CN105646192B - A kind of chloroacetic chloride discoloration method - Google Patents
A kind of chloroacetic chloride discoloration method Download PDFInfo
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- CN105646192B CN105646192B CN201610167844.4A CN201610167844A CN105646192B CN 105646192 B CN105646192 B CN 105646192B CN 201610167844 A CN201610167844 A CN 201610167844A CN 105646192 B CN105646192 B CN 105646192B
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- chloroacetic chloride
- discoloration method
- hydrogen peroxide
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- peracetic acid
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- C—CHEMISTRY; METALLURGY
- 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 method, is related to organic matter decolouring field, and this method comprises the following steps：The Peracetic Acid that concentration is 3.5~9.8% is prepared, by mass parts, at least 5 parts of Peracetic Acids are added in the chloroacetic chloride to change colour to 100 parts, not higher than 80 DEG C progress rectifying are warming up to after stirring and are extremely stopped.The present invention to the impurity in chloroacetic chloride by analysing in depth, it is determined that the material for causing chloroacetic chloride to change colour is ketenes, and removes the organic matter for causing discoloration in chloroacetic chloride by Peracetic acid, while being purified to chloroacetic chloride, prevent chloroacetic chloride from changing colour, improve the use value of chloroacetic chloride.
Description
Technical field
The present invention relates to organic matter decolouring field, and in particular to a kind of chloroacetic chloride discoloration method.
Background technology
It can be given birth to during industrially using acetic anhydride and methyl trichlorosilane reaction synthesizing methyl triacetoxysilane
Into accessory substance chloroacetic chloride.
Chloroacetic chloride is as organic synthesis raw material, and medical for producing agricultural chemicals, chlorination occurs for novel electroplating complexing agent, carboxylic acid
Catalyst, acetylation reagent and other a variety of Minute Organic Synthesis intermediates of 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
Put with transportation, trace impurity property is unstable, causes darkening for chloroacetic chloride.
Current chloroacetic chloride from the colourless duration being changed into the distinguishable color gamut of naked eyes be about 7 days, if accumulating temperature
Too 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 transportation, not only influence outward appearance, and 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
, can it is an object of the invention to provide a kind of chloroacetic chloride discoloration method for defect present in prior art
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, improve 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, comprises the following steps：
The Peracetic Acid that concentration is 3.5~9.8% is prepared, by mass parts, is added at least in the chloroacetic chloride to change colour to 100 parts
5 parts of Peracetic Acids, it is warming up to after stirring and rectifying is carried out not higher than 80 DEG C to cutout.
On the basis of above-mentioned technical proposal, the middle concentration for preparing includes following step for 3.5~9.8% Peracetic Acid
Suddenly：Aceticanhydride is put into flask, is heated up 40 DEG C~50 DEG C, the dioxygen that concentration is 20~35% is at the uniform velocity added dropwise under agitation
The mass ratio of water, hydrogen peroxide and aceticanhydride is 1：7~12, destainer is made in 40~100min of stirring, and the destainer is
CH3COOOH。
On the basis of above-mentioned technical proposal, the concentration of the hydrogen peroxide is 30%.
On the basis of above-mentioned technical proposal, the mass ratio of the hydrogen peroxide and aceticanhydride is 1：10.
On the basis of above-mentioned technical proposal, the rate of addition of the hydrogen peroxide is 2~4g/min.
On the basis of above-mentioned technical proposal, the mixing time of the obtained destainer is 60min.
On the basis of above-mentioned technical proposal, the temperature of rectifying is 60~80 DEG C.
On the basis of above-mentioned technical proposal, it is agitated uniformly after be warming up to 65 DEG C carry out rectifying to stop.
Compared with prior art, the advantage of the invention is that：
(1) the chloroacetic chloride discoloration method in the present invention, by being analysed in depth to the impurity in chloroacetic chloride, it is determined that causing
The material of chloroacetic chloride discoloration is ketenes, and the organic matter for causing discoloration in chloroacetic chloride is removed by Peracetic acid, to second
While acyl chlorides is purified, the secondary discoloration of chloroacetic chloride is prevented, improves the use value of chloroacetic chloride.
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：
A, prepare Peracetic acid that concentration is 3.5~9.8% (in the present embodiment, the concentration of Peracetic acid for 6.1%),
In actual use, the concentration of Peracetic acid can be 4.5~8.0%, 5.0~7.5% or 6.0~7%, be put into flask
Aceticanhydride, after being warming up to 40 DEG C, it is 40 DEG C~50 DEG C (optimal is 45 DEG C), under stirring according to speed is 2~4g/min drops in temperature
Add the hydrogen peroxide that mass concentration is 20~35% (optimal is 30%), the mass ratio of hydrogen peroxide and aceticanhydride is 1：7~12 (this implementation
In example, the mass ratio of hydrogen peroxide and aceticanhydride is 1：10), stir 40~100min (optimal is 1h) and destainer is made, destainer is
CH3COOOH。
B, by mass parts, at least 5 parts of destainers are added in the chloroacetic chloride of 100 parts of discolorations, in temperature no more than 80 DEG C
Under the conditions of rectifying, in the present embodiment, when temperature is 60 DEG C~70 DEG C (optimal is 65 DEG C), remain a constant speed rectifying, cut output
Speed slowly heats up after slowing down, and in the case of no more than 80 DEG C, evaporates untill cutout.Reaction mechanism approximately as：
(CH3CO)2O+H2O2→CH3COOOH (Peracetic acid, destainer active ingredient)+CH3COOH；
(CH3CO)2O+H2O→2CH3COOH (destainer accessory substance)；
2CH3COOOH→2CH3COOH+O2(destainer decomposition mechanism)；
CH3The unstable object of COOOH+ properties → property stabilization and colourless organic matter.
At present, can not be considered on storing the specific color products of generation in chloroacetic chloride, the present invention passes through to all anti-
Thing 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
Decompose, caused ketenes is the composition for easily causing to change colour and being difficult to remove.
But because industrial chloroacetic chloride purity is usually more than 98%, wherein also contain other impurities, and ethene
The content of ketone is very few, it is difficult to is judged by the detection methods (such as gas-chromatography, liquid chromatogram, mass spectrum etc.) of routine causing discoloration
Whether material is ketenes, and therefore, the industry fails preferably to solve always chloroacetic chloride and changed colour this problem.
When producing chloroacetic chloride, because 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 141~143 DEG C, is above 51 DEG C of the boiling point of chloroacetic chloride, therefore, can pass through distillation
Mode, low temperature fraction chloroacetic chloride is obtained, and because the boiling point of chloroacetic chloride is relatively low, therefore, can be by way of rectifying to acetyl
Chlorine is purified；But be at normal temperatures gas because the boiling point of ketenes is -56 DEG C, when being obtained by way of distillation or
When person purifies chloroacetic chloride, ketenes inevitably can enter in chloroacetic chloride, and ketenes can be dissolved in chloroacetic chloride, i.e. second
Micro ketenes residual can be remained in acyl chlorides, is also difficult to remove by multiple rectifying.
Added in the chloroacetic chloride that the present invention is 99% to purity mass ratio be 0.2~0.5% (scope be inventor according to
Test of many times result obtains, and can not match in the range of other with control group) ketenes as experimental group, will be existing
Accessory substance chloroacetic chloride as a control group, using purity be 99% chloroacetic chloride as blank group, in the bar of other conditions all same
(or transport) is deposited 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 the causing chloroacetic chloride to change colour for impurity ketenes can be estimated according to this experiment.
Because following reaction can occur with ketenes for Peracetic acid：Ketenes+Peracetic acid=acetic anhydride, acetic anhydride can
Isolated by rectification process in chloroacetic chloride system, therefore, the present invention removes the ethene in chloroacetic chloride according to the mechanism of the reaction
Ketone, although the mechanism of reaction is fairly simple, the present invention is by just determining to cause to change colour after studying and exploring for a long time
The reason for, result of the invention can be obtained without being simple consulting literatures.
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 transportation in, generally store a week after colourity for 50~60 it is black once.
It is described in detail below by 6 specific embodiments.
Embodiment 1
Aceticanhydride 200g is disposably put into 500ml three-necked flasks, warming while stirring, treats that temperature is raised to 40 DEG C or so,
It is 30% hydrogen peroxide to start that 20g mass concentrations are added dropwise with dropping funel, keeps 2~4g/min rate of addition to be at the uniform velocity added dropwise, drips
Control temperature that destainer is made after at the uniform velocity stirring 1h at 40 DEG C~50 DEG C during adding.
Chloroacetic chloride 200g and the 10g destainer to have changed colour is disposably put into 500ml three-necked flasks, sets 65 DEG C,
Stirring rectifying is started to warm up, extraction early stage cut may be quicker, starts after the comparison on cut rate of withdrawal side is slow
Heating, temperature-rise period should not be too fast, and in the case of no more than 80 DEG C, untill cutout, the cut of collection is sealed for rectifying.
Embodiment 2
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The quality of the hydrogen peroxide of dropwise addition is dense
Spend for 20%, aceticanhydride and hydrogen peroxide mass ratio are 7：1, the quality of the destainer added is 20g.
Embodiment 3
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The quality of the hydrogen peroxide of dropwise addition is dense
Spend for 35%, aceticanhydride and hydrogen peroxide mass ratio are 12：1, the quality of the destainer added is 18g.
Embodiment 4
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The quality of the destainer added
For 15g.
Embodiment 5
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The destainer quality added is
5g。
Embodiment 6
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：The destainer quality added is
0g。
Embodiment 7
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：During the reaction of hydrogen peroxide and aceticanhydride
Between be 40min.
Embodiment 8
The operating procedure of the present embodiment is substantially the same manner as Example 1, and difference is as follows：During the reaction of hydrogen peroxide and aceticanhydride
Between be 100min.
The chloroacetic chloride purifying obtained after being handled by embodiment 1 to 6 is colourless transparent liquid, by aforementioned four chloroacetic chloride
Purification of samples is placed in experimental group, control group and blank group, under the same conditions, after placing 7 days, embodiment 5 and implementation
There is macroscopic discoloration in example 6, wherein, the color of embodiment 5 for 45 it is black once, the sample in embodiment 6 was at the 30th day
When appearance color be changed into 30 it is black once；There is macroscopic discoloration after storing 15 days in embodiment 3 and embodiment 4；Embodiment 7
There is extremely slight discoloration after storing 2 months with embodiment 8；Sample in embodiment 1 and embodiment 2 storage 3 months with
Appearance color does not still change afterwards, it follows that when the mass ratio of chloroacetic chloride and destainer is more than or equal to 20:When 1, tool
There is preferable decolorizing effect, consider from maximization of economic benefit, the optimal proportion of discoloration chloroacetic chloride and destainer is 20：1.
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, some 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 prior art known to professional and technical personnel in the field.
Claims (8)
- A kind of 1. chloroacetic chloride discoloration method, it is characterised in that：Comprise the following steps：The Peracetic Acid that concentration is 3.5~9.8% is prepared, by mass parts, at least 5 parts are added in the chloroacetic chloride to change colour to 100 parts Peracetic Acid, it is warming up to after stirring and rectifying is carried out not higher than 80 DEG C to cutout.
- A kind of 2. chloroacetic chloride discoloration method as claimed in claim 1, it is characterised in that：It is described it is middle preparation concentration be 3.5~ 9.8% Peracetic Acid comprises the following steps：Aceticanhydride is put into flask, is heated up 40 DEG C~50 DEG C, under agitation at the uniform velocity Concentration is added dropwise as 20~35% hydrogen peroxide, the mass ratio of hydrogen peroxide and aceticanhydride is 1：7~12,40~100min of stirring is made de- Color liquid, the destainer are CH3COOOH。
- A kind of 3. chloroacetic chloride discoloration method as claimed in claim 2, it is characterised in that：The concentration of the hydrogen peroxide is 30%.
- A kind of 4. chloroacetic chloride discoloration method as claimed in claim 3, it is characterised in that：The mass ratio of the hydrogen peroxide and aceticanhydride For 1：10.
- A kind of 5. chloroacetic chloride discoloration method as claimed in claim 2, it is characterised in that：The rate of addition of the hydrogen peroxide is 2 ~4g/min.
- A kind of 6. chloroacetic chloride discoloration method as claimed in claim 2, it is characterised in that：The mixing time of the obtained destainer For 60min.
- A kind of 7. chloroacetic chloride discoloration method as claimed in claim 1, it is characterised in that：The temperature of rectifying is 60~80 DEG C.
- A kind of 8. chloroacetic chloride discoloration method as claimed in claim 7, it is characterised in that：It is agitated uniformly after be warming up to 65 DEG C and enter Row rectifying extremely stops.
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| CN108117487B (en) * | 2017-12-27 | 2021-01-05 | 湖北新蓝天新材料股份有限公司 | Acetyl chloride decoloring method and application of acidic strong oxidant in acetyl chloride decoloring |
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| SU458541A1 (en) * | 1972-06-08 | 1975-01-30 | Сумгаитский Филиал Ордена Трудового Красного Знамени Института Нефтехимических Процессов Им.Акад.Ю.Г.Мамедалиева | Acetyl Chloride Production Method |
| JPS56127329A (en) * | 1980-03-10 | 1981-10-06 | Daicel Chem Ind Ltd | Preparation of monochloroacetic acid |
| CN101921289A (en) * | 2010-08-23 | 2010-12-22 | 湖北新蓝天新材料股份有限公司 | Method for producing methyltriacetoxysilane |
| CN102584894A (en) * | 2011-01-18 | 2012-07-18 | 孟永 | Novel process for producing hydroxyl ethyl diphosphate phosphate with 10-ton kettle |
| CN103319527A (en) * | 2013-07-08 | 2013-09-25 | 杨涛 | Production process for 1-hydroxy ethylidene-1,1-diphosphonic acid and acetylchloride |
| CN104262440A (en) * | 2014-09-10 | 2015-01-07 | 江西赣亮医药原料有限公司 | Preparation method of 16alpha-hydroxyprednisolone |
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2016
- 2016-03-22 CN CN201610167844.4A patent/CN105646192B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU458541A1 (en) * | 1972-06-08 | 1975-01-30 | Сумгаитский Филиал Ордена Трудового Красного Знамени Института Нефтехимических Процессов Им.Акад.Ю.Г.Мамедалиева | Acetyl Chloride Production Method |
| JPS56127329A (en) * | 1980-03-10 | 1981-10-06 | Daicel Chem Ind Ltd | Preparation of monochloroacetic acid |
| CN101921289A (en) * | 2010-08-23 | 2010-12-22 | 湖北新蓝天新材料股份有限公司 | Method for producing methyltriacetoxysilane |
| CN102584894A (en) * | 2011-01-18 | 2012-07-18 | 孟永 | Novel process for producing hydroxyl ethyl diphosphate phosphate with 10-ton kettle |
| CN103319527A (en) * | 2013-07-08 | 2013-09-25 | 杨涛 | Production process for 1-hydroxy ethylidene-1,1-diphosphonic acid and acetylchloride |
| CN104262440A (en) * | 2014-09-10 | 2015-01-07 | 江西赣亮医药原料有限公司 | Preparation method of 16alpha-hydroxyprednisolone |
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