, corrosion inhibiter and photosensitive material as fine chemical material
Material etc..Such as benzenethiol can be used for the substitute Thiamphenicol of the medical chloramphenicol of production, and agricultural chemicals Hinosan etc. and rubber processed are again
Raw agent, petroleum additive etc.；It is important agricultural chemicals and medicine intermediate to chlorothio-phenol, adds available for synthesis plasticizer, oils
Plus agent and wetting agent；And 4,4'- dimercapto diphenyl sulfides can be then a kind of excellent optical resin for synthesis photosensitive material
Monomer etc..
In present technology, the preparation of fragrant thiophenol mainly has a diazotising method, chlorosulfonation-reducing process, disulfide cracking process,
Chlorobenzene catalysis method etc..(1) diazotising method, i.e. arylamine are that raw material obtains xanthate after diazotising with xanthates reaction,
Then fragrant thiophenol is obtained in alkali lye reclaimed water solution.The shortcoming of such method is that synthetic route is longer, and yield is than relatively low, course of reaction
It is middle to produce a large amount of contaminated wastewater environment, and diazo-reaction danger is larger.(2) chlorosulfonation-reducing process, i.e., with aromatic radical chemical combination
Thing is raw material, is made through chlorosulfonation, iron powder or zinc powder reduction.Its reaction equation is as follows:
Wherein, n=1-5 integer, R is hydrogen, alkyl.
Chlorosulfonic acid consumption in the method is big, and raw material sources are nervous, and its corrosivity is big, meets water and acts on violent, to work
Skill, equipment and conveyer belt come difficult, and this method complex process, and reaction time is long, and total recovery is low, and cost is high, maximum weakness
It is exactly that the three wastes are not disposable.(3) disulfide cracking process, is exactly, using fragrant disulfide as raw material, to be split using different methods
Solve as fragrant thiophenol, its reaction equation is as follows:
Wherein, n=1-5 integer, R is hydrogen, alkyl.
The raw materials used fragrant disulfide compound of the method is not easy to obtain, and gained yield is not high.(4) 1- chlorinated aromatics
Compound catalysis method, i.e., using 1- chlorinated aromatic compounds and hydrogen sulfide as raw material, react under catalyst action and be made, its reaction equation
It is as follows：
Na2S+2HCl→H2S+NaCl
Wherein, n=1-5 integer, R is hydrogen, alkyl.
This method raw material is easy to get, and reaction temperature is 450~500 DEG C, and catalyst is made with ZnS and zinc acetate.There are two problems still
It is to be solved：One is that catalyst service life is short, can only operate 300h, and the catalyst after poisoning not yet finds preferable regeneration side
Method；Two be that catalyst is prepared with zinc acetate and 5# activated carbons, both raw material sources are few, price is high, especially zinc acetate
It is expensive.
The content of the invention
The present invention is fragrant without production under catalyst action there is provided one kind for the shortcoming of 1- chlorinated aromatic compound catalysis methods
The method of thiophenol.
The technical scheme is that：
A kind of method without the fragrant thiophenol of production under catalyst action, using 1- halogenated aromatic compounds as reaction raw materials, with
Hydrogen sulfide during refinery exhaust is reclaimed reacts the fragrant thiophenol of generation at 550-700 DEG C.Adjust reaction temperature, it is material proportion, anti-
The yield of fragrant thiophenol should be made to reach maximum the residence time.
On the basis of above scheme, described 1- halogenated aromatic compound formulas are：
Wherein, n=1-5 integer, R is hydrogen, alkyl.X is F, Cl, Br, I.
On the basis of above scheme, the ratio between described hydrogen sulfide and the amount of material of 1- halogenated aromatic compounds are 2:1-
6:1, by adjusting the ratio of the component of gas phase two, solve the problem of reactant is carbonized under high temperature.
By the flow for increasing hydrogen sulfide, on the one hand, 1- halogenated aromatic compounds is reacted in hydrogen sulfide atmosphere, improve
The conversion ratio of expensive reaction mass, improves product selectivity and once through yield.Secondly, can be by adjusting reaction mass
Ratio, the direction that regulation reaction occurs, reaches maximization of economic benefit.Finally, due to which this reaction is needed under without catalyst environment
600-700 DEG C of high temperature is wanted, easily causes organic compound 1- halogenated aromatic compounds and product to be carbonized in tubular reactor, again
Because this reaction is exothermic reaction, easily cause danger when being carbonized serious.Increase the ratio of hydrogen sulfide in gas phase reaction system, subtract
The amount of organic compound in subsection volume, and then reduce carbonization.
The method that fragrant thiophenol is produced on the basis of above scheme, under no catalyst action, comprises the following steps：
Step 1：Hydrogen sulfide and 1- halogenated aromatic compounds are first preheating to 200-400 DEG C in preheating can respectively；
Step 2：By hydrogen sulfide and 1- halogenated aromatic compound hybrid reactions, the reaction time is 15-60s；
Step 3：By condensing heat-exchange, fragrant thiol compounds are condensed into liquid, and unreacted excess hydrogen sulfide is reclaimed and followed
Ring enters hydrogen sulfide preheating can.
It is preferred that, described preheating temperature is 300 DEG C, and described reaction temperature is 650 DEG C, described hydrogen sulfide and 1- halogen
The ratio between amount of material for aromatic compound is 3:1, the reaction time is 20s.
It is preferred that, the hybrid reaction described in step 2, first with the oxygen in nitrogen sparge tube formula reactor, then it is logical described
Hydrogen sulfide gas, makes to be full of after hydrogen sulfide in tubular reactor, then leads to the steam of the 1- halogenated aromatic compounds of preheating, makes 1- halogen
Reacted for aromatic compound in hydrogen sulfide atmosphere.
Present invention reaction is as follows：
Side reaction includes：
Wherein, n=1-5 integer, R is hydrogen, alkyl.X is F, Cl, Br, I.
The beneficial effects of the invention are as follows：
1) effectively using the hydrogen sulfide in refinery exhaust, excessive hydrogen sulfide can be recycled.
2) without using catalyst, production cost is greatlyd save.
3) 1- halogenated aromatic compounds is reacted in hydrogen sulfide atmosphere, improve the conversion ratio of the reaction mass of costliness,
Improve product selectivity and once through yield.
4) can be by adjusting the ratio of reaction mass, the direction that regulation reaction occurs reaches maximization of economic benefit.
Brief description of the drawings
Accompanying drawing 1 is the flow sheet of the fragrant phenyl-sulfhydrate compounds of the specific embodiment of the invention.
Embodiment
The embodiment of the present invention is as follows：(1- halogenated aromatic compounds produce benzenethiol by taking 1- chlorobenzenes as an example)
Reaction is as follows：
Embodiment 1：
Step 1：Hydrogen sulfide and chlorobenzene are first preheating to 200 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 2 to make the ratio between amount of material for the hydrogen sulfide and chlorobenzene for entering 600 DEG C of tubular reactors:When 1,
Residence time about 20s in tubular reactor, continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide reclaims and is recycled into hydrogen sulfide preheating can, unconverted
Chlorobenzene can be recycled into reaction system.Product A selectivity is 18.94%, and accessory substance B is selectively 12.80%, product
C selectivity is 10.20%.Now tubular reactor has more black coke to adhere to.
Embodiment 2：
Step 1：Hydrogen sulfide and chlorobenzene are first preheating to 300 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 2.5 to make the ratio between amount of material for the hydrogen sulfide and chlorobenzene for entering 600 DEG C of tubular reactors:When 1,
Residence time about 20s in tubular reactor, continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide reclaims and is recycled into hydrogen sulfide preheating can, unconverted
Chlorobenzene can be recycled into reaction system.Product A selectivity is 41.88%, and accessory substance B is selectively 16.35%, product
C selectivity is 4.91%.Coke attachment is slightly reduced compared with embodiment 1 in tubular reactor, but still more serious.
Embodiment 3：
Step 1：Hydrogen sulfide and chlorobenzene are first preheating to 300 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 3.5 to make the ratio between amount of material for the hydrogen sulfide and chlorobenzene for entering 650 DEG C of tubular reactors:When 1,
Residence time about 25s in tubular reactor, continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide reclaims and is recycled into hydrogen sulfide preheating can, unconverted
Chlorobenzene can be recycled into reaction system.Product A selectivity is 75.30%, and accessory substance B is selectively 11.50%, product
C selectivity is 1.41%.Coke attachment is slightly reduced compared with embodiment 1 in tubular reactor.
Embodiment 4：
Step 1：Hydrogen sulfide and chlorobenzene are first preheating to 400 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 6 to make the ratio between amount of material for the hydrogen sulfide and chlorobenzene for entering 700 DEG C of tubular reactors:When 1,
Residence time about 25s in tubular reactor, continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide reclaims and is recycled into hydrogen sulfide preheating can, unconverted
Chlorobenzene can be recycled into reaction system.Product A selectivity is 48.8%, and accessory substance B is selectively 9.73%, product C
Selectivity be 0.86%.Coke attachment is significantly reduced compared with embodiment 1 in tubular reactor, and color is switched to light brown by black.
Embodiment 5：
Step 1：Hydrogen sulfide and chlorobenzene are first preheating to 400 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 6 to make the ratio between amount of material for the hydrogen sulfide and chlorobenzene for entering 650 DEG C of tubular reactors:When 1,
Residence time about 60s in tubular reactor, continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide reclaims and is recycled into hydrogen sulfide preheating can, unconverted
Chlorobenzene can be recycled into reaction system.Product A selectivity is 24.03%, and accessory substance B is selectively 4.88%, product C
Selectivity be 6.14%.Basic Non-carbonized in tubular reactor.
Embodiment 6：
In summary embodiment,
Step 1：Hydrogen sulfide and chlorobenzene are first preheating to 300 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 3 to make the ratio between amount of material for the hydrogen sulfide and chlorobenzene for entering 650 DEG C of tubular reactors:When 1,
Residence time about 20s in tubular reactor, continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide reclaims and is recycled into hydrogen sulfide preheating can, unconverted
Chlorobenzene can be recycled into reaction system.Product A selectivity is 71.34%, and accessory substance B is selectively 20.42%, product
C selectivity is 0.23%.Tubular reactor carbonization is less, and comprehensive benefit is larger.
Embodiment 7：
Step 1：Hydrogen sulfide and 4- toluene bromides are first preheating to 300 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 3 to make the ratio between amount of material for the hydrogen sulfide and 4- toluene bromides for entering 650 DEG C of tubular reactors:1
When, the residence time about 20s in tubular reactor continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide reclaims and is recycled into hydrogen sulfide preheating can.Product pair
The selectivity 76.34% of methylbenzene phenyl-sulfhydrate.
Embodiment 8：
Step 1：Hydrogen sulfide and 4- iodotoluenes are first preheating to 300 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 3 to make the ratio between amount of material for the hydrogen sulfide and 4- iodotoluenes for entering 650 DEG C of tubular reactors:1
When, the residence time about 20s in tubular reactor continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide reclaims and is recycled into hydrogen sulfide preheating can.Product pair
The selectivity 81.18% of methylbenzene phenyl-sulfhydrate.
Embodiment 9：
Step 1：First by hydrogen sulfide and 2,4- dimethyl bromobenzenes are preheating to 400 DEG C, pressure 0.3MPa in preheating can respectively；
Step 2：The oxygen in 1h in nitrogen purging device, removing device is first used, in order to avoid being impacted to reaction, passes through control
Regulating valve processed and flowmeter, it is 3 to make the ratio between amount of material for the hydrogen sulfide and 4- toluene bromides for entering 650 DEG C of tubular reactors:1
When, the residence time about 20s in tubular reactor continuously produces 30min；
Step 3：By condensing heat-exchange, unreacted excess hydrogen sulfide, which is reclaimed, is recycled into hydrogen sulfide preheating can, product 2,
The selectivity of 4- thiophenol dimethyl benzenes is 71.56%.
Claims (5)
1. a kind of without the method that fragrant thiophenol is produced under catalyst action, it is characterised in that using 1- halogenated aromatic compounds be anti-
Raw material is answered, the fragrant thiophenol of generation is reacted at 650 DEG C with hydrogen sulfide；The material of described hydrogen sulfide and 1- halogenated aromatic compounds
The ratio between amount be 3:1；Before being reacted, hydrogen sulfide and 1- halogenated aromatic compounds are first preheating to 300-400 DEG C respectively；Production
Hydrogen sulfide gas is first passed through in course of reaction, after be passed through preheating 1- halogenated aromatic compounds steam；The selectivity of product is big
In 71.34%.
2. it is according to claim 1 without the method that fragrant thiophenol is produced under catalyst action, it is characterised in that described 1-
Halogenated aromatic compound
Wherein, n=1-5 integer, R is hydrogen, alkyl, and X is F, Cl, Br, I.
3. it is according to claim 1 or 2 without the method that fragrant thiophenol is produced under catalyst action, it is characterised in that including
Following steps：
Step 1：Hydrogen sulfide and 1- halogenated aromatic compounds are first preheating to 200-400 DEG C in preheating can respectively；
Step 2：By hydrogen sulfide and 1- halogenated aromatic compound hybrid reactions, the reaction time is 15-60s；
Step 3：By condensing heat-exchange, fragrant thiol compounds are condensed into liquid, unreacted excess hydrogen sulfide reclaim circulate into
Enter hydrogen sulfide preheating can.
4. it is according to claim 3 without the method that fragrant thiophenol is produced under catalyst action, it is characterised in that described is pre-
Hot temperature is 300 DEG C, and described reaction temperature is 650 DEG C, described hydrogen sulfide and the amount of the material of 1- halogenated aromatic compounds
The ratio between be 3:1, the reaction time is 20s.
5. it is according to claim 4 without the method that fragrant thiophenol is produced under catalyst action, it is characterised in that in step 2
Described hybrid reaction, first with the oxygen in nitrogen sparge tube formula reactor, then leads to the hydrogen sulfide gas, makes tubular reactor
In be full of after hydrogen sulfide, then the 1- halogenated aromatic compounds of logical preheating steam, make 1- halogenated aromatic compounds in stink damp
Reacted in atmosphere.
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| CN106432013B (en) * | 2016-09-05 | 2018-01-26 | 江西仁明医药化工有限公司 | The method that overcritical hydrogen sulfide pipeline is combined to benzenethiol |
| CN106432012B (en) * | 2016-09-05 | 2018-01-19 | 江西仁明医药化工有限公司 | The method of overcritical hydrogen sulfide synthesis benzenethiol |
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| US3799989A (en) * | 1971-07-29 | 1974-03-26 | Phillips Petroleum Co | Cleavage of aromatic thioether |
| IL59616A (en) * | 1979-04-02 | 1984-10-31 | Stauffer Chemical Co | Production of thiophenol |
| UA75374C2 (en) * | 2000-10-11 | 2006-04-17 | Сінгента Партісіпейшнс Аг | A process for the preparation of thiophenols |
| CN1590371A (en) * | 2004-03-16 | 2005-03-09 | 浙江工业大学 | Preparation method of substituted thiophenol |
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