CN104540799A - Method of producing bisphenol a - Google Patents
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- CN104540799A CN104540799A CN201380031512.8A CN201380031512A CN104540799A CN 104540799 A CN104540799 A CN 104540799A CN 201380031512 A CN201380031512 A CN 201380031512A CN 104540799 A CN104540799 A CN 104540799A
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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
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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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
- C07C37/88—Use of additives, e.g. for stabilisation
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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
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A method of producing bisphenol A in the condensation reaction of acetone with phenol in the presence of strongly acidic, sulphonic ion-exchange resins wherein the reaction mixture containing acetone, phenol and products of the reaction between phenol and acetone is contacted with an ion-exchange catalyst in at least two reactors until the total water content is not greater than 2.5 cg/g, and acetone and phenol are fed into reactor (1) and the post-reaction mixture from reactor (1), mixed in mixer (2) with the post-crystallization liquors from crystallizers (8) and acetone, is fed into reactor (3), the post-reaction mixture after reactor (3) is mixed in mixer (4) with part of the phenol solution not greater than 40 cg/g, obtained by contacting the dewatering mixture containing at maximum 1.0% of water with anion-exchange catalyst in at least one reactor (5), the post-reaction mixture from mixer (4) is contacted in adsorber (6) at a temperature of up to 150 DEG C and flow rate not greater than 10 m/h with a phenol solution pH stabilizer in the form of a fixed bed with grain size not greater than 1.2 mm, containing carboxyl and/or hydroxyl and/or amide groups, until the post-reaction mixture reaches a pH of 5-6 after adsorber (6), the post-reaction mixture in adsorber (6) is concentrated in distillation column(7) by partial or total evaporation of volatile substances as a distillate containing phenol, acetone and water at the boiling point under normal pressure not greater than 200 DEG C, and bisphenol A is crystallized from the distillation residue, at least 60% of thephenol solution in reactor (5) is contacted in adsorber (9), at a temperature of up to 150 DEG C and flow rate not greater than 10 m/h, with a phenol solution pH stabilizer in the form of a fixed bed with grain size not greater than 1.2 mm, containing carboxyl and/or hydroxyl and/or amide groups, until the mixture after adsorber (9) reaches a pH of 5-6 and the resulting solution is mixed with the distillate from distillation column (7) containing phenol, acetone and water, and fed into distillation column(10), phenol separated in column (10) is recycled to reactor (1), acetone to reactor (1) and/or (3), and the water fraction is removed from the installation as waste water.
Description
The present invention relates to and a kind of manufacture for the production of the dihydroxyphenyl propane of plastics (more particularly polycarbonate resin) and it is for production structure assembly in the automotive industry, method for the production of the adulterant of medical treatment device and sporting equipment and daily object.
In addition, dihydroxyphenyl propane [2,2-pair-(4-hydroxyphenyl) propane] (also referred to as p, p'-BPA or referred to as BPA) for the manufacture of the additive of epoxy, unsaturated polyester resin, poly-sulfonate resin and polyetherimide and plastic material, such as fire retardant, as tetrabromo-bisphenol, dihydroxyphenyl propane phenyl-phosphate and the thermo-stabilizer gathering (vinylchlorid).
Dihydroxyphenyl propane obtains by condensation acetone and phenol under highly acidic catalyzer (such as bronsted (Bronsted) or Louis (Lewis) acid) existence.At present, dihydroxyphenyl propane passes through in acidic lon exchange catalysts (as sulphonated stryrene divinyl base benzene multipolymer) and optionally increase reaction yield and optionally promotor (mercaptan compound mostly, such as 2,2-dimethyl-1,3-thiazoles alkane and 2-aminoethane thiol) exist the condensation reaction of acetone and phenol to obtain.
The synthesis unit of dihydroxyphenyl propane comprises the multiphase system of the flow reactor of fixed bed connected via heat exchanger in series, and described heat exchanger allows to maintain the target temperature range in each reactor.Acetone and the method for post-crystallization liquor that obtains in the BPA abstraction and purification stage of coming into operation changes according to embodiment.
Make likely to split the acetone solution stream between the reactor that is connected in series about the embodiment (as described in No. 6414199, patent US) of described reactor assembly, allow the better distribution of temperature in catalyst bed and the larger control to BPA synthesis thus, and transmit substantive benefit with longer catalyst life and higher condensation reaction preference form.
Many embodiments are post-crystallization liquor to be recycled to enriching stage, subsequent crystallisation with nonreactive phenol and amorphous BPA form, and this significantly can reduce raw-material consumption.Be that restriction forms 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl) propane (so-called o by by mother liquor recycle to another advantage that synthesis phase causes, p'-BPA isomer), because system then more close proximity p, the equilibrium state of p'-BPA and o, p'-BPA isomer.In the method that the multiphase system using flow reactor of fixed bed is provided, reclaim mother liquor by several methods and make its supply first stage of condensation reaction or follow-up phase of this reaction.O is formed about restriction, the sharpest edges of p'-BPA isomer are that mother liquor recycle is to the first synthesis phase, and the embodiment that therefore first patent documentation comprises by being formed to different synthesis phase by a part of mother liquor recycle does not indicate gained advantage (US6858759) as only optional possibility.Many side reactions are related to from phenol and acetone bisphenol synthesis in the reaction forming pp'-BPA isomer, produce o, p'-BPA isomer, o, o'-BPA isomer, codimerization thing, to isopropenyl phenol, australol, straight chain dimer, cyclic dimer, trisphenol and many up to now without differentiate other compound.By product can gather in process streams, and this is well-known common effect at industrial scale, has detrimentally affect to product quality.It is control by-products content in liquid stream to make BPA from the stable as far as possible system of the condition of mixture separation after reaction and purifying that BPA manufactures the foundation stone of modern technologies.
After reaction, the pure BPA of mixture separation is extremely important synthesis phase.Vacuum distilling is most commonly used to the phenol removing acetone, water and not significant quantity.BPA-phenol adducts carrys out crystallization by cooling rest part.Phenol through vacuum distilling with from be separated adducts crystal obtain BPA.Many methods for separating of larger purity bis-phenol are described.No. 0330146, patent EP describes the process of bisphenol a/phenol adduct crystallization.In addition, a kind of method obtains patent right, and it is the fusion-crystallization by the crude bisphenol obtained from the nonreactive acetone of condensation reaction products fractionation by distillation, water and phenol.
In No. 0035847, patent WO, present the suspension crystallization of BPA/ phenol adducts, it is separated from mother liquor by filtering, the fractional crystallization of thick BPA that adducts is decomposed by vacuum distilling phenol and obtains.Obtainable patent documentation provides different BPA purification process: from reaction environment with BPA-phenol adducts isolated in form BPA, and by carrying out purifying with purified petroleum benzin phenol or phenol-water mixture washing,
-thick BPA from solvent or ORGANIC SOLVENT MIXTURES crystallization,
-molecular distillation.
By mixture distillation after the reaction of synthesizing from BPA to remove nonreactive composition and water.At high temperature, BPA is degraded into phenol and isopropenyl phenol, the reaction further of its experience, and increases by product per-cent thus, and comprise the color complex body of metal and phenol, this causes the height of thick BPA painted.The method reducing BPA degraded is to neutralize by introducing neutralization compound (carbonate and alkali metal hydroxide) acidic impurities be present in the rear mixture of reaction, filters thick BPA by Zeo-karb (Na, K, Li, Ca, Mg) or inorganic ion exchanger (No. 6512148, patent US).
As known from patent specification, the method reducing by product formation scale comprises such as o, p'-BPA to p, the isomerization reaction (JP 08333290) of p'-BPA, this make use of the following fact: after the crystallization of BPA/ phenol adducts, the concentration ratio equilibrium concentration of o, p'-BPA isomer is high, and catalytic decomposition process occurs under acid (WO0040531) or alkalescence (PL 181992) catalysts influence.
Dihydroxyphenyl propane is unstable compound and experiences under the impact of temperature, light under the existence of acid, alkali and oxygen progressively to degrade.Decomposing appears due to the unstable of the key between quaternary carbon atom and phenolic hydroxyl group in dihydroxyphenyl propane molecule.In polycarbonate synthesis, product degradation (even if to be present in BPA on a small quantity) Inhibitory molecules amount can increase and reduce machinery and the optical property of polymkeric substance.Degraded causes and form much BPA impurity during BPA thermal treatment and purifying.
The BPA forming color complex body and larger stability can use stablizer to realize.Stablizer is the compound be incorporated into a small amount of (1%-2%) in material.Allow to select to be suitable for treat that stable material and its expection store by the diversity of the type of the compound of used as stabilizers and structure, use or the stablizer of processing conditions.Phosphoric acid (1) is joined the formation (EP 0816319) of the color complex body that can suppress Heat Treatment metal and phenol derivatives and BPA in thick BPA before the purifying based on distillation.Different stabilization by the temperature of 185-220 DEG C in non-oxygen atmosphere BPA from the method (JP 6025045) of phenol crystallization or realize by introducing additive such as boric acid, alkyl titanate, Tetra hydro Phthalic anhydride, alkali metal phosphate (V) and (III) (CS 272518).
The object of the invention is to develop a kind of method manufacturing dihydroxyphenyl propane, wherein the feature of catalysis system is more long lifetime and the feature of synthetic product is larger thermostability.
Be that applying sulfonic acid ion exchange resin manufactures the technique of dihydroxyphenyl propane as in the multistage reactive system of condensation catalyst from phenol and acetone, there is many rings by product in liquid stream after synthesis, to reaction kinetics and catalyst life (because it is deposited on catalyst surface), there is effect, and reduce avtive spot thus to the accessibility of reactant.Learn unexpectedly, add phenol solution pH stablizer and can suppress secondary process, allow more long-life condensation catalyst thus, and improve the thermostability of final product.
The key element of the inventive method is the following fact:
Reaction mixture containing acetone, phenol and the reaction product between phenol with acetone contacts with ion-exchange catalyst at least two reactors until total water-content is no more than 2.5cg/g, wherein acetone and phenol are fed in reactor 1, and mix with from the post-crystallization liquor of crystallizer 8 and acetone in mixing tank 2 carry out the reaction of autoreactor 1 after mixture be fed in reactor 3
After described reaction after reactor 3, mixture mixes with a part for the phenol solution being no more than 40cg/g in mixing tank 4, described phenol solution obtains due to the contact between the dehydrating mixt containing maximum 1.0% water and ion-exchange catalyst at least one reactor 5
The phenol solution pH stablizer in fixed bed form being no more than 1.2mm from mixture after the described reaction of mixing tank 4 in adsorber 6 under the maximum temperature of 150 DEG C with the flow velocity being no more than 10m/h with the particle diameter containing carboxyl and/or hydroxyl and/or amide group contacts, until mixture reaches the pH of 5-6 after described reaction at adsorber 6
After described reaction in adsorber 6, mixture concentrates in the following manner in distillation tower 7: volatile matter is partly or entirely evaporated to the overhead product containing phenol, acetone and water that boiling point is at ambient pressure no more than 200 DEG C, and dihydroxyphenyl propane crystallization from described distillation residue;
The described phenol solution of in reactor 5 at least 60% is no more than 1.2mm in adsorber 9 under the maximum temperature of 150 DEG C with the flow velocity the being no more than 10m/h phenol solution pH stablizer in fixed bed form with the particle diameter containing carboxyl and/or hydroxyl and/or amide group contacts, until described mixture reaches the pH of 5-6 at adsorber 9, and gained solution mixes with the described overhead product containing phenol, acetone and water from distillation tower 7, and be fed in distillation tower 10
By the phenol recovery of separation in tower 10 to reactor 1, recover acetone is to reactor 1 and/or 3, and described water section is removed from described equipment with waste water formation.
Preferably, the dehydrating mixt containing maximum 1cg/g water contacts with ion-exchange catalyst in reactor 5 under the maximum temperature of 95 DEG C with the flow velocity being no more than 2.0m/h.
Preferably, reactor 1 and the reaction mixture in 3 contact with ion-exchange catalyst under maximum temperature and the flow velocity being no more than 6m/h of 85 DEG C.
Preferably, reaction mixture or dehydrating mixt can be fed to by possible demand in each reactor.
Preferably, phenol solution pH stablizer uses with the mol ratio of the hydroxyl (-OH) Yu carboxyl (-COOH) that are no more than 1:1.
Preferably, phenol solution pH stablizer is to be no more than the amide group (-CONH of 1:2
2) use with the mol ratio of carboxyl (-COOH).
example
The schematic diagram of BPA synthesis unit is shown in the accompanying drawings.
The synthesis of bis-phenol is 0.5dm comprising 3 separately
3ion exchange reaction device reactive system in carry out.Identical catalyzer is put in described reactor.
The feature of the ion-exchange catalyst of the condensation reaction being used for phenol and acetone shown by table 1.
Reactor 1 and 3 reaction mixture feed, and reactor 5 dehydrating mixt charging.Reactor 1 in continuous foundation with the reaction mixture be made up of acetone, water and phenol with the flow velocity charging of 1.0kg/h.
The composition of the reaction mixture of reactor 1 ingress and synthesis condition are shown in table 2.
The condition of BPA synthesis in table 2. reactor 1.
Due to the condensation reaction in sour environment of phenol and acetone, obtain the mixture with the composition illustrated in table 3.
The reaction mixture in table 3. reactor 1 exit.
| Parameter | Value |
| Water | 1.52 |
| Acetone | 1.12 |
| Phenol | 83.54 |
| p,p'-BP A | 12.96 |
| o,p'-BP A | 0.80 |
| Trisphenol | 0.03 |
| Other by product | 0.03 |
The reaction mixture carrying out autoreactor 1 mixes with the post-crystallization liquor from crystallizer 8, and described post-crystallization liquor is obtained by the combined method of suspension crystallization and fractional crystallization between the separation period of synthetic product p, p'-BPA isomer.Solution is being equipped with the 5.0dm of the horseshoe agitator of 120rpm and temperature adjustable plate heater within the scope of 25-100 DEG C
3mix in mixing tank.Post-crystallization liquor mixes at the temperature of 72.5 DEG C with the reaction soln carrying out autoreactor 1 in mixing tank 2, and then the gained solution obtained by mixed solution stream is cooled to 55 DEG C, and adds 80.8g acetone.After mixing thoroughly, mixture is fed in reactor 3.
Table 4 shows composition and the quantity of often kind of solution.
The solution obtained by mixed solution stream is cooled to 55 DEG C, and adds 80.8g acetone.After mixing thoroughly, mixture is fed in reactor 3.
The condition of bis-phenol synthesis in reactor 3 shown by table 5.
Meanwhile, in reactor 5, carry out the technique of being dewatered by ion-exchange catalyst.The reactor 5 dehydrating mixt charging be made up of 0.3% water and 99.70% phenol.
The condition that reactor 5 intermediate ion exchange catalysts dewaters shown by table 6.
The phenol solution carrying out autoreactor 5 is divided into two liquid streams with the ratio of 32% to 68%.The less liquid stream of 174.7g/h (0.174kg/h) mixes with solution after the reaction carrying out autoreactor 3 (2.127kg/h).Solution is at 3.0dm
3mixing tank 4 in mix at the temperature of 72 DEG C, and obtain the mixture of 2.301kg/h, described mixture is then fed in the adsorber 6 of filling with phenol solution pH stablizer.Adsorber 6 is equipped with 0.5dm
3the particle diameter containing carboxyl (-COOH) and hydroxyl (-OH) functional group be 0.2 polymer packing arriving 1.1mm.
The feature of packing material in adsorber shown by table 7.
After the reaction of in the future autoreactor 3, a part for mixture and phenol solution is directed in mixing tank 4, and then all liquid flow through the stablizer bed in adsorber 6 and filter at the temperature of the flow velocity of 4.2m/h and 72 DEG C.PH be 5.5 the mixture after adsorber 6 concentrated with the overhead product of 3.0:1 and reflux ratio in the tower 7 being filled with glass ring under the pressure of 21kPa by vacuum distilling.At fluid temperature in tower tank maintains 135 DEG C.Due to vacuum distilling, the mixture after adsorber 6 is divided into two liquid streams:
For separating of the enriched product liquid stream of p, p'-BPA isomer,
Overhead product.
Forming of the liquid stream produced by concentrated synthetic product solution shown by table 8.
Another part phenol solution (68%, 0.372kg/h) carrying out autoreactor 5 is being equipped with 0.2dm by making itself and pH stablizer
3contact in the adsorber 9 of filler and stablize.Phenol solution be stabilized in the temperature of 72 DEG C under carry out with the filler (feature of adsorber filler in table 7) identical with the filler stable for the pH of synthetic product liquid stream in adsorber 6.Adsorber 9 in continuous foundation with the flow velocity charging of 1.2m/h.PH is 5.5 and the phenol solution after adsorber 9 that flow velocity is 0.372kg/h then mixes with the overhead product (0.496kg/h) (composition of overhead product in table 8) from distillation tower 7.The mixture distillation of the 0.868kg/h that will be made up of water (5.27%), acetone (5.02%) and phenol (89.71%), consequently can by phenol and recover acetone in reactive system with water after separating reaction.Being separated in the system of two towers 10 with structured packing of acetone-water-phenol mixture is carried out, and mixture is separated into phenol and boiling part in the first tower, and then acetone is separated in another tower from acetone-water part.Composition from each liquid stream of the fractionation by distillation of acetone-water-phenol solution is illustrated in table 9.P, p'-BPA isomer (main synthetic product) is obtained by two-stage crystallization in crystallizer 8, and described two-stage crystallization is the combination of suspension crystallization and fractional crystallization.
The separation of acetone-water-phenol mixture in table 9. distillation tower 10.
| Composition (%) | Distillation feedback material | Phenol | Acetone | Distillation waste |
| Acetone | 5.02 | 99.50 | ||
| Water | 5.27 | 0.30 | 0.50 | 100* |
| Phenol | 89.71 | 99.70 | ||
| Flow velocity (kg/h) | 0.868 | 0.765 | 0.044 | 0.059 |
* phenol content is lower than 100ppm
The suspension crystallization of bisphenol a/phenol adducts uses the enriched product mixture of the 1.804kg/h illustrated in table 8 to carry out.Crystallization processes carries out in crystallizer 8.
Following liquid stream mixes at the temperature of 80 DEG C in the stirred type crystallizer with heating and cooling chuck, this make likely fine adjustment fluid temperature within the scope of 20 to 100 DEG C:
For being separated p in tower 7 under the flow velocity of 1.804kg/h, the enriched product liquid stream of p'-BPA isomer;
A part for post-crystallization liquor under the flow velocity of 0.620kg/h after the isomerization of o, p'-BPA isomer,
From the effluent of distribution fusion-crystallization under the flow velocity of 0.021kg/h.
In abundant mixing element and after obtaining homogeneous composition, the inclusion of crystallizer cools at 80 DEG C with the speed of 7 DEG C/h within the scope of 52 DEG C.Once reach the temperature of 52 DEG C, just stop the crystallization from the bisphenol a/phenol adducts of phenol solution.Bisphenol a/phenol adducts crystal is separated with post-crystallization liquor by filtering.Each use is mutually equipped with mesh size to be that the pressure filter of the dividing plate of 10 μm is separated.Filter and carry out at the temperature of 52 DEG C in inert atmosphere of nitrogen.A part of post-crystallization liquor being recovered to reactive system enters in mixing tank 2, and another part liquid (0.886kg/h) experience is concentrated and o, p'-BPA isomer to the isomerization of p, p'-BPA, and will p be rich in, the complete soln of p'-BPA isomer is recovered to the suspension crystallization stage.The adducts crystal of 0.483kg/h to be transferred in rotatory evaporator and then to melt at the temperature of 110 DEG C, and composition equalization.Thick p, p'-BPA isomer progressively distills and obtains due to adducts thermolysis and phenol at the temperature more than 120 DEG C.The distillation of phenol is carried out under 25mm Hg reduces pressure.During phenol distillation, temperature is increased to 165 DEG C with the speed of 50 DEG C/h gradually from 110 DEG C.When the phenol content in dihydroxyphenyl propane is reduced to 0.07%, stop the decomposition of adducts.The decomposition of adducts produces the crude bisphenol of 0.315kg/h, and it is then by fractional crystallization purifying in tubular crystallizer.Carry out purifying by fractional crystallization and produce final product-the have dihydroxyphenyl propane as the 0.294kg/h of parameter illustrated in table 10.
Claims (6)
1. under strongly-acid sulfonic acid ion exchange resin exists, in the condensation reaction of acetone and phenol, manufacture a method for dihydroxyphenyl propane, it is characterized in that:
The reaction mixture of the product containing acetone, phenol and the described reaction between phenol with acetone contacts with ion-exchange catalyst at least two reactors until total water-content is no more than 2.5cg/g, wherein acetone and phenol are fed in reactor (1), and mix with from the post-crystallization liquor of crystallizer (8) and acetone in mixing tank (2) carry out the reaction of autoreactor (1) after mixture be fed in reactor (3)
After described reaction after reactor (3), mixture mixes with a part for the phenol solution being no more than 40cg/g in mixing tank (4), described phenol solution obtains by making containing the dehydrating mixt being no more than 1.0% water contacts at least one reactor (5) with ion-exchange catalyst
The phenol solution pH stablizer in fixed bed form being no more than 1.2mm from mixture after the described reaction of mixing tank (4) in adsorber (6) at the temperature of maximum 150 DEG C with the flow velocity being no more than 10m/h with the particle diameter containing carboxyl and/or hydroxyl and/or amide group contacts, until mixture reaches the pH of 5-6 after described reaction at adsorber (6)
After described reaction in adsorber (6), mixture concentrates in the following manner in distillation tower (7): volatile matter is partly or entirely evaporated to the overhead product containing phenol, acetone and water that boiling point is at ambient pressure no more than 200 DEG C, and dihydroxyphenyl propane crystallization from described distillation residue
The described phenol solution of in reactor (5) at least 60% is no more than 1.2mm in adsorber (9) at the temperature of maximum 150 DEG C with the flow velocity the being no more than 10m/h phenol solution pH stablizer in fixed bed form with the particle diameter containing carboxyl and/or hydroxyl and/or amide group contacts, until described mixture reaches the pH of 5-6 at adsorber (9), and gained solution mixes with the described overhead product containing phenol, acetone and water from distillation tower (7), and be fed in distillation tower 10
The phenol recovery that will be separated in tower (10) is to reactor (1), and recover acetone is to reactor (1) and/or (3), and described water section is removed from described equipment with waste water formation.
2. method according to claim 1, is characterized in that the described dehydrating mixt containing being no more than 1cg/g water contacts with ion-exchange catalyst in reactor (5) at the temperature of maximum 95 DEG C with the flow velocity being no more than 2.0m/h.
3. method according to claim 1, is characterized in that reactor (1) and the described reaction mixture in (3) contact with ion-exchange catalyst under temperature and the flow velocity being no more than 6m/h of maximum 85 DEG C.
4. method according to claim 1, is characterized in that described reaction mixture or described dehydrating mixt can be fed to by possible demand in each reactor.
5. method according to claim 1, is characterized in that phenol solution pH stablizer uses with the mol ratio of the hydroxyl (-OH) Yu carboxyl (-COOH) that are no more than 1:1.
6. method according to claim 1, is characterized in that phenol solution pH stablizer is to be no more than the amide group (-CONH of 1:2
2) use with the mol ratio of carboxyl (-COOH).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PLP.398819 | 2012-04-16 | ||
| PL398819A PL217484B1 (en) | 2012-04-16 | 2012-04-16 | Process for preparing bisphenol A |
| PCT/PL2013/050005 WO2013157972A2 (en) | 2012-04-16 | 2013-02-07 | Method of producing bisphenol a |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104540799A true CN104540799A (en) | 2015-04-22 |
| CN104540799B CN104540799B (en) | 2017-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380031512.8A Expired - Fee Related CN104540799B (en) | 2012-04-16 | 2013-02-07 | Method of producing bisphenol a |
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| Country | Link |
|---|---|
| CN (1) | CN104540799B (en) |
| DE (1) | DE112013002048T5 (en) |
| PL (1) | PL217484B1 (en) |
| RU (1) | RU2619461C2 (en) |
| WO (1) | WO2013157972A2 (en) |
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| DE102016116078B3 (en) | 2016-08-29 | 2018-01-04 | Epc Engineering Consulting Gmbh | Process for producing a polycarbonate using a stripping device |
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|---|---|---|---|---|
| US4950806A (en) * | 1988-02-22 | 1990-08-21 | Mitsui Toatsu Chemicals, Inc. | Process for crystallizing adduct of bisphenol A with phenol |
| WO2000035847A1 (en) * | 1998-12-15 | 2000-06-22 | General Electric Company | Process for the manufacture of bisphenol-a |
| CN1300273A (en) * | 1999-04-13 | 2001-06-20 | 出光石油化学株式会社 | Process for the preparation of bisphenol A |
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|---|---|---|---|---|
| US3326986A (en) * | 1965-01-22 | 1967-06-20 | Dow Chemical Co | Process for purifying 4, 4'-isopropylidenediphenol |
| JPS5764519A (en) | 1980-10-08 | 1982-04-19 | Nippon Synthetic Chem Ind Co Ltd:The | Process for film forming of ethylene-vinyl acetate copolymer saponified matter |
| CS272518B1 (en) | 1988-12-15 | 1991-02-12 | Wiesner Ivo | Thermooxidatively stabilized diane |
| JPH08333290A (en) | 1995-06-12 | 1996-12-17 | Mitsubishi Chem Corp | Production of bisphenol a |
| PL181992B1 (en) | 1996-01-10 | 2001-10-31 | Inst Ciezkiej Syntezy Orga | Method of processing high-boiling by-products from the bisphenol a production process |
| US5705714A (en) | 1996-07-01 | 1998-01-06 | General Electric Company | Removal of metals and color bodies from chemically recycled bisphenol-A |
| US6133486A (en) | 1998-12-30 | 2000-10-17 | General Electric Company | Phenol recovery from BPA process waste streams |
| JP3903634B2 (en) * | 1999-03-31 | 2007-04-11 | 三菱化学株式会社 | Method for producing bisphenol A |
| RU2195444C1 (en) * | 2001-06-15 | 2002-12-27 | ЗАО Стерлитамакский нефтехимический завод | Space-hindered bis-phenol production process |
| US6858759B2 (en) * | 2002-12-20 | 2005-02-22 | General Electric Company | Process for manufacture of bisphenols |
| EP1683779A4 (en) * | 2003-11-13 | 2007-08-29 | Mitsubishi Chem Corp | Process for producing bisphenol a |
-
2012
- 2012-04-16 PL PL398819A patent/PL217484B1/en unknown
-
2013
- 2013-02-07 CN CN201380031512.8A patent/CN104540799B/en not_active Expired - Fee Related
- 2013-02-07 RU RU2014145957A patent/RU2619461C2/en not_active IP Right Cessation
- 2013-02-07 DE DE112013002048.3T patent/DE112013002048T5/en not_active Ceased
- 2013-02-07 WO PCT/PL2013/050005 patent/WO2013157972A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4950806A (en) * | 1988-02-22 | 1990-08-21 | Mitsui Toatsu Chemicals, Inc. | Process for crystallizing adduct of bisphenol A with phenol |
| WO2000035847A1 (en) * | 1998-12-15 | 2000-06-22 | General Electric Company | Process for the manufacture of bisphenol-a |
| CN1300273A (en) * | 1999-04-13 | 2001-06-20 | 出光石油化学株式会社 | Process for the preparation of bisphenol A |
Also Published As
| Publication number | Publication date |
|---|---|
| PL217484B1 (en) | 2014-07-31 |
| RU2619461C2 (en) | 2017-05-16 |
| WO2013157972A3 (en) | 2014-07-24 |
| WO2013157972A2 (en) | 2013-10-24 |
| DE112013002048T5 (en) | 2015-03-05 |
| CN104540799B (en) | 2017-05-24 |
| PL398819A1 (en) | 2013-10-28 |
| RU2014145957A (en) | 2016-06-10 |
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