CN100368382C - Process of crystallizing separating amino methyl phenoxide mixture - Google Patents
Process of crystallizing separating amino methyl phenoxide mixture Download PDFInfo
- Publication number
- CN100368382C CN100368382C CNB200610085491XA CN200610085491A CN100368382C CN 100368382 C CN100368382 C CN 100368382C CN B200610085491X A CNB200610085491X A CN B200610085491XA CN 200610085491 A CN200610085491 A CN 200610085491A CN 100368382 C CN100368382 C CN 100368382C
- Authority
- CN
- China
- Prior art keywords
- anisidine
- para
- ether mixture
- methyl alcohol
- crystallization
- 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
Images
Abstract
The present invention relates to a crystallization separation technology for mixtures of aminobenzene and methyl ether. Mixtures of aminobenzene and methyl ether are used as raw materials and carry out warming dissolution, decolouring trash extraction and heat filtration in a methanol solvent, and fine liquor is obtained; the fine liquor uses cooling crystallisation and filtration step by step, p-amino phenyl mether crude products and o-amino phenyl mether crude products are respectively obtained and are respectively separated and refined through recrystallization in the methanol solvent, and p-amino phenyl mether products and o-amino phenyl mether products are obtained. The present invention has the advantages of less investment, low cost, good quality, safe production process especially, no three waste and maximum application and extension value.
Description
Technical field
The invention belongs to the fine chemical technology field, specifically, the crystallization separation process that relates to a kind of aminobenzoic ether mixture is that raw material carries out the technology that Crystallization Separation is produced Para-Anisidine and Ortho Anisidine in methanol solvate with the aminobenzoic ether mixture promptly.
Background technology
The normal fractionation by distillation that adopts anisidine in the prior art, anisidine exists facility investment and drawbacks such as process cost is big, operational condition harshness in the fractionation by distillation process.
Solution crystallization is a liquid phase production solid crystal product unit process commonly used, and the Crystallization Separation technology has wide development space in modern industry.Crystallization technique is compared with other unit processes has following advantage:
(1) less energy consumption: the crystallization of most compounds is exothermic process, and with rectifying, the unit operation that energy consumptions such as drying are big is compared, and crystallization phases changes potential and only is 1/3～1/7 of rectifying, and separating energy consumption only is 10～30% of rectifying.
(2) be applicable to the separation of complicated systems such as azeotrope: nearly 90% organism compound system is the eutectic type, and the boiling point difference is little, uses the conventional distillation method to be difficult to reach the purpose of separating and purifying.Use extraction,, be subjected to the restriction of physical conditions such as selection of Extractant in operating and be difficult to reach complete isolating purpose though methods such as azeotropic distillation can be separated in theory; Moreover the introducing of other components such as extraction agent increases operational path, increases investment and process cost, and inevitably influences the quality of the finished product.With extraction, rectifying is compared, and does not have the introducing of other materials in the crystallisation process, and the selectivity height of crystallization operation can be produced highly purified product.
(3) the crystallization operation temperature is lower, and is little to the equipment corrosion degree.Particularly to the boiling point height, the system of blast separates easily, the safety performance of crystallization operation, good reliability.
(4) improve operating environment, reduce environmental pollution.The physicochemical property of aminobenzoic ether mixture: the boiling point of the isomers of various anisidines is all than higher, and low temperature is stable down, and pyrolytic decomposition is emitted poisonous gas, especially anisidine is inflammable, and chance naked light, high heat, friction, bump have the incendiary of causing danger.Emit deleterious irritating smog during burning.Form explosive mixture with the oxygenant mixing energy.Therefore crystallization process separates the separation method that the anisidine mixture is a first-selection.
Summary of the invention
The crystallization separation process that the purpose of this invention is to provide a kind of aminobenzoic ether mixture, this technology is fully used fusing point difference (fusing point of Ortho Anisidine, an amino-chloro-benzene and Para-Anisidine sees Table 1) and their dissolubility properties in methyl alcohol of Para-Anisidine and Ortho Anisidine, has overcome anisidine and have facility investment and drawbacks such as process cost is big, operational condition harshness in the fractionation by distillation process.
The technical scheme that realizes above-mentioned purpose is: the aminobenzoic ether mixture adopts the Crystallization Separation method to obtain Para-Anisidine and Ortho Anisidine crude product in methanol solvate, Para-Anisidine and Ortho Anisidine crude product carry out the recrystallization separation and purification respectively in methanol solvate, produce Para-Anisidine and o-amino benzoyl ether product.The described technology step is poly-as follows:
The first step, in stirring and dissolving equipment, add aminobenzoic ether mixture and methyl alcohol, heating makes temperature reach 50 ℃～methanol eddy temperature while stirring, make material dissolution, the aminobenzoic ether mixture contains Para-Anisidine, Ortho Anisidine and a spot of impurity;
Add the removal of impurities discoloring agent in second step, the material after dissolving and decolour except that miscellaneous operation, filtered while hot, filtrate enters cooling crystallizer for the first time, and filter cake is recyclable after treatment to be used again;
The 3rd step, in first time cooling crystallizer, will make with extra care material and be cooled to 7～20 ℃, the Para-Anisidine crystallization is separated out, is filtered, filtrate enters cooling crystallizer for the second time, filter cake enters the Para-Anisidine recrystallizer;
The 4th step, in second time cooling crystallizer, the previous step feed liquid is continued to be cooled to 0-6 ℃, the Ortho Anisidine crystallization is separated out, is filtered, filtrate turns back in the first step stirring and dissolving equipment, filter cake enters the Ortho Anisidine recrystallizer;
The 5th step, in the Para-Anisidine recrystallizer, add a certain amount of methyl alcohol, rising temperature for dissolving, crystallisation by cooling, filtration then, filtrate turned back to for the 3rd step for the first time in the crystallisation by cooling separator, filter cake gets the Para-Anisidine product through vacuum-drying;
The 6th step, in the Ortho Anisidine recrystallizer, add a certain amount of methyl alcohol, rising temperature for dissolving, crystallisation by cooling, filtration then, filtrate turned back to for the 4th step for the second time in the cooling crystallizer, filter cake gets the o-amino benzoyl ether product through vacuum-drying.
Further, the aminobenzoic ether mixture also contains water, methyl alcohol, and the ratio of solid materials and methyl alcohol is in the Crystallization Separation process: 100g: 100ml is to 500g: between the 500ml.
Further, the service temperature in the Crystallization Separation process is 0 ℃ and arrives between the reflux temperature of methyl alcohol that working pressure is between 0.1 to 10.0MPa.
Further, the sorbent material that the adsorption bleaching removal of impurities is adopted is activated carbon, diatomite, adsorbent of molecular sieve or the mixture of two components or three components wherein, and decolouring removal of impurities and filtering temperature are 50～65 ℃, and adsorption and decoloration device is a stirring tank.
After adopting the invention described above to adopt the Crystallization Separation technical scheme, have the following advantages:
(1) less energy consumption: separating energy consumption only is 10～30% of rectifying.
(2) the selectivity height of crystallization operation, the purity height of product.
(3) the crystallization operation temperature is lower, and is little to the equipment corrosion degree.Safety performance, the good reliability of operation.
(4) improve operating environment, reduce environmental pollution.The physicochemical property of aminobenzoic ether mixture: the boiling point of the isomers of various anisidines is all than higher, and low temperature is stable down, and pyrolytic decomposition is emitted poisonous gas, especially anisidine is inflammable, and chance naked light, high heat, friction, bump have the incendiary of causing danger.Emit deleterious irritating smog during burning.Form explosive mixture with the oxygenant mixing energy.Therefore crystallization process separates the separation method that the anisidine mixture is a first-selection.
In addition, select for use methyl alcohol to make the Crystallization Separation solvent three advantages arranged:
(1) boiling point of methyl alcohol is lower, is easy to reclaim.
(2) the direct recycled of the recovery liquid of methyl alcohol.
(3) viscosity of methanol solution is lower, the mixture of anisidine Crystallization Separation in methanol solution, and crystal formation is relatively more perfect.
The fusing point of table 1 Ortho Anisidine and Para-Anisidine
| Chemical substance | Ortho Anisidine | Para-Anisidine | Between amino-chloro-benzene |
| Fusing point/℃ | 6.22 | 57.2 | 46 |
Description of drawings
Accompanying drawing is the process flow sheet of the Crystallization Separation of a kind of aminobenzoic ether mixture of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Embodiment one
A kind of crystallization separation process of aminobenzoic ether mixture is a raw material with the aminobenzoic ether mixture promptly, produces the separating technology of Para-Anisidine and Ortho Anisidine, and processing step is as follows:
In the stirring and dissolving still, add aminobenzoic ether mixture and methyl alcohol, the ratio of aminobenzoic ether mixture and methyl alcohol is: 100g: 500ml, heat while stirring, be warming up to the methanol eddy temperature, make material dissolution; In the dissolving material, add adsorbent of molecular sieve and decolour except that miscellaneous operation, filtered while hot, filtrate enters crystallisation by cooling still for the first time; In first time cooling crystallizer, will make with extra care material and be cooled to 10 ℃, the Para-Anisidine crystallization is separated out, is filtered, and filtrate enters crystallisation by cooling still for the second time, and filter cake enters the Para-Anisidine recrystallizer; In second time cooling crystallizer, the previous step feed liquid is continued to be cooled to 0 ℃, the Ortho Anisidine crystallization is separated out, is filtered, and filter cake enters the Ortho Anisidine recrystallizer; In the Para-Anisidine recrystallizer, the ratio that adds Para-Anisidine and methyl alcohol is: 100g: 500ml, under agitation condition, be warming up to the methanol eddy temperature, make material dissolution, be cooled to 10 ℃ of crystallizations, filtration then, filter cake gets the Para-Anisidine product through vacuum-drying, and purity reaches more than 98%; In the Ortho Anisidine recrystallizer, the ratio that adds Ortho Anisidine and methyl alcohol is: 100g: 500ml under agitation condition, makes material dissolution, be cooled to 2 ℃ of crystallizations, filtration then, filter cake gets the Ortho Anisidine product purity through vacuum-drying and reaches more than 98%.
Embodiment two
A kind of crystallization separation process of aminobenzoic ether mixture is a raw material with the aminobenzoic ether mixture promptly, produces the separating technology of Para-Anisidine and Ortho Anisidine, and processing step is as follows:
In the stirring and dissolving still, add aminobenzoic ether mixture and methyl alcohol, the ratio of aminobenzoic ether mixture and methyl alcohol is: 200g: 500ml, heat while stirring, be warming up to 80 ℃, make material dissolution; In the dissolving material, add adsorbent of molecular sieve and decolour except that miscellaneous operation, filtered while hot, filtrate enters crystallisation by cooling still for the first time; In first time cooling crystallizer, will make with extra care material and be cooled to 18 ℃, the Para-Anisidine crystallization is separated out, is filtered, and filtrate enters crystallisation by cooling still for the second time, and filter cake enters the Para-Anisidine recrystallizer; In second time cooling crystallizer, the previous step feed liquid is continued to be cooled to 5 ℃, the Ortho Anisidine crystallization is separated out, is filtered, and filter cake enters the Ortho Anisidine recrystallizer; In the Para-Anisidine recrystallizer, the ratio that adds Para-Anisidine and methyl alcohol is: 200g: 500ml, under agitation condition, be warming up to the methanol eddy temperature, make material dissolution, be cooled to 10 ℃ of crystallizations, filtration then, filter cake gets the Para-Anisidine product through vacuum-drying, and purity reaches more than 98%; In the Ortho Anisidine recrystallizer, the ratio that adds Ortho Anisidine and methyl alcohol is: 200g: 500ml under agitation condition, makes material dissolution, be cooled to 2 ℃ of crystallizations, filtration then, filter cake gets the Ortho Anisidine product purity through vacuum-drying and reaches more than 98%.
Embodiment three
A kind of crystallization separation process of aminobenzoic ether mixture is a raw material with the aminobenzoic ether mixture promptly, produces the separating technology of Para-Anisidine and Ortho Anisidine, and processing step is as follows:
In the stirring and dissolving still, add aminobenzoic ether mixture and methyl alcohol, the ratio of aminobenzoic ether mixture and methyl alcohol is: 300g: 500ml, heat while stirring, be warming up to the methanol eddy temperature, make material dissolution; In the dissolving material, add adsorbent of molecular sieve and decolour except that miscellaneous operation, filtered while hot, filtrate enters crystallisation by cooling still for the first time; In first time cooling crystallizer, will make with extra care material and be cooled to 7 ℃, the Para-Anisidine crystallization is separated out, is filtered, and filtrate enters crystallisation by cooling still for the second time, and filter cake enters the Para-Anisidine recrystallizer; In second time cooling crystallizer, the previous step feed liquid is continued to be cooled to 1 ℃, the Ortho Anisidine crystallization is separated out, is filtered, and filter cake enters the Ortho Anisidine recrystallizer; In the Para-Anisidine recrystallizer, the ratio that adds Para-Anisidine and methyl alcohol is: 300g: 500ml, under agitation condition, be warming up to the methanol eddy temperature, make material dissolution, be cooled to 10 ℃ of crystallizations, filtration then, filter cake gets the Para-Anisidine product through vacuum-drying, and purity reaches more than 99%; In the Ortho Anisidine recrystallizer, the ratio that adds Ortho Anisidine and methyl alcohol is: 300g: 500ml under agitation condition, makes material dissolution, be cooled to 2 ℃ of crystallizations, filtration then, filter cake gets the Ortho Anisidine product purity through vacuum-drying and reaches more than 98%.
Claims (5)
1. the crystallization separation process of an aminobenzoic ether mixture, it is characterized in that: described processing step is as follows:
The first step, in stirring and dissolving equipment, add aminobenzoic ether mixture and methyl alcohol, heating makes temperature reach 50 ℃～methanol eddy temperature while stirring, make material dissolution, the aminobenzoic ether mixture contains Para-Anisidine, Ortho Anisidine and a spot of impurity;
Add the removal of impurities discoloring agent in second step, the material after dissolving and decolour except that miscellaneous operation, filtered while hot, filtrate enters cooling crystallizer for the first time, and filter cake is recyclable after treatment to be used again;
The 3rd step, in first time cooling crystallizer, will make with extra care material and be cooled to 7～20 ℃, the Para-Anisidine crystallization is separated out, is filtered, filtrate enters cooling crystallizer for the second time, filter cake enters the Para-Anisidine recrystallizer;
The 4th step, in second time cooling crystallizer, the previous step feed liquid is continued to be cooled to 0-6 ℃, the Ortho Anisidine crystallization is separated out, is filtered, filtrate turns back in the first step stirring and dissolving equipment, filter cake enters the Ortho Anisidine recrystallizer;
The 5th step, in the Para-Anisidine recrystallizer, add a certain amount of methyl alcohol, rising temperature for dissolving, crystallisation by cooling, filtration then, filtrate turned back to for the 3rd step for the first time in the crystallisation by cooling separator, filter cake gets the Para-Anisidine product through vacuum-drying;
The 6th step, in the Ortho Anisidine recrystallizer, add a certain amount of methyl alcohol, rising temperature for dissolving, crystallisation by cooling, filtration then, filtrate turned back to for the 4th step for the second time in the cooling crystallizer, filter cake gets the o-amino benzoyl ether product through vacuum-drying.
2. the crystallization separation process of aminobenzoic ether mixture according to claim 1 is characterized in that: described stirring and dissolving equipment is the stirring and dissolving still.
3. the crystallization separation process of aminobenzoic ether mixture according to claim 1, it is characterized in that: the aminobenzoic ether mixture also contains water, methyl alcohol, and the ratio of solid materials and methyl alcohol is in the Crystallization Separation process: 100g: 100ml is to 500g: between the 500ml.
4. the crystallization separation process of aminobenzoic ether mixture according to claim 1 is characterized in that:. the service temperature in the Crystallization Separation process is 0 ℃ and arrives between the reflux temperature of methyl alcohol that working pressure is between 0.1 to 10.0MPa.
5. the crystallization separation process of aminobenzoic ether mixture according to claim 2, it is characterized in that: the sorbent material that the adsorption bleaching removal of impurities is adopted is activated carbon, diatomite, adsorbent of molecular sieve or the mixture of two components or three components wherein, decolouring removal of impurities and filtering temperature are 50～65 ℃, and adsorption and decoloration device is a stirring tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610085491XA CN100368382C (en) | 2006-06-19 | 2006-06-19 | Process of crystallizing separating amino methyl phenoxide mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610085491XA CN100368382C (en) | 2006-06-19 | 2006-06-19 | Process of crystallizing separating amino methyl phenoxide mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1861572A CN1861572A (en) | 2006-11-15 |
| CN100368382C true CN100368382C (en) | 2008-02-13 |
Family
ID=37389116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610085491XA Expired - Fee Related CN100368382C (en) | 2006-06-19 | 2006-06-19 | Process of crystallizing separating amino methyl phenoxide mixture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100368382C (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298841A (en) * | 1999-12-09 | 2001-06-13 | 上海江东化工有限公司 | Process for treating waste water generated by synthesizing p(o)-nitroanisole |
-
2006
- 2006-06-19 CN CNB200610085491XA patent/CN100368382C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298841A (en) * | 1999-12-09 | 2001-06-13 | 上海江东化工有限公司 | Process for treating waste water generated by synthesizing p(o)-nitroanisole |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1861572A (en) | 2006-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100494159C (en) | Process of producing nitrobenzether aminobenzether amidobenzether from chlorobenzene | |
| RU2007138831A (en) | METHOD AND DEVICE FOR THE PRODUCTION OF AROMATIC CARBONIC ACIDS (OPTIONS) | |
| JP2008538213A5 (en) | ||
| CN104027996A (en) | A pervaporation rectification coupled system and a use thereof | |
| CN103395925A (en) | Treatment method for recycling para-hydroxybenzoic acid wastewater | |
| CN100368382C (en) | Process of crystallizing separating amino methyl phenoxide mixture | |
| CN103467252B (en) | Method for increasing purity of di-trimethylolpropane | |
| CN100402482C (en) | Method for producing aromatic carboxylic acid | |
| CN101823928B (en) | Clean production process for derivatives of para aminobenzoic acid by reactor coupled simulated moving bed | |
| CN101781282A (en) | Method for producing high-purity ether used for HPLC | |
| US4008255A (en) | Recovery of phthalic anhydride | |
| CN109704990B (en) | Refining method of high-purity acetonitrile | |
| CN107778140A (en) | A kind of purification method of ethylene glycol sorption extraction deep dehydration removal of impurities | |
| CN106543196B (en) | A method of extracting sesamin from sesame oil | |
| RU2517524C2 (en) | Method and apparatus for processing hydrogen in purification unit of terephthalic acid purification device | |
| CN106187698B (en) | The separation and refining method of butanol and octanol waste liquid back end hydrogenation | |
| CN104220404A (en) | Method for producing hydrogenated biphenol | |
| CN103113179A (en) | Thermal coupling system and method for extractive distillation of normal hexane, isohexane and benzene | |
| KR20230022033A (en) | Recovery method of dimethylformamide from the waste solution of polyimide production process | |
| US10781153B2 (en) | Recovery of ethyl hexanol from recycle streams in 2-ethyl hexanol process | |
| CN112125793B (en) | 2, 4-Di-n-octoxybenzophenone and synthetic method and application thereof | |
| CN110540486B (en) | Separation system and separation method for byproduct high-boiling-point substances in tetrachloroethylene production | |
| CN100338021C (en) | Crystallizing separating tech. of nitro methyl-phenoxide mixture | |
| CN106187700A (en) | The separation method of butanol and octanol waste liquid back end hydrogenation | |
| CN112125793A (en) | 2, 4-di-n-octyloxy benzophenone and synthesis method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| 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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Anhui Haihua Chemical Co., Ltd. Assignor: Yangzhou University| Changzhou Jiasen Chemical Co Ltd Contract record no.: 2012340000130 Denomination of invention: Process of crystallizing separating amino methyl phenoxide mixture Granted publication date: 20080213 License type: Exclusive License Open date: 20061115 Record date: 20120417 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080213 Termination date: 20130619 |