GB1565667A - Deculouration of bipshenol-a recycle stream with cation exchange resin - Google Patents
Deculouration of bipshenol-a recycle stream with cation exchange resin Download PDFInfo
- Publication number
- GB1565667A GB1565667A GB3918676A GB3918676A GB1565667A GB 1565667 A GB1565667 A GB 1565667A GB 3918676 A GB3918676 A GB 3918676A GB 3918676 A GB3918676 A GB 3918676A GB 1565667 A GB1565667 A GB 1565667A
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- GB
- United Kingdom
- Prior art keywords
- phenol
- water
- mother liquor
- recycle stream
- bisphenol
- 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.)
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Classifications
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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
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) DECOLORATION OF BISPHENOL-A RECYCLE
STREAM WITH CATION EXCHANGE RESIN
(71) We, UNION CARBIDE CORPORATION, a Corporation organized and existing under the laws of the State of New York, United States of America, of 270 Park Avenue, New York, State of New York 10017, United States of America, (assignee of STEPHEN HOWARD MASON; and FREDERICK MILLER
KONRAD), do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The invention relates to a process for reducing the content of color bodies in 4,4'-bisphenol-A recycle stream by contacting all or part of the bisphenol-A process mother liquor recycle stream with an acidic cation exchange resin which is periodically reactivated by washing cloth a phenol/water mixture.
2,2-Bis(4-hydroxyphenyl)propane ("4,4'-bisphenol-A") is produced by reacting a stoichiometric excess of phenol with acetone in the presence of an acidic catalyst. For instance, see F.N. Apel et al., U.S. Patent No. 3,049,569, and Farnham et al, U.S. Patent No. 3,242,219, which describe processes for producing 4,4'bisphenol-A utilizing an acidic cation exchange resin as the acidic catalyst. The effluent from the phenol/acetone reaction contains unreacted starting materials, 4,4'-bisphenol-A, water, and by-products. After removal of volatile materials (e.g., acetone, water, and some phenol), the effluent is cooled to about 400-500C. to form a crystalline 1:1 (molar) adduct of phenol and 4,4'-bisphenol-A. The crystalline adduct is then separated from the mother liquor and is processed further to remove the phenol and recover substantially pure 4,4'-bisphenol-A. After separation from the adduct, the mother liquor is recycled. The mother liquor contains about 80 weight per cent phenol, plus 4,4'-bisphenol-A and impurities.
The principal component of the impurities is 2,4'-bisphenol-A. If 2,4'-bisphenol-A were the only impurity, all of the mother liquor could be recycled, because the principal reaction of phenol with acetone forms an equilibrium mixture of the 4,4'- and 2,4'-isomers. There would then be no net loss of raw material to by-products. However, a small but significant proportion of other byproducts is also formed. These other by-products include trisphenols, higher polyphenols, Dianin's compound, and a very small proportion of highly colored compounds characterized by intense absorption of ultra-violet light. Dianin's compound is a material having the following formula:
If all of the mother liquor were recycled, the concentration of these materials (especially the highly colored compounds) in the process stream would gradually build up to an unacceptable level. In some processes, therefore, a portion of the mother liquor is continuously drawn off or purged. The purged mother liquor is subjected to evaporation to recover most of the phenol contained therein, and the remaining material is discarded. This represents a raw material loss of the order of 0.1 pound per pound of product.
An improvement wherein much of the purged mother liquor can be reclaimed is described in Freudewald, British Patent No. 1,340,869. In accordance with
Freudewald's process, the purged mother liquor is subjected to elevated temperature in the presence of an alkaline catalyst. Much of the bisphenols and other impurities in the mother liquor are thereby cleaved to form phenol and paraisopropenyl-phenol ("IPP"), with only a small amount of unusable residue being formed. The phenol and IPP cleavage products (including IPP dimer) are processed in a reactor wherein the phenol and IPP or IPP dimer combine in the presence of acid catalyst to form 4,4'-bisphenol-A. This stream is recombined with the mother liquor recycle stream. Therefore, in accordance with Freudewald's improvement, some of the residue from the purged mother liquor that had therefore been discarded, is recovered. The raw material loss is reduced to the order of 0.05 pound per pound of product.
It is characteristic of both of the above-described modes of operating the bisphenol-A process that a certain percentage of the raw materials must be discarded in order to avoid build-up of highly colored compounds or color bodies.
This is true regardless of the grade of 4,4'-bisphenol-A being produced. Thus, while epoxy resin grade 4,4'-bisphenol-A can tolerate higher proportions of the 2,4'isomer, trisphenols, etc., than polycarbonate grade, color bodies are undesirable in both. Therefore, even though the amount of color bodies in the process stream is quite small, an unavoidable loss of raw material in an amount much greater than the proportion of color bodies, must be incurred in order to prevent the production of a discolored product. Obviously, a means for selectively removing the color bodies from the 4,4'-bisphenol-A process stream would be desirable as a means for reducing the loss of raw material.
In accordance with the present invention, a process is provided for removing color bodies in 4,4'-bisphenol-A process recycle stream, wherein a stoichiometric excess of phenol is reacted with acetone in a reaction mixture containing an acid catalyst to produce a product mixture containing phenol and 4,4'-bisphenol-A, wherein said product mixture is separated into a 4,4'-bisphenol-A/phenol adduct and a mother liquor recycle stream, wherein said mother liquor recycle stream is recycled to said reaction mixture, wherein at least a portion of said mother liquor recycle stream is contacted with an adsorbent comprising a substantially insoluble acidic cationic exchange resin for a period of time and at a temperature sufficient to reduce the content of color bodies contained in said mother liquor recycle stream, prior to recycling said mother liquor to said reaction mixture, wherein said adsorbent is periodically reactivated by washing with a phenol/water mixture to remove adsorbed color bodies therefrom, and wherein the water content of said adsorbent is substantially in equilibrium with the water content of said mother liquor recycle stream.
An understanding of the invention will be apparent from the following detailed description and the accompanying drawings, in which the sole Figure is a schematic flow diagram illustrating two embodiments of the invention.
Referring now to the drawing, a stoichiometric excess of phenol and acetone are fed to a reactor 12 that is maintained at a temperature of, for instance 65"- 95"C., and which contains an acid catalyst such as sulfonated styrenedivinylbenzene ion exchange resin. In the reactor 12, the reaction of phenol with acetone to produce 4,4'-bisphenol-A occurs. The product stream flowing from the reactor 12 contains phenol, 4,4'-bisphenol-A, some unreacted acetone, water, and by-products. The product stream flows from the reactor 12 to a dehydrator 14, in which the acetone, water, and some of the phenol are stripped from the product stream. The dehydrated product stream flows from the dehydrator 14 to a crystallizer 16, in which 4,4'-bisphenol-A/phenol adduct crystals are precipitated by cooling. The slurry of mother liquor and adduct crystals flows from the crystallizer to a solid-liquid separator such as a centrifuge 18, in which the mother liquor and adduct crystals are separated. The 4,4'-bisphenol-A product is recovered from the adduct crystals by known techniques (not shown). The mother liquor flows from the centrifuge 18 to a mother liquor storage container 22, prior to being recycled to the reactor 12. At least a portion of the mother liquor flowing from the centrifuge 18 may be introduced into a purge recovery reactor 20, in which it is subjected to elevated temperature (e.g., 1000 to 3000C., and preferably 1500 to 250"C.) in the presence of a base catalyst, to cleave the bisphenols and other polyphenols present in the mother liquor to phenol and IPP, including IPP dimer. The phenol and IPP products of the cleavage reaction are continuously removed from the purge recovery reactor 20, as by distillation, and the cleavage reaction product stream 21 is returned to the mother liquor recycle stream 19.
Before being recycled to the reactor 12, at least a portion of the mother liquor recycle stream 19 flows from the mother liquor storage container 22 to an adsorption column 24, in which it is contacted with an acidic cation exchange resin, under conditions that will be more fully described below. In the adsorption column 24, color bodies that are present in the mother liquor recycle stream 19 are removed. In the Figure, the adsorption column 24 is located in the flow stream between the mother liquor storage 22 and the reactor 12. Alternatively, an adsorption column 24a can be located between the centrifuge 18 and the mother liquor storage 22, where it can receive all or some of that portion of the mother liquor recycle stream 19a that did not pass through the purge recovery reactor 20.
In some cases, as when making epoxy resin grade 4,4'-bisphenol-A, the purge
recovery reactor 20 can be by-passed altogether.
The acidic cation exchange resin employed in the invention is a macroreticular
cation exchange resin in the acid form. For instance, sulphonated divinylbenzene
styrene copolymers are illustrative of useful ion exchange resins. The ion exchange
resin should be substantially anhydrous. That is, the water content of the ion
exchange resin should be substantially in equilibrium with the water content of the
mother liquor. Thus, when the water content of the mother liquor is about 2 weight
per cent, the ion exchange resin should contain not more than about 5 to 10 weight
per cent water.
The temperature in the adsorption column is not narrowly critical.
Temperatures within the range of from 40 to 150"C., and preferably from 400 to 800 C., are usually employed. At temperatures below about 40"C., the phenol in the mother liquor may freeze, and at temperatures above about 1500C., the ion exchange resin may become unstable.
The throughput rate of the mother liquor recycle stream through the adsorption column is also not narrowly critical. For instance, the throughput rate
can be up to about 15 ion exchange resin bed volumes per hour. The preferred throughput rate is from about 1 to about 3 bed volumes per hour.
The adsorbed color bodies can be desorbed from the acidic cation exchange resin bed by a phenol/water wash. The phenol/water wash can contain from 2 to 70, and preferably from 20 to 50, weight per cent water.
The present invention will now be further described by way of the following
Examples.
In the Examples below, the content of color bodies in the mother liquor - recycle stream was measured as the absorbance of an ultraviolet wave length of 350 nm (microns). The procedure used for measuring the absorbance was the following:
1. Purpose
la This method is used to obtain an absorbance at 350 nm of bisphenol-A process samples.
2. Apparatus
2a UV Spectrophotometer (Bausch and Lomb Spectronic 505, or equivalent), capable of being used with 10-centimeter cells. ("Spectronic" is a Trade Mark).
2b A matched pair of cylindrical silica cells with 10.0 centimeter path length.
2c Analytical balance.
2d Erlenmeyer flasks, glass stoppered, 250 milliliters.
3. Reagents
3a Methanol, reagent grade, suitable for spectrophotometry.
4. Procedure
4a. The weight of sample used for the determination is dependent on the source of the sample. A 1.001t0.01 gram sample is used for samples from the reaction system, dehydrator, crystallizer, mother liquor recycle stream, or purge
pl it. A 10.0+0.1 gram sample is used for samples from anywhere in the process
a ,r the crystallizer through to final product.
> 4b Using an analytical balance, add the appropriate weight (see 4a) of process
Sample to a 250 millimeter Erlenmeyer flask. To 1 gram samples, add 110 milliliters of methanol; to 10 gram samples 110 milliliters of methanol: Mix thoroughly.
4c Fill two clean 10.0-centimeter matched silica cells with methanol and place
them in the sample and reference beams of the spectrophotometer.
4d. Set the wavelength of the spectrophotometer to 350 nm and, after waiting 2
minutes for equilibration, zero the instrument.
4e Remove the cell from the sample compartment of the spectrophotometer
and discard the methanol.
4f Fill the cell with sample solution and place back into the sample
compartment of the spectrophotometer.
4g Allow 2 minutes for equilibration, then measure the absorbance of the
sample solution at 350 nm versus methanol as reference either by recording at the
fixed wavelength or by scanning from 320360 nm.
4h Remove the sample cell, discard the solution, and clean the cell thoroughly.
Fill the cell once again with methanol and recheck the instrument zero at 350 nm.
If original zero setting is maintained use absorbance value recorded in 4g. If zero
has changed, repeat the measurement beginning with 4e.
5. Calculations
A,xlO
4a A*=
S.W.
where:
A*=an absorbance calculated on the basis of a concentration of 10 grams of
sample in 100 milliliters of methanol.
As=observed absorbance of the methanolic solution of the sample at 350 nm.
S.W.=sample weight in grams.
6. Report
6a Report A* as the absorbance of the sample.
The Examples which follow illustrate the invention. (All percentages are by weight, unless otherwise specified).
EXAMPLE 1
A 25 millimeter diameter glass column was charged with 210 milliliters of phenol-swollen, macroporous, sulfonated styrene-divinylbenzene ion-exchange resin beads of 1-50 mesh size (standard U.S. Sieve Series). The column was jacketed for heating with tempered water. The resin was washed with a solution of 20 weight per cent water dissolved in pure phenol. A total of 16 column volumes of wash solvent were pumped through the hydraulically full resin bed downflow at 70 grams/hour and 70"C. The last effluent had an absorbance of 0.5 at 350 nm.
measured on a solution of 10 grams effluent diluted with 100 milliliters of methanol
in a 10 centimeter cell.
After washing, the resin column was made anhydrous by purging with 10
column volumes of anhydrous phenol at 70 grams/hour and 70"C.
An anhydrous mother liquor (taken from the centrifuge filtrate) which originated from the cation-exchange resin catalyzed condensation of phenol and acetone was used to test the adsorptive capacity of the washed ion-exchange resin described above. This mother liquor had an absorbance of 5.0 and the following
composition: 84 per cent phenol, 10 per cent 4,4'-bisphenol-A, and 6 per cent impurities.
Sixty column volumes of mother liquor were pumped downflow through the
ion-exchange resin at 80 grams/hour and 70"C. An overall absorbance reduction of
30 per cent was obtained as shown in Table I.
TABLE I
Reduction in 350 Absorbance of Bisphenol-A Mother Liquor by
Ion-Exchange Resin Treatment
Absorbance, 10 grams
Diluted With
100 ml.
Methanol in 10 cm.
Cell At 350 nm.
Feed 5.0
initial Effluent 2.0
Final Effluent 4.5
Composite of Total Effluent 3.5
The loaded ion-exchange resin was washed under the same conditions described above with 8 column volumes of wet phenol (20 per cent water) to desorb the chromophoric impurities. The absorbance of the total wash effluent was equivalcnt to 18.0 on the basis described above.
EXAMPLE 2
100 Grams of the anhydrous (15 X" water by Karl Fisher) acidic cation exchange resin described in Example I was charged to a l-inch diameter glass column. The resin was washed with 1000 grams of phenol (80 /")/water (20 /") mixture at 700C. at 600 grams/hour. The resin was then dried by passing 2000 grams of anhydrous phenol ( < 0.1% H2O) through the bed at 600 grams/hour. Sixty bed volumes (210 milliliters/bed volume) of 4,4'-bisphenol-A process mother liquor having an absorbance of 2.5 were treated by passing it downflow through the bed at a rate of 600 milliliters per hour. The initial effluent had an absorbance of 1.3final effluent 2.0. Absorbance of total effluent 1.6 or a reduction of 36%.
Table Il shows the rate that the absorptivity of the acidic cation exchange resin depreciates as the feed is passed through the adsorption bed: TABLE 11 Adsorption of Color with Adsorbent
Cumulative Absorbance Absorbance
Feed of Feed of Effluent
(ml) (350 nm) (350 nm) AA
620 2.5 1.3 1.2
3100 25 1.3 1.2
5580 2.5 1.6 0.9
8060 2.5 1.6 0.9
10540 2.5 1.7 0.8
13020 2.5 2.0 0.5
The resin was washed with 1000 grams of phenol (80%)/water (20%) mixture passed downflow through the bed at 600 grams/hour. The bed was then dried by passing 1000 grams of anhydrous phenol down flow through the bed at 600 grams/hour. Thirty-one bed volumes of regular 4,4'-bisphenol-A process mother liquor with an absorbance of 2.7 was treated by passing it downflow at 600 grams/hour. Absorbance of initial effluent was 1.5 - final effluent 2.0 -- Total effluent 1.6 for a reduction of 41%
Table Ill shows the results of the second adsorption run after the cationexchange resin was regenerated as described above. A comparison of Table III with Table II indicated that the ion-exchange resin adsorptive capacity was completely restored by the regeneration step.
TABLE III
Adsorption of Color with Regenerated Adsorbent
Cumulative Adsorbance Absorbance
Feed of Feed of Effluent
(ml) (350 nm) (350 nm) AA
600 2.7 1.5 1.2
1200 2.7 1.4 1.3
3000 2.7 1.5 1.2
3600 2.7 1.5 1.2
4800 2.7 1.7 1.0
6000 2.7 1.8 0.9
6600 2.7 2.0 0.7
EXAMPLE III
In this experiment, several one-gram samples of the acidic cation exchange resin described in Example 1 were saturated with color-bearing impurities. Each sample was then soaked in four grams of solvent at 700 C. for 20 hours. The ratio of phenol to water was varied over a wide range as shown in the table below.
Immediately after soaking the solvent was decanted from the resins and its absorbance in the U.V. and visible light region was measured by the procedure described above. The data indicate maximum color desorption when 2030% by weight of water is in the solvent.
TABLE IV
Desorption of 1 Gram Resin with 4 Grams Solvent
Phenol Water Absorbance at Absorbance at
Batch No. (wt.%) (wt.%) 350 nm 470 nm
1 100 - 5.4 .65
2 99 1 7.7 .90
3 98 2 7.6 .92
4 96 4 8.4 1.2
5 92 8 10.7 1.7
6 84 16 15.8 4.1
7 78 22 22.8 10.1
8 70 30 26.9 7.6
9 68 32 20.5 6.5
10 32 64 15.0 4.4
After decantation and prior to measurement of absorbance the solvent from batch 10 was allowed to cool to 250C. It separated into two liquid layers - an upper aqueous layer containing 10% phenol, and a lower layer containing 70 , phenol. The upper aqueous layer was clear and colorless whereas the lower layer was a deep red-brown color. This indicated that the solubility of color bearing impurities in water is low.
The temperature at which the resin bed is washed with the phenol/water mixture is not narrowly critical. As a practical matter, the temperature would not normally be above the boiling point of water. It would be undesirable to carry out the wash above about 1200C. because desulfonation of the resin could occur. The minimum temperature would be the freezing point of the mixture.
Similarly, the quantity of the phenol/water mixture needed is not narrowly critical. The minimum amount needed is of the order of 1 to 1-1/2 adsorbent bed volumes. The maximum is dictated by economics, and other similar factors.
The contact time with the wash is also not critical. Ordinarily, a minimum contact time of about I hour will be used, although longer contact times can be used, if desired.
WHAT WE CLAIM IS:
1. A process for removing color bodies from 4,4'-bisphenol-A process recycle stream wherein a stoichiometric excess of phenol is reacted with acetone in a reaction mixture containing an acid catalyst to produce a product mixture
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (10)
1 100 - 5.4 .65
2 99 1 7.7 .90
3 98 2 7.6 .92
4 96 4 8.4 1.2
5 92 8 10.7 1.7
6 84 16 15.8 4.1
7 78 22 22.8 10.1
8 70 30 26.9 7.6
9 68 32 20.5 6.5
10. A process for removing colour bodies from 4,4'-bisphenol-A process recycle stream as defined in Claim 1 and substantially as hereinbefore described with reference to Example II or Example III.
10 32 64 15.0 4.4
After decantation and prior to measurement of absorbance the solvent from batch 10 was allowed to cool to 250C. It separated into two liquid layers - an upper aqueous layer containing 10% phenol, and a lower layer containing 70 , phenol. The upper aqueous layer was clear and colorless whereas the lower layer was a deep red-brown color. This indicated that the solubility of color bearing impurities in water is low.
The temperature at which the resin bed is washed with the phenol/water mixture is not narrowly critical. As a practical matter, the temperature would not normally be above the boiling point of water. It would be undesirable to carry out the wash above about 1200C. because desulfonation of the resin could occur. The minimum temperature would be the freezing point of the mixture.
Similarly, the quantity of the phenol/water mixture needed is not narrowly critical. The minimum amount needed is of the order of 1 to 1-1/2 adsorbent bed volumes. The maximum is dictated by economics, and other similar factors.
The contact time with the wash is also not critical. Ordinarily, a minimum contact time of about I hour will be used, although longer contact times can be used, if desired.
WHAT WE CLAIM IS:
1. A process for removing color bodies from 4,4'-bisphenol-A process recycle stream wherein a stoichiometric excess of phenol is reacted with acetone in a reaction mixture containing an acid catalyst to produce a product mixture
containing phenol and 4,4'-bisphenol-A, wherein said product mixture is separated into a 4,4'-bisphenol-A/phenol adduct and a mother liquor recycle stream, wherein said mother liquor recycle stream is recycled to said reaction mixture, wherein at least a portion of said mother liquor recycle stream is contacted with an adsorbent comprising a substantially insoluble acidic cationic exchange resin for a period of time and at a temperature sufficient to reduce the content of color bodies contained in said mother liquor recycle stream, prior to recycling said mother liquor to said reaction mixture, wherein said adsorbent is periodically washed with a phenol/water mixture to remove adsorbed color bodies therefrom, and wherein the water content of said adsorbent is substantially in equilibrium with the water content of said mother liquor recycle stream.
2. A process as claimed in Claim 1, wherein said mother liquor recycle stream is contacted with said acidic cationic exchange resin at a temperature within the range of from 40 to 1500C.
3. A process as claimed in Claim 2, wherein the temperature is within the range of from 40 to 800C.
4. A process as claimed in any one of Claims I to 3, wherein said acidic cationic exchange resin is a sulphonated divinylbenzene-styrene copolymer.
5. A process as claimed in any one of Claims 1 to 4, wherein said acidic cationic exchange resin is substantially anhydrous.
6. A process as claimed in any one of Claims 1 to 5, wherein the phenoi/water mixture contains from 2 to 70 weight per cent water.
7. A process as claimed in Claim 6, wherein the phenol/water mixture contains from 20 to 50 weight per cent water.
8. A process as claimed in Claim 7, wherein the phenol/water mixture contains from 20 to 30 weight per cent water.
9. A process for removing colour bodies from 4,4'-bisphenol-A process recycle stream as claimed in Claim 1 and substantially as hereinbefore described with reference to Example I.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US61602675A | 1975-09-23 | 1975-09-23 | |
US69672676A | 1976-06-16 | 1976-06-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1565667A true GB1565667A (en) | 1980-04-23 |
Family
ID=27087657
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB3918676A Expired GB1565667A (en) | 1975-09-23 | 1976-09-22 | Deculouration of bipshenol-a recycle stream with cation exchange resin |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS5242861A (en) |
DE (1) | DE2642596A1 (en) |
FR (1) | FR2325627A1 (en) |
GB (1) | GB1565667A (en) |
IT (1) | IT1071481B (en) |
NL (1) | NL7610522A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4954661A (en) * | 1988-03-11 | 1990-09-04 | Mitsui Toatsu Chemicals, Inc. | Process for preparing high-purity bisphenol A |
EP1149816A1 (en) * | 1999-12-03 | 2001-10-31 | Mitsui Chemicals, Inc. | High-quality bisphenol a and process for producing the same |
US6680270B2 (en) | 2001-04-24 | 2004-01-20 | General Electric Company | Regeneration of catalysts used in the manufacture of bisphenols |
US7696388B2 (en) | 2008-07-09 | 2010-04-13 | Sabic Innovative Plastics Ip B.V. | Process for producing bisphenol-A |
CN104379546A (en) * | 2012-06-28 | 2015-02-25 | 出光兴产株式会社 | Process for producing bisphenol A |
US11312822B2 (en) | 2017-01-17 | 2022-04-26 | Sabic Global Technologies B.V. | Reduced color polycarbonate compositions, methods of manufacture, and articles thereof |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4051079A (en) * | 1976-06-22 | 1977-09-27 | Union Carbide Corporation | Regeneration of acidic cation exchange resin using acidified phenol-water mixture |
EP0001863B1 (en) * | 1977-11-09 | 1981-07-15 | Shell Internationale Researchmaatschappij B.V. | Preparation of bisphenols |
JPS6079907U (en) * | 1983-11-04 | 1985-06-03 | 株式会社クボタ | Line drawing marker structure of riding rice transplanter |
US4636393A (en) * | 1984-11-28 | 1987-01-13 | Campbell Soup Company | Method of processing meat for inclusion in high acid type foods and product thereof |
JPH01211544A (en) * | 1988-02-19 | 1989-08-24 | Mitsui Toatsu Chem Inc | Production of bisphenol a |
JPH0365408U (en) * | 1989-10-30 | 1991-06-26 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2222607A1 (en) * | 1972-05-09 | 1973-11-22 | Rheinstahl Ag | RING ROLLING MILL |
-
1976
- 1976-09-22 GB GB3918676A patent/GB1565667A/en not_active Expired
- 1976-09-22 FR FR7628514A patent/FR2325627A1/en not_active Withdrawn
- 1976-09-22 DE DE19762642596 patent/DE2642596A1/en not_active Ceased
- 1976-09-22 NL NL7610522A patent/NL7610522A/en not_active Application Discontinuation
- 1976-09-22 IT IT2751276A patent/IT1071481B/en active
- 1976-09-22 JP JP11316276A patent/JPS5242861A/en active Granted
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4954661A (en) * | 1988-03-11 | 1990-09-04 | Mitsui Toatsu Chemicals, Inc. | Process for preparing high-purity bisphenol A |
EP1149816A1 (en) * | 1999-12-03 | 2001-10-31 | Mitsui Chemicals, Inc. | High-quality bisphenol a and process for producing the same |
EP1149816A4 (en) * | 1999-12-03 | 2004-04-07 | Mitsui Chemicals Inc | High-quality bisphenol a and process for producing the same |
US6680270B2 (en) | 2001-04-24 | 2004-01-20 | General Electric Company | Regeneration of catalysts used in the manufacture of bisphenols |
US7696388B2 (en) | 2008-07-09 | 2010-04-13 | Sabic Innovative Plastics Ip B.V. | Process for producing bisphenol-A |
CN104379546A (en) * | 2012-06-28 | 2015-02-25 | 出光兴产株式会社 | Process for producing bisphenol A |
CN104379546B (en) * | 2012-06-28 | 2018-10-09 | 出光兴产株式会社 | Process for producing bisphenol A |
US11312822B2 (en) | 2017-01-17 | 2022-04-26 | Sabic Global Technologies B.V. | Reduced color polycarbonate compositions, methods of manufacture, and articles thereof |
Also Published As
Publication number | Publication date |
---|---|
DE2642596A1 (en) | 1977-04-07 |
JPS5534779B2 (en) | 1980-09-09 |
IT1071481B (en) | 1985-04-10 |
NL7610522A (en) | 1977-03-25 |
JPS5242861A (en) | 1977-04-04 |
FR2325627A1 (en) | 1977-04-22 |
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