CN103739441A - Method for increasing proportion of paradichlorobenzene in benzene chlorination product - Google Patents
Method for increasing proportion of paradichlorobenzene in benzene chlorination product Download PDFInfo
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- CN103739441A CN103739441A CN201410010582.1A CN201410010582A CN103739441A CN 103739441 A CN103739441 A CN 103739441A CN 201410010582 A CN201410010582 A CN 201410010582A CN 103739441 A CN103739441 A CN 103739441A
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- benzene
- santochlor
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- paradichlorobenzene
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Abstract
The invention discloses a method for increasing a proportion of paradichlorobenzene in a benzene chlorination product. The method comprises the steps: adding a combined catalyst in benzene, introducing chlorine under a stirring condition, to obtain the chlorination product with high paradichlorobenzene content, wherein the temperature of the whole process is controlled to be 50-80 DEG C, and the amount of the introduced chlorine is controlled to ensure that the conversion rate of the benzene is more than 99 percent and the conversion rate of chlorobenzene is more than 93 percent, and in addition, the combined catalyst comprises a main catalyst and a co-catalyst, the main catalyst is one of iron powder, ferric trichloride, aluminum trichloride, antimony trichloride, antimony pentachloride or tin tetrachloride, the co-catalyst is a dibenzo thiazepine organic matter, and the weight ratio of the main catalyst to the co-catalyst is 1:1. According to the method, the proportion of the paradichlorobenzene in the product is effectively increased, the ratio of the paradichlorobenzene to orthodichlorobenzene can reach 4.8, the content of the orthodichlorobenzene is less than 0.4 percent, and the content of phenyl polychloride is less than 1 percent.
Description
Technical field
The present invention relates to a kind of method that improves santochlor ratio in benzene chlorizate.The technical field that belongs to benzene chlorination,
Background technology
Santochlor (Isosorbide-5-Nitrae-dichlorobenzene) is a kind of important organic chloride chemical product, is colourless or white crystal under normal temperature, and easily distillation, has special aromatic odour at normal temperatures.Since nearly 30 years, santochlor has a wide range of applications [Chinese chlor-alkali 2009 at aspects such as medicine, agricultural chemicals, engineering plastics, dyestuff, catalyzer, 7:1-4], topmost purposes is to manufacture mothproof mildew preventive, the naphthalene naphthalene ball processed using due to tradition is potential carcinogenic substance, since the eighties in last century, forbids naphthalene abroad and manufactures naphthalene ball.Aspect agricultural chemicals, santochlor can be used for manufacturing sterilant and sterilant, as is prepared with the intermediate 2 of machine phosphorus insecticide chlorfenvinpho, 5-chloro-acetophenone, the intermediate 3 of the efficient germicides such as preparation dichlozolin, dimethachlon, 5-dichlorphenamide bulk powder.In dyestuffs industries, santochlor can be used as intermediate and the raw material of dyestuff color base pigment, as for the production of 2,5-dichloronitrobenzene etc.In paper industry, santochlor can be used as the making beating part of fibrous tissue.
It is raw material that the industrial production of santochlor normally be take benzene or chlorobenzene, after dichloride, generate main component and be santochlor and orthodichlorobenzene mixture, through conventional rectifying separation, obtain santochlor, simultaneously by-product orthodichlorobenzene.Because dichlorobenzene near santochlor purposes is many and consumption is large, therefore industrial often by adding the method for different catalysts to improve the ratio of santochlor in mixed solution.According to the difference of catalyst system, be divided into zeolite-catalyzed reaction system and Louis acid catalysis reaction system.Molecular sieve, as zeolite L, y-type zeolite can be used as catalyzer, thereby can be used to the chlorination of catalysis virtue core.The principal element of this catalysts influence selectivity of product is the exchangable ion of zeolite, the acidity of zeolite and permeability.Its outstanding advantages is that transformation efficiency is high, and benzene transformation efficiency can reach 100%, and chlorobenzene transformation efficiency also can reach more than 90%.And, santochlor selectivity in mixed dichlorobenzene is good, the ratio of santochlor and orthodichlorobenzene (p/o) can reach more than 8, shortcoming is, after zeolites catalyzer is used, because the strong acid HCl generating in chlorination reaction destroys zeolite lattice, to cause its catalytic activity greatly to reduce, expensive, easily poisoning and deactivation, is difficult to regeneration and uses, and has limited its industrial applications.
Iron powder and other Louis are as FeCl
3, AlCl
3, ZnCl
2, SbCl
5deng being the conventional catalyzer of aromatic hydrocarbons chlorination industry; its main weak point is while using benzene chlorination; in chlorizate mixed dichlorobenzene, para-selectivity is lower; p/o is only 1.5 left and right; conventionally also need to add certain cocatalysts to improve the selectivity of contraposition product; the people such as MANDAL have synthesized the substituted diphenylamine promotor of a series of aromatic rings, and with lewis acid catalyst coupling, in experimental result dichlorobenzene, p/o approaches 3.0[PTCNO0600185].The people such as Franz-josefMais, by adding a series of benzo thiodiphenylamine to make promotor in lewis acid catalyst, will bring up to more than 4.7 [US5210343] to neighbour's ratio in benzene chlorizate dichlorobenzene.But this cocatalyst complex structure, synthetic difficulty causes more greatly cost higher.
Summary of the invention
Technical problem: the problem to be solved in the present invention is to improve the deficiency of existing background technology, invent a kind of method that improves santochlor ratio in benzene chlorizate, by adopting a kind of dichloride of novel combined catalyst benzene to react, santochlor ratio in product dichlorobenzene mixture is greatly improved.
Technical scheme: the present invention is achieved by the following technical solutions: add a kind of combined catalyzer in benzene, under stirring, pass into chlorine, the temperature of whole process is controlled at 50-80 ℃, controlling logical chlorine dose makes the transformation efficiency of benzene be greater than 99%, the transformation efficiency of chlorobenzene is greater than 93%, obtains the chlorizate that contains high-content santochlor;
Described combined catalyzer comprises Primary Catalysts and promotor; Primary Catalysts is wherein a kind of of iron powder, iron trichloride, aluminum chloride, butter of antimony, antimony pentachloride or tin tetrachloride, and promotor is dibenzo sulphur azatropylidene type organic; The part by weight of Primary Catalysts and promotor is: 1:1.
The amount ranges of Primary Catalysts and promotor accounts for respectively the 0.004%-5% of benzene feedstock massfraction.
The general structure of described dibenzo sulphur azatropylidene type organic is as follows:
R wherein
1=NHOH, Cl, NH
2; Title is respectively dibenzo sulphur azatropylidene-N-dicarbonyl chloride, dibenzo sulphur azatropylidene hydroxamic acid, dibenzo sulphur azatropylidene-N-methane amide, and its amount ranges accounts for the 0.004%-5% of benzene feedstock massfraction.
Beneficial effect: method of the present invention has improved the ratio of santochlor in chlorinated mixture effectively, in product, santochlor can reach 4.8 with orthodichlorobenzene ratio, and Meta Dichlorobenzene content is less than 0.4%, and polystream content is less than 1%.
Embodiment
Below embodiments of the invention are elaborated, the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
The present invention is achieved by the following technical solutions, and by combined catalyzer, for benzene dichloride, the temperature of whole chlorination process is controlled at 50-80 ℃, controls logical chlorine dose and make the transformation efficiency of benzene be greater than 99%, and the transformation efficiency of chlorobenzene is greater than 93%.
In combined catalyzer in the present invention, Primary Catalysts can be the Lewis acids such as iron powder or iron trichloride, aluminum chloride, butter of antimony, antimony pentachloride, tin tetrachloride, and promotor is dibenzo sulphur azatropylidene type organic.The amount ranges of Primary Catalysts and promotor accounts for respectively the 0.004%-5% of benzene feedstock massfraction, and comparatively ideal scope is 0.04%-0.5%.
The general structure of the promotor dibenzo sulphur azatropylidene class in the present invention is as follows:
R wherein
1=NHOH, Cl, NH
2;
Embodiment 1
The preparation of promotor dibenzo sulphur azatropylidene-N-dicarbonyl chloride: take 68.10g dibenzo [b, f] [Isosorbide-5-Nitrae] sulphur azatropylidene-11-[10H] ketone,, 26.10g pyridine, 300ml toluene, joins in 2000ml there-necked flask successively.Separately 32.64g triphosgene is dissolved in 300ml toluene, joins in constant pressure funnel.In stirring at room condition downhill reaction bottle, drip triphosgene solution, in 3 hours, drip off, continue stirring and be warming up to and reflux 1 hour after 1 hour, change the most of toluene of Distillation recovery into.Stop heating, after crystallisation by cooling, filter.Solid cleans 2 times with 0 ℃ of frozen water, puts into 35 ℃ of vacuum drying ovens and dries to obtain dibenzo sulphur azatropylidene-N-dicarbonyl chloride.
Embodiment 2
Take about 30g benzene, iron powder 35mg, dibenzo sulphur azatropylidene-N-dicarbonyl chloride 35mg, stirs lower evenly slowly logical chlorine 4 hours, and whole process temperature scope control, at 60-70 ℃, after reaction finishes, filters, washing, anhydrous sodium sulfate drying, filters.Gas chromatographic detection is carried out in sampling, benzene transformation efficiency 99.8%, and chlorobenzene transformation efficiency 92.7%, santochlor is about 4.8, the content 0.36% of a toluene dichloride with the content ratio of adjacent dichloro chlorobenzene.
Embodiment 3
Take about 30g benzene, iron powder 20mg, dibenzo sulphur azatropylidene hydroxamic acid 20mg, stirs lower evenly slowly logical chlorine 5.5 hours, and whole process temperature scope control, at 50-60 ℃, after reaction finishes, filters, washing, anhydrous sodium sulfate drying, filters.Gas chromatographic detection is carried out in sampling, benzene transformation efficiency 99.8%, and chlorobenzene transformation efficiency 90.0%, santochlor is about 4.7, the content 0.20% of Meta Dichlorobenzene with the content ratio of orthodichlorobenzene.
Reference examples
Take about 30g benzene, iron powder 20mg, stirs lower evenly slowly logical chlorine 5 hours, and whole process temperature scope control, at 50-60 ℃, after reaction finishes, filters, washing, and anhydrous sodium sulfate drying, filters.Gas chromatographic detection is carried out in sampling, benzene transformation efficiency 99.7%, and chlorobenzene transformation efficiency 93.6%, santochlor is about 1.4, the content 2.5% of a toluene dichloride with the content ratio of orthodichlorobenzene.
Claims (3)
1. a method that improves santochlor ratio in benzene chlorizate, it is characterized in that: in benzene, add a kind of combined catalyzer, under stirring, pass into chlorine, the temperature of whole process is controlled at 50-80 ℃, controlling logical chlorine dose makes the transformation efficiency of benzene be greater than 99%, the transformation efficiency of chlorobenzene is greater than 93%, obtains the chlorizate that contains high-content santochlor;
Described combined catalyzer comprises Primary Catalysts and promotor; Primary Catalysts is wherein a kind of of iron powder, iron trichloride, aluminum chloride, butter of antimony, antimony pentachloride or tin tetrachloride, and promotor is dibenzo sulphur azatropylidene type organic; The part by weight of Primary Catalysts and promotor is: 1:1.
2. the method for santochlor ratio in raising benzene chlorizate as claimed in claim 1, is characterized in that described dibenzo sulphur azatropylidene type organic, and its general structure is as follows:
R wherein
1=NHOH, Cl, NH
2.
3. the method for santochlor ratio in raising benzene chlorizate as claimed in claim 1, is characterized in that: the amount ranges of Primary Catalysts and promotor accounts for respectively the 0.004%-5% of benzene feedstock massfraction.
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| CN201410010582.1A CN103739441A (en) | 2014-01-09 | 2014-01-09 | Method for increasing proportion of paradichlorobenzene in benzene chlorination product |
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| CN201410010582.1A CN103739441A (en) | 2014-01-09 | 2014-01-09 | Method for increasing proportion of paradichlorobenzene in benzene chlorination product |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899615A (en) * | 2017-11-03 | 2018-04-13 | 天津普莱化工技术有限公司 | A kind of catalyst for oriented chlorination and preparation method and application |
| CN112194554A (en) * | 2020-11-05 | 2021-01-08 | 湖北山水化工有限公司 | Preparation process and production process system of (o) p-chlorotoluene |
| CN113831214A (en) * | 2021-09-08 | 2021-12-24 | 爱斯特（成都）生物制药股份有限公司 | Method for synthesizing 2, 5-dichlorotrifluorotoluene by continuous flow catalytic chlorination |
Citations (5)
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|---|---|---|---|---|
| US4851596A (en) * | 1987-05-28 | 1989-07-25 | Bayer Aktiengesellschaft | Process for nucleus-chlorination of aromatic hydrocarbons |
| CN1678550A (en) * | 2002-09-04 | 2005-10-05 | 吴羽化学工业株式会社 | Method for producing p-dichlorobenzene |
| CN102746107A (en) * | 2012-07-18 | 2012-10-24 | 常州新东化工发展有限公司 | Method for preparing monochlorotoluene with toluene chloridizing method |
| CN102836731A (en) * | 2012-10-08 | 2012-12-26 | 江苏省格林艾普化工股份有限公司 | Catalyst used in preparation of paradichlorobenzene and method for preparing paradichlorobenzene by using such catalyst |
| CN102976888A (en) * | 2011-09-06 | 2013-03-20 | 江苏鹏宇化工有限公司 | Synthesizing method of p-dichlorobenzene |
-
2014
- 2014-01-09 CN CN201410010582.1A patent/CN103739441A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851596A (en) * | 1987-05-28 | 1989-07-25 | Bayer Aktiengesellschaft | Process for nucleus-chlorination of aromatic hydrocarbons |
| CN1678550A (en) * | 2002-09-04 | 2005-10-05 | 吴羽化学工业株式会社 | Method for producing p-dichlorobenzene |
| CN102976888A (en) * | 2011-09-06 | 2013-03-20 | 江苏鹏宇化工有限公司 | Synthesizing method of p-dichlorobenzene |
| CN102746107A (en) * | 2012-07-18 | 2012-10-24 | 常州新东化工发展有限公司 | Method for preparing monochlorotoluene with toluene chloridizing method |
| CN102836731A (en) * | 2012-10-08 | 2012-12-26 | 江苏省格林艾普化工股份有限公司 | Catalyst used in preparation of paradichlorobenzene and method for preparing paradichlorobenzene by using such catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899615A (en) * | 2017-11-03 | 2018-04-13 | 天津普莱化工技术有限公司 | A kind of catalyst for oriented chlorination and preparation method and application |
| CN112194554A (en) * | 2020-11-05 | 2021-01-08 | 湖北山水化工有限公司 | Preparation process and production process system of (o) p-chlorotoluene |
| CN113831214A (en) * | 2021-09-08 | 2021-12-24 | 爱斯特（成都）生物制药股份有限公司 | Method for synthesizing 2, 5-dichlorotrifluorotoluene by continuous flow catalytic chlorination |
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Application publication date: 20140423 |