CN110407725A - A kind of preparation method of 2 mercapto ethanol - Google Patents
A kind of preparation method of 2 mercapto ethanol Download PDFInfo
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- CN110407725A CN110407725A CN201910762041.7A CN201910762041A CN110407725A CN 110407725 A CN110407725 A CN 110407725A CN 201910762041 A CN201910762041 A CN 201910762041A CN 110407725 A CN110407725 A CN 110407725A
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- mercapto ethanol
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- hydrogen sulfide
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- 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
Abstract
The invention belongs to chemical fields, and in particular to a kind of preparation method of 2 mercapto ethanol.The present invention uses microchannel reaction technology, amount of by-products is lower than 0.3% in reaction process, after rectifying removes solvent, catalyst, material content is the requirement for reaching existing market >=99.5% in tower reactor, while reducing by-product, mercaptoethanol yield (in terms of ethylene oxide) is improved to 99% or more, and reduces a rectifying frequency, and then reduces isolated energy consumption and cost.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of preparation method of 2 mercapto ethanol.
Background technique
Adopt epoxyethane method production 2 mercapto ethanol both at home and abroad at present, technique is generally hydrogen sulfide and ethylene oxide molten
2 mercapto ethanol is directly synthesized at a temperature of agent, catalyst and certain pressure；Production technology according to reaction pressure be divided into non-pressure process and
Two kinds of pressurization, external to use high-pressure process, reaction pressure is from 1.0-3.5MPa, reaction time 5-60min more；The country is using all
For non-pressure process, for reaction pressure in 0.1-0.5MPa, non-pressure process is not high to equipment requirement, but by-product is more, thus conversion ratio and
Yield all relatively high pressure methods are lower.
The prior art: the country is to 2 mercapto ethanol synthetic method it has been reported that such as Sichuan chemical industry 04 phase in 2018 at present
Liquid phase LP synthesizing technique is mentioned in [with the synthesising process research of desulfurization exhaust gas production 2 mercapto ethanol], it is organic to use liquid
Alkali compounds makees catalyst, raw material hydrogen sulfide be absorbed by liquid absorption after in a liquid-like manner and reacting ethylene oxide, ethylene oxide
It is fed with gaseous state or liquid form.Workshop section is recycled before reaction product is isolated solvent and catalyst and returned through distillation.Slightly
Product obtains qualified 2 mercapto ethanol product through rectification under vacuum.Though raffinate can further recycle to obtain thiodiglycol product,
Thiodiglycol market is small, and the Thiodiglycol coloration recycled is higher, so that its value substantially reduces.
Low pressure liquid phase method amount of by-products is higher, and to ensure that 2 mercapto ethanol content is higher than 99.5%, urges in removing solvent
After agent, also needs to carry out secondary rectifying to 2 mercapto ethanol, allow 2 mercapto ethanol in overhead extraction, this process makes 2 mercapto ethanol
Yield is again lowered to (95%-96%), and secondary rectifying also increases energy consumption.
Summary of the invention
In order to overcome the above technical defects, the present invention uses microchannel reaction technology, and amount of by-products is lower than in reaction process
0.3%, after rectifying removes solvent, catalyst, material content is the requirement for reaching existing market >=99.5% in tower reactor, is reduced secondary
While product, mercaptoethanol yield (in terms of ethylene oxide) raising to 99% or more, and a rectifying frequency is reduced, in turn
Reduce isolated energy consumption and cost.
Specifically, the technical solution adopted by the present invention is, a kind of preparation method of 2 mercapto ethanol, comprising:
Step 1: a certain amount of solvent, catalyst being added in autoclave, after being adjusted to required temperature, is passed through stink damp
Body continues logical hydrogen sulfide and rises to certain pressure when kettle temperature, which starts, to be reduced；
Step 2: step 1 gained mixed liquor being squeezed into micro passage reaction with certain flow, while control ring in proportion
Oxidative ethane enters the flow in micro passage reaction, controls reaction temperature and pressure, is reacted, obtaining crude product, (reaction temperature is steady
Start to collect crude product after fixed)；
Step 3: crude product being added in rectifying column, carries out rectification under vacuum, kettle liquid is after removing hydrogen sulfide, solvent, catalyst
For 2 mercapto ethanol product.
Solvent is one of methanol, tetrahydrofuran, chloroform, water or a variety of in step 1；
Solvent, catalyst preferred mass ratio are 1~6:1, preferably 1~4:1, more preferable 1.5~2.5:1 in step 1；
Catalyst described in step 1 is triethylamine；
Temperature described in step 1 is 0-15 DEG C, preferably 6-10 DEG C；
Pressure is 0.3~1.2Mpa, preferably 0.5-1.0Mpa in step 1；
Hydrogen sulfide absorption liquid and ethylene oxide quality proportioning are 8~15:1, preferably 10~13:1 in step 2；
The preferred residence time is 60~120s, preferably 90-110s in micro passage reaction in step 2.
30~70 DEG C of preferable reaction temperature in step 2, preferably 40~60 DEG C.
Reaction pressure is 0.5~1.2mpa, preferably 0.5~1.0Mpa in step 2.
Present invention is characterized in that using micro passage reaction, (reactor is the prior art, and conventional commercial can obtain, example
It such as: healthy and free from worry G1 glass reactor) synthesizes, is conducive to the contact probability and mass-and heat-transfer performance that increase reactant and catalyst, mentions
High reaction efficiency；30-70 DEG C of reaction temperature, preferably 40-60 DEG C improve reaction rate, reduce the reaction time；Absorb hydrogen sulfide
Solvent uses tetrahydrofuran, methanol (prior art is generally using methanol as solvent), hydrogen sulfide absorption liquid and ethylene oxide quality
8-15:1 and reaction pressure 0.5-1.2Mpa is matched, operation difficulty is reduced while improving the selectivity of mercaptoethanol, is dropped
Low cost, and by mercaptoethanol selectivity by using the 97-98% of tubular reactor to improve to 99.5% or more makes thio two sweet
Alcohol content≤0.3%, product can reach quality requirement without separating with by-product, reduce separating energy consumption.In conclusion this hair
It is bright to use microchannel reaction technology, W-response is improved, so that by-product Thiodiglycol content is low in reaction process
In 0.3%, after rectifying removes solvent, catalyst, material content is the requirement for reaching existing market >=99.5% in tower reactor, and is being dropped
While low side reaction, a rectifying frequency is reduced, further reduced separating energy consumption and cost.
Specific embodiment
The specific embodiment of form by the following examples does further specifically above content of the invention
It is bright, but the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention, and it is complete to be all made of conventional prior unless otherwise specified, in following embodiments
At.
Embodiment 1
Methanol, triethylamine are pressed into 2:1 proportional arrangement 500g in autoclave, reducing temperature is 10 DEG C, is passed through hydrogen sulfide extremely
Pressure is stablized to 0.3mpa, and temperature control module is started, and hydrogen sulfide absorption liquid and ethylene oxide is passed through by the mass ratio of 10:1 micro-
Channel reactor controls 40 DEG C of reaction temperature, reaction pressure 0.7mpa, reaction time 60s, removed under reduced pressure hydrogen sulfide, first
After alcohol, triethylamine, mercaptoethanol content 99.52% in kettle liquid, Thiodiglycol content 0.38%, the sulfydryl second in terms of ethylene oxide
Alcohol yield 99.02%.
Embodiment 2
Methanol, water, triethylamine are configured into 500g by the mass ratio of 3:0.5:1 in autoclave, cooling temperature is 5 DEG C,
It is passed through hydrogen sulfide to pressure to stablize to 0.5mpa, starts temperature control module, hydrogen sulfide absorption liquid and ethylene oxide are pressed to the matter of 13:1
Amount ratio is passed through micro passage reaction, controls 50 DEG C of reaction temperature, reaction pressure 0.5mpa, reaction time 90s, decompression is de-
After vulcanisation hydrogen, methanol, water, triethylamine, mercaptoethanol content 99.68% in kettle liquid, Thiodiglycol content 0.21%, with ring
Oxidative ethane meter mercaptoethanol yield 99.21%.
Embodiment 3
Methanol, chloroform, triethylamine are configured into 500g by the mass ratio of 3:0.5:1 in autoclave, cooling temperature is 5
DEG C, it is passed through hydrogen sulfide to pressure and stablizes to 0.7mpa, start temperature control module, by hydrogen sulfide absorption liquid and ethylene oxide by 15:1's
Mass ratio is passed through micro passage reaction, controls 60 DEG C of reaction temperature, reaction pressure 0.6mpa, reaction time 75s, decompression
After removing hydrogen sulfide, methanol, chloroform, triethylamine, mercaptoethanol content 99.5% in kettle liquid, Thiodiglycol content 0.43%,
The mercaptoethanol yield 97.3% in terms of ethylene oxide.
Embodiment 4
Tetrahydrofuran, triethylamine are configured into 500g by the mass ratio of 4:1 in autoclave, cooling temperature is 10 DEG C, is led to
Enter hydrogen sulfide to pressure to stablize to 0.6mpa, start temperature control module, hydrogen sulfide absorption liquid and ethylene oxide are pressed to the quality of 10:1
Ratio is passed through micro passage reaction, controls 55 DEG C of reaction temperature, reaction pressure 0.7mpa, reaction time 75s, removed under reduced pressure
After hydrogen sulfide, tetrahydrofuran, triethylamine, mercaptoethanol content yield 99.69% in kettle liquid, Thiodiglycol content 0.11%,
The mercaptoethanol yield 99.34% in terms of ethylene oxide.
Embodiment 5
Press tetrahydrofuran, water, triethylamine in autoclave: the mass ratio configuration 500g of 4:0.2:1, cooling temperature are
It 5 DEG C, is passed through hydrogen sulfide to pressure and stablizes to 0.5mpa, start temperature control module, hydrogen sulfide absorption liquid and ethylene oxide are pressed into 13:1
Mass ratio be passed through micro passage reaction, control 35 DEG C of reaction temperature, reaction pressure 0.7mpa, reaction time 90s subtract
After the vulcanisation hydrogen of pressure-off, tetrahydrofuran, water, triethylamine, mercaptoethanol content 99.88% in kettle liquid, Thiodiglycol content
0.07%, the mercaptoethanol yield 99.42% in terms of ethylene oxide.
Comparative example 1
Methanol, triethylamine are configured into 500g by the mass ratio of 2:1 in autoclave, cooling temperature is 5 DEG C, is passed through vulcanization
Hydrogen to pressure is stablized to 0.6mpa, starts temperature control module, hydrogen sulfide absorption liquid and ethylene oxide are led to by the mass ratio of 15:1
Enter tubular reactor, controls 40 DEG C of reaction temperature, reaction pressure 0.5mpa, reaction time 160s, removed under reduced pressure hydrogen sulfide,
After methanol, triethylamine, mercaptoethanol content 97.02% in kettle liquid, Thiodiglycol content 2.94%, the sulfydryl in terms of ethylene oxide
Ethanol yield 95.11%.
Comparative example 2
Methanol, triethylamine are configured into 500g by the mass ratio of 4:1 in autoclave, cooling temperature is 5 DEG C, is passed through vulcanization
Hydrogen to pressure is stablized to 0.6mpa, starts temperature control module, hydrogen sulfide absorption liquid and ethylene oxide are led to by the mass ratio of 10:1
Enter tubular reactor, controls 50 DEG C of reaction temperature, reaction pressure 1.0mpa, reaction time 160s, removed under reduced pressure hydrogen sulfide,
After methanol, triethylamine, mercaptoethanol content 97.43% in kettle liquid, Thiodiglycol content 2.38%, the sulfydryl in terms of ethylene oxide
Ethanol yield 95.8%.
Claims (10)
1. a kind of preparation method of 2 mercapto ethanol, which is characterized in that specific steps include:
Step 1: solvent, catalyst being added in autoclave, after being adjusted to required temperature, is passed through hydrogen sulfide gas, is opened to kettle temperature
When beginning to reduce, continues logical hydrogen sulfide and rise to certain pressure；
Step 2: step 1 gained mixed liquor being squeezed into micro passage reaction, ethylene oxide enters in micro passage reaction, control
Reaction temperature and pressure, are reacted, and crude product is obtained；
Step 3: crude product being subjected to rectification under vacuum, kettle liquid is 2 mercapto ethanol product after removing hydrogen sulfide, solvent, catalyst.
2. a kind of preparation method of 2 mercapto ethanol according to claim 1, which is characterized in that solvent is first in step 1
One of alcohol, tetrahydrofuran, chloroform, water are a variety of.
3. a kind of preparation method of 2 mercapto ethanol according to claim 1, which is characterized in that solvent, catalysis in step 1
Agent mass ratio is 1~6:1；Catalyst described in step 1 is triethylamine.
4. a kind of preparation method of 2 mercapto ethanol according to claim 3, which is characterized in that solvent, catalysis in step 1
Agent preferred mass ratio is 1~4:1.
5. a kind of preparation method of 2 mercapto ethanol according to claim 1, which is characterized in that temperature described in step 1
Degree is 0-15 DEG C；Pressure is 0.3~1.2Mpa in step 1.
6. a kind of preparation method of 2 mercapto ethanol according to claim 1, which is characterized in that solvent, catalysis in step 1
Agent preferred mass ratio is 1.5~2.5:1；The temperature is 6-10 DEG C；Pressure is 0.5-1.0Mpa.
7. a kind of preparation method of 2 mercapto ethanol according to claim 1, which is characterized in that hydrogen sulfide is inhaled in step 2
It receives liquid and ethylene oxide quality proportioning is 8~15:1.
8. a kind of preparation method of 2 mercapto ethanol according to claim 1, which is characterized in that microchannel plate in step 2
Answering the residence time in device is 60~120s；30~70 DEG C of reaction temperature.
9. a kind of preparation method of 2 mercapto ethanol according to claim 1, which is characterized in that reaction pressure in step 2
For 0.5~1.2mpa.
10. a kind of preparation method of 2 mercapto ethanol according to claim 1, which is characterized in that hydrogen sulfide is inhaled in step 2
It receives liquid and ethylene oxide quality proportioning is 10~13:1；The residence time is 90-110s in micro passage reaction；Reaction temperature 40~
60℃；Reaction pressure is 0.5~1.0Mpa.
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| CN201910762041.7A CN110407725B (en) | 2019-08-16 | 2019-08-16 | Preparation method of 2-mercaptoethanol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582891A (en) * | 2021-03-25 | 2021-11-02 | 南京大学 | H catalysis with ionic liquid as catalyst2Method for preparing mercaptoalcohol with high additional value by reacting S with epoxy and enol |
| CN115521231A (en) * | 2022-09-23 | 2022-12-27 | 天宝动物营养科技股份有限公司 | Environment-friendly clean preparation method of taurine |
Citations (1)
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|---|---|---|---|---|
| WO2016024012A1 (en) * | 2014-08-15 | 2016-02-18 | Basf Se | Method for producing 2-mercaptoethanol |
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2019
- 2019-08-16 CN CN201910762041.7A patent/CN110407725B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016024012A1 (en) * | 2014-08-15 | 2016-02-18 | Basf Se | Method for producing 2-mercaptoethanol |
Non-Patent Citations (2)
| Title |
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| 梁虎: "用脱硫废气生产2-巯基乙醇的合成工艺研究", 《四川化工》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582891A (en) * | 2021-03-25 | 2021-11-02 | 南京大学 | H catalysis with ionic liquid as catalyst2Method for preparing mercaptoalcohol with high additional value by reacting S with epoxy and enol |
| CN115521231A (en) * | 2022-09-23 | 2022-12-27 | 天宝动物营养科技股份有限公司 | Environment-friendly clean preparation method of taurine |
| CN115521231B (en) * | 2022-09-23 | 2024-02-09 | 天宝动物营养科技股份有限公司 | Environment-friendly clean preparation method of taurine |
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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. |