CN105801347B - The minimizing technology of nitrile organic matter in a kind of tetrachloro-ethylene and carbon tetrachloride - Google Patents
The minimizing technology of nitrile organic matter in a kind of tetrachloro-ethylene and carbon tetrachloride Download PDFInfo
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- CN105801347B CN105801347B CN201610247221.8A CN201610247221A CN105801347B CN 105801347 B CN105801347 B CN 105801347B CN 201610247221 A CN201610247221 A CN 201610247221A CN 105801347 B CN105801347 B CN 105801347B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound
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Abstract
The invention discloses a kind of minimizing technologies of nitrile organic matter in tetrachloro-ethylene and carbon tetrachloride, its step are as follows: (1) having the aqueous solution for the alkali that 6kg is put into the 20L reaction kettle of visor toward discharge port, the surfactant of 60g is put into again, fluorine temperature is controlled at 10~200 DEG C simultaneously, and starts to stir, then the tetrachloro-ethylene solution containing tri chloropropene nitrile or the carbon tetrachloride solution containing the chloro- butyronitrile of 4- are added into reaction kettle by feeding device；(2) after feeding, it is further continued for reaction 30min, will be detected after reaction except the lower organic layer after nitrile separates, and detect the residual volume of wherein nitrile.The present invention provides a kind of minimizing technologies of nitrile organic matter in tetrachloro-ethylene and carbon tetrachloride, nitriles substance is removed by the method being saponified, this method is suitable for the carbon tetrachloride or tetrachloro-ethylene solution of different nitrile contents, the product quality of tetrachloro-ethylene can be greatly improved, with industrialization prospect, product quality is effectively increased.
Description
Technical field
The present invention relates to the minimizing technologies of nitrile organic matter, and in particular to there is nitrile in a kind of tetrachloro-ethylene and carbon tetrachloride
The minimizing technology of machine object.
Background technique
Tetrachloro-ethylene is widely used, is mainly used as organic solvent, dry cleaning agent, degreasing metal solvent, also serves as antihelmintic.
Tetrachloro-ethylene can be used as fatty kind of extractants, extinguishing chemical and screening smoke etc., it may also be used for synthesis trichloro ethylene and fluorine-containing organise
Close object etc..
The industrialization route of tetrachloro-ethylene is mainly prepared using carbon tetrachloride as raw material at present, but in carbon tetrachloride
Often there is the residual of the chloro- isobutyronitrile of nitrogen bis-isobutyronitrile (AIBN) decomposition product 2-, further reaction can generate tri chloropropene nitrile, and logical
It crosses conventional distillation and is difficult that tetrachloro-ethylene and tri chloropropene nitrile is completely isolated, this will largely effect on the product matter of tetrachloro-ethylene
Amount and production efficiency, therefore there is an urgent need to find the chloro- isobutyronitrile of 2- or tetrachloro in the effective removal carbon tetrachloride of one kind at present
The method of tri chloropropene nitrile in ethylene.
The removal of tri chloropropene nitrile there are no the report of pertinent literature and patent, 2- in carbon tetrachloride at present in tetrachloro-ethylene
The minimizing technology of chloro- isobutyronitrile is without it has been reported that but similar except nitrile report has CN104119200A, CN104130099A
Two patents, main method are method the adsorbent such as molecular sieve, active carbon using physical absorption, mainly remove carbon tetrachloride
In the chloro- butyronitrile of 4-, but the major defect of the method is used to be adsorbent while can also adsorb a large amount of carbon tetrachloride to cause to produce
The loss of product, while the replacement and activation trouble of adsorbent, the removal that in addition this method is only applicable to the nitrile of low content, which has, answers
Use limitation.
Summary of the invention
Present invention aims at provide in a kind of tetrachloro-ethylene and carbon tetrachloride for deficiency of the prior art
The minimizing technology of nitrile organic matter, present device is simple, easily operated, rapid reaction, the technique road with industrial prospect
Line, i.e., the method for removing nitrile organic matter in carbon tetrachloride and tetrachloro-ethylene using saponification, while the reality for passing through this method
Apply the key intermediate-tri chloropropene hydrochlorate that can also obtain preparing tri chloropropene acid.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is nitrile in a kind of tetrachloro-ethylene and carbon tetrachloride
The minimizing technology of type organic, it is characterised in that the following steps are included:
(1) there is the aqueous solution for the alkali that 6kg is put into the 20L reaction kettle of visor toward discharge port, the concentration of alkali is 1~50%,
The surfactant of 60g is put into again, while controlling fluorine temperature at 10~200 DEG C, and start to stir, so that surfactant dissolves
The tetrachloro-ethylene solution containing tri chloropropene nitrile is added into reaction kettle or contains in the aqueous solution of alkali, then through feeding device
Nitrile content is between 0~100% in the carbon tetrachloride solution of the chloro- butyronitrile of 4-, carbon tetrachloride or tetrachloro-ethylene solution, reaction temperature
It is 10~200 DEG C.
(2) after feeding, it is further continued for reaction 30min, progress will be separated except the lower organic layer after nitrile after reaction
Detection detects the residual volume of wherein nitrile, adds alkali after the lye layer centralized recovery of upper layer and recycled.
Further, in step (1), the molar ratio of alkali and nitrile is greater than 1:1, wherein nitriles substance content 0~100% it
Between.
Further, in step (1), alkali is inorganic base, and inorganic base is lithium hydroxide, potassium hydroxide, sodium hydroxide, hydrogen-oxygen
Change one of calcium, aluminium hydroxide, sodium carbonate or potassium carbonate, the addition of alkali, which can both be catalyzed the hydrolysis of nitrile or neutralize, gives birth to
At acid.
After it is preferred that, alkali is one of lithium hydroxide, potassium hydroxide, sodium hydroxide or calcium hydroxide.
Further, in step (1), nitrile content is 0~30% in carbon tetrachloride or tetrachloro-ethylene solution, and this method is applicable in
In the sample of different content nitrile, that is, it is suitable for nitrile content in the carbon tetrachloride or tetrachloro-ethylene solution of 0~100% content, especially
The reaction solution removal effect low to nitrile content becomes apparent from, so the solution that nitrile content is 0~30% is more advantageous to the life of this method
It produces.
Further, in step (1), the concentration of alkali is 2~20%, the too low meeting of alkali concentration so that reaction rate is too slow, but
It is the too high loss that material is caused it will cause the alkaline hydrolysis of tetrachloro-ethylene and carbon tetrachloride of alkali concentration.
Further, in step (1), surfactant be neopelex, stearic acid, quarternary ammonium salt compound or
Crown ether-like, although this reaction is not added surfactant and can be reacted yet, reaction speed is slower, passes through surfactant
Addition can accelerate reaction speed.
After it is preferred that, surfactant is one of tetramethyl ammonium chloride, 18- crown- 6 or neopelex.
Further, in step (1), reaction temperature are as follows: 30~120 DEG C, reaction temperature influences bigger, temperature to reaction
Too low, reaction can not carry out, and lye can cause product to damage with tetrachloro-ethylene and carbon tetrachloride reaction if reaction temperature is excessively high
It loses.
The invention mainly relates to reaction are as follows:
The present invention compared with prior art, has the advantage that
1, using saponification except the method for nitrile is suitable for the carbon tetrachloride or tetrachloro-ethylene product of different content, have application wide
General property.
2, the method for removing nitrile using saponification, can accomplish applying for lye, while nitrile can also be converted medicine intermediate,
Meet environmental requirement and there is Atom economy.
3, the method for removing nitrile using saponification only needs to isolate lower layer's organic products layer by layering after reaction
Come, the labor intensity that will be greatly reduced in this way improves separative efficiency.
4, equipment is simple, removal rate height of process stabilizing, nitrile is easier to industrialization.
The present invention provides a kind of minimizing technologies of nitrile organic matter in tetrachloro-ethylene and carbon tetrachloride, that is, pass through saponification
Method removes nitriles substance, and this method is suitable for the carbon tetrachloride or tetrachloro-ethylene solution of different nitrile contents, can substantially mention
The product quality of high tetrachloro-ethylene has industrialization prospect, effectively increases product quality.
Specific embodiment
The present invention is a kind of minimizing technology of nitrile organic matter in tetrachloro-ethylene and carbon tetrachloride, comprising the following steps:
(1) there is the aqueous solution for the alkali that 6kg is put into the 20L reaction kettle of visor toward discharge port, the concentration of alkali is 1~50%,
The concentration of alkali is 2~20%, and the too low meeting of alkali concentration is so that reaction rate is too slow, but alkali concentration is too high that it will cause tetrachloro-ethylenes
Alkaline hydrolysis with carbon tetrachloride is to cause the loss of material, and alkali is inorganic base, and inorganic base is lithium hydroxide, potassium hydroxide, hydrogen-oxygen
Change one of sodium, calcium hydroxide, aluminium hydroxide, sodium carbonate or potassium carbonate, the hydrolysis that the addition of alkali both can be catalyzed nitrile can also
To neutralize acid generated, preferably after, alkali is one of lithium hydroxide, potassium hydroxide, sodium hydroxide or calcium hydroxide, then is thrown
Enter the surfactant of 60g, surfactant is neopelex, stearic acid, quarternary ammonium salt compound or crown ether-like, sheet
Although reaction is not added surfactant and can be reacted yet, reaction speed is slower, can be with by the addition of surfactant
Accelerate reaction speed, preferably after, surfactant be tetramethyl ammonium chloride, 18- crown- 6 or neopelex in one
Kind, while fluorine temperature is controlled at 10~200 DEG C, and starts to stir, so that surfactant is dissolved in the aqueous solution of alkali, then lead to
It crosses feeding device and the tetrachloro-ethylene solution containing tri chloropropene nitrile or the carbon tetrachloride containing the chloro- butyronitrile of 4- is added into reaction kettle
Nitrile content is between 0~100% in solution, carbon tetrachloride or tetrachloro-ethylene solution, nitrile in carbon tetrachloride or tetrachloro-ethylene solution
Content is 0~30%, and this method is suitable for the sample of different content nitrile, that is, is suitable for nitrile content in the tetrachloro of 0~100% content
Change carbon or tetrachloro-ethylene solution, reaction solution removal effect especially low to nitrile content become apparent from, so nitrile content is 0~30%
Solution is more advantageous to the production of this method, and reaction temperature is 10~200 DEG C, reaction temperature are as follows: and 30~120 DEG C, reaction temperature pair
Reaction influence is bigger, and temperature is too low, and reaction can not carry out, and lye can be with tetrachloro-ethylene and tetrachloro if reaction temperature is excessively high
Changing carbon reaction causes product to lose, and the molar ratio of alkali and nitrile is greater than 1:1, and wherein nitriles substance content is between 0~100%.
(2) after feeding, it is further continued for reaction 30min, progress will be separated except the lower organic layer after nitrile after reaction
Detection detects the residual volume of wherein nitrile, adds alkali after the lye layer centralized recovery of upper layer and recycled.
By the following examples to the present invention carry out more specific description, but the present invention is not limited to embodiment.
Embodiment 1
The aqueous solution 6kg of the lithium hydroxide of 1% concentration is put into the 20L reaction kettle that discharge port has visor, then puts into 60g
Tetramethyl ammonium chloride, control fluorine temperature opens stirring after 30 DEG C, is quickly continuously contained toward being added in kettle by feeding device
The tetrachloro-ethylene solution 8kg of 0.01% tri chloropropene nitrile, the molar ratio for controlling alkali and nitrile are greater than 1:1, continue after charging anti-
Stop reaction after answering 30min, the residual volume for carrying out detecting nitrile will be separated except the lower organic layer after nitrile, detected nitrile and be not detected.
Embodiment 2
The aqueous solution 6kg of the sodium hydroxide of 20% concentration is put into the 20L reaction kettle that discharge port has visor, then is put into
The 18- crown- 6 of 60g, control fluorine temperature open stirring after 120 DEG C, are quickly continuously contained toward being added in kettle by feeding device
The tetrachloro-ethylene solution 8kg of 0.1% tri chloropropene nitrile, the molar ratio for controlling alkali and nitrile are greater than 1:1, and the reaction was continued after charging
Stop reaction after 30min, the residual volume for carrying out detecting nitrile will be separated except the lower organic layer after nitrile, detected nitrile and be not detected.
Embodiment 3
The aqueous solution 6kg of the potassium hydroxide of 5% concentration is put into the 20L reaction kettle that discharge port has visor, then puts into 60g
Neopelex, control fluorine temperature opens stirring after 50 DEG C, is quickly continuously contained toward being added in kettle by feeding device
There is the carbon tetrachloride solution 8kg of the chloro- isonitrile of 5%2-, the molar ratio for controlling alkali and nitrile is greater than 1:1, and the reaction was continued after charging
Stop reaction after 30min, the residual volume for carrying out detecting nitrile will be separated except the lower organic layer after nitrile, detected nitrile and be not detected.
Embodiment 4
The aqueous solution 6kg of the calcium hydroxide of 10% concentration is put into the 20L reaction kettle that discharge port has visor, then is put into
The tetramethyl ammonium chloride of 60g, control fluorine temperature open stirring after 80 DEG C, are quickly continuously contained toward being added in kettle by feeding device
The carbon tetrachloride solution 8kg of the chloro- isonitrile of 30%2-, the molar ratio for controlling alkali and nitrile are greater than 1:1, and the reaction was continued after charging
Stop reaction after 30min, the residual volume for carrying out detecting nitrile will be separated except the lower organic layer after nitrile, the content through detecting nitrile is
0.1%, removal rate 99.67%.
Embodiment 5
The aqueous solution 6kg of the calcium hydroxide of 15% concentration is put into the 20L reaction kettle that discharge port has visor, then is put into
The tetramethyl ammonium chloride of 60g, control fluorine temperature open stirring after 100 DEG C, are quickly continuously contained toward being added in kettle by feeding device
There is the tetrachloro-ethylene solution 8kg of 20% tri chloropropene nitrile, the molar ratio for controlling alkali and nitrile is greater than 1:1, continues after charging anti-
Stop reaction after answering 30min, the residual volume for carrying out detecting nitrile will be separated except the lower organic layer after nitrile, the content through detecting nitrile is
0.01%, removal rate 99.95%.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technical effect, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (4)
1. the minimizing technology of nitrile organic matter in a kind of tetrachloro-ethylene and carbon tetrachloride, which comprises the following steps:
(1) there is the aqueous solution for the alkali that 6kg is put into the 20L reaction kettle of visor toward discharge port, the concentration of the alkali is 2~20%,
The alkali is one of lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, aluminium hydroxide, sodium carbonate or potassium carbonate,
The surfactant of 60g is put into again, while controlling kettle temperature at 10~200 DEG C, and start to stir, so that surfactant dissolves
In the aqueous solution of alkali, the surfactant is neopelex, stearic acid, quarternary ammonium salt compound or crown ether
Class, then the tetrachloro-ethylene solution containing tri chloropropene nitrile is added into reaction kettle or containing the chloro- butyronitrile of 4- by feeding device
Nitrile content is between 0.01~30% in carbon tetrachloride solution, carbon tetrachloride or tetrachloro-ethylene solution, the reaction temperature are as follows: 30
~120 DEG C；
(2) after feeding, it is further continued for reaction 30min, will be detected after reaction except the lower organic layer after nitrile separates,
The residual volume of wherein nitrile is detected, alkali is added after the lye layer centralized recovery of upper layer and is recycled.
2. the minimizing technology of nitrile organic matter, feature in a kind of tetrachloro-ethylene according to claim 1 and carbon tetrachloride
Be: in the step (1), the molar ratio of the alkali and nitrile is greater than 1:1.
3. the minimizing technology of nitrile organic matter, feature in a kind of tetrachloro-ethylene according to claim 1 and carbon tetrachloride
Be: the alkali is one of lithium hydroxide, potassium hydroxide, sodium hydroxide or calcium hydroxide.
4. the minimizing technology of nitrile organic matter, feature in a kind of tetrachloro-ethylene according to claim 1 and carbon tetrachloride
Be: the surfactant is one of tetramethyl ammonium chloride, 18- crown- 6 or neopelex.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131145A (en) * | 1995-01-26 | 1996-09-18 | 标准石油公司 | Acetonitrile purification via adsorption-based process |
| CN1362402A (en) * | 2000-12-28 | 2002-08-07 | 花王株式会社 | Ether amide production method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4072469B2 (en) * | 2003-08-01 | 2008-04-09 | 株式会社日立グローバルストレージテクノロジーズ | Magnetic head slider and magnetic disk apparatus |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131145A (en) * | 1995-01-26 | 1996-09-18 | 标准石油公司 | Acetonitrile purification via adsorption-based process |
| CN1362402A (en) * | 2000-12-28 | 2002-08-07 | 花王株式会社 | Ether amide production method |
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