CN108440353A - A kind of chloromethanes reacts the method for preparing methyl mercaptan with hydrogen sulfide - Google Patents
A kind of chloromethanes reacts the method for preparing methyl mercaptan with hydrogen sulfide Download PDFInfo
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- hydrogen sulfide
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- 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
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Abstract
The invention discloses a kind of methods that chloromethanes hydrogen sulfide produces methyl mercaptan, include the following steps：Quantitative chloromethanes and hydrogen sulfide gas are passed in the reactor that catalyst is added, chemically reacted under certain temperature and pressure, reaction terminates cooling, and separation obtains methyl mercaptan.The reaction that the present invention uses is easy to operate for gas-solid/liquid/gas reactions, and target product selectivity is high and purity is high, does not generate any waste water in the process, and pollution is few, and by-product is mainly hydrogen chloride, can be used as product sale, has larger economic implications.
Description
Technical field
The present invention relates to methyl mercaptan preparation method technical fields more particularly to a kind of chloromethanes to react preparation first with hydrogen sulfide
The method of mercaptan.
Background technology
Methyl mercaptan is a kind of colourless gas at normal temperatures and pressures, there is offending smell, not soluble in water, is dissolved in ethyl alcohol, second
The organic solvents such as ether, for organic synthesis and raw material, the catalyst etc. of insecticide, the huge market demand.Industrially often by methanol
It is acted on hydrogen sulfide, or is reacted and be made with dimethyl suflfate by NaHS, but two kinds of modes of production generate a large amount of waste water,
Processing cost is high.
Number of patent application be 97123454.X patent be related to a kind of method of continuous production of methyl mercaptan, including make methanol and
The feed gas mixtures of hydrogen sulfide are at 300-500 DEG C of temperature and the pressure of 5-15bar in the catalyst containing aluminium oxide
Bed on reacted, feed gas mixtures through the following steps that obtain：A) compression hydrogen sulfide make-up gas is among one
Pressure, while liquid methanol is added, b) mixing circulation hydrogen sulfide gas and make-up gas, and mixture is compressed to operation pressure
Power, c) into compressed gas mixtures, addition supplement methanol is to generate feed gas mixtures in the form of methanol steam, vulcanization
The molar ratio of hydrogen and methanol is 1.1-3, d) feed gas mixtures are heated to 150-200 DEG C of preheating temperature, e) utilize and urging
The reaction heat released in agent bed further heats feed gas mixtures in heat exchanger and is being urged to reaction temperature and f)
Methanol is set to react production methyl mercaptan with hydrogen sulfide in agent bed.
Number of patent application be 200680011532.9 patent, be related to the continuous catalysis preparation method of methyl mercaptan, by
At 200-600 DEG C of temperature and the pressure of 1.5-40bar in the gas phase methanol of reaction and hydrogen sulfide and carry out, wherein：A) by institute
The catalyst distribution for the amount of having is at least two regions being separated from each other；B) it is provided with including methanol and vulcanization in first region
The admixture of gas of hydrogen；C) at first, second between other regions for being optionally present, in the form of liquid or gas
Feed methanol and methyl mercaptan that d) separation is formed, e) used in hydrogen sulfide and the integral molar quantity ratio of methanol be 1: 1 to 10: 1,
Preferably 1: 1 to 5: 1.
The patent that number of patent application is 201210567018.0, is related to a kind of method preparing methyl mercaptan, including following step
Suddenly：(1) preparation of catalyst：Potassium tungstate is loaded on carrier γ-Al2O3 using conventional impregnation method, zinc chloride is then added
Solution, it is 2%-20% to make mass content of the zinc chloride in entire catalyst, impregnates 3-30h at 20-60 DEG C later,
After being dried to constant weight in 50-150 DEG C of baking oven 1-6h is roasted at 200-600 DEG C；(2) pretreatment of raw material：By hydrogen sulfide and liquid
Methanol 1-10 mixed feedings in molar ratio preheat vaporization at 260-300 DEG C；(3) reaction treatment：The unstripped gas that pretreatment is completed
It is passed through reactor and comes into full contact with catalyst and reacted, adjust 320-390 DEG C of reaction temperature, pressure 0.5-1.0MPa, when reaction
Between 2-4h, obtain mixed gas；(4) separating treatment：Mixed gas pressure release to 0.2-0.5MPa is obtained into target production through separating treatment
Object methyl mercaptan.
But process above, hydrogen sulfide is all made of with methanol as raw material, is found in actual production, above-mentioned technique, it is secondary
Product is more, and if there are many methyl sulfide, dimethyl disulfide or other impurities in product, yield is not high, and the selectivity of reaction is not high, is easy
Series connection side reaction occurs such as
CH3OH+H2S→CH3SH+H2O
CH3SH+CH3SH→CH3SCH3+H2S
CH3SH+CH3SH→CH3S—SCH3+H2。
Meanwhile at present prepare methyl mercaptan using more NaHS and dimethyl suflfate method, in production process then
Generate a large amount of waste water, it is difficult to handle, not meet " Green Chemistry " theory.
In small-scale production, has instead to give birth in sodium hydroxide solution with hydrogen sulfide using chloromethanes and react, but exist secondary
Product is more, and yield is low and has the shortcomings that pollution.
Therefore, a kind of new methyl mercaptan production method is developed, not only there is urgent researching value, it may have good warp
Benefit of helping and commercial application potentiality, where this power that exactly present invention is accomplished and basis.
Invention content
In order to overcome the defect of the prior art as indicated above, the present inventor to have made intensive studies this, paying
After a large amount of creative works, so as to complete the present invention.
Specifically, the technical problem to be solved by the present invention is to：A kind of chloromethanes hydrogen sulfide production methyl mercaptan is provided
Method, to reduce wastewater flow rate and byproduct of reaction.
In order to solve the above technical problems, the technical scheme is that：
A kind of method of chloromethanes hydrogen sulfide production methyl mercaptan, includes the following steps：It will quantitative chloromethanes and stink damp
Body passes in the reactor that catalyst is added, and is chemically reacted under certain temperature and pressure, and reaction terminates cooling, detaches,
Obtain methyl mercaptan.
In the present invention, as a kind of perferred technical scheme, described method includes following steps：
(1) catalyst is added, the air excluded in reactor is replaced with nitrogen；
(2) it is passed through reaction gas chloromethanes and hydrogen sulfide gas, controlling reaction temperature and pressure, is reacted；
(3) reaction terminates, and cools down, adjusts pressure, detaches product, obtain high-purity methyl mercaptan and byproduct hydrogen chloride.
In the present invention, as a kind of perferred technical scheme, in step (1), catalyst is using in tungsten, molybdenum, iron, cobalt, nickel
One kind.
In the present invention, as a kind of perferred technical scheme, in step (1), catalyst uses VI B races metallic element.
In the present invention, as a kind of perferred technical scheme, in step (1), catalyst uses tungsten.
In the present invention, as a kind of perferred technical scheme, in step (1), reactor uses fixed bed reactors.
In the present invention, as a kind of perferred technical scheme, setting is to carry with gama-alumina in the fixed bed reactors
Body impregnates tungstenic metal ion solution, and high-temperature calcination is with fixed catalytic bed.
In the present invention, as a kind of perferred technical scheme, the calcination temperature is 800~1200 DEG C.
In the present invention, as a kind of perferred technical scheme, in step (2), gas chloromethanes and hydrogen sulfide molar ratio are
CH3Cl：H2S=1:1.0-1.2.
In the present invention, as a kind of perferred technical scheme, in step (2), chloromethanes is 1 with hydrogen sulfide molar ratio:1.
In the present invention, as a kind of perferred technical scheme, in step (2), it is warming up to 100 DEG C first, into reactor
It is passed through methyl chloride gas, is continuously heating to 150 DEG C, starts to be passed through hydrogen sulfide gas.
In the present invention, as a kind of perferred technical scheme, in step (2), 260 DEG C -320 DEG C of controlling reaction temperature, pressure
Power 0.8MPa-1.5MPa.
In the present invention, as a kind of perferred technical scheme, in step (3), adjustment pressure is 0.7-0.9MPa, is cooled to
20-30 DEG C, by the isolated high-purity methyl mercaptan of gas-liquid separation, while obtaining the dry hydrogen chloride gas of by-product.
Inventor has found under study for action, loads the metal catalytics such as tungsten, molybdenum, iron, cobalt, nickel respectively in fixed bed reactors
Agent, under optimum reaction condition, the selectivity of methyl mercaptan is followed successively by 96%, 92%, 59%, 60%, therefore, using optimal tungsten
Catalyst is as catalysts.
The amount ratio of chloromethanes and hydrogen sulfide is in molar ratio CH3Cl：H2S=1:1.0~1.2 feed intake, and ensure chlorine
Methane is completely converted into object, and since product methyl mercaptan amount is not much different, adjustment molar ratio is 1:1.
In the presence of 260 DEG C~320 DEG C, pressure 0.8MPa~1.5MPa of reaction temperature, catalyst, chloromethanes with
Following reaction occurs for hydrogen sulfide：
The gas that the present invention finally obtains is mainly methyl mercaptan and hydrogen chloride, is existed as a mixture, according to the two
Boiling point it is different, under a certain pressure, reduce temperature, methyl mercaptan is changed into liquid by gaseous state, and hydrogen chloride remains gaseous state, enters
Gas-liquid separator is detached.
After using above-mentioned technical proposal, the beneficial effects of the invention are as follows：
When the present invention makees raw material using chloromethanes, the activity of chloromethanes is relatively high, and reaction is made to be easier to occur, reaction speed
Faster, selectivity is also more preferable, and general yield is up to 98% for rate.
General methanol is reacted with hydrogen sulfide or NaHS, and the methyl mercaptan of generation is dissolved in the water more, influences the pure of product
Degree；And the method for preparing methyl mercaptan using more NaHS and dimethyl suflfate at present, it then generates in production process a large amount of
Waste water, it is difficult to handle, not meet " Green Chemistry " theory.The byproduct of reaction that the present invention obtains is dry hydrogen chloride gas, is had
Compared with high added value, principal product is opposite with anti-product easily separated, and product purity is higher.
The reaction that the present invention uses is easy to operate for gas-solid/liquid/gas reactions, and target product selectivity is high and purity is high, in the process
Any waste water is not generated, and pollution is few, and by-product is mainly hydrogen chloride, can be used as product sale, has larger economic implications.
Specific implementation mode
With reference to specific embodiment, the present invention is further described.But the purposes and mesh of these exemplary embodiments
Be only used for enumerating the present invention, any type of any restriction not is constituted to the real protection scope of the present invention, it is more non-to incite somebody to action this
The protection domain of invention is confined to this.
Embodiment 1
A kind of method of chloromethanes hydrogen sulfide production methyl mercaptan, described method includes following steps：
(1) catalyst is added, the air excluded in reactor is replaced with nitrogen, wherein reactor uses fixed bed reaction
Device is arranged inside using gama-alumina as carrier impregnation tungstenic metal ion solution and high-temperature calcination is with fixed catalytic bed, forges
It is 800 DEG C to burn temperature；
(2) it is passed through reaction gas chloromethanes and hydrogen sulfide gas, gas chloromethanes and hydrogen sulfide molar ratio are CH3Cl：H2S
=1:1.1,260 DEG C of controlling reaction temperature, pressure 0.8MPa is reacted, and the reaction time of mixed gas in the reactor is
13min；
(2) reaction terminates, and adjustment pressure is 0.7MPa, is cooled to 20 DEG C, detaches product, isolated by gas-liquid separation
High-purity methyl mercaptan and byproduct hydrogen chloride.
Methyl mercaptan 821g and hydrogen chloride 617g is obtained, conversion ratio 96.3%, by-product is mainly hydrogen chloride, and content is
98.4%.
Embodiment 2
A kind of method of chloromethanes hydrogen sulfide production methyl mercaptan, described method includes following steps：
(1) catalyst is added, the air excluded in reactor is replaced with nitrogen, wherein reactor uses fixed bed reaction
Device is arranged inside using gama-alumina as carrier impregnation tungstenic metal ion solution and high-temperature calcination is with fixed catalytic bed, forges
It is 1200 DEG C to burn temperature；
(2) it is passed through reaction gas chloromethanes and hydrogen sulfide gas, gas chloromethanes and hydrogen sulfide molar ratio are CH3Cl：H2S
=1:1.2,320 DEG C of controlling reaction temperature, pressure 1.5MPa is reacted, and the reaction time of mixed gas in the reactor is
1min；
(2) reaction terminates, and adjustment pressure is 0.9MPa, is cooled to 30 DEG C, detaches product, isolated by gas-liquid separation
High-purity methyl mercaptan and byproduct hydrogen chloride.
Methyl mercaptan 827g and hydrogen chloride 619g is obtained, other micro by-products, conversion ratio 96.5%, by-product is mainly chlorination
Hydrogen, content 98.3%.
Embodiment 3
A kind of method of chloromethanes hydrogen sulfide production methyl mercaptan, described method includes following steps：
(1) catalyst is added, the air excluded in reactor is replaced with nitrogen, wherein reactor uses fixed bed reaction
Device is arranged inside using gama-alumina as carrier impregnation tungstenic metal ion solution and high-temperature calcination is with fixed catalytic bed, forges
It is 1000 DEG C to burn temperature；
(2) 100 DEG C are warming up to, methyl chloride gas is passed through into reactor, is continuously heating to 150 DEG C, starts to be passed through vulcanization
Hydrogen；Chloromethanes is 1 with hydrogen sulfide molar ratio:1,290 DEG C of controlling reaction temperature, pressure 1.1MPa is reacted, gaseous mixture
The reaction time of body in the reactor is 15min；
(2) reaction terminates, and adjustment pressure is 0.8MPa, is cooled to 25 DEG C, detaches product, isolated by gas-liquid separation
High-purity methyl mercaptan and byproduct hydrogen chloride.
Methyl mercaptan 841g and hydrogen chloride 625g is obtained, conversion ratio 97.5%, by-product is mainly hydrogen chloride, and content is
99.1%.
Embodiment 4
Into 5L fixed bed reactors using gama-alumina as carrier impregnation tungstenic metal ion solution, and high-temperature calcination with
It is fixed；800 DEG C of calcination temperature.
Nitrogen is passed through into reactor, the pressure in each reaction device is controlled in 0.5MPa, in triplicate, it is ensured that in reaction
Air is replaced completely；
100 DEG C are warming up to, methyl chloride gas is passed through into reactor, is continuously heating to 150 DEG C, starts to be passed through stink damp
Body；
300 DEG C or so are continuously heating to, control pressure is in 0.8Mpa, the reaction time of mixed gas in the reactor
20min, into piece-rate system；
In piece-rate system, greenhouse cooling to 25 DEG C, gas-liquid separation obtains methyl mercaptan 834g and hydrogen chloride 620g, conversion ratio
96.3%, by-product is mainly hydrogen chloride, content 98.8%.
Embodiment 5
The gamma-aluminium oxide carrier for having loaded tungsten catalyst is added into 100L fluidized-bed reactors；
It is passed through air in nitrogen metathesis reactor；
Heating is opened, reactant is passed through into reactor, amounts to and 20L methyl chloride gas, 10.5L hydrogen sulfide gas is added；
Wait for that temperature rises to 300 DEG C or so, control pressure is in 1.5MPa, mixed gas reaction time 5min, into gas-liquid point
From system；
Cool down in piece-rate system, waits for that temperature is less than 25 DEG C, carry out gas-liquid separation, obtain methyl mercaptan 16.61Kg, chlorination
Hydrogen 12.30Kg, conversion ratio 96.2%, by-product are mainly hydrogen chloride, content 98.3%.
Comparative example 1
According to the scheme of patent 97123454.X, methyl mercaptan is produced.Using methanol and hydrogen sulfide as raw material, at 300-500 DEG C
Temperature and 5-15bar pressure under reacted in the catalyst bed containing aluminium oxide.
Byproduct compounds complexity is obtained, wherein methyl sulfide 54%, dimethyl disulfide 21%, surplus are other impurities.
Product average yield is 91.7%.
Comparative example 2
According to the methyl mercaptan continuous catalysis preparation method of patent 200680011532.9, by 200-600 DEG C of temperature
With under the pressure of 1.5-40bar in the gas phase methanol of reaction and hydrogen sulfide and carry out.
Byproduct compounds complexity is obtained, wherein methyl sulfide 61%, dimethyl disulfide 17%, surplus are other impurities.
Product average yield is 92.1%.
Comparative example 3
According to the method that patent 201210567018.0 prepares methyl mercaptan, the preparation of (1) catalyst：Using conventional impregnation method
Potassium tungstate is loaded on carrier γ-Al2O3, liquor zinci chloridi is then added, makes quality of the zinc chloride in entire catalyst
Content is 2%-20%, impregnates 3-30h at 20-60 DEG C later, in 200-600 after being dried to constant weight in 50-150 DEG C of baking oven
1-6h is roasted at DEG C；(2) pretreatment of raw material：By hydrogen sulfide and liquid methanol 1-10 mixed feedings in molar ratio, at 260-300 DEG C
Preheating vaporization；(3) reaction treatment：Unstripped gas that pretreatment is completed is passed through reactor and comes into full contact with catalyst and is reacted, is adjusted
320-390 DEG C of reaction temperature is saved, pressure 0.5-1.0MPa, reaction time 2-4h obtain mixed gas；(4) separating treatment：It will mixing
Air venting obtains target product methyl mercaptan to 0.2-0.5MPa through separating treatment.
Byproduct compounds complexity is obtained, wherein methyl sulfide 51%, dimethyl disulfide 19%, surplus are other impurities.Also,
Generate a large amount of waste water.
Product average yield is 93.7%.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limitation protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within and are protected defined by the application the appended claims
Within the scope of shield.
Claims (10)
1. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan, it is characterised in that：Include the following steps：Will quantitative chloromethanes with
Hydrogen sulfide gas passes in the reactor that catalyst is added, and is chemically reacted under certain temperature and pressure, and reaction terminates drop
Temperature, separation, obtains methyl mercaptan.
2. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as described in claim 1, it is characterised in that：Including walking as follows
Suddenly：
(1) catalyst is added, the air excluded in reactor is replaced with nitrogen；
(2) it is passed through reaction gas chloromethanes and hydrogen sulfide gas, controlling reaction temperature and pressure, is reacted；
(3) reaction terminates, and cools down, adjusts pressure, detaches product, obtain high-purity methyl mercaptan and byproduct hydrogen chloride.
3. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as claimed in claim 2, it is characterised in that：In step (1),
Catalyst is using one kind in tungsten, molybdenum, iron, cobalt, nickel.
4. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as described in claim 1, it is characterised in that：In step (1),
Reactor uses fixed bed reactors.
5. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as described in claim 1, it is characterised in that：The fixed bed
It is arranged using gama-alumina as carrier impregnation tungstenic metal ion solution in reactor, and high-temperature calcination is with fixed catalytic bed.
6. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as described in claim 1, it is characterised in that：The calcining temperature
Degree is 800~1200 DEG C.
7. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as described in claim 1, it is characterised in that：In step (2),
Gas chloromethanes and hydrogen sulfide molar ratio are CH3Cl：H2S=1:1.0-1.2.
8. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as described in claim 1, it is characterised in that：In step (2),
It is warming up to 100 DEG C first, methyl chloride gas is passed through into reactor, is continuously heating to 150 DEG C, starts to be passed through hydrogen sulfide gas.
9. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as described in claim 1, it is characterised in that：In step (2),
260 DEG C -320 DEG C of controlling reaction temperature, pressure 0.8MPa-1.5MPa.
10. a kind of method of chloromethanes hydrogen sulfide production methyl mercaptan as described in claim 1, it is characterised in that：Step (3)
In, adjustment pressure is 0.7-0.9MPa, is cooled to 20-30 DEG C, by the isolated high-purity methyl mercaptan of gas-liquid separation, simultaneously
To the dry hydrogen chloride gas of by-product.
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Citations (4)
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|---|---|---|---|---|
| CN101155778A (en) * | 2005-04-09 | 2008-04-02 | 德古萨有限责任公司 | Method for the continuous production of methyl mercaptan |
| JP2012056898A (en) * | 2010-09-09 | 2012-03-22 | Sumitomo Seika Chem Co Ltd | Method for producing alkane thiol |
| CN102993067A (en) * | 2012-12-24 | 2013-03-27 | 贵州大学 | Method for preparing methanthiol |
| CN103443088A (en) * | 2011-03-18 | 2013-12-11 | 住友精化株式会社 | Method for producing 1,2-enzisothiazol-3-one compound |
-
2018
- 2018-04-25 CN CN201810379636.XA patent/CN108440353A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101155778A (en) * | 2005-04-09 | 2008-04-02 | 德古萨有限责任公司 | Method for the continuous production of methyl mercaptan |
| JP2012056898A (en) * | 2010-09-09 | 2012-03-22 | Sumitomo Seika Chem Co Ltd | Method for producing alkane thiol |
| CN103443088A (en) * | 2011-03-18 | 2013-12-11 | 住友精化株式会社 | Method for producing 1,2-enzisothiazol-3-one compound |
| CN102993067A (en) * | 2012-12-24 | 2013-03-27 | 贵州大学 | Method for preparing methanthiol |
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| Title |
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