CN1066262A - The preparation method of para-dichlorobenzene - Google Patents
The preparation method of para-dichlorobenzene Download PDFInfo
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- CN1066262A CN1066262A CN 92100499 CN92100499A CN1066262A CN 1066262 A CN1066262 A CN 1066262A CN 92100499 CN92100499 CN 92100499 CN 92100499 A CN92100499 A CN 92100499A CN 1066262 A CN1066262 A CN 1066262A
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- benzene
- dichlorobenzene
- preparation
- chlorated liquid
- para
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Abstract
The invention belongs to the preparation of the para-chloroaromatic derivative of benzene.With benzene and chlorine is raw material, at a small amount of Sb
2S
3Catalyzer exists down, and chlorated liquid is isolated in washing again after logical chlorine was prepared the chlorated liquid of benzene, pickling, washing, alkali cleaning in 2.30～3.30 hours under 60～70 ℃ of temperature, the agitation condition, and freezing, crystallization, separation can prepare para-dichlorobenzene.The present invention uses very a spot of single catalyst, reduces facility investment significantly, and cost is low, simple to operate, and stable reaction conditions is well suited for suitability for industrialized production.
Description
The invention belongs to the preparation of the para-chloroaromatic derivative of benzene.
Para-dichlorobenzene is an important chemical material, people have carried out a large amount of research and exploration work in decades, seek the optimal condition of making the feedstock production para-dichlorobenzene with benzene and chlorine, wherein the major issue that will solve is to improve the transformation efficiency of chlorination degree and benzene, dichlorobenzene yield, the para-dichlorobenzene ratio in dichlorobenzene and the generation of restriction polystream.United States Patent (USP) (U.S.Pat.2,976,330) and French Patent (Fr 1,209,222) have been made report, have adopted active higher chlorination catalyst and directional catalyst to solve the problems referred to above preferably.But this method need prepare directional catalyst individually, needs the Separation and Recovery directional catalyst after chlorination is finished, thereby has increased facility investment and process cost; In addition, in chlorination process, the operation of temperature of reaction and logical chlorine speed control more complicated and reaction times are longer, thereby make troubles to suitability for industrialized production.
The object of the present invention is to provide a kind of improved method for preparing para-dichlorobenzene, use few single catalyst of trying one's best, reaction times weak point and higher yields and selectivity are strong, make the ratio that generates monochlor(in)ate benzene and polystream minimum, simple to operate, facility investment is few, and expense is low, is suitable for suitability for industrialized production.
Concrete technical solution of the present invention is the Sb that selects the better activity of few as far as possible and significant quantity for use and directive action is arranged
2S
3Be catalyzer, at comparatively high temps with carry out the chlorination reaction of benzene, preparation para-dichlorobenzene under than high pass chlorine rate conditions.
Described catalyst S b
2S
3Add-on for throwing 0.03%～0.75% of benzene amount, under 60～70 ℃ of temperature, stir, logical chlorine speed is 250～300 Grams Per Hours, time of chlorinating is 2.30～3.30 hours, the chlorination degree reaches more than 95～99%, the proportion (d of chlorated liquid
15 4): 1.28～1.30, with salt acid elution chlorated liquid, washing again behind the decant, the alkali cleaning chlorated liquid is washed to neutral then, and freezing, the crystallization of last isolated chlorated liquid promptly obtains crystal para-dichlorobenzene finished product.
The present invention adopts intermittent type or continous way to carry out, and uses industrial purified petroleum benzin (H
2O＜0.05%), Sb
2S
3Catalyzer is no less than 68% with Sb calculating, and wherein chlorizating agent can be liquid chlorine or chlorine, and purity is greater than 99.5%, and is moisture less than 0.06%.
The present invention is under the chlorization condition of optimum, and proportion is more than 95% in chlorated liquid for dichlorobenzene, and mono chloro benzene accounts for below 5%, and polystream accounts for below 0.3%, and para-dichlorobenzene accounts for 72～75% in the dichlorobenzene fraction.The present invention to be because to adopt be single catalyst, and the add-on of catalyzer is reduced to 1/17～1/20 of prior art than prior art much less, greatly reduces cost.Because the present invention avoids using directional catalyst, the mixture of the horizontal acid of sulfuric acid and benzene, so do not need to prepare separately directional catalyst, do not exist directional catalyst to separate yet and reclaim with chlorated liquid, so just reduced facility investment and process cost significantly, and simple to operate, in addition, the selected chlorization condition of the present invention is more stable, so be well suited for suitability for industrialized production.
The method applied in the present invention is applicable to the preparation of the para-chloroaromatic derivative of other benzene.
Example 1:
500 gram technical benzenes are placed the chlorination reaction bottle, drop into the weight of 0.25%(in benzene) Sb
2S
3Open electronic stirring, 100 rev/mins of stirring velocitys, heating in water bath, treat that benzene heats up near 60 ℃, begin to feed chlorine, speed 250 Grams Per Hours, about 60 ℃ of constant temperature, the logical chlorine of stop when the chlorination degree reaches 96%, reaction times is three hours 15 minutes, and chlorated liquid weighs 802 grams, and 13.6% benzene is taken away and reclaimed with hydrogen chloride gas.After chlorated liquid under agitation washs several minutes with 1: 3 hydrochloric acid, decant separates, then with 50～60 ℃ the water washing of a certain amount of (chlorated liquid heavy 8-10%) once with chlorated liquid, after the stirred for several minute, decant is isolated chlorated liquid, be neutralized to neutrality with 5% the NaOH aqueous solution then, wash again once with 50～60 ℃ water again, after the stirred for several minute, decant is isolated chlorated liquid, above-mentioned pickling, chlorated liquid is all reclaimed in washing, the final chlorated liquid that obtains is through gas chromatographic analysis, (wt) is as follows for its composition: mono chloro benzene 5.84%, para-dichlorobenzene 72.02%, 0-dichlorobenzene 22.14%.The chlorated liquid freezing and crystallizing is isolated the crystal para-dichlorobenzene, go out para-dichlorobenzene with salt solution or ice repeated freezing solution separating.Adopt the method for distillation and rectifying to isolate mono chloro benzene and 0-dichlorobenzene to mother liquor then.
Example 2:
Experiment condition wherein drops into 0.15% powdery Sb with example 1
2S
3, temperature of reaction is 70 ℃, chlorination degree 98%, time of chlorinating 2 hours 55 minutes, chlorated liquid weight 824 grams, the composition of gained chlorated liquid (wt): monochlor(in)ate benzene 3.17%, para-dichlorobenzene 73.7%, 0-dichlorobenzene 23.13%.
Example 3:
In benzene, drop into 0.025% powdery Sb
2S
3, 70 ℃ of temperature of reaction, chlorination degree 99%, chlorated liquid weighs 821 grams, and in 2 hours 52 minutes reaction times, other experiment condition is identical with example 1, and analytical results (wt) is: monochlor(in)ate benzene 1.15%, para-dichlorobenzene 75.9%, 0-dichlorobenzene 22.9%.
Claims (6)
1, a kind of is raw material with benzene and chlorine, uses Sb
2S
3Make the method for Preparation of Catalyst para-dichlorobenzene, it is characterized in that benzene is at significant quantity Sb
2S
3Exist and 60～70 ℃ of temperature, stir down logical chlorine and carried out chlorination in 2.30～3.30 hours and prepare chlorated liquid, use the salt acid elution then, decant separates, and washes; Alkali lye is washed chlorated liquid to neutral, washes, isolates chlorated liquid; The crystal para-dichlorobenzene is isolated in freezing, crystallization.
2, according to claim 1 said preparation method, it is characterized in that said Sb
2S
3Adding weight be 0.03%～0.75% of benzene, the speed of logical chlorine is 250～300 Grams Per Hours.
3, according to claim 1 said preparation method, the chlorination degree that it is characterized in that said chlorated liquid is 95～99%, proportion (d
15 4) be 1.28～1.30.
4,, it is characterized in that said hydrochloric acid is 1: 3 hydrochloric acid according to claim 1 said preparation method.
5,, it is characterized in that said alkali lye is the 5%NaOH aqueous solution according to claim 1 said preparation method.
6, according to claim 1 said system method, it is characterized in that said washing is to carry out under 50～60 ℃ of temperature, the weight of water is 8～10% of chlorated liquid weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100499A CN1035610C (en) | 1992-01-29 | 1992-01-29 | P-dichloco-benzene and prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92100499A CN1035610C (en) | 1992-01-29 | 1992-01-29 | P-dichloco-benzene and prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1066262A true CN1066262A (en) | 1992-11-18 |
| CN1035610C CN1035610C (en) | 1997-08-13 |
Family
ID=4938623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92100499A Expired - Fee Related CN1035610C (en) | 1992-01-29 | 1992-01-29 | P-dichloco-benzene and prepn. method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1035610C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819307A (en) * | 2014-02-12 | 2014-05-28 | 葫芦岛锦化化工工程设计有限公司 | Method for preparing chlorobenzene, p-dichlorobenzene and o-dichlorobenzene in benzene chlorination |
| CN105801334A (en) * | 2016-05-03 | 2016-07-27 | 四川福思达生物技术开发有限责任公司 | Synthetic method of 2,5-dichlorophenol |
| CN105964015A (en) * | 2016-07-11 | 2016-09-28 | 安徽省化工设计院 | Continuous type separating device for hydrochloric acid, benzene and chlorobenzene |
| CN106565415A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Method for preparing monochlorobenzene |
| CN106854136A (en) * | 2015-12-08 | 2017-06-16 | 中国石油化工股份有限公司 | A kind of method that batch process prepares mixed dichlorobenzene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397234B (en) * | 2007-09-30 | 2011-06-15 | 浙江省常山长盛化工有限公司 | Method for preparing dichlorobenzene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2976330A (en) * | 1958-07-03 | 1961-03-21 | Electro Chimie Metal | Method of obtaining chlorinated derivatives |
| US4017551A (en) * | 1975-01-27 | 1977-04-12 | Ppg Industries, Inc. | Liquid phase chlorination of aromatic hydrocarbons using manganese chloride catalyst |
-
1992
- 1992-01-29 CN CN92100499A patent/CN1035610C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819307A (en) * | 2014-02-12 | 2014-05-28 | 葫芦岛锦化化工工程设计有限公司 | Method for preparing chlorobenzene, p-dichlorobenzene and o-dichlorobenzene in benzene chlorination |
| CN103819307B (en) * | 2014-02-12 | 2016-08-17 | 葫芦岛锦化化工工程设计有限公司 | The method preparing chlorobenzene, paracide and o-dichlorohenzene during benzene chlorination |
| CN106565415A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Method for preparing monochlorobenzene |
| CN106854136A (en) * | 2015-12-08 | 2017-06-16 | 中国石油化工股份有限公司 | A kind of method that batch process prepares mixed dichlorobenzene |
| CN105801334A (en) * | 2016-05-03 | 2016-07-27 | 四川福思达生物技术开发有限责任公司 | Synthetic method of 2,5-dichlorophenol |
| CN105964015A (en) * | 2016-07-11 | 2016-09-28 | 安徽省化工设计院 | Continuous type separating device for hydrochloric acid, benzene and chlorobenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1035610C (en) | 1997-08-13 |
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