CN107445810A - The method for producing parahydroxyben-zaldehyde as primary industry to toluene ester using chloro-carbonic acid - Google Patents
The method for producing parahydroxyben-zaldehyde as primary industry to toluene ester using chloro-carbonic acid Download PDFInfo
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- CN107445810A CN107445810A CN201610362363.9A CN201610362363A CN107445810A CN 107445810 A CN107445810 A CN 107445810A CN 201610362363 A CN201610362363 A CN 201610362363A CN 107445810 A CN107445810 A CN 107445810A
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- carbonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
- C07C45/43—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis of >CX2 groups, X being halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
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Abstract
The method for producing parahydroxyben-zaldehyde as primary industry to toluene ester using chloro-carbonic acid, its step are：Using phosgene and paracresol reaction generation chloro-carbonic acid to toluene ester；Actinolite is distilled, tower top obtains chloro-carbonic acid and chlorination is gone to toluene ester, and bottoms goes alkaline hydrolysis to reclaim paracresol；Chlorination of the chloro-carbonic acid to toluene ester, chlorizate is tracked with gas-chromatography, when the dichloro- thing content on methyl reaches between 55 70%, rectifying separates under a high vacuum to the mixture of monochloride and dichloride；Overhead monochloride and a small amount of dichloride, which loop back, continues chlorination, the dichloride distillation of bottom, then hydrolyzes, crystallizes, filtering, cold desalination washing crystallization, obtains 99% parahydroxyben-zaldehyde product；After circulation is repeated several times, yield 75%.
Description
Technical field
The invention belongs to phosgene is photochemical, chlorination and rectifying field, and in particular to a kind of industrial production parahydroxyben-zaldehyde
New method, it is characterized in that chloro-carbonic acid chloride rectifying, is steamed to toluene ester chlorination to the bottom dichloride obtained by rectifying
Evaporate, then hydrolyze, crystallization obtains parahydroxyben-zaldehyde.Chloro-carbonic acid, which is that raw material is directly photochemical by phosgene and paracresol to toluene ester, to be obtained
Arrive.
Background technology
The method of conventional industrial production parahydroxyben-zaldehyde is classified with raw material, mainly there is three major types：Formed respectively by phenol,
Para-nitrotoluene and three kinds of process routes that paracresol is initiation material.The technique reacted by phenol and trichloroacetaldehyde is due to cost
Height, post processing is difficult, eliminates already at present；Phenol chloroform method is because total aldehyde yield is relatively low, serious three wastes, without too big work
Industry is worth；It is subject to the technique that improved beta-cyclodextrin makees catalyst to this method although having been reported that, can be significantly increased to hydroxyl
The yield of benzaldehyde, but industrialized report is seen at end；Phenol formaldehyde (PF) method is first adjacent, right using phenol and formaldehyde reaction generation
Salicylic alcohol, it is then parahydroxyben-zaldehyde and o-hydroxy first with air or dioxygen oxidation under the catalysis of precious metal palladium
Aldehyde.This technique has that substantial amounts of brine waste containing phenol is not disposable, and complex process, cost aspect do not have advantage yet.To nitre
Base toluene method is to generate para aminotenzaldehyde under sodium polysulfide catalysis by para-nitrotoluene, then diazotising again, this method three wastes
It is seriously polluted, in the case where increasingly emphasizing environmental protection, produced in this way without producer.Paracresol method, divide again
For paracresol esterification process and paracresol direct oxidation method.Current existing paracresol esterification process is reacted by paracresol and acetic anhydride,
Paracresol acetic acid esters is produced, the methyl chloride of paracresol acetic acid esters is then turned into dichloride, this dichloride, which hydrolyzes, to be produced
Parahydroxyben-zaldehyde.The maximum advantage of such a technique is that almost do not have three-waste pollution, but because this method esterification yield is relatively low, into
This height is without economic value.Most competitive at present, it is paracresol direct oxidation method to study most active technique, and this technique is adopted
It is raw material with paracresol, in the basic conditions, under the catalysis of cobalt-cerium catalyst, using oxygen or air as oxidant,
Direct oxidation turns into parahydroxyben-zaldehyde.This technique is by constantly improve for many years, and technology full maturity, cost is in mesh
It is most competitive in preceding various techniques, so paracresol oxidizing process instead of other techniques comprehensively, turn into para hydroxybenzene
The key industry production line of formaldehyde, domestic production producer is using this method production parahydroxyben-zaldehyde.
Paracresol oxidizing process there is also some it is intrinsic the shortcomings that：Firstly, since still there is 3-5% paracresol not after oxidation
Can complete oxidation, still there is substantial amounts of phenol wastewater to discharge；Secondly, cobalt chloride-copper catalyst that oxidizing process uses is reacting
Afterwards it is difficult to reclaim, discharged with phenol wastewater, form heavy metal pollution；3rd, oxidizing process protects hydroxyl with substantial amounts of sodium hydroxide
Base, this part sodium hydroxide is finally neutralized with hydrochloric acid, form saline pollution；The yield of last oxidizing process still can not make us full
Meaning, oxidizing process, which produces 1 ton of parahydroxyben-zaldehyde, at present about needs 1.3 tons of paracresol, and produces para hydroxybenzene first per ton in theory
Aldehyde only needs 0.89 ton of paracresol, still has substantial amounts of paracresol to become pollutant, causes environmental pollution.All these, all
Making this technique for looking nice of oxidizing process, not extremely successful large enterprise occurs, production capacity all very littles, and
And after recent two decades are produced, still there are within 2015 many factories because environmental issue is forced to stop production.
The present invention is exactly to propose the shortcomings that being directed to paracresol oxidation technology, it is desirable to which it is lower to find a kind of production cost, environment
More friendly parahydroxyben-zaldehyde industrial product route.
The content of the invention
The present invention be directed to proposed the shortcomings that paracresol oxidizing process widely used at present.It is of the invention using phosgene and right
Cresols directly reacts generation chloro-carbonic acid to toluene ester and the mixture of full ester, and mixture is distilled, obtains pure chloro-carbonic acid
To toluene ester.With the chloro-carbonic acid of gained toluene ester chlorination is mixed one, dichloro- thing, then by the one of mixing, dichloride
Thing rectifying separates, and the chloro thing and a small amount of dichloro- thing that tower top obtains return to chlorination system chlorination again, and bottom of towe is obtained
Dichloro- thing distill, hydrolyze, crystallize, filter, be drying to obtain parahydroxyben-zaldehyde.
Chloro-carbonic acid is produced by the way of phosgene and paracresol directly react to toluene ester, rather than generally first will be to first
Phenol and sodium hydroxide reaction generation paracresol sodium solution.The mode so directly reacted can save substantial amounts of sodium hydroxide, drop
Low cost, and without the discharge containing phenol and brine waste.Reaction is carried out at a temperature of 70-150 DEG C, preferably 70-110
DEG C, the positive ester of carbonic acid can be generated as few as possible at such temperatures, and object can be generated quickly.In order to preferably
Using phosgene, secondary kettle is connected in course of reaction to react end in main still and reacts complete phosgene, and with gas-chromatography to reacting
Journey is tracked, and when paracresol content is less than 0.1% in main still reaction solution, photochemical reaction terminates.
Obtain is that chloro-carbonic acid only has to toluene ester and the mixture of its positive ester, wherein chloro-carbonic acid to toluene ester due to photochemical
90% or so, it is therefore desirable to mixture is distilled, to obtain the chloro-carbonic acid of high-purity to toluene ester, the bottoms after distillation
Recovery paracresol is reacted with alkali.
Chlorination is carried out in special Light chlorimation kettle, and chlorination temperature is carried out between 80-120 DEG C；Chlorination tank uses enamel
For kettle to prevent from corroding, chlorination tank is provided with thang-kng glass tube, and glass tube is directly inserted from above in kettle, in order to lead into kettle
Light.Glass tube has six to eight, or more, is distributed in a ring, so that equably thang-kng is catalyzed to reaction.Chlorination is certainly
Reacted by base, carried out under photocatalysis；Preferable light source is 365nm blue streak, and the depth that it irradiates in the solution is greater than general
Lead to more than one times of ultraviolet light, be best catalysis light source.
The important feature of the present invention is to carry out endless perchlorinating, and chlorination process is tracked analysis with gas-chromatography, works as chlorine
When in compound between chloro-carbonic acid bis-chloromethylated benzene ester content 55-70%, rectifying separation is carried out to resulting chlorinated mixture.This
The purpose of sample design technology is the generation in order to reduce chloro-carbonic acid to greatest extent to trichloromethyl phenyl ester, is improved most possibly
Yield.
Distillation process is carried out under a high vacuum, and the temperature that can reduce rectifying is the advantages of high vacuum, when reducing rectifying
The generation of the side reaction such as chloride polymeric in kettle, the monochloride and the mixture (dichloro of a small amount of dichloride that tower top obtains
Account for 20-30%) return to chlorination system continuation chlorination；To bottoms high vacuum distillation, gained distillation is used to hydrolyze.
Bottom distillation is hydrolyzed with desalted water, after the completion of hydrolysis, hydrolyzate is cooled down, crystallizes, filtering, with 5-10 DEG C
Desalination washing crystallization for several times, is dried, produces product.The product purity such as obtained is inadequate, can be with a small amount of desalted water again to crystallization
Cleaned, you can obtain the product of high-purity, for chloride repeatedly after circulation, yield can reach more than 75%.
Embodiment
1000 kilograms of paracresol are fitted into the photochemical kettle of enamel with mechanical seal stirring, 120 DEG C is heated to, is passed through light
Gas carries out photochemical reaction, and phosgene enters reactor by gas distributor and material contacts, and to reduce the volume of bubble, increases gas
Body and the area of material contact.Tail gas passes through hydrochloric acid absorption tower absorbing hydrogen chloride, enters back into washing tower (for removing CO2) and destroys remaining phosgene, with
The progress of reaction, between kettle temperature is slowly transferred to 80-100 DEG C, with gas-chromatography following response, paracresol content is less than 0.1%
When, terminate thang-kng reaction, esterification products are sent to distillation process, and the chloro-carbonic acid of high-purity is obtained by distilling to toluene ester, is sent to
Chloride process, bottoms then go alkaline hydrolysis process, reclaim paracresol.
The chloro-carbonic acid obtained will be distilled in toluene ester addition chlorination tank, opening uviol lamp, start logical chlorine after being warming up to 130 DEG C
Chlorination, after chlorinated exhaust continues reaction into secondary kettle, hydrochloric acid is absorbed with water, it is responseless that remaining tail gas is sent into washing tower (for removing CO2) destruction
Residual chlorine.After question response proceeds by, temperature is slowly dropped to 80-120 DEG C or so, chlorination reaction mistake is followed the trail of with gas-chromatography
Journey, when chloro-carbonic acid dichloromethyl phenyl ester accounts for 55-70% in reaction solution, stop logical chlorine, chlorated liquid is sent to distillation system.
The rectifying of chloride is carried out under vacuo, and under 10mm mercury column, tower top collects 125-146 DEG C of cut, returns to chlorination
System chlorination again；Some dichloro distillates with a chlorine in tower top distillation process, and the 20-30% for constituting about total distillate is left
The right side, but the dichloro that this part steams simply consumes part energy, has no effect on course of reaction, the chlorinity of bottom one reaches 2%
When following, rectifying terminates, and flash distillation is carried out to bottoms, and distillation gains are used to hydrolyze.
Add 4 tons of water in 6 tons of kettle, be heated to 85-95 DEG C, slowly distillation is added in kettle, stirring hydrolysis, add fast
Degree can not be too fast, avoids bumping water rushes kettle.After adding material 2-3 hour of hydrolysis, the material of a small amount of bottom end hydrolysis is released, Ran Houleng
But crystallize, filter, with 5-10 DEG C of desalination washing crystallization for several times, crystallization is washed till close to neutrality, crystallizing and drying, got product to hydroxyl
586.3 kilograms of benzaldehyde, purity 99.1%.Meanwhile an also chlorine and two chloroformate mixtures that 485.5 kilograms of tower tops fractionate out can
To continue cycling through reaction production product.
After chloride rectifying circulates five times, yield reaches more than 75%.
Claims (6)
1. produce the method for parahydroxyben-zaldehyde as primary industry to toluene ester using chloro-carbonic acid, it is characterized in that：
Chloro-carbonic acid obtains to toluene ester phosgene and paracresol directly reaction：
1) photochemical reaction as claimed in claim 1, preferably carried out at 70-110 DEG C；
2) photochemical reaction as claimed in claim 1, phosgene enter blistering reaction in kettle by gas distributor；
2. the actinolite of pair gained distills, tower top obtains the chloro-carbonic acid of high-purity to toluene ester, and bottoms then goes alkaline hydrolysis work
Sequence, reclaim paracresol.
3. the purity that pair distillation obtains carries out chlorination up to more than 99.5% chloro-carbonic acid to toluene ester：
1) chlorination reaction as claimed in claim 3, carried out under ultraviolet light catalyst；
2) chlorination reaction as claimed in claim 3, reaction temperature control are carried out between 80-120 DEG C；
3) chlorination reaction as claimed in claim 3, chlorination process use chromatogram tracking, dichloro of the chloro-carbonic acid to toluene ester chloro
During for thing content between 55%-70%, chlorination terminates.
4. rectifying is separated into the chlorine of tower top high content one and bottom high content two to chloride of the chloro-carbonic acid to toluene ester under a high vacuum
Chloride：
1) distillation process as claimed in claim 4, the minimum 10-15mm mercury column of required top vacuum degree；
2) distillation process as claimed in claim 4, tower top rectifying extraction pipe and return duct are incubated with steam adjoining pipe；
3) distillation process as claimed in claim 4, overhead extraction thing will control certain reflux ratio to ensure continuous production
In there are a high chlorinity and two as few as possible chlorinities；
4) distillation process as claimed in claim 4, a chlorine substituent and a small amount of dichloro substituent obtained by overhead extraction return
Chlorination system, and chloro-carbonic acid are returned to continuing chlorination, rectifying after the mixing of toluene ester；
5) distillation process as claimed in claim 4, carries out chromatography in distillation process to bottoms, and a chlorinity is less than
Rectifying terminates when 2%.
5. bottoms high vacuum flash distillation obtained by pair rectifying.
6. pair hydrolysis of flash distillation gains and crystallisation by cooling, filtering, obtain parahydroxyben-zaldehyde product：
1) hydrolytic process as described in requiring right 6, hydrolysis used are desalted water with water；
2) crystallization process as described in requiring right 6 with 5-10 DEG C of desalted water, it is necessary to clean the acid of crystallization, and purify knot for several times
It is brilliant；
3) crystallization process as described in requiring right 6, when the purity of crystallization does not reach 99%, cleaned with 5-10 DEG C of desalted water
Crystallization 1-2 times.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610362363.9A CN107445810A (en) | 2016-05-30 | 2016-05-30 | The method for producing parahydroxyben-zaldehyde as primary industry to toluene ester using chloro-carbonic acid |
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| CN201610362363.9A CN107445810A (en) | 2016-05-30 | 2016-05-30 | The method for producing parahydroxyben-zaldehyde as primary industry to toluene ester using chloro-carbonic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717077A (en) * | 2021-09-22 | 2021-11-30 | 重庆长风化学工业有限公司 | Salicylic nitrile impurity and preparation method thereof |
| CN114534721A (en) * | 2022-02-24 | 2022-05-27 | 河南科技大学 | Preparation method and application of Au @ Pd core-shell structure ultra-long nanowire in water phase |
-
2016
- 2016-05-30 CN CN201610362363.9A patent/CN107445810A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717077A (en) * | 2021-09-22 | 2021-11-30 | 重庆长风化学工业有限公司 | Salicylic nitrile impurity and preparation method thereof |
| CN114534721A (en) * | 2022-02-24 | 2022-05-27 | 河南科技大学 | Preparation method and application of Au @ Pd core-shell structure ultra-long nanowire in water phase |
| CN114534721B (en) * | 2022-02-24 | 2023-10-17 | 河南科技大学 | Preparation method and application of Au@Pd core-shell structure super-long nanowire in water phase |
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Application publication date: 20171208 |
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