CN108752176A - A kind of trichloroacetone production technology - Google Patents
A kind of trichloroacetone production technology Download PDFInfo
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- CN108752176A CN108752176A CN201810724525.8A CN201810724525A CN108752176A CN 108752176 A CN108752176 A CN 108752176A CN 201810724525 A CN201810724525 A CN 201810724525A CN 108752176 A CN108752176 A CN 108752176A
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- trichloroacetone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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Abstract
The present invention relates to chemicals production technical field, specially a kind of trichloroacetone production technology can relatively significantly improve the content of trichloroacetone in the crude product that one step of trichloroacetone produces, and improve product purity.Specifically include following steps：S1：Acetone is mixed with ethylene glycol, accelerating agent is added thereto, heats, stir evenly, carries out addition reaction；S2：It is passed through chlorine in the mixture prepared to S1, and catalyst is added, is stirred and evenly mixed, chlorination reaction is carried out；S3：Sour water solution is added in the mixture prepared to S2, prepares trichloroacetone crude product；S4：The trichloroacetone crude product prepared in S3 is purified for the first time with water；S5：Continued to carry out second of purification to trichloroacetone crude product with benzene；S6：Third time purification is carried out to trichloroacetone crude product with alcohol；S7：Product after S6 step process is recrystallized, trichloroacetone finished product is obtained.
Description
Technical field
The present invention relates to chemicals production technical field, specially a kind of trichloroacetone production technology.
Background technology
Primary raw material of the trichloroacetone as folic acid crude product, the quality stablized are the guarantees of folic acid quality.But it is domestic
Trichloroacetone content on the market is mostly 50% or so, and the higher trichloroacetone price of quality is the 2 of common trichloroacetone
It is more again.In actual production, trichloroacetone is extracted by water, by trichloroacetone high chlorine and low chlorine remove, so not
But a large amount of water of consumption, and still contain some low chlorine in trichloroacetone Aqueous extracts, influence crude product reaction.
Pertinent literature Jiangsu radio university journal, 2002,13 (6)：57-58 reports related trichloroacetone with high purity
Preparation method, but only illustrate that special solvent, which is added, carries out crystallization and purification, it is what not illustrate special solvent, thus
It can not realize that the yield in document is very low according to document narration, only 45%.And document is emphasized in solution to be crystallized,
Trichloroacetone content has to be larger than 50%, is not to be directed to all trichloroacetone crude products.
The patent of CN101768066A describes a kind of preparation method of trichloroacetone with high purity, it is disclosed that：First
Step is once recrystallized using the trichloroacetone of 50% purity of mixed solvent pair of hydrocarbon solvent and polar solvent, and second step is adopted
The trichloroacetone crude product that the first step obtains is recrystallized again with the mixed solvent of aliphatic ester and hydrocarbon solvent, it could be by low-purity
Trichloroacetone is increased to 80% and 98% or more.It is recrystallized using these organic solvents, not only cost improves, and inflammable, easy
It is quick-fried, pollute environment.
Invention content
The object of the present invention is to provide a kind of trichloroacetone production technologies, can relatively significantly improve one step of trichloroacetone
The content of trichloroacetone in obtained crude product is produced, product purity is improved.
The present invention above-mentioned technical purpose technical scheme is that：
A kind of trichloroacetone production technology, includes the following steps：
S1：Acetone is mixed with ethylene glycol, accelerating agent is added thereto, heats, stir evenly, carries out addition reaction；
S2：It is passed through chlorine in the mixture prepared to S1, and catalyst is added, is stirred and evenly mixed, chlorination reaction is carried out；
S3：Sour water solution is added in the mixture prepared to S2, prepares trichloroacetone crude product；
S4：The trichloroacetone crude product prepared in S3 is purified for the first time with water；
S5：Continued to carry out second of purification to trichloroacetone crude product with benzene；
S6：Third time purification is carried out to trichloroacetone crude product with alcohol；
S7：Product after S6 step process is recrystallized, trichloroacetone finished product is obtained.
Further, accelerating agent described in S1 steps is nickel.
Further, catalyst described in S2 steps is diethylamine.
Further, the acid being added in S3 steps is dust technology.
Further, the volume ratio of water and trichloroacetone crude product is 3~4 in S4 steps:1.
Further, the volume ratio of benzene and trichloroacetone crude product is 2~3 in S5 steps:1.
Further, the volume ratio of alcohol and trichloroacetone crude product is 2~3 in S6 steps:1.
Further, trichloroacetone crude product is recrystallized by the way of gradient cooling in S7 steps, and crystallizes temperature
Degree control is at 5~25 DEG C.
The invention has the advantages that：
1. first, the present invention first handles acetone, makes itself and second before acetone contacts progress chlorination reaction with chlorine
Glycol carries out addition reaction, and the carbonyl in acetone is made to eliminate, and increases the hydroxy radical content in molecule.Since the activity of carbonyl is higher,
There is a large amount of side reaction when making it with chlorine reaction, to contain a large amount of monochloroacetone, dichloroacetone, trichlorine in product
Acetone, tetrachloroacetone, five chlroacetones, hexachloroacetone and its isomer, and we eliminate carbonyl, after increasing hydroxyl, hydroxyl
Base makes the electropositivity of central carbon atom reduce, reduces electrophilic ability, reactivity is made to decline, to carry as electron donating group
The selectivity of high trichloroacetone.
2. when preparing trichloroacetone crude product, sour water solution is added into mixture, hydroxyl is made to be oxidized to carbonyl, ensures production
The normal output of object trichloroacetone.
3. when carrying out greening reaction, using diethylamine as catalyst, diethylamine can reduce in acetone molecules freely
The reactivity of base keeps the activity for the acetone not reacted completely in addition reaction consistent, trichloroacetone is further increased with this
Selectivity, improve its yield and content.
When 4. the present invention recrystallizes product by the way of gradient cooling, being purified, and cooled down, cooling pipe is by silicon
Material is made, and silicon materials have higher corrosion resistance, can significantly improve the service life of cooling pipe.
Specific implementation mode
Technical solution is clearly and completely described below in conjunction with specific embodiments of the present invention.Obviously, described
Embodiment be only the present invention a part of the embodiment, instead of all the embodiments.Based on the embodiment of the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained without making creative work, belongs to guarantor of the present invention
The range of shield.
The present invention discloses a kind of trichloroacetone production technologies, and specific production stage is as follows shown in each embodiment.
Embodiment 1
S1：Acetone 580kg and ethylene glycol 600kg are mixed in tower consersion unit, accelerating agent nickel is added thereto
30kg is heated to 30 DEG C, stirs evenly, and keeps the temperature and maintain 20min, carries out addition reaction.
S2：Stop temperature control, temperature is made to keep room temperature, the mixture then prepared to S1 by air pump and conveyance conduit
In be passed through chlorine, and catalyst diethylamine 25kg is added, stirs and evenly mixs, carry out chlorination reaction, maintain reaction 1h.
S3：The dust technology 5L that 3mol/L is added in mixture into S2 after chlorination reaction is hydrolyzed, and prepares trichlorine third
Ketone crude product.
S4：Water is added in the trichloroacetone crude product prepared into S3, the volume ratio of wherein water and trichloroacetone crude product is 3:
1, it is mixed evenly, stands 30min later, purified for the first time.
S5：To S4 treated mixture filterings, filter residue is mainly monochloroacetone and dichloroacetone, and filtrate is trichloroacetone
4mol/L benzene is added into filtrate for crude product, and the wherein volume ratio of benzene and filtrate is 2:1, it is mixed evenly, stands later
30min carries out second and purifies.
S6：The organic layer of stratification is detached with water layer after S5 is handled, and volume by volume concentration 90% is added into organic layer
Ethyl alcohol, wherein the volume ratio of ethyl alcohol and organic layer be 2:1, it is mixed evenly, stands 30min later, carry out third time and carry
It is pure.
S7：It to the product after S6 step process, is recrystallized by the way of gradient cooling, specifically, to S6
While alcohol extract after reason stirs, 25 DEG C or so are cooled to, a small amount of crystal seed, then slow cooling is added to 15 DEG C or so, keeps the temperature
2h is crystallized, a large amount of crystal are precipitated, continues to be cooled to 5 DEG C or so, maintains 15min.Filtering, crystal is removed, in filtrate mainly at
It is divided into trichloroacetone.The cooling pipe used when cooling in the present embodiment is fabricated from a silicon, this kind of cooling pipe it is corrosion-resistant
Performance is higher, can significantly improve the service life of cooling pipe.
Embodiment 2
S1：Acetone 550kg and ethylene glycol 600kg are mixed in tower consersion unit, accelerating agent nickel is added thereto
30kg is heated to 30 DEG C, stirs evenly, and keeps the temperature and maintain 20min, carries out addition reaction.
S2：Stop temperature control, temperature is made to keep room temperature, the mixture then prepared to S1 by air pump and conveyance conduit
In be passed through chlorine, and catalyst diethylamine 20kg is added, stirs and evenly mixs, carry out chlorination reaction, maintain reaction 1h.
S3：The dust technology 5L that 3mol/L is added in mixture into S2 after chlorination reaction is hydrolyzed, and prepares trichlorine third
Ketone crude product.
S4：Water is added in the trichloroacetone crude product prepared into S3, the volume ratio of wherein water and trichloroacetone crude product is 4:
1, it is mixed evenly, stands 30min later, purified for the first time.
S5：To S4 treated mixture filterings, filter residue is mainly monochloroacetone and dichloroacetone, and filtrate is trichloroacetone
4mol/L benzene is added into filtrate for crude product, and the wherein volume ratio of benzene and filtrate is 2.5:1, it is mixed evenly, stands later
30min carries out second and purifies.
S6：The organic layer of stratification is detached with water layer after S5 is handled, and volume by volume concentration 90% is added into organic layer
Ethyl alcohol, wherein the volume ratio of ethyl alcohol and organic layer be 2.5:1, it is mixed evenly, stands 30min later, carry out third time
Purification.
S7：It to the product after S6 step process, is recrystallized by the way of gradient cooling, specifically, to S6
While alcohol extract after reason stirs, 25 DEG C or so are cooled to, a small amount of crystal seed, then slow cooling is added to 15 DEG C or so, keeps the temperature
2h is crystallized, a large amount of crystal are precipitated, continues to be cooled to 5 DEG C or so, maintains 15min.Filtering, crystal is removed, in filtrate mainly at
It is divided into trichloroacetone.
Embodiment 3
S1：Acetone 500kg and ethylene glycol 620kg are mixed in tower consersion unit, accelerating agent nickel is added thereto
30kg is heated to 30 DEG C, stirs evenly, and keeps the temperature and maintain 20min, carries out addition reaction.
S2：Stop temperature control, temperature is made to keep room temperature, the mixture then prepared to S1 by air pump and conveyance conduit
In be passed through chlorine, and catalyst diethylamine 20kg is added, stirs and evenly mixs, carry out chlorination reaction, maintain reaction 1h.
S3：The dust technology 5L that 3mol/L is added in mixture into S2 after chlorination reaction is hydrolyzed, and prepares trichlorine third
Ketone crude product.
S4：Water is added in the trichloroacetone crude product prepared into S3, the volume ratio of wherein water and trichloroacetone crude product is
3.5:1, it is mixed evenly, stands 30min later, purified for the first time.
S5：To S4 treated mixture filterings, filter residue is mainly monochloroacetone and dichloroacetone, and filtrate is trichloroacetone
4mol/L benzene is added into filtrate for crude product, and the wherein volume ratio of benzene and filtrate is 3:1, it is mixed evenly, stands later
30min carries out second and purifies.
S6：The organic layer of stratification is detached with water layer after S5 is handled, and volume by volume concentration 90% is added into organic layer
Ethyl alcohol, wherein the volume ratio of ethyl alcohol and organic layer be 2.5:1, it is mixed evenly, stands 30min later, carry out third time
Purification.S7：It to the product after S6 step process, is recrystallized by the way of gradient cooling, specifically, after handling S6
Alcohol extract stirring while, be cooled to 25 DEG C or so, a small amount of crystal seed, then slow cooling be added to 15 DEG C or so, heat preservation crystallization
A large amount of crystal are precipitated in 2h, continue to be cooled to 5 DEG C or so, maintain 15min.Filtering, crystal is removed, main component is in filtrate
Trichloroacetone.
Embodiment 4
S1：Acetone 560kg and ethylene glycol 620kg are mixed in tower consersion unit, accelerating agent nickel is added thereto
30kg is heated to 30 DEG C, stirs evenly, and keeps the temperature and maintain 20min, carries out addition reaction.
S2：Stop temperature control, temperature is made to keep room temperature, the mixture then prepared to S1 by air pump and conveyance conduit
In be passed through chlorine, and catalyst diethylamine 20kg is added, stirs and evenly mixs, carry out chlorination reaction, maintain reaction 1h.
S3：The dust technology 4L that 3mol/L is added in mixture into S2 after chlorination reaction is hydrolyzed, and prepares trichlorine third
Ketone crude product.
S4：Water is added in the trichloroacetone crude product prepared into S3, the volume ratio of wherein water and trichloroacetone crude product is
3.5:1, it is mixed evenly, stands 30min later, purified for the first time.
S5：To S4 treated mixture filterings, filter residue is mainly monochloroacetone and dichloroacetone, and filtrate is trichloroacetone
4mol/L benzene is added into filtrate for crude product, and the wherein volume ratio of benzene and filtrate is 3:1, it is mixed evenly, stands later
30min carries out second and purifies.
S6：The organic layer of stratification is detached with water layer after S5 is handled, and volume by volume concentration 90% is added into organic layer
Ethyl alcohol, wherein the volume ratio of ethyl alcohol and organic layer be 3:1, it is mixed evenly, stands 30min later, carry out third time and carry
It is pure.
S7：It to the product after S6 step process, is recrystallized by the way of gradient cooling, specifically, to S6
While alcohol extract after reason stirs, 25 DEG C or so are cooled to, a small amount of crystal seed, then slow cooling is added to 15 DEG C or so, keeps the temperature
2h is crystallized, a large amount of crystal are precipitated, continues to be cooled to 5 DEG C or so, maintains 15min.Filtering, crystal is removed, in filtrate mainly at
It is divided into trichloroacetone.
Experimental result
Gas chromatographic detection is carried out to the sample after each step process of each embodiment, measures corresponding trichloroacetone (1,1,3-
Trichloroacetone) percentage composition.Specifically chromatographic condition is：Shimadzu SC-6 type gas-chromatographies, long 1m, the stainless steel column of internal diameter 3mm,
102 stationary phase of white carrier of 50% Dienthyeneglycol succinate of interior filling, 80-100 mesh, 100 DEG C of column temperature, vapourizing temperature
200 DEG C, FID：150℃.Carrier gas (nitrogen) flow velocity：35mL/min；Hydrogen flow rate：30mL/min；Air velocity 400mL/min,
0.6 μ L of sample size.Sample can sample introduction after filter membrane is handled.
| Number | S3 | S4 | S5 | S6 | S7 |
| Embodiment 1 | 67% | 87% | 92% | 98% | 99% |
| Embodiment 2 | 66.5% | 88% | 93% | 97% | 99.3% |
| Embodiment 3 | 66.8% | 87% | 90% | 98% | 99% |
| Embodiment 4 | 67.5% | 88% | 92% | 98% | 99% |
By above-mentioned experimental result it is found that the trichloroacetone of the preparation process production using the present invention, prepares through S3 steps
The content of trichloroacetone has reached 67% or so in the crude product gone out, has been apparently higher than domestic step production and has reached 60% or so
Level, through subsequently gradually purifying, the content of finally obtained trichloroacetone is up in 99%, especially embodiment 2, obtained production
Product content reaches 99.3%.
Claims (8)
1. a kind of trichloroacetone production technology, which is characterized in that include the following steps：
S1：Acetone is mixed with ethylene glycol, accelerating agent is added thereto, heats, stir evenly, carries out addition reaction；
S2：It is passed through chlorine in the mixture prepared to S1, and catalyst is added, is stirred and evenly mixed, chlorination reaction is carried out；
S3：Sour water solution is added in the mixture prepared to S2, prepares trichloroacetone crude product；
S4：The trichloroacetone crude product prepared in S3 is purified for the first time with water；
S5：Continued to carry out second of purification to trichloroacetone crude product with benzene；
S6：Third time purification is carried out to trichloroacetone crude product with alcohol；
S7：Product after S6 step process is recrystallized, trichloroacetone finished product is obtained.
2. a kind of trichloroacetone production technology according to claim 1, it is characterised in that：Accelerating agent is described in S1 steps
Nickel.
3. a kind of trichloroacetone production technology according to claim 1, it is characterised in that：Catalyst is described in S2 steps
Diethylamine.
4. a kind of trichloroacetone production technology according to claim 1, it is characterised in that：The acid being added in S3 steps is dilute
Nitric acid.
5. a kind of trichloroacetone production technology according to claim 1, it is characterised in that：Water and trichloroacetone in S4 steps
The volume ratio of crude product is 3~4:1.
6. a kind of trichloroacetone production technology according to claim 1, it is characterised in that：Benzene and trichloroacetone in S5 steps
The volume ratio of crude product is 2~3:1.
7. a kind of trichloroacetone production technology according to claim 1, it is characterised in that：Alcohol and trichloroacetone in S6 steps
The volume ratio of crude product is 2~3:1.
8. a kind of trichloroacetone production technology according to claim 1, it is characterised in that：Gradient cooling is used in S7 steps
Mode trichloroacetone crude product is recrystallized, and crystallization temperature control at 5~25 DEG C.
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| CN201810724525.8A CN108752176A (en) | 2018-07-04 | 2018-07-04 | A kind of trichloroacetone production technology |
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| CN201810724525.8A CN108752176A (en) | 2018-07-04 | 2018-07-04 | A kind of trichloroacetone production technology |
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| CN108752176A true CN108752176A (en) | 2018-11-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784861A (en) * | 2022-11-04 | 2023-03-14 | 南通市常海食品添加剂有限公司 | Method for producing trichloroacetone by continuous microchannel technology |
-
2018
- 2018-07-04 CN CN201810724525.8A patent/CN108752176A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784861A (en) * | 2022-11-04 | 2023-03-14 | 南通市常海食品添加剂有限公司 | Method for producing trichloroacetone by continuous microchannel technology |
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