CN201171992Y - Recovery utilization system of chlorination mother liquor - Google Patents
Recovery utilization system of chlorination mother liquor Download PDFInfo
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- CN201171992Y CN201171992Y CNU2008200855777U CN200820085577U CN201171992Y CN 201171992 Y CN201171992 Y CN 201171992Y CN U2008200855777 U CNU2008200855777 U CN U2008200855777U CN 200820085577 U CN200820085577 U CN 200820085577U CN 201171992 Y CN201171992 Y CN 201171992Y
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Abstract
The utility model relates to a chlorating mother liquor recycling system used in an anion exchange resin automation production system; white balls and chloromethylether are respectively conveyed into a chloromethylation reaction kettle by a pneumatic conveying system and a pump to be mixed at normal temperature and are added with ferric trichloride which is dissolved in the chloromethylether after being expanded to produce the exothermic reaction; the adding speed of the chloromethylether is adjusted according to the temperature, chlorine balls are obtained when the temperature reaches 48 degrees, and after 10 hours, the temperature is lowered, the separated chlorine balls are arranged in a washing kettle to be cleaned by methanol chloride twice and by methanol once in sequence; then the solid-liquid separation is carried out, the solid chlorine balls undergo the amination reaction, and the liquid chlorating mother liquor and the chlorine ball cleaning mixture enter into a chlorating solution recovery reaction kettle; the methanol chloride produced by the chlorating solution recovery reaction kettle enters into the chloromethylether reaction kettle, at this moment, solid methanol and chlorine hydride are added into the chloromethylether reaction kettle for reaction, the chloromethylether volatilized in the reaction process is condensed by a condenser to enter into the chloromethylation reaction kettle, and gas which is not condensed enters into an alkali spray tower to be absorbed and treated.
Description
Technical field
The utility model relates to the recycling system of chlorination mother solution in a kind of anion exchange resin mechanized production system, belongs to anion exchange resin production system and makes the field.
Background technology
In chloromethyl ether is produced, generally adopt liquid formaldehyde and hydrochloric acid to participate in chloromethyl ether production, owing to be formaldehyde below 37 in the liquid formaldehyde, more than 63% water, therefore will produce a large amount of waste liquids aborning.Because this waste liquid after-treatment cost is high, the general user does not handle its liquid, but directly discharges, and environment is caused greatly pollute, and directly increased the production cost of anion exchange resin; The 2nd, adopt hydrochloric acid to react, and from the reaction of hydrochloric acid, obtain hydrogen chloride gas.Only account for about 30% owing to contain hydrogen chloride in the hydrochloric acid, therefore obtain hydrogen chloride, not only increased production cost with hydrochloric acid, and when obtaining hydrogen chloride, produce a large amount of waste liquids, cause environmental pollution, Given this, most producers have to purchase chloromethyl ether and are used for resin anion (R.A.) production.
Summary of the invention
Purpose of design: avoid the weak point in the background technology, design a kind of liquid formaldehyde and hydrochloric acid of need not and participate in chloromethyl ether production and have the production of the waste water of reduction, help environmental protection; The 2nd, directly chlorination mother solution is reclaimed synthetic chloromethyl ether, be used further to the recycling system of the chlorination mother solution of anion exchange resin production.
Design: the reaction equation that negative resin is given birth to: negative resin carries out Friedel-Crafts reaction (chloromethylation) with chloromethyl ether by Archon and obtains the chlorine ball under the catalytic action of iron chloride, answer (amination) with corresponding amine again, makes after the conversion.Its reaction equation is as follows: 1, chloromethylation:
2, aminating reaction: aminating reaction adopts trimethylamine or dimethylamine and the reaction of chlorine ball, wherein, produces a kind of negative resin product and uses trimethylamine to be raw material; Produce another kind of negative resin product and use dimethylamine, the aminating reaction equation is respectively:
One of negative resin production process is made up of operations such as chloromethylation, the cleaning of chlorine ball, aminating reaction, amination cleaning and washings.Produce continuously because the existence of the still of getting the raw materials ready, two batches can between open simultaneously and carry out, every batch of production time 16h, its process chart is seen accompanying drawing 1.
Chloromethylation: Archon and chloromethyl ether are delivered in the reactor through flow delivery systems and pump respectively, normal temperature stirs down, after the expansion, add the Ferric Chloride that is dissolved in chloromethyl ether, because exothermic heat of reaction according to the adding speed of adjustment chloromethyl ether, waits to be warming up to 48 ℃, be incubated and make the chlorine ball after 10 hours, cooling.Separation of Solid and Liquid, the liquid phase chlorination mother liquor enters the chlorated liquid recovery system, expects chlorine ball washing still under the solid phase chlorine ball.The chloromethyl ether that volatilizees in the course of reaction is back to technology through condenser condenses, and fixed gas enters the alkali spray column and absorbs processing.
The chlorine ball cleans: isolated chlorine ball is used the chlorination washed with methanol 2 times, with washed with methanol once successively in the washing still.
The chlorated liquid that produces enters the chlorated liquid recovery system.
Chlorination methyl alcohol comes from the chlorated liquid recovery system.Form by formaldehyde, methyl alcohol, dimethoxym ethane, hydrochloric acid, chlorination dimethoxym ethane.
Aminating reaction: the chlorine ball enters the amination still, after the expansion, drips and presses methylamine, progressively accelerate to drip amine speed, and the control temperature is lower than 45 ℃; Stable back insulation (38 ℃), cooling after 6 hours, Separation of Solid and Liquid, the amination mother liquor is solid to amination washing still to amination mother liquor still.
In amination mother liquor still, the amination mother liquor of per 5 batches of generations returns the chlorine ball reaction of amination still and 1 batch after the mixing, recycling trimethylamine and methyl alcohol wherein, because the variation of mixing of materials ratio, changes the process condition and the parameter of this operation.The amination mother liquor is after reclaiming, and the aminating reaction operation is the amination liquid amination liquid recovery system of generation finally.
Methyl alcohol and trimethylamine that volatilization produces are back to after condensation in the technology, and fixed gas enters sour spray column and absorbs.
The amination still is provided with thief hole.Producing early stage, meeting sample analysis in the insulating process to determine the technological parameters such as proportioning of material, after production is stable, is not taken a sample.
Sampling process can produce a small amount of uncontrollable discharge.Be sampled as repeatedly the discontinuity operation, sample time is indefinite, and maximum is no more than 0.5h.
Amination is cleaned: solid phase in amination washing still after the soft water washing, with 4%, about salt acid for adjusting pH value to 2, filter the back and clean 2 times with soft water, filtration once more, amination liquid enters the amination liquid recovery system, is solid to filter.
Washing: clean 4 times with soft water in filter, wherein once with 60 ℃ hot water cleaning, cleaning becomes qualified resin after removing surface impurity.
Remove and clean waste water together as next still first road rinse water at last, all the other clean waste water (W
5-1) enter Waste Water Treatment.
Two of negative resin production process: form by chloromethylation, the cleaning of chlorine ball, aminating reaction, amination cleaning and washing etc.Except that the aminating reaction operation was different with above-mentioned negative resin, all the other operations were all identical.The aminating reaction difference mainly is embodied in following aspect:
1. replace three amine to carry out aminating reaction with dimethylamine.
2. the aminating reaction process conditions are adjusted to some extent: dimethylamine drips when entering the amination still, and the control temperature is lower than 65 ℃; Holding temperature after stable is 58 ℃, and temperature retention time is 8 hours.Negative resin technological process of production figure sees accompanying drawing 2.
Technical scheme: the recycling system of chlorination mother solution, the recycling system of chlorination mother solution, the import of chloromethylation still is communicated with the outlet that flow delivery systems and pump are carried respectively, import with chlorine ball washing reaction still is connected with valve by pipeline in the outlet of chloromethylation still, the chlorine ball that chlorine ball washing reaction still produces enters the aminating reaction system by pipeline and the valve that is connected with its outlet, it is characterized in that: chlorination mother solution that chlorine ball washing reaction still produces and chlorine ball cleaning solution by the pipeline that is connected with its outlet and valve with advance the import of chlorated liquid recovery reactor and be communicated with, the waste liquid that chlorated liquid reclaims the reactor generation is communicated with the waste liquid holder by connected pipeline and valve, the chlorination methyl alcohol that chlorated liquid reclaims the reactor generation is communicated with the import of chloromethyl ether reactor by connected pipeline and valve, chloromethyl ether reactor outlet is communicated with through condenser inlet with chloromethyl ether by connected pipeline and valve, and chloromethyl ether is leaded up to connected pipeline through condensator outlet, valve and pipeline are communicated with the import of chloromethylation still.
The utility model is compared with background technology, and the one, utilize the recycling system of chlorination mother solution, greatly reduce the discharging of organic liquid waste, reduced the production cost of ion exchange resin simultaneously, improved economic benefit; The 2nd, utilize solid formaldehyde to produce chloromethyl ether, reduced the output of waste water, eliminated and used liquid formaldehyde production in the traditional handicraft, and produced the rough sledding of a large amount of waste liquids, greatly reduce the environmental protection cost that ion exchange resin is produced, improved economic benefit; The 3rd, utilize hydrogen chloride gas to replace hydrochloric acid to react, eliminated and used hydrochloric acid production in the traditional handicraft, and produced the rough sledding of a large amount of waste liquids, greatly reduce the environmental protection cost that ion exchange resin is produced, improved economic benefit.
Description of drawings
Fig. 1 is the schematic diagram of the recycling system of chlorination mother solution.
The specific embodiment
Embodiment 1: with reference to accompanying drawing 1.The recycling system of chlorination mother solution, the processing and manufacturing of chloromethylation still 1 is a prior art, is not described herein at this.The import of chloromethylation still 1 is communicated with the outlet that flow delivery systems and pump are carried respectively, import with chlorine ball washing reaction still 2 is connected with valve by pipeline in the outlet of chloromethylation still 1, the processing and manufacturing of chlorine ball washing reaction still 2 is a prior art, is not described herein at this.The chlorine ball that chlorine ball washing reaction still 2 produces enters aminating reaction system 3 by pipeline and the valve that is connected with its outlet, and the processing and manufacturing of chlorine ball washing reaction still 2 is a prior art, is not described herein at this.Chlorination mother solution that chlorine ball washing reaction still 2 produces and chlorine ball cleaning solution by the pipeline that is connected with its outlet and valve with advance 4 imports of chlorated liquid recovery reactor and be communicated with, the processing and manufacturing of chlorated liquid recovery reactor 4 is a prior art, is not described herein at this.The waste liquid that chlorated liquid reclaims reactor 4 generations is communicated with the waste liquid holder by connected pipeline and valve, the chlorination methyl alcohol that chlorated liquid reclaims reactor 4 generations is communicated with 6 imports of chloromethyl ether reactor by connected pipeline and valve, the waste liquid 5 that chlorated liquid reclaims reactor 4 generations advances storage tank, 6 outlets of chloromethyl ether reactor are communicated with through condenser 7 imports with chloromethyl ether by connected pipeline and valve, chloromethyl ether is leaded up to connected pipeline through condenser 7 outlet, valve and pipeline 9 are communicated with 1 import of chloromethylation still, the processing and manufacturing of condenser 7 is a prior art, is not described herein at this.Chloromethyl ether layering reactor 7 outlet is leaded up to connected pipeline, valve and is communicated with lower floor fluid reservoir 8 imports.With reference to accompanying drawing 1.The recoverying and utilizing method of chlorination mother solution: Archon and chloromethyl ether are delivered in the chloromethylation still through flow delivery systems and pump respectively, normal temperature stirs down, after the expansion, add the ferric trichloride catalytic that is dissolved in chloromethyl ether, produce exothermic reaction, according to the adding speed of adjustment chloromethyl ether, temperature is in 20 ℃～48 ℃ scopes, and the adding speed of its chloromethyl ether and Archon is controlled in 2 tons/hour.Wait to be warming up to 40～55 ℃, be incubated and make the chlorine ball after 8～12 hours, cooling, isolated chlorine ball is in the washing still, with chlorination methyl alcohol the chlorine ball is cleaned 1～3 time successively, with methyl alcohol the chlorine ball is cleaned once or secondary, Separation of Solid and Liquid then, solid phase chlorine ball enters aminating reaction, liquid phase chlorination mother liquor and chlorine ball cleaning solution enter chlorated liquid and reclaim in the reactor, and the chlorination methyl alcohol that chlorated liquid reclaims the reactor generation enters the chloromethyl ether reactor, and add solid methanol at the chloromethyl ether reactor this moment, hydrogen chloride reacts, the chloromethyl ether that volatilizees in the course of reaction enters in the chloromethylation still through condenser condenses, and fixed gas enters the alkali spray column and absorbs processing.
What need understand is: though the foregoing description is to the utility model detailed text description of contrasting; but these text descriptions; it is text description to the utility model mentality of designing; rather than to the restriction of the utility model mentality of designing; any combination, increase or modification that does not exceed the utility model mentality of designing all falls in the protection domain of the present utility model.
Claims (2)
1, a kind of recycling system of chlorination mother solution, the import of chloromethylation still is communicated with the outlet that flow delivery systems and pump are carried respectively, import with chlorine ball washing reaction still is connected with valve by pipeline in the outlet of chloromethylation still, the chlorine ball that chlorine ball washing reaction still produces enters the aminating reaction system by pipeline and the valve that is connected with its outlet, it is characterized in that: chlorination mother solution that chlorine ball washing reaction still produces and chlorine ball cleaning solution by the pipeline that is connected with its outlet and valve with advance the import of chlorated liquid recovery reactor and be communicated with, the waste liquid that chlorated liquid reclaims the reactor generation is communicated with the waste liquid holder by connected pipeline and valve, the chlorination methyl alcohol that chlorated liquid reclaims the reactor generation is communicated with the import of chloromethyl ether reactor by connected pipeline and valve, chloromethyl ether reactor outlet is communicated with through condenser inlet with chloromethyl ether by connected pipeline and valve, and chloromethyl ether is leaded up to connected pipeline through condensator outlet, valve and pipeline are communicated with the import of chloromethylation still.
2, the recycling system of chlorination mother solution according to claim 1 is characterized in that: chloromethyl ether layering reactor outlet is leaded up to connected pipeline, valve and is communicated with lower floor fluid reservoir import.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU2008200855777U CN201171992Y (en) | 2008-04-16 | 2008-04-16 | Recovery utilization system of chlorination mother liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNU2008200855777U CN201171992Y (en) | 2008-04-16 | 2008-04-16 | Recovery utilization system of chlorination mother liquor |
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| CN201171992Y true CN201171992Y (en) | 2008-12-31 |
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| CNU2008200855777U Expired - Lifetime CN201171992Y (en) | 2008-04-16 | 2008-04-16 | Recovery utilization system of chlorination mother liquor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955766A (en) * | 2021-11-25 | 2022-01-21 | 山东聚优新材料科技有限公司 | Method for preparing zinc borate by using zinc chloride in anion resin chlorination mother liquor |
-
2008
- 2008-04-16 CN CNU2008200855777U patent/CN201171992Y/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955766A (en) * | 2021-11-25 | 2022-01-21 | 山东聚优新材料科技有限公司 | Method for preparing zinc borate by using zinc chloride in anion resin chlorination mother liquor |
| CN113955766B (en) * | 2021-11-25 | 2022-12-02 | 山东聚优新材料科技有限公司 | Method for preparing zinc borate by using zinc chloride in anion resin chlorination mother liquor |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: NINGBO ZHENGGUANG RESIN CO., LTD. Free format text: FORMER OWNER: ZHEJIANG ZHENGGUANG INDUSTRIAL CO., LTD. Effective date: 20120312 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 311106 HANGZHOU, ZHEJIANG PROVINCE TO: 315024 NINGBO, ZHEJIANG PROVINCE |
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| TR01 | Transfer of patent right |
Effective date of registration: 20120312 Address after: B. Ningbo Petrochemical Economic and Technological Development Zone Road, Zhenhai District 315024 Zhejiang city of Ningbo province No. 6 Patentee after: Ningbo Zhengguang Resin Co., Ltd. Address before: 311106 Industrial Zone, Tangqi Town, Yuhang District, Zhejiang, Hangzhou Patentee before: Zhejiang Zhengguang Industrial Co., Ltd. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20081231 |
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| CX01 | Expiry of patent term |