CN104529916B - Method for separating high-purity phenazine from waste material generated in chemical product production - Google Patents
Method for separating high-purity phenazine from waste material generated in chemical product production Download PDFInfo
- Publication number
- CN104529916B CN104529916B CN201410825895.2A CN201410825895A CN104529916B CN 104529916 B CN104529916 B CN 104529916B CN 201410825895 A CN201410825895 A CN 201410825895A CN 104529916 B CN104529916 B CN 104529916B
- Authority
- CN
- China
- Prior art keywords
- tower
- removing column
- purity
- azophenlyene
- lightness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Abstract
The invention provides a method for separating high-purity phenazine from a waste material generated in chemical product production. A light component removing tower and a heavy component removing tower are adopted, wherein the light component removing tower is provided with a tower top condenser and a tower kettle re-boiler; the heavy component removing tower is provided with a tower top condenser and a tower kettle re-boiler. The method is characterized by comprising the following steps: allowing a phenazine-containing raw material liquid to enter the middle part of the light component removing tower after heat is exchanged by a raw material preheater; removing phenylamine and azobenzene from the tower top to obtain the phenylamine of which the purity is larger than 97% for recycle; allowing a material flow of the light component removing tower to enter the middle part of the heavy component removing tower; removing a 4-amino diphenylamine heavy component from the tower bottom to obtain 4-amino diphenylamine of which the purity is larger than 99%, and directly taking the 4-amino diphenylamine as a product or using the 4-amino diphenylamine in the next stage of refining; and obtaining a phenazine product of which the purity is larger than 99.5% at the top of the heavy component removing tower. According to the method disclosed by the invention, continuous operation is adopted, and a thermal-coupled rectification separation process is adopted during the overall method, so the energy consumption of a system is reduced. According to the method disclosed by the invention, the two towers adopt decompression distillation and are packed towers, so the separation efficiency is higher, and the pressure reduction and tower kettle temperature are reduced as well.
Description
Technical field
The present invention relates to the method isolating and purifying azophenlyene, separating high-purity particularly a kind of production waste material from chemical products
The method of azophenlyene, belongs to azophenlyene and isolates and purifies field.
Background technology
Also known as phenazine, English name: phenazine, molecular formula is c12h8n2 to azophenlyene, in colourless or faint yellow
Acicular crystal, is practically insoluble in water, is slightly dissolved in ethanol, ether and benzene, is dissolved in mineral acid yellowly to red solution.Azophenlyene is having
There is certain special status in chemical machine field.Azophenlyene and its earliest application of derivant are dyestuffs, then find that they have life
Thing activity, can serve as antibacterial.Azophenlyene is in the application in the fields such as medicine, pesticide, chromogen, conductor and battery material in recent years
More and more extensive.
Azophenlyene mainly passes through the side such as 2- amino or nitrodiphenylamine ring closure reaction, o-phenylenediamine and catechol condensation reaction
Prepared by method, building-up process is complicated, and yield is medium, relatively costly.And with Nitrobenzol and aniline for raw material production 4- ADP
During amine, by-product azophenlyene can be produced, cannot remove in separation process, with 4-ADPA, aniline, diphenyl diimide etc.
Form waste material mixture, direct discharge can cause environmental pollution, and burning disposal causes very big waste again.Between having enterprise to adopt at present
The method of rectification of having a rest carries out to mixture separating, and the azophenlyene content after process is only 80%.
The invention provides a kind of produce, from chemical products, the method that waste material, highly efficient distilling purifies azophenlyene, obtain high-purity
The azophenlyene product of degree.
Content of the invention
It is an object of the invention to provide a kind of produce, from chemical products, the method that waste material, highly efficient distilling purifies azophenlyene, obtain
Obtain the azophenlyene product that purity is more than 99.5%, and obtain good yield.
The purpose of the present invention to complete by following technical solution:
A kind of method producing separating high-purity azophenlyene waste material from chemical products, using lightness-removing column and weight-removing column, takes off light
Tower is provided with overhead condenser and tower reactor reboiler, and weight-removing column is provided with overhead condenser and tower reactor reboiler；It is characterized in that containing azophenlyene
Material liquid enters the middle part of lightness-removing column after feed preheater heat exchange, and tower top is sloughed aniline and diphenyl diimide, obtained purity and be more than
97% aniline, is recycled；Lightness-removing column tower reactor logistics enters the middle part of weight-removing column, and bottom of towe sloughs 4-ADPA weight
Component, obtains the 4-ADPA that purity is more than 99%, refines directly as product or entrance next stage；Weight-removing column tower top obtains
It is more than 99.5% azophenlyene product to purity.
Lightness-removing column tower top operating pressure is 1～10kpa, and bottom of towe operation temperature is 214～262 DEG C, and reflux ratio is 2～6, reason
It is 20～40 altogether by series；Weight-removing column tower top operating pressure is 1～6kpa, and bottom of towe operation temperature is 217～253 DEG C, reflux ratio
For 8～10, theoretical stage is 30～50 altogether.
Material liquid containing azophenlyene enters lightness-removing column after the restructuring lease making feed preheater heat exchange flowed out with weight-removing column bottom
Middle part, after heat exchange contain azophenlyene material liquid enters tower temperature degree be 105～125 DEG C.
Described lightness-removing column and weight-removing column are packed tower.
The present invention, by carrying out rectification under vacuum to system, reduces the boiling point of higher-boiling compound in material liquid containing azophenlyene,
Its separation efficiency is more efficient, reduces tower reactor kettle temperature simultaneously；In addition in the rectification separating technology of the present invention, raw material containing azophenlyene
Liquid carries out heat exchange by the azophenlyene product flowing out with weight-removing column top through feed preheater, separates with respect to traditional rectification
Technique, process total energy consumption reduces about 20% about.
The invention has the advantage that
(1) using continuous operation, whole invention simultaneously adopts thermal coupling rectification separating technology, reduces system the present invention
Energy consumption.
(2) present invention all using rectification under vacuum and is packed tower because of two towers, so separation efficiency is more efficient, drops simultaneously
Low pressure drop and tower reactor kettle temperature.
(3) azophenlyene product purity >=99.5% that present invention process produces, aniline total content ＜ 0.01%, diphenyl diimide ＜
0.25%, 4-ADPA ＜ 0.2% are it is seen that the present invention can effectively improve azophenlyene product purity it is ensured that the performance of product refers to
Mark.
Brief description
Accompanying drawing 1: the process flow diagram of the present invention.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but the present invention is not limited to this.
Using the connected mode of accompanying drawing 1, lightness-removing column 3 is provided with overhead condenser 4 and tower reactor reboiler 7, and weight-removing column 9 is provided with tower
Top condenser 10 and tower reactor reboiler 13.Material liquid containing azophenlyene 1 enters lightness-removing column 3 by pipeline after feed preheater 2 heat exchange
Middle part, sloughs aniline and diphenyl diimide 6, and its tower reactor logistics 8 enters the middle part of weight-removing column 9, sloughs 4-ADPA heavy constituent simultaneously
Lose a small amount of azophenlyene 14, its tower top obtains purity and is more than 99.5% azophenlyene product 12.
Chemical products produce waste material (aniline 47～55%, diphenyl diimide 0.6～1.5%, azophenlyene 6～10%, 4- ADP
Amine 35～42%) in highly efficient distilling purify the system of azophenlyene, lightness-removing column is provided with overhead condenser and tower reactor reboiler, and weight-removing column sets
There are overhead condenser and tower reactor reboiler.Material liquid containing azophenlyene enters the middle part of lightness-removing column, tower top after feed preheater heat exchange
Slough aniline and diphenyl diimide, obtain the aniline that purity is more than 97%, recycled.Lightness-removing column tower reactor logistics enters weight-removing column
Middle part, bottom of towe sloughs 4-ADPA heavy constituent and loses a small amount of azophenlyene, obtains the 4- amino two that purity is more than 99%
Aniline, can refine directly as product or entrance next stage.Weight-removing column tower top obtains the azophenlyene product that purity is more than 99.5%.
Lightness-removing column of the present invention and weight-removing column are preferably packed tower.
Lightness-removing column tower top operating pressure is 1～10kpa, and bottom of towe operation temperature is 214～262 DEG C, and reflux ratio is 2～6, reason
It is 20～40 altogether by series；Weight-removing column tower top operating pressure is 1～6kpa, and bottom of towe operation temperature is 217～253 DEG C, reflux ratio
For 8～10, theoretical stage is 30～50 altogether.
The material liquid containing azophenlyene of the present invention is by laggard with the restructuring lease making feed preheater heat exchange that weight-removing column bottom is flowed out
Enter the middle part of lightness-removing column, the tower temperature degree that enters containing azophenlyene material liquid after heat exchange is 105～125 DEG C.
Embodiment 1:
Process the purification containing azophenlyene raw material of 6000kg per hour, feed composition is as follows: aniline 55%, azophenlyene 6%, azo
Benzene 1.5%, 4-ADPA 37.5%.
Technological process each tower operating condition
| Lightness-removing column | Weight-removing column | |
| Tower type | Packed tower | Packed tower |
| Tower diameter (mm) | 2600 | 1200 |
| Wire feeding | Stainless steel cloth structured packing | Stainless steel cloth structured packing |
| Theoretical stage | 20 | 30 |
| Tower top operating pressure (absolute pressure)/kpa | 1 | 1 |
| Bottom of towe operation temperature/DEG C | 214 | 217 |
| Reflux ratio | 2 | 8 |
Note: after raw material heat exchange, inlet temperature of stabilizer is 105 DEG C
The azophenlyene product leading indicator producing under above-mentioned process conditions is as follows:
| Leading indicator | |
| Product purity | 99.54% |
| Aniline content | 0.01% |
| Diphenyl diimide | 0.25% |
| 4-ADPA | 0.20% |
| Product recovery rate | 95.3% |
Embodiment 2:
Process the purification containing azophenlyene raw material of 6000kg per hour, feed composition is as follows: aniline 50%, azophenlyene 8%, azo
Benzene 1%, 4-ADPA 41%.
Technological process each tower operating condition
| Lightness-removing column | Weight-removing column | |
| Tower type | Packed tower | Packed tower |
| Tower diameter (mm) | 2600 | 1200 |
| Wire feeding | Corrosion resistant plate corrugated regular filler | Corrosion resistant plate corrugated regular filler |
| Theoretical stage | 30 | 40 |
| Tower top operating pressure (absolute pressure)/kpa | 3 | 3 |
| Bottom of towe operation temperature/DEG C | 232 | 236 |
| Reflux ratio | 4 | 9 |
Note: after raw material heat exchange, inlet temperature of stabilizer is 115 DEG C
The azophenlyene product leading indicator producing under above-mentioned process conditions is as follows:
| Leading indicator | |
| Product purity | 99.87% |
| Aniline content | 3ppm |
| Diphenyl diimide | 0.032% |
| 4-ADPA | 0.098% |
| Product recovery rate | 98.8% |
Embodiment 3:
Process the purification containing azophenlyene raw material of 6000kg per hour, feed composition is as follows: aniline 47.4%, azophenlyene 10%,
Diphenyl diimide 0.6%, 4-ADPA 42%.
Technological process each tower operating condition
| Lightness-removing column | Weight-removing column | |
| Tower type | Packed tower | Packed tower |
| Tower diameter (mm) | 2600 | 1200 |
| Wire feeding | Stainless steel cloth structured packing | Stainless steel cloth structured packing |
| Theoretical stage | 40 | 50 |
| Tower top operating pressure (absolute pressure)/kpa | 10 | 6 |
| Bottom of towe operation temperature/DEG C | 262 | 253 |
| Reflux ratio | 6 | 10 |
Note: after raw material heat exchange, inlet temperature of stabilizer is 125 DEG C
The azophenlyene product leading indicator producing under above-mentioned process conditions is as follows:
| Leading indicator | |
| Product purity | 99.52% |
| Aniline content | 0.002% |
| Diphenyl diimide | 0.473% |
| 4-ADPA | 0.002% |
| Product recovery rate | 99.5% |
As seen from the above table, the present invention is feasible, and not only technological operation is simple for whole separation process, energy consumption is less,
And separation efficiency is very high.
A kind of method producing highly efficient distilling purification azophenlyene waste material from chemical products proposed by the present invention, passes through preferably
Examples of implementation are described, and person skilled substantially can be to this paper institute in without departing from present invention, spirit and scope
The rectification and purification method stated is modified or suitably change to realize the technology of the present invention with combining.Specifically, institute
There is similar replacement and change apparent to those skilled in the art, they are considered as including in the present invention
In spirit, scope and content.
Claims (3)
1. a kind of method producing separating high-purity azophenlyene waste material from chemical products, using lightness-removing column and weight-removing column, lightness-removing column
It is provided with overhead condenser and tower reactor reboiler, weight-removing column is provided with overhead condenser and tower reactor reboiler；It is characterized in that former containing azophenlyene
Feed liquid enters the middle part of lightness-removing column after feed preheater heat exchange, and tower top sloughs aniline and diphenyl diimide, obtains purity and is more than 97%
Aniline, recycled；Lightness-removing column tower reactor logistics enters the middle part of weight-removing column, and bottom of towe sloughs 4-ADPA restructuring
Point, obtain the 4-ADPA that purity is more than 99%, refine directly as product or entrance next stage；Weight-removing column tower top obtains
The azophenlyene product that purity is more than 99.5%；Lightness-removing column tower top operating pressure is 1～10kpa, and bottom of towe operation temperature is 214～262
DEG C, reflux ratio is 2～6, and theoretical stage is 20～40 altogether；Weight-removing column tower top operating pressure is 1～6kpa, and bottom of towe operation temperature is
217～253 DEG C, reflux ratio is 8～10, and theoretical stage is 30～50 altogether.
2. the method for claim 1, is characterized in that material liquid containing azophenlyene by the heavy constituent flowing out with weight-removing column bottom
Enter the middle part of lightness-removing column after feed preheater heat exchange, the tower temperature degree that enters containing azophenlyene material liquid after heat exchange is 105～125 DEG C.
3. the method for claim 1, is characterized in that described lightness-removing column and weight-removing column are packed tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410825895.2A CN104529916B (en) | 2014-12-25 | 2014-12-25 | Method for separating high-purity phenazine from waste material generated in chemical product production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410825895.2A CN104529916B (en) | 2014-12-25 | 2014-12-25 | Method for separating high-purity phenazine from waste material generated in chemical product production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104529916A CN104529916A (en) | 2015-04-22 |
| CN104529916B true CN104529916B (en) | 2017-01-25 |
Family
ID=52845595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410825895.2A Expired - Fee Related CN104529916B (en) | 2014-12-25 | 2014-12-25 | Method for separating high-purity phenazine from waste material generated in chemical product production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104529916B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543011B (en) * | 2015-09-16 | 2018-08-07 | 中国石油化工股份有限公司 | A kind of processing method of 4-aminodiphenylamine production waste material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
| CN1189445C (en) * | 2003-07-04 | 2005-02-16 | 程千文 | Method for refining 4-amino diphenylamine |
| CN101381315B (en) * | 2008-10-17 | 2010-12-08 | 山西翔宇化工有限公司 | Preparation method of p-aminodiphenylamine |
| CN203295403U (en) * | 2013-06-04 | 2013-11-20 | 山西翔宇化工有限公司 | Device system used for extracting and refining azophenylene in RT base waste |
-
2014
- 2014-12-25 CN CN201410825895.2A patent/CN104529916B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104529916A (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102039058B (en) | Large-scale methanol multi-effect energy-saving rectifying device and process | |
| CN109053355B (en) | Method for purifying biphenyl by continuous rectification | |
| CN104447299A (en) | M-phthaloyl chloride production process and production device thereof | |
| JP6681676B2 (en) | Method and apparatus for the cyclic treatment and purification of propylene | |
| CN102320969A (en) | System and method for rectifying and purifying food grade ethyl lactate into electronic grade ethyl lactate | |
| CN102701994A (en) | Process method for separating and refining rough aniline | |
| CN104529916B (en) | Method for separating high-purity phenazine from waste material generated in chemical product production | |
| CN108774100B (en) | Combined method for preparing methyl tert-butyl ether and isobutene from tert-butyl alcohol and methanol | |
| CN103524308B (en) | Method for preparing halogenated phenol compounds | |
| CN100424055C (en) | Parallel trimethyl benzene separating apparatus and method | |
| CN103933751B (en) | Thionyl chloride differential pressure heat coupling rectification method and apparatus | |
| CN203803139U (en) | Thionyl chloride differential pressure thermal coupling distillation equipment | |
| US9102586B2 (en) | Method for producing DADPM | |
| CN105315238B (en) | The production equipment of expoxy propane | |
| CN105272808B (en) | The equipment of propylene recovery | |
| CN205398517U (en) | Processing apparatus behind aniline | |
| CN215480650U (en) | Product separation and purification device for preparing ethanol from acetic acid | |
| CN103570577A (en) | Preparation method of N,N-dimethyl propionamide | |
| CN103664616A (en) | Method and device for producing benzyl benzoate | |
| CN106492495A (en) | Improved vacuum distillation tower and acetonitrile refining system | |
| CN105037078A (en) | Method for recovering dichloromethane in chlorone mother liquid | |
| CN214693949U (en) | Device for producing DMAC (dimethylacetamide) under catalyst-free and low-pressure conditions | |
| CN112723992A (en) | Process for preparing high-purity decanediol by side-line vacuum rectification | |
| CN201525814U (en) | Isopropyl amine crude product purifying device | |
| CN103113179A (en) | Thermal coupling system and method for extractive distillation of normal hexane, isohexane and benzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170125 Termination date: 20201225 |