CN107793296B - Method for preparing bisphenol A by adopting combined process of suspension crystallization and falling film crystallization - Google Patents
Method for preparing bisphenol A by adopting combined process of suspension crystallization and falling film crystallization Download PDFInfo
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- CN107793296B CN107793296B CN201710990086.0A CN201710990086A CN107793296B CN 107793296 B CN107793296 B CN 107793296B CN 201710990086 A CN201710990086 A CN 201710990086A CN 107793296 B CN107793296 B CN 107793296B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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Abstract
The invention discloses a method for preparing bisphenol A by adopting a combined process of suspension crystallization and falling film crystallization, which comprises multistage suspension crystallization and multistage melt crystallization. The present invention can prepare bisphenol A with purity higher than 99.9%, and is more economical than suspension crystallization and recrystallization/distillation purification.
Description
Technical Field
The present invention relates to a process for the preparation of bisphenol A.
Background
A known method for producing bisphenol a (2, 2-bis (4' -hydroxyphenyl) propane) involves reacting acetone with an excess of phenol in the presence of a strong acid catalyst such as a sulfonic acid-type cation exchange resin. The reaction forms a product mixture containing primarily BPA and water in addition to unreacted phenol and small amounts of acetone, and also produces small amounts of by-products typical of condensation reactions, such as 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane (ortho, para-BPA), substituted indanes, hydroxyphenyl indanols, hydroxyphenyl chromans, spirobiindanes, substituted indenols, substituted xanthenes, and higher condensed compounds having three or more benzene rings in the molecular backbone.
The product is typically cooled to form a roughly equimolar crystalline adduct of bisphenol a/phenol, and the BPA and phenol are separated from the reaction mixture. This operation is carried out by cooling the reaction mixture and crystallizing the bisphenol A-phenol adduct by means of suspension crystallization. The bisphenol A-phenol adduct crystals are then separated from the liquid phase by suitable equipment for solid-liquid separation, such as rotary filters or centrifuges. Impurities adhering to the surface of the adduct crystals may be removed by washing with a suitable solvent, which typically contains one or more components selected from: acetone, water, phenol, BPA and minor components. The solid/liquid separated crystals of BPA/phenol complex are typically subjected to further purification steps including, for example, distillation, desorption or extraction processes in which phenol can be removed and the concentration of minor components in the BPA can be reduced.
In order to obtain high purity bisphenol A, it is usually necessary to use n-stage suspension crystallization of n > 1 and to conduct repeated recrystallization operations, and it is necessary to increase the number of separation apparatuses for the crystalline adduct and the number of dissolution tanks for the crystalline adduct, which causes problems of large-scale apparatus and high apparatus cost; there is also a method of purifying bisphenol A by distillation from a melt thereof, and it has been found that bisphenol A is thermally decomposed to form impurities such as phenol, isopropenylphenol and the like during the treatment for removing phenol, and it is difficult to avoid decomposition of bisphenol A in the step of removing phenol only by controlling the distillation conditions
Disclosure of Invention
The invention aims to provide a convenient and effective method for preparing bisphenol A by adopting a combined process of suspension crystallization and falling film crystallization.
The technical solution of the invention is as follows:
a method for preparing bisphenol A by adopting a combined process of suspension crystallization and falling film crystallization is characterized by comprising the following steps: comprises the following steps:
(I) suspension crystallization
(1) Adjusting the reaction solution to phenol at 65-75 deg.C to make the content of p, p-bisphenol A25-35 wt%;
(2) at the temperature, the reaction solution is filled into n-stage serial suspension crystallizers with the number n of crystallization reactors more than 1, the reaction solution is circulated in each crystallizer, and the circulation rate is more than or equal to 2000m3Hour/hour;
(3) in the tandem crystallizer, the temperature gradient is arranged from 60 ℃ in the first crystallizer, 50 ℃ in the second crystallization reactor and 40 ℃ in the final crystallization reactor
(4) Washing and/or dissolving by using phenol to obtain a bisphenol A/phenol crystal adduct; at least a part of the phenol for washing and/or dissolution is purified phenol.
(II) melt crystallization
(1) Removing phenol in the bisphenol A/phenol crystallization adduct at the temperature of 150 ℃ and 175 ℃ and under the vacuum of 1-150 mbar, wherein the finally obtained molten bisphenol A liquid phase contains less than 1% of phenol;
(2) filling molten bisphenol A liquid into n-grade serial falling film crystallizers with n being more than 1, and carrying out multi-step molten liquid falling film crystallization operation; obtaining the product.
In the step (II), in the melting crystallization, the steps of loading materials into the crystallizer, crystallizing, discharging residual liquid, sweating, completely melting and discharging purified products are sequentially carried out in each stage of falling film crystallizer; in the charging, crystallization and residual liquid discharging stages, a temperature slope gradually decreasing from 160-125 ℃ is set, and in the sweating, total melting and purified product discharging stages, a temperature slope gradually increasing from 125-160 ℃ is set.
And (II) before the molten bisphenol A liquid enters the falling film crystallizer, adding 1-50ppm of sodium bicarbonate and controlling the pH value to be 5.05-5.10.
The invention adopts the combined process of suspension crystallization and falling film crystallization, can maximize the product purity, yield and comprehensive device economic benefit, and can prepare bisphenol A with the purity higher than 99.9 percent. Phase specific gravity crystallization/distillation purification is more economical. In the parallel operation mode of the crystallizer in the first stage, during the melting process in the crystallizer, the other crystallizers continue to operate at the same temperature, and the output quantity and the quality of the product can be synchronously maintained at a high level, so that the utilization rate of a system can be improved, and the purity of the product can be improved; the concept of serial falling film crystallization, multistage reverse operation, of the second crystallization stage, preset in combination with carefully controlled material balance, heat balance, can produce products of any desired purity, which can gain considerable market potential and reduce manufacturing costs due to the ease with which the control settings can be changed to meet changes in product specifications.
The present invention will be further described with reference to the following examples.
Detailed Description
A method for preparing bisphenol a by a combined process of suspension crystallization and falling film crystallization, comprising the steps of:
(I) suspension crystallization
(1) Adjusting the reaction solution to phenol at 65-75 deg.C to make the content of p, p-bisphenol A25-35 wt%;
(2) at the temperature, the reaction solution is filled into n-stage serial suspension crystallizers with the number n of crystallization reactors more than 1, the reaction solution is circulated in each crystallizer, and the circulation rate is more than or equal to 2000m3Hour/hour;
(3) in the tandem crystallizer, the temperature gradient is arranged from 60 ℃ in the first crystallizer, 50 ℃ in the second crystallization reactor and 40 ℃ in the final crystallization reactor
(4) Washing and/or dissolving by using phenol to obtain a bisphenol A/phenol crystal adduct; at least a part of the phenol for washing and/or dissolution is purified phenol.
(II) melt crystallization
(1) Removing phenol in the bisphenol A/phenol crystallization adduct at the temperature of 150 ℃ and 175 ℃ and under the vacuum of 1-150 mbar, wherein the finally obtained molten bisphenol A liquid phase contains less than 1% of phenol;
(2) filling molten bisphenol A liquid into n-grade serial falling film crystallizers with n being more than 1, and carrying out multi-step molten liquid falling film crystallization operation; obtaining the product.
In the step (II), in the melting crystallization, the steps of loading materials into the crystallizer, crystallizing, discharging residual liquid, sweating, completely melting and discharging purified products are sequentially carried out in each stage of falling film crystallizer; in the charging, crystallization and residual liquid discharging stages, a temperature slope gradually decreasing from 160-125 ℃ is set, and in the sweating, total melting and purified product discharging stages, a temperature slope gradually increasing from 125-160 ℃ is set.
And (II) before the molten bisphenol A liquid enters the falling film crystallizer, adding 1-50PPm of sodium bicarbonate and controlling the pH value to be 5.05-5.10, so that the decomposition loss of the p, p-bisphenol A is less than 0.5 percent, and the product has good hue.
Specific process parameters are as follows:
the main operation conditions of suspension crystallization are as follows:
(1) composition of feed materials
Bisphenol A: 25% by weight, phenol: 65 wt%, others: 10% by weight
(2) Number of crystallization reactors n = 2;
a crystallization tower A: temperature: 60 ℃, residence time: 120min
A crystallization tower B: temperature: 50 ℃, residence time: 120min
(3) Composition of discharged solution
Bisphenol A: 47 wt%, phenol: 52 wt%, others: 1% by weight. The cleaning amount of the purified phenol is adjusted, so that the components of BPA relative to the by-products can be effectively controlled.
(II) melt crystallization
(1) Phenol is removed by a multistage vacuum evaporation system, and the main operation conditions are as follows:
feeding temperature: 120 deg.C
First-stage evaporation: temperature 150 ℃ pressure: 10 torr
Secondary evaporation: temperature 160 ℃ pressure: 5 torr
Three-stage evaporation: temperature 165 ℃ pressure: 1 torr
Discharging molten bisphenol A: the purity was 97.5% p, p-BPA, 1% phenol, 1.5% other impurities (determination: gas chromatography ASTM method).
(2) The multistage falling film crystallization has the following main operation conditions:
feeding temperature: 170 deg.C
A first-stage falling film: at the temperature of 170 ℃ and the temperature of 125 ℃ for 150min
Secondary falling film: the temperature is 170 ℃ and 125 ℃, and the time is 140min
Three-stage falling film: at the temperature of 170 ℃ and the temperature of 125 ℃ for 120min
The product bisphenol A: the purity was 99.92% p, p-BPA, 185ppm, o, p-BPA, 150ppm of other high-boiling impurities (determination: liquid chromatography ASTM method).
Claims (4)
1. A method for preparing bisphenol A by adopting a combined process of suspension crystallization and falling film crystallization is characterized by comprising the following steps: comprises the following steps:
(I) suspension crystallization
(1) Adjusting the reaction solution to phenol at 65-75 deg.C to make the content of p, p-bisphenol A25-35 wt%;
(2) in thatAt the temperature, the reaction solution is filled into n-stage serial suspension crystallizers with the number n of crystallization reactors more than 1, the reaction solution circulates in each crystallizer, and the circulation rate of the reaction solution circulating in each crystallizer is more than or equal to 2000m3Hour/hour; n in the n-stage serial suspension crystallizer is 2; in the serial crystallizers, the temperature gradient is arranged to be 60 ℃ in a first crystallizer and 50 ℃ in a second crystallization reactor;
(3) washing and/or dissolving by using phenol to obtain a bisphenol A/phenol crystal adduct;
(II) melt crystallization
(1) Removing phenol in the bisphenol A/phenol crystallization adduct at the temperature of 150 ℃ and 175 ℃ and under the vacuum of 1-150 mbar, wherein the finally obtained molten bisphenol A liquid phase contains less than 1% of phenol;
(2) before the molten bisphenol A liquid enters a falling film crystallizer, adding 1-50ppm of sodium bicarbonate and controlling the pH value to be 5.05-5.10; filling the obtained molten bisphenol A liquid into n-grade serial falling film crystallizers with n being more than 1, and carrying out multi-step molten liquid falling film crystallization operation to obtain a product; wherein each stage of falling film crystallizer sequentially comprises the steps of loading materials into the crystallizer, crystallizing, discharging residual liquid, sweating, completely melting, purifying products and unloading; setting a temperature slope gradually decreasing from 170-125 ℃ in the stages of charging, crystallization and residual liquid discharge; during the sweating, total melting and purified product discharge phases, a temperature ramp was set that was gradually increased from 125-170 ℃.
2. The process of claim 1 for the preparation of bisphenol a by a combined suspension crystallization and falling film crystallization process, characterized in that: in the step (one), purified phenol is used as at least a part of the phenol for washing and/or dissolution.
3. The process of claim 1 for the preparation of bisphenol a by a combined suspension crystallization and falling film crystallization process, characterized in that: and (5) adopting a multistage vacuum evaporation system in the step (II) of removing phenol in vacuum.
4. The process of claim 1 for the preparation of bisphenol a by a combined suspension crystallization and falling film crystallization process, characterized in that: the content of p, p-bisphenol A in the step (one) is 25 wt%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710990086.0A CN107793296B (en) | 2015-08-12 | 2015-08-12 | Method for preparing bisphenol A by adopting combined process of suspension crystallization and falling film crystallization |
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| CN201710990086.0A CN107793296B (en) | 2015-08-12 | 2015-08-12 | Method for preparing bisphenol A by adopting combined process of suspension crystallization and falling film crystallization |
| CN201510489640.8A CN105130758B (en) | 2015-08-12 | 2015-08-12 | The method that bisphenol-A is prepared using the group technology of suspension crystallization and film-falling crystallization |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2090562A1 (en) * | 2008-02-06 | 2009-08-19 | Maciej Kiedik | A method to obtain polycarbonate-grade bisphenol A |
| CN101525276A (en) * | 2009-04-10 | 2009-09-09 | 南通星辰合成材料有限公司 | Process for synthesizing bisphenol A by utilizing cation resin |
| CN101525274A (en) * | 2008-01-09 | 2009-09-09 | 拜尔材料科学股份公司 | Crystallization process for the preparation of bisphenols |
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| PL210812B1 (en) * | 2007-02-14 | 2012-03-30 | Inst Ciężkiej Syntezy Organicznej Blachownia | The manner of obtaining of bisphenol A |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525274A (en) * | 2008-01-09 | 2009-09-09 | 拜尔材料科学股份公司 | Crystallization process for the preparation of bisphenols |
| EP2090562A1 (en) * | 2008-02-06 | 2009-08-19 | Maciej Kiedik | A method to obtain polycarbonate-grade bisphenol A |
| CN101525276A (en) * | 2009-04-10 | 2009-09-09 | 南通星辰合成材料有限公司 | Process for synthesizing bisphenol A by utilizing cation resin |
Non-Patent Citations (1)
| Title |
|---|
| 双酚A生产过程中的化学工程问题;张勇;《石油化工》;20011231;第30卷(第1期);第59-62页 * |
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| CN105130758B (en) | 2017-12-08 |
| CN107793296A (en) | 2018-03-13 |
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