CN108117487A - The application of chloroacetic chloride discoloration method and acid strong oxidizer in chloroacetic chloride decoloration - Google Patents
The application of chloroacetic chloride discoloration method and acid strong oxidizer in chloroacetic chloride decoloration Download PDFInfo
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- CN108117487A CN108117487A CN201711450586.1A CN201711450586A CN108117487A CN 108117487 A CN108117487 A CN 108117487A CN 201711450586 A CN201711450586 A CN 201711450586A CN 108117487 A CN108117487 A CN 108117487A
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- chloroacetic chloride
- strong oxidizer
- acid
- chloroacetic
- discoloration
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention discloses a kind of chloroacetic chloride discoloration methods, comprise the following steps：S1：Under the conditions of temperature is not higher than 45 DEG C, acid strong oxidizer is added in into the chloroacetic chloride of discoloration while stirring；The mass ratio of the acidity strong oxidizer and the chloroacetic chloride is 1:250~1:1000；S2：Fraction appearance has been warming up to, and has carried out total reflux reaction；S3：After total reflux reaction, the rectifying extremely cutout under the conditions of temperature is not higher than 85 DEG C.The invention also discloses application of the acid strong oxidizer in chloroacetic chloride decoloration.Method disclosed by the invention can remove in chloroacetic chloride containing unsaturated bond and the more active organic matter of property, effectively prevent chloroacetic chloride from changing colour in transport and storage, improve the use value of chloroacetic chloride.
Description
Technical field
The present invention relates to organic matter decoloration fields, and in particular to a kind of chloroacetic chloride discoloration method and acid strong oxidizer are in second
Application in acyl chlorides decoloration.
Background technology
It can be given birth to during industrially using acetic anhydride and methyl trichlorosilane reaction synthesizing methyl triacetoxysilane
Into by-product chloroacetic chloride.Chloroacetic chloride is as organic synthesis raw material, for producing pesticide, medicine, novel electroplating complexing agent, carboxylic acid hair
Catalyst, acetylation reagent and other a variety of Minute Organic Synthesis intermediates of raw chlorination reaction.
Due to also having the presence of other side reactions in process of production, the chloroacetic chloride with the active organic matter of property is being deposited
It puts in transportational process, trace impurity property is unstable, causes darkening for chloroacetic chloride.
To become the duration in the distinguishable color gamut of naked eyes be about 7 days to current chloroacetic chloride from colourless, if accumulating temperature
Excessively high, color change duration can be shorter.
Contain trace impurity in the chloroacetic chloride to have changed colour, and the chloroacetic chloride of discoloration is subjected to purification and rectifying again
Afterwards, it still can change colour in the storage in later stage and transportational process, not only influence appearance, but also impurity can participate in chloroacetic chloride
Reaction have an impact, be unfavorable for its normal use as reaction raw materials in the various fields in downstream, at present, due to chloroacetic chloride
Itself is more active, and generally use activated carbon decolourizes to it, and effect is poor.
The content of the invention
For defect in the prior art, it is an object of the invention to provide a kind of chloroacetic chloride discoloration methods, can
Remove in chloroacetic chloride containing unsaturated bond and the more active organic matter of property, effectively prevent chloroacetic chloride from becoming in transport and storage
Color improves the use value of chloroacetic chloride.
To achieve the above objectives, the present invention adopts the technical scheme that：A kind of chloroacetic chloride discoloration method, including following step
Suddenly：
S1：Under the conditions of temperature is not higher than 45 DEG C, acid strong oxidizer is added in into the chloroacetic chloride of discoloration while stirring；Institute
The mass ratio for stating acid strong oxidizer and the chloroacetic chloride is 1:250~1:1000；
S2：Fraction appearance has been warming up to, and has carried out total reflux reaction；
S3：After total reflux reaction, the rectifying extremely cutout under the conditions of temperature is not higher than 85 DEG C.
Further, the mass ratio of the acid strong oxidizer and the chloroacetic chloride is 1:500.
Further, it is dense not less than 70% to include concentrated nitric acid, potassium permanganate and mass fraction for the acid strong oxidizer
One kind in sulfuric acid.
Further, the mass fraction of the concentrated sulfuric acid is 98%.
Further, when the acid strong oxidizer is in a liquid state, it is added to by the way of dropwise addition in the chloroacetic chloride；
When the acid strong oxidizer is in solid-state, it is added to by the way of gradation in the chloroacetic chloride.
Further, in the S1 steps, the acidity strong oxidizer adds in 30min~60min.
Further, in the S2 steps, the total reflux reaction time is 60min~120min.
Further, the S1 steps include the following steps：Described in disposably being added in into the chloroacetic chloride while stirring
Temperature is risen to 62 DEG C by acid strong oxidizer after addition in 10min.
The present invention also provides application of the acid strong oxidizer in chloroacetic chloride decoloration.
Further, it is dense not less than 70% to include concentrated nitric acid, potassium permanganate and mass fraction for the acid strong oxidizer
One kind in sulfuric acid.
Compared with prior art, the advantage of the invention is that：
(1) the chloroacetic chloride discoloration method in the present invention, by analysing in depth the impurity in chloroacetic chloride, determines to cause
The main matter of chloroacetic chloride discoloration is ketenes, and passes through acid strong oxidizer and be changed into the substance for causing discoloration in chloroacetic chloride
The more stable novel substance of property, and purification operations have been carried out to chloroacetic chloride in subsequent distillation process, prevent chloroacetic chloride storage
The quality abnormal of discoloration is deposited, improves the use value of chloroacetic chloride.
(2) implementation of the invention is easy to operate, safe and reliable, and decolorising agent easily obtains and additive amount is few.Industrialization
Implement simple, safe, easy.
Specific embodiment
The present invention is described in further detail with reference to embodiments.
The embodiment of the present invention provides a kind of chloroacetic chloride discoloration method, comprises the following steps：
S1：Under the conditions of temperature is not higher than 45 DEG C, acid strong oxidizer is added in into the chloroacetic chloride of discoloration while stirring；Acid
Property strong oxidizer and chloroacetic chloride mass ratio be 1:250~1:1000；
S2：Fraction appearance has been warming up to, and has carried out total reflux reaction；
S3：After total reflux reaction, the rectifying extremely cutout under the conditions of temperature is not higher than 85 DEG C.
The mass ratio of acid strong oxidizer and chloroacetic chloride is 1:When 500, economic benefit is optimal.
Acid strong oxidizer includes one kind in the concentrated sulfuric acid of concentrated nitric acid, potassium permanganate and mass fraction not less than 70%.
The mass fraction of the concentrated sulfuric acid preferably 98%, potassium permanganate preferably use powdered potassium permanganate.
When acid strong oxidizer is in a liquid state, it is added to by the way of dropwise addition in chloroacetic chloride；
When acid strong oxidizer is in solid-state, it is added to by the way of gradation in chloroacetic chloride.
In S1 steps, acid strong oxidizer adds in 30min~60min.
In S2 steps, the total reflux reaction time is 60min~120min.
S1 steps include the following steps：Acid strong oxidizer is disposably added in into chloroacetic chloride while stirring, after addition
Temperature is risen to 62 DEG C in 10min.
Method provided by the invention when carrying out chloroacetic chloride decoloration, by the chloroacetic chloride to have changed colour add in rectifying,
It is then interior supreme using adding in by several times or by the way of dropwise addition by acid strong oxidizer when 0.5-1 is small in the device of reflux measure
It states in device, temperature should be controlled in the process very much not in 45 DEG C, and whole process starts stirring.Then heating to the device kind has fraction
Distill out, and carry out total reflux reaction 1-2 it is small when.Rectifying collection technology operation is carried out after the reaction treatment stage, according to work
The qualified chloroacetic chloride of condition suitable control reflux ratio acquisition, until acquisition stops, rectifying still temperature is no more than 85 DEG C in distillation process.Instead
Answer mechanism approximately as：
The acid unstable object of strong oxidizer+property → property stabilization and colourless organic matter.
At present, can not be considered on the specific color products that generation is stored in chloroacetic chloride, the present invention passes through to all anti-
Object and the side reaction involved by reaction product is answered to be analyzed, through inferring that reaction raw materials acetic anhydride occurs during high temperature production
It decomposes, the ketenes of generation is to be easy to cause to change colour and be difficult to the main component removed.
But since industrial chloroacetic chloride purity is usually more than 98%, wherein also contain other impurities, and ethylene
The content of ketone is very few, it is difficult to causing discoloration by conventional detection methods (such as gas-chromatography, liquid chromatogram, mass spectrum etc.) judgement
Whether substance is ketenes, and therefore, the industry fails preferably to solve the problems, such as that chloroacetic chloride changes colour this always.
When producing chloroacetic chloride, since the boiling point of acetic acid is 117.9 DEG C, the boiling point of methyl trichlorosilane is 66.5 DEG C, first
The boiling point of base triacetoxysilane is 110~112 DEG C/17mmHg, is above 51 DEG C of the boiling point of chloroacetic chloride, therefore, Ke Yitong
The mode of distillation is crossed, obtains low temperature fraction chloroacetic chloride, and since the boiling point of chloroacetic chloride is relatively low, the side of rectifying can be passed through
Formula purifies chloroacetic chloride；But it is at normal temperatures gas, when the side by distillation since the boiling point of ketenes is -56 DEG C
When formula obtains or purifies chloroacetic chloride, ketenes can inevitably enter in chloroacetic chloride, and ketenes can be dissolved in acetyl
In chlorine, i.e., micro ketenes residual can be remained in chloroacetic chloride, is also difficult to remove by multiple rectifying.
Added in the chloroacetic chloride that the present invention is 99% to purity mass ratio be 0.1~0.5% (scope for inventor according to
Test of many times result obtains, and cannot match in the range of other with control group) ketenes as experimental group, will be existing
By-product chloroacetic chloride as a control group, using purity be 99% chloroacetic chloride as blank group, in the item of other conditions all same
(or transport) is stored under part, it is basically identical to obtain Coloring Time and the color of experimental group and control group, and blank group does not have
Discoloration, discoloration of the reason for chloroacetic chloride is caused to change colour for impurity ketenes can be estimated according to this experiment.
Due to acid strong oxidizer can with ketenes occur redox reaction and generate production physico-chemical property it is more stable
Novel substance, therefore, the present invention remove the ketenes in chloroacetic chloride according to the mechanism of the reaction, although the mechanism of reaction is simpler
The reason for single, but the present invention is by just determining to cause discoloration after studying and exploring for a long time is not simple access text
Result of the invention can just be obtained by offering.
To those skilled in the art, the standard of chloroacetic chloride discoloration is black more than 30 once and existing for the colourity of solution
Chloroacetic chloride store and transportational process in, usually store a week after colourity for 50~60 it is black once.
It is described in detail below by 12 specific embodiments.
Embodiment 1
Into the 500ml four-hole boiling flasks with devices such as thermometer, mechanical agitation, reflux condensing tube, constant pressure funnels
Disposably put into pending chloroacetic chloride 200g.Three-necked flask is immersed in cooling water after feeding intake and starts stirring.By 0.2g
Mass fraction is added in constant pressure funnel and is at the uniform velocity added dropwise in chloroacetic chloride, temperature during dropwise addition not less than 98% concentrated sulfuric acid
No more than 45 DEG C, time for adding 0.5-1h.The concentrated sulfuric acid removes cooling water after being added dropwise and is changed to electric heating cover, removes constant pressure
Dropping funel is changed to sealing-plug.It is slowly heated up to chloroacetic chloride up to infinite reflux, when reflux time is 1 small.Back flow reaction
After reflux is changed to rectifier unit, rectification and purification is carried out to chloroacetic chloride, finally obtain content more than 98%, it is colourless
Bright acetyl chlorine products.Temperature is no more than 85 DEG C during rectification and purification.
Embodiment 2
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The mass fraction of dropwise addition is not less than
98% concentrated sulfuric acid is 0.8g.
Embodiment 3
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The mass fraction of dropwise addition is not less than
98% concentrated sulfuric acid is 0.1g.
Embodiment 4
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The mass fraction of 0.4g is not less than
98% concentrated sulfuric acid adds in be disposable, and temperature rises to 62 DEG C by 24 DEG C in 10min after addition.
Embodiment 5
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：Reflux time is 0.5h.
Embodiment 6
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：Reflux time is 2h.
Embodiment 7
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：Temperature is during rectification and purification
90℃.The content for finally obtaining chloroacetic chloride is 96.2%, and appearance is light yellow clear liquid.
Embodiment 8
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The acid strong oxidizer being added dropwise
For nitric acid, dropwise addition total amount is 0.4g.
Embodiment 9
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The acid strong oxidizer added in
For potassium permanganate, for feed postition to add in by several times, addition total amount is 0.4g.
Embodiment 10
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The acid strong oxidizer being added dropwise
The concentrated sulfuric acid for being 70% for mass fraction, dropwise addition total amount are 0.55g.
Embodiment 11
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The acid strong oxidizer being added dropwise
The concentrated sulfuric acid for being 80% for mass fraction, dropwise addition total amount are 0.5g.
Embodiment 12
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：There is no Plus acidic strong oxidizer.
In addition to embodiment 7, the chloroacetic chloride purifying that is obtained after the processing of other 11 groups of embodiments is colourless transparent liquid, second
Acyl chlorides content is more than 98%.Above-mentioned 12 chloroacetic chloride purification of samples are placed in experimental group, control group and blank group, identical
Under conditions of, after placing 3 days, there is macroscopic discoloration in embodiment 10, color become 40 it is black once；The face of embodiment 10
Color for 55 it is black once；The color of embodiment 3 for 50 it is black once.After placing 30 days, embodiment 3,5,10,11 occurs macroscopic
Discoloration, wherein, the color of embodiment 3 for 45 it is black once, the color in embodiment 5 become 40 it is black once；The color sample for applying example 7 is still
Light yellow clear liquid, color are not deepened.Other embodiment sample appearance color after storing 3 months does not still occur
Significant change.It follows that when the mass ratio of acid strong oxidizer and the chloroacetic chloride of discoloration is 1:250~1:When 1000 have compared with
Good decolorizing effect considers that the optimal proportion of acid strong oxidizer and the chloroacetic chloride of discoloration is 1 from maximization of economic benefit：
500。
The present invention also provides application of the acid strong oxidizer in chloroacetic chloride decoloration.
Acid strong oxidizer is one kind in the concentrated sulfuric acid of concentrated nitric acid, potassium permanganate and mass fraction not less than 70%.It is dense
The mass fraction of sulfuric acid preferably 98%.
The present invention is not limited to the above-described embodiments, for those skilled in the art, is not departing from
On the premise of the principle of the invention, several improvements and modifications can also be made, these improvements and modifications are also considered as the protection of the present invention
Within the scope of.The content not being described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.
Claims (10)
1. a kind of chloroacetic chloride discoloration method, which is characterized in that comprise the following steps：
S1：Under the conditions of temperature is not higher than 45 DEG C, acid strong oxidizer is added in into the chloroacetic chloride of discoloration while stirring；The acid
Property strong oxidizer and the chloroacetic chloride mass ratio be 1:250~1:1000；
S2：Fraction appearance has been warming up to, and has carried out total reflux reaction；
S3：After total reflux reaction, the rectifying extremely cutout under the conditions of temperature is not higher than 85 DEG C.
2. chloroacetic chloride discoloration method as described in claim 1, it is characterised in that：The acidity strong oxidizer and the chloroacetic chloride
Mass ratio be 1:500.
3. chloroacetic chloride discoloration method as described in claim 1, it is characterised in that：It is described acidity strong oxidizer include concentrated nitric acid,
One kind in the concentrated sulfuric acid of potassium permanganate and mass fraction not less than 70%.
4. chloroacetic chloride discoloration method as claimed in claim 3, it is characterised in that：The mass fraction of the concentrated sulfuric acid is 98%.
5. the chloroacetic chloride discoloration method as described in Claims 1-4 is any, it is characterised in that：
When the acid strong oxidizer is in a liquid state, it is added to by the way of dropwise addition in the chloroacetic chloride；
When the acid strong oxidizer is in solid-state, it is added to by the way of gradation in the chloroacetic chloride.
6. chloroacetic chloride discoloration method as described in claim 1, it is characterised in that：In the S1 steps, the acidity Strong oxdiative
Agent adds in 30min~60min.
7. chloroacetic chloride discoloration method as described in claim 1, it is characterised in that：In the S2 steps, the total reflux reaction time
For 60min~120min.
8. chloroacetic chloride discoloration method as described in claim 1, it is characterised in that：The S1 steps include the following steps：While it stirs
It mixes side and the acid strong oxidizer is disposably added in into the chloroacetic chloride, temperature is risen to 62 DEG C in 10min after addition.
9. application of the acid strong oxidizer in chloroacetic chloride decoloration.
10. application of the acidity strong oxidizer as claimed in claim 9 in chloroacetic chloride decoloration, it is characterised in that：The acidity
Strong oxidizer includes one kind in the concentrated sulfuric acid of concentrated nitric acid, potassium permanganate and mass fraction not less than 70%.
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| CN201711450586.1A CN108117487B (en) | 2017-12-27 | 2017-12-27 | Acetyl chloride decoloring method and application of acidic strong oxidant in acetyl chloride decoloring |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646192A (en) * | 2016-03-22 | 2016-06-08 | 湖北新蓝天新材料股份有限公司 | Acetylchloride decoloring method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646192A (en) * | 2016-03-22 | 2016-06-08 | 湖北新蓝天新材料股份有限公司 | Acetylchloride decoloring method |
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