CN109942392B - Preparation method of hexachloroacetone - Google Patents
Preparation method of hexachloroacetone Download PDFInfo
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- CN109942392B CN109942392B CN201811636470.1A CN201811636470A CN109942392B CN 109942392 B CN109942392 B CN 109942392B CN 201811636470 A CN201811636470 A CN 201811636470A CN 109942392 B CN109942392 B CN 109942392B
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- chlorine
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- hexachloroacetone
- acetone
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- DOJXGHGHTWFZHK-UHFFFAOYSA-N Hexachloroacetone Chemical compound ClC(Cl)(Cl)C(=O)C(Cl)(Cl)Cl DOJXGHGHTWFZHK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 50
- 239000000460 chlorine Substances 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 15
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012043 crude product Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 9
- UNCQVRBWJWWJBF-UHFFFAOYSA-N 2-chloropyrimidine Chemical compound ClC1=NC=CC=N1 UNCQVRBWJWWJBF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 125000000714 pyrimidinyl group Chemical group 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000004821 distillation Methods 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- RVSIFWBAGVMQKT-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropan-2-one Chemical compound ClC(Cl)C(=O)C(Cl)(Cl)Cl RVSIFWBAGVMQKT-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- SMZHKGXSEAGRTI-UHFFFAOYSA-N 1,1,1-trichloropropan-2-one Chemical compound CC(=O)C(Cl)(Cl)Cl SMZHKGXSEAGRTI-UHFFFAOYSA-N 0.000 claims description 2
- DJWVKJAGMVZYFP-UHFFFAOYSA-N 1,1,3,3-tetrachloropropan-2-one Chemical compound ClC(Cl)C(=O)C(Cl)Cl DJWVKJAGMVZYFP-UHFFFAOYSA-N 0.000 claims description 2
- CSVFWMMPUJDVKH-UHFFFAOYSA-N 1,1-dichloropropan-2-one Chemical compound CC(=O)C(Cl)Cl CSVFWMMPUJDVKH-UHFFFAOYSA-N 0.000 claims description 2
- IIHQNAXFIODVDU-UHFFFAOYSA-N pyrimidine-2-carbonitrile Chemical compound N#CC1=NC=CC=N1 IIHQNAXFIODVDU-UHFFFAOYSA-N 0.000 claims description 2
- ZWILTCXCTVMANU-UHFFFAOYSA-N tetrachloroacetone Natural products ClCC(=O)C(Cl)Cl ZWILTCXCTVMANU-UHFFFAOYSA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 abstract description 15
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 19
- 239000000498 cooling water Substances 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- FILKGCRCWDMBKA-UHFFFAOYSA-N 2,6-dichloropyridine Chemical compound ClC1=CC=CC(Cl)=N1 FILKGCRCWDMBKA-UHFFFAOYSA-N 0.000 description 1
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 1
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a preparation method of hexachloroacetone, belonging to the technical field of organic chemical gas preparation. Mixing the compound A and the chlorine molecule B to react at 30-150 ℃ under the action of a catalyst, wherein the reaction product is a mixture containing hexachloroacetone and the catalyst; separating the catalyst from the mixture to obtain a crude product; purifying the crude product to obtain hexachloroacetone; the compound A is at least one of acetone and chloropropanone with the chlorine atom number of 1-5; the chlorine molecule B is chlorine or a mixture of chlorine and diluent gas, and the diluent gas is inert gas or nitrogen; the catalyst is pyrimidine, 2-chloropyrimidine, 2-nitrile pyrimidine or s-triazine. The method is easy to recover the catalyst, and can obtain the hexachloroacetone with extremely low impurity content in high yield.
Description
Technical Field
The invention relates to a preparation method of hexachloroacetone, belonging to the technical field of organic chemical gas preparation.
Background
Patents US2199934, US2635117, US3265740, JP2015556795, CN2013103226 and CN201580003850 are known for the preparation of hexachloroacetone at present. Among them, US2199934, US3265740 and JP2015556795 are methods of reacting acetone with chlorine molecule B using pyridine as a catalyst; CN2013103226 is a method of reacting acetone with chlorine molecule B using triphenylphosphine as a catalyst; US2635117 and CN201580003850 are methods of reacting acetone with chlorine molecule B using activated carbon as a catalyst; the chlorine molecule B is chlorine or a mixture of chlorine and diluent gas, and the diluent gas is inert gas or nitrogen and other gases which do not participate in the reaction. Pyridine and triphenylphosphine are used as a catalyst, and the catalyst and its chloride are dissolved in the hexachloroacetone product, so that it is difficult to recover and reuse the catalyst and its chloride, and even when the catalyst and its chloride are removed by distillation purification of the crude product, a trace amount of the catalyst and its chloride remains in the hexachloroacetone, so that it is difficult to obtain high-purity hexachloroacetone. By adopting the activated carbon as a catalyst, the chloroacetone with 1-5 chlorine atoms is easy to polymerize, so that a compound with a high boiling point is easy to generate, and the yield of the hexachloroacetone is generally lower than 80%.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of hexachloroacetone, which is easy to recover a catalyst and can obtain hexachloroacetone with extremely low impurity content in high yield.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A preparation method of hexachloroacetone comprises the following steps: mixing the compound A and the chlorine molecule B, and reacting under the action of a catalyst, wherein a reaction product is a mixture containing hexachloroacetone and the catalyst; separating the catalyst from the mixture to obtain a crude product; the crude product was purified to obtain hexachloroacetone.
The compound A is at least one of acetone and chloropropanone with the chlorine atom number of 1-5, wherein the acetone is used as a raw material, and the chloropropanone with the chlorine atom number of 1-5 is an intermediate product generated in the reaction process of the raw material acetone and chlorine molecule B.
Preferably, the mass percent of water in the compound A is less than 2%; more preferably, the mass percentage of the water in the compound A is less than 0.5 percent; most preferably, the mass percent of the water in the compound A is less than 0.1 percent.
The acetone may contain diacetone alcohol (DAA) impurities, and the content of DAA in acetone is preferably 1% by mass or less, and more preferably 0.1% by mass or less.
The chlorine molecule B is chlorine or a mixture of chlorine and diluent gas, and the diluent gas is inert gas or nitrogen and other gases which do not participate in the reaction.
The mol ratio of chlorine molecules in the chlorine molecules B to hydrogen atoms in the compound A is preferably 1: 1-1.5: 1, and the mol ratio of chlorine molecules in the chlorine molecules B to hydrogen atoms in the compound A is more preferably 1.1: 1-1.2: 1.
The catalyst is pyrimidine, 2-chloropyrimidine, 2-cyanopyrimidine or s-triazine; preferably, the catalyst is pyrimidine or 2-chloropyrimidine.
The molar ratio of the catalyst to the compound A is 1: 5-1: 100; preferably, the molar ratio of the catalyst to the compound A is 1: 10-1: 20.
The reaction is a gas-liquid mixed reaction and can be realized in a reaction kettle with stirring, a tubular reactor or a plate-type tower-shaped reactor and the like; it can also be achieved by mixing the gas with the liquid through a gas distributor.
The reaction mode is a batch type or a continuous type.
The reaction speed can be adjusted by the flow rate of the chlorine molecule B, the temperature, the amount of the catalyst and the like.
The reaction temperature is 30-150 ℃.
Preferably, when the compound A is used as a raw material, acetone reacts with the chlorine molecule B, and the reaction temperature is 30-40 ℃; with the increase of the adding amount of the chlorine molecule B, when the molar ratio of the chlorine molecule in the chlorine molecule B to the hydrogen atom in the compound A is 2:1, converting the acetone into a mixture of monochloroacetone, dichloroacetone and trichloroacetone; adding a catalyst, and self-heating to 110-120 ℃ by virtue of reaction heat, wherein when the molar ratio of chlorine molecules in the chlorine molecules B to hydrogen atoms in the compound A is 5:1, the reaction product is a mixture of tetrachloroacetone, pentachloroacetone and hexachloroacetone; heating to 140-150 deg.C. Preferably, after the compound A is used as a raw material, acetone reacts with the chlorine molecule B to generate pentachloroacetone, and the reaction temperature is 140-150 ℃ until the reaction is finished.
The reaction pressure was normal pressure.
Preferably, nitrogen is introduced after the reaction is finished to purge out residual chlorine and hydrogen chloride in the reaction.
The catalyst can be separated from the mixture by settling separation, water washing or drying to obtain a crude product.
The crude product can be purified by distillation under reduced pressure to obtain hexachloroacetone with extremely low impurity content; the degree of vacuum for purification by vacuum distillation is preferably 0.1KPa to 5KPa, and more preferably 0.1KPa to 0.5 KPa.
Advantageous effects
The invention provides a preparation method of hexachloroacetone, which is easy to recover a catalyst and can obtain hexachloroacetone with extremely low impurity content in high yield.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to the following examples.
Example 1
295g (5mol) of acetone (with the water content of below 0.1 wt%) is added into a 1L glass reactor with a stirrer, a thermometer, a gas inlet pipe and a condenser, the mixture is stirred, then chlorine gas is introduced into the acetone at the flow rate of 4g/min, the reactor is kept at the temperature of 30-40 ℃ by cooling water until about 710g (10mol) of chlorine gas is introduced, the cooling water is removed, 20.3g (0.25mol) of pyrimidine is added, the temperature is raised to 110-120 ℃ by the reaction heat, about 1775g (25mol) of chlorine gas is introduced, the temperature is raised to 140-150 ℃ by heating until about 2343g (33mol) of chlorine gas is added, nitrogen gas is introduced for purging to remove residual chlorine gas and hydrogen chloride, the product is separated after the catalyst and the product are layered, the product is washed for three times by water, the calcium chloride is dried, and the final product is obtained by reduced pressure distillation at 0.1KPa, and the yield is 94.5%.
The final product was subjected to gas chromatography and found to be: the method comprises the following steps of (1) not detecting chloroacetone with 1-4 chlorine atoms, wherein the mass percentage of pentachloroacetone is 0.02%, the mass percentage of high-boiling residues is not detected, and the mass percentage of hexachloroacetone is 99.98%.
Example 2
295g (5mol) of acetone (with the water content of less than 0.1 wt%) is added into a 1L glass reactor with a stirrer, a thermometer, a gas inlet pipe and a condenser, the mixture is stirred, then chlorine gas is introduced into the acetone at the flow rate of 4g/min, the reactor is kept at the temperature of 30-40 ℃ by cooling water until about 710g (10mol) of chlorine gas is introduced, the cooling water is removed, 57.3g (0.50mol) of 2-chloropyrimidine is added, the temperature is raised from 110 ℃ to about 1775g (25mol) of chlorine gas is introduced by the reaction heat, the temperature is raised to 140-150 ℃ by heating until about 2812g (39.6mol) of chlorine gas is added, nitrogen gas is introduced to purge and remove residual chlorine gas and hydrogen chloride, the product is separated after the catalyst and the product are layered, the product is washed for three times, calcium chloride is dried, and the final product is obtained by reduced pressure distillation at 0.1KPa, and the yield is 94.1%.
The final product was subjected to gas chromatography and found to be: the method comprises the following steps of (1) not detecting chloroacetone with 1-4 chlorine atoms, wherein the mass percentage of pentachloroacetone is 0.06%, high-boiling residues are not detected, and the mass percentage of hexachloroacetone is 99.94%.
Example 3
295g (5mol) of acetone (with the water content of less than 0.1 wt%) is added into a 1L glass reactor with a stirrer, a thermometer, a gas inlet pipe and a condenser, the mixture is stirred, then chlorine gas is introduced into the acetone at the flow rate of 4g/min, the reactor is kept at the temperature of between 30 and 40 ℃ by cooling water until about 710g (10mol) of chlorine gas is introduced, the cooling water is removed, 36.8g (0.35mol) of 2-cyanopyridine is added, the temperature is raised to between 110 and 120 ℃ by the reaction heat until about 1775g (25mol) of chlorine gas is introduced, the temperature is raised to between 140 and 150 ℃ by heating until about 2450g (34.5mol) of chlorine gas is added, nitrogen gas is introduced to purge residual chlorine gas and hydrogen chloride, the product is separated after the catalyst and the product are layered, the product is washed for three times by water, the calcium chloride is dried, and the final product is obtained by reduced pressure distillation under the pressure of 0.1KPa, and the yield is 93.8%.
The final product was subjected to gas chromatography and found to be: the method comprises the following steps of (1) not detecting chloroacetone with 1-4 chlorine atoms, wherein the mass percentage of pentachloroacetone is 0.05%, the high-boiling residues are not detected, and the mass percentage of hexachloroacetone is 99.95%.
Example 4
295g (5mol) of acetone (with the water content of less than 0.1 wt%) is added into a 1L glass reactor with a stirrer, a thermometer, a gas inlet pipe and a condenser, the mixture is stirred, then chlorine gas is introduced into the acetone at the flow rate of 4g/min, the reactor is kept at the temperature of 30-40 ℃ by cooling water until about 710g (10mol) of chlorine gas is introduced, the cooling water is removed, 54.8g (0.25mol) of s-triazine is added, the temperature is raised to 110-120 ℃ by the reaction heat, about 1775g (25mol) of chlorine gas is introduced, the temperature is heated to 140-150 ℃ by heating until about 2450g (34.5mol) of chlorine gas is added, nitrogen gas is introduced to purge and remove residual chlorine gas and hydrogen chloride, the product is separated after the catalyst and the product are layered, the product is washed for three times by water, the calcium chloride is dried, and the final product is obtained by reduced pressure distillation under the pressure of 0.1KPa, and the yield is 93.6%.
The final product was subjected to gas chromatography and found to be: the method comprises the following steps of (1) not detecting chloroacetone with 1-4 chlorine atoms, wherein the mass percentage of pentachloroacetone is 0.11%, high-boiling residues are not detected, and the mass percentage of hexachloroacetone is 99.89%.
Comparative example 1
295g (5mol) of acetone (with the water content of less than 0.1 wt%) is added into a 1L glass reactor with a stirrer, a thermometer, a gas inlet pipe and a condenser, the mixture is stirred, then chlorine gas is introduced into the acetone at the flow rate of 4g/min, cooling water is introduced into the reactor, the temperature is kept between 30 and 40 ℃ until about 710g (10mol) of chlorine gas is introduced, the cooling water is removed, 39.6g (0.50mol) of pyridine is added, the temperature is automatically raised to 110 ℃ by the reaction heat until about 1775g (25mol) of chlorine gas is introduced, the temperature is raised to 140 to 150 ℃ until about 2450g (34.5mol) of chlorine gas is added, nitrogen gas is introduced to purge and remove residual chlorine gas and hydrogen chloride, the product is separated after the catalyst and the product are layered, the product is washed for three times, calcium chloride is dried, and the final product is obtained by reduced pressure distillation under the pressure of 0.1KPa, and the yield is 91.3%.
The final product was subjected to gas chromatography and found to be: the method comprises the following steps of (1) not detecting chloroacetone with 1-4 chlorine atoms, wherein the mass percentage of pentachloroacetone is 1.3%, the mass percentage of 2-chloropyridine is 0.3%, the mass percentage of 2, 6-dichloropyridine is 0.7%, high-boiling residues are not detected, and the mass percentage of hexachloroacetone is 97.7%.
Comparative example 2
295g (5mol) of acetone (with the water content of below 0.1 wt%) is added into a 1L glass reactor with a stirrer, a thermometer, a gas inlet pipe and a condenser, the mixture is stirred, then chlorine gas is introduced into the acetone at the flow rate of 4g/min, the reactor is kept at the temperature of 30-40 ℃ by cooling water until about 710g (10mol) of chlorine gas is introduced, the cooling water is removed, 65.6g (0.25mol) of triphenylphosphine is added, the temperature is automatically raised to 110 ℃ by the reaction heat until about 1775g (25mol) of chlorine gas is introduced, the temperature is raised to 140-150 ℃ by heating until about 2450g (34.5mol) of chlorine gas is added, nitrogen gas is introduced to purge residual chlorine gas and hydrogen chloride, the product is separated after the catalyst and the product are layered, the product is washed for three times by water, the calcium chloride is dried, and the final product is obtained by reduced pressure distillation at 0.1KPa, and the yield is 92.4%.
The final product was subjected to gas chromatography and found to be: the method comprises the following steps of (1) not detecting chloroacetone with 1-4 chlorine atoms, wherein the mass percentage of pentachloroacetone is 2.3%, the mass percentage of phenol is 0.5%, high-boiling residues are not detected, and the mass percentage of hexachloroacetone is 97.2%.
Claims (10)
1. A method for preparing hexachloroacetone is characterized by comprising the following steps: the method comprises the following steps: reacting the raw material A with the chlorine molecule B under the action of a catalyst, wherein the reaction product is a mixture containing hexachloroacetone and the catalyst; separating the catalyst from the mixture to obtain a crude product; purifying the crude product to obtain hexachloroacetone;
the raw material A is at least one of acetone and chloropropanone with the chlorine atom number of 1-5;
the chlorine molecule B is chlorine or a mixture of chlorine and diluent gas, and the diluent gas is inert gas or nitrogen;
the catalyst is pyrimidine, 2-chloropyrimidine, 2-cyanopyrimidine or s-triazine;
the reaction temperature is 30-150 ℃.
2. The method according to claim 1, wherein the method comprises the following steps: when the raw material A is acetone and chlorine molecule B, the reaction temperature is 30-40 ℃; with the increase of the adding amount of the chlorine molecule B, when the mole ratio of the chlorine molecule in the chlorine molecule B to the hydrogen atom in the raw material A is 2:1, converting the acetone into a mixture of monochloroacetone, dichloroacetone and trichloroacetone; adding a catalyst, and self-heating to 110-120 ℃ by virtue of reaction heat, wherein when the molar ratio of chlorine molecules in the chlorine molecules B to hydrogen atoms in the raw material A is 5:1, the reaction product is a mixture of tetrachloroacetone, pentachloroacetone and hexachloroacetone; heating to 140-150 ℃ until the reaction is finished.
3. The method according to claim 1 or 2, wherein the method comprises the following steps: the catalyst is pyrimidine or 2-chloropyrimidine.
4. The method according to claim 1, wherein the method comprises the following steps: the mol ratio of chlorine molecules in the chlorine molecules B to hydrogen atoms in the raw material A is 1: 1-1.5: 1; the molar ratio of the catalyst to the raw material A is 1: 5-1: 100.
5. The method according to claim 1, wherein the method comprises the following steps: the mol ratio of chlorine molecules in the chlorine molecules B to hydrogen atoms in the raw material A is 1.1: 1-1.2: 1; the molar ratio of the catalyst to the raw material A is 1: 10-1: 20.
6. The method according to claim 1 or 2, wherein the method comprises the following steps: the mass percentage of water in the raw material A is below 2%; the mass percentage of DAA in the acetone is less than 1 percent; the crude product is purified by reduced pressure distillation at 0.1KPa to 5KPa to obtain hexachloroacetone with extremely low impurity content.
7. The method according to claim 1 or 2, wherein the method comprises the following steps: the mass percentage of water in the raw material A is less than 0.5%; the mass percentage of DAA in the acetone is less than 0.1 percent; the crude product is purified by reduced pressure distillation at 0.1KPa to 0.5KPa to obtain hexachloroacetone with extremely low impurity content.
8. The method according to claim 1, wherein the method comprises the following steps: the catalyst is pyrimidine or 2-chloropyrimidine;
the mol ratio of chlorine molecules in the chlorine molecules B to hydrogen atoms in the raw material A is 1: 1-1.5: 1; the molar ratio of the catalyst to the raw material A is 1: 5-1: 100;
the mass percentage of water in the raw material A is below 2%; the mass percentage of DAA in the acetone is less than 1 percent; the crude product is purified by reduced pressure distillation at 0.1KPa to 5KPa to obtain hexachloroacetone with extremely low impurity content.
9. The method according to claim 1, wherein the method comprises the following steps: the catalyst is pyrimidine or 2-chloropyrimidine;
the mol ratio of chlorine molecules in the chlorine molecules B to hydrogen atoms in the raw material A is 1.1: 1-1.2: 1; the molar ratio of the catalyst to the raw material A is 1: 10-1: 20;
the mass percentage of water in the raw material A is less than 0.5%; the mass percentage of DAA in the acetone is less than 0.1 percent; the crude product is purified by reduced pressure distillation at 0.1KPa to 0.5KPa to obtain hexachloroacetone with extremely low impurity content.
10. The method according to claim 9, wherein the hexachloroacetone is prepared by: the mass percentage of the water in the raw material A is less than 0.1 percent.
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| CN201811636470.1A CN109942392B (en) | 2018-12-29 | 2018-12-29 | Preparation method of hexachloroacetone |
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| CN201811636470.1A CN109942392B (en) | 2018-12-29 | 2018-12-29 | Preparation method of hexachloroacetone |
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| Publication Number | Publication Date |
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| CN109942392A CN109942392A (en) | 2019-06-28 |
| CN109942392B true CN109942392B (en) | 2022-01-21 |
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| CN201811636470.1A Active CN109942392B (en) | 2018-12-29 | 2018-12-29 | Preparation method of hexachloroacetone |
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| US2199934A (en) * | 1936-01-28 | 1940-05-07 | Ig Farbenindustrie Ag | Process of preparing higher halogenated ketones |
| US2635117A (en) * | 1949-05-12 | 1953-04-14 | Allied Chem & Dye Corp | Preparation of polychloroacetones |
| US3265740A (en) * | 1962-07-11 | 1966-08-09 | Du Pont | Process for chlorinating acetone and acetylacetone |
| CN1139923A (en) * | 1994-02-03 | 1997-01-08 | 奥林公司 | Process for preparing 2,6-dichloropyridine |
| CN104710296A (en) * | 2013-12-12 | 2015-06-17 | 西安近代化学研究所 | Method for preparing 1,1,1,3,3,3-hexafluoroacetone by gas phase fluorination |
| CN105899482A (en) * | 2014-01-08 | 2016-08-24 | 旭硝子株式会社 | Production method for hexachloroacetone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2199934A (en) * | 1936-01-28 | 1940-05-07 | Ig Farbenindustrie Ag | Process of preparing higher halogenated ketones |
| US2635117A (en) * | 1949-05-12 | 1953-04-14 | Allied Chem & Dye Corp | Preparation of polychloroacetones |
| US3265740A (en) * | 1962-07-11 | 1966-08-09 | Du Pont | Process for chlorinating acetone and acetylacetone |
| CN1139923A (en) * | 1994-02-03 | 1997-01-08 | 奥林公司 | Process for preparing 2,6-dichloropyridine |
| CN104710296A (en) * | 2013-12-12 | 2015-06-17 | 西安近代化学研究所 | Method for preparing 1,1,1,3,3,3-hexafluoroacetone by gas phase fluorination |
| CN105899482A (en) * | 2014-01-08 | 2016-08-24 | 旭硝子株式会社 | Production method for hexachloroacetone |
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Address after: 056027 No. 17, Exhibition Road, Handan, Hebei Patentee after: 718th Research Institute of China Shipbuilding Corp. Address before: 056027 No. 17, Exhibition Road, Handan, Hebei Patentee before: Handan Purifying Equipment Research Institute |
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