WO2000040531A1 - Phenol recovery from bpa process waste streams - Google Patents
Phenol recovery from bpa process waste streams Download PDFInfo
- Publication number
- WO2000040531A1 WO2000040531A1 PCT/US1999/024872 US9924872W WO0040531A1 WO 2000040531 A1 WO2000040531 A1 WO 2000040531A1 US 9924872 W US9924872 W US 9924872W WO 0040531 A1 WO0040531 A1 WO 0040531A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phenol
- bisphenol
- sulfonic acid
- ketone
- aromatic sulfonic
- Prior art date
Links
- 0 *c1cc(*)c(*)c(O)c1* Chemical compound *c1cc(*)c(*)c(O)c1* 0.000 description 2
Classifications
-
- 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
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
Definitions
- the invention relates to processes for synthesis of bisphenols and more particularly to recovery of phenol from waste streams, the effluent of bisphenol synthesis.
- Bisphenols are commercially prepared by condensing 2 moles of phenol with a mole of ketone in the presence of an acid catalyst. The phenol is present in a molar excess of the stoichiometric requirement. During the condensation, a number of isomeric forms of the product bisphenol are formed which are contaminants of the desired bisphenol.
- the second commercial synthesis reaction consists of passing phenol
- bisphenol include costly multi-step purification procedures entailing distillations, crystallizations, solvent extractions, evaporations and like procedures. Where bisphenol is separated from the contaminants and purified by crystallization, a mother liquor is obtained which contains (after dewatering) lower boiling reaction by-products, bisphenol and higher boiling
- Patent 4,327,229 "it has been calculated that substantial amounts of phenol and re-usable bisphenol-A values can be derived from the tars and liquors derived from the process of making bisphenol-A, and there still remains the need to treat the tars and residues resulting from the initial reaction of the phenol and acetone to recover all useful products in order to enhance the value of the bisphenol-A process.”
- the present invention is an improvement in the utilization of the tar residues of the commercial bisphenol process, using it as a feedstock to recover phenols.
- the process comprises cracking the tars to obtain phenols.
- a preferred embodiment of the present invention is an improvement in the utilization of the tar residues of the commercial acidic ion exchange resin catalyst bisphenol process wherein phenol, acetone and recycled by-product are passed through a stationary bed of the ion exchange resin which is used as a feedstock to recover phenols.
- the invention comprises a process for the preparation of phenols 5 which comprises; providing a tarry residue of higher boiling by-products of the condensation of a phenol and a ketone obtained by distillation/ evaporation of a mother liquor obtained after separation of bisphenol; cracking the tarry residue with a catalytic proportion of an aromatic l o sulf onic acid; and separating the resulting phenols.
- the method of the present invention provides an economical means to recover bisphenol-A and other valuable residues from admixture with contaminant materials resulting from the bisphenol-A preparative process in effluent streams, employing improved cracking procedures to convert bisphenol-A back to phenol and acetone.
- a preferred embodiment of the present invention provides an economical means to recover bisphenol-A and other valuable residues from admixture with contaminant materials resulting from the bisphenol-A preparative process in effluent streams, employing improved cracking procedures to convert bisphenol-A back to phenol and acetone.
- method of the present invention provides an economical means to recover bisphenol-A and other valuable residues from admixture with contaminant materials resulting from the acidic ion exchange resin catalyst process for producing bisphenol-A in effluent streams, employing the improved cracking procedures to convert bisphenol-A back to phenol and acetone for recycling
- reaction step comprising reacting phenol and acetone.
- the commercially important processes for preparing bisphenol-A comprise condensation of 2 moles of phenol with a mole of acetone in the presence of an acid catalyst and a stoichiometric excess of the phenol reactant; see for example the U.S. Patents 4,766,254 and 4,847,433 mentioned above.
- the reaction zone effluent is conventionally continuously withdrawn and fed to a system for separation of the desired product bisphenol-A. As mentioned earlier, this effluent comprises unreacted phenol, unreacted acetone, acid residues of the catalyst, water and by-products and isomers of bisphenol-A in admixture with the desired bisphenol-A.
- the isomers of interest are position isomers wherein the hydroxy groups are other than in the p-configuration.
- the effluent may be treated first by cooling to precipitate a crystalline 1:1 adduct of bisphenol-A with phenol, and separating the solid adduct.
- the remaining mother liquor generally contains appreciable quantities of residual bisphenol-A and valuable isomers thereof. It is this liquor which may provide a starting material for the method of the present invention.
- At least a portion of the mother liquor may be treated by heating to a temperature within the range of from about 55° C. to 95° C. to promote isomerization of related isomers to bisphenol-A or recycled through the reaction zone described above for subsequent condensations in the process line.
- a portion of the mother liquor may also be treated with ion-exchange resins, filtered, distilled to remove phenol and solvents.
- the feedstock employed in the process of the present invention is obtained from a portion of the mother liquor, distilled/ evaporated to leave a tarry residue of higher boiling by-products of the ketone-phenol condensation, after separation (usually by crystallization and filtration) of the desired bisphenol.
- the mother liquor is purged from the bisphenol-A synthesis line and subjected to distillation/ evaporation under progressively (sequentially) higher vacuum/ temperature conditions in order to separate the stream into four fractions.
- a first distillation column is operated under vacuum and temperature conditions to remove an overhead fraction containing relatively pure phenol (e.g.
- the bottoms of the first column are fed to a second distillation column.
- This second column operates under reduced pressures and elevated temperature conditions which remove a colored "light" fraction consisting mainly of residual isomers of bisphenol-A and Chroman along with other byproducts with known and unknown chemical structure. This lights fraction can be purged from the plant and discarded, or subjected to additional recovery by this or other processes.
- the bottoms of the second column are fed to a third column.
- the overheads of this third column typically contain 60-90% pure bisphenol-A depending on the temperature and pressure conditions used.
- the bottoms of the third column contain "heavies" or tars which are purged from the process and used as the feedstock in the present invention.
- the mother liquor is distilled in a vacuum distillation column and is removed as the bottom product.
- This bottom product is recycled to the bisphenol reactor but a small purge stream is fed to a second vacuum distillation column (phenol recovery column).
- the bottom product of this second vacuum distillation column is the tarry feed to the conversion section where, employing the process of the present invention, heavies are converted to, among other compositions, phenols.
- the phenols thus formed are recovered through recycling to the phenol recovery column again.
- the mother liquor purge stream is treated in any suitable distillation unit with one of the end products being a tarry bottom stream, this stream being the feed to the conversion treatment according to the present invention wherein the tarry feedstock is cracked with an aromatic sulfonic acid catalyst.
- Aromatic sulfonic acid catalysts are a well known class of compounds as are methods of their preparation.
- Aromatic sulfonic acids may be represented by the general formula RC6H4SO3H in which R may be in any position in the phenyl ring and a preferred class may be represented by the general formula: wherein R represents hydrocarbyl having 1 to 25 carbon atoms, inclusive.
- hydrocarbyl as used herein means the monovalent moiety obtained upon removal of a hydrogen atom from a parent hydrocarbon.
- Representative of hydrocarbyl is alkyl of 1 to 25 carbon atoms, inclusive, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, decyl, dodecyl, octadecyl, nonodecyl, eicosyl, heneicysyl, docosyl, tricosyl, tetracosyl, pentacosyl and the isomeric forms thereof; aryl of 6 to 25 carbon atoms, inclusive, such as a phenyl, tolyl, xylyl, napthyl, biphenyl, tetraphenyl and the like; aralkyl of 7 to 25 carbon atoms, inclusive, such as benzyl,
- (I) are p-toluenesulfonic acid and dodecylbenzene sulfonic acid.
- a catalytic proportion is generally within the range of from about 100 to 10,000 ppm of tar residue, preferably 1000 to 5000 ppm.
- Efficient cracking occurs at temperatures of between about 100° C. to 300°C, preferably 140° C. to 250° C, and more preferably 180° C. to 200° C. at atmospheric pressure. Under these conditions quantitative amounts of phenol with high purity and low residual/ nondetectable catalyst levels have been recovered.
- heating is carried out under an inert atmosphere, such as nitrogen gas atmospheres. Progress of the reaction may be followed by conventional analytic procedures. Upon completion of the desired reaction, the product phenols may be separated by conventional techniques such as precipitation, distillation, crystallization, filtration and like procedures.
- reaction effluent 82.5% phenol, 11.8% bisphenol-A, 1.6% 2-(4-hydroxy- ⁇ henyl)2-(2-hydroxyphenyl) propane and 4.1% other by-products
- reaction effluent 82.5% phenol, 11.8% bisphenol-A, 1.6% 2-(4-hydroxy- ⁇ henyl)2-(2-hydroxyphenyl) propane and 4.1% other by-products
- vessel containing Rohm & Haas Amberlyst A-21 weakly basic anionic resin, an ion exchange resin, to reduce the concentration of acidic species to ⁇ 2ppm.
- At least a portion of the resulting solution is then fed to a phenol distillation column which operates at a pressure of 30 mm of mercury and a temperature of 218° C. This removes the phenol as an approximately 99%
- the bottoms contain about 1% phenol and is continuously fed to a second distillation column which operates at a temperature of 224° C. and approximately l-2mm of Hg.
- the overhead stream from this column consists mainly of bisphenol-A isomers, primarily o, p-bisphenol-A, 2,2,4-trimethyl-4(4-hydroxyphenol), Chroman, bisphenol-A
- the bottoms is fed to a third distillation column which operates at a temperature of 260° C to 290° C. (500-550°F) and a pressure of 1-2 mm of Hg.
- the column overheads consist of circa 80+% pure bisphenol-A which can be recycled back to the bisphenol-A manufacturing process.
- the bottoms of the last column contain a highly colored tar ( ⁇ 30% bisphenol-A and >70% heavy phenolic process byproducts) which is the feedstock for the following example.
- the tar is held at a temperature of about 100° C. to 200° C. before proceeding to crack as in the following example.
- a 250 ml three neck flask equipped with an overhead stirrer, a thermometer, a temperature controller, a condenser, a dean stark trap, a nitrogen inlet and outlet was charged with 1,000 ppm of p-toluene sulfonic acid and 60 grams of BPA Tar from Preparation 1, supra. Using an oil bath, the charge delineated above was heated to 160°C.
- the reaction temperature was maintained at 160° C. for two hours along with a flow of nitrogen. Stirring of the reaction mixture was started after the reactants had melted. After two hours at 160° C, the reaction mixture was allowed to cool to 110° C, followed by the addition of 200 ml of water. At this stage, nitrogen flow was stopped.
- Ri, R2, and R3 each independently represents hydrocarbyl as defined above.
- the tars employed results from processes for the preparation of bisphenols (II) wherein Ri, and R2 are alkyl, aryl, alkaryl, cycloalkyl, cycloalkylaryl, halogen substituted alkyl, or alkoxy; preferably having 1 to 10 carbon atoms and most preferably 1 to 6 carbon atoms.
- R3 is preferably hydrogen, halogen, alkyl as 1 to 6 carbon atoms, cycloalkyl of 4 to 6 carbon atoms, aryl; most preferably hydrogen, alkyl of 1 to 6 carbon atoms or halogen.
- the process of the invention will crack these tars to recover the phenol and ketone starting reactants.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69914632T DE69914632T2 (en) | 1998-12-30 | 1999-10-22 | RECOVERY OF PHENOL FROM WASTE FLOWS FROM THE BPA PROCESS |
JP2000592243A JP2002534401A (en) | 1998-12-30 | 1999-10-22 | Recovery of phenols from BPA process waste stream |
EP99956644A EP1140753B1 (en) | 1998-12-30 | 1999-10-22 | Phenol recovery from bpa process waste streams |
AT99956644T ATE258908T1 (en) | 1998-12-30 | 1999-10-22 | RECOVERY OF PHENOL FROM BPA PROCESS WASTE STREAMS |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/222,980 | 1998-12-30 | ||
US09/222,980 US6133486A (en) | 1998-12-30 | 1998-12-30 | Phenol recovery from BPA process waste streams |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000040531A1 true WO2000040531A1 (en) | 2000-07-13 |
Family
ID=22834502
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/024872 WO2000040531A1 (en) | 1998-12-30 | 1999-10-22 | Phenol recovery from bpa process waste streams |
Country Status (7)
Country | Link |
---|---|
US (1) | US6133486A (en) |
EP (1) | EP1140753B1 (en) |
JP (1) | JP2002534401A (en) |
CN (1) | CN1151108C (en) |
AT (1) | ATE258908T1 (en) |
DE (1) | DE69914632T2 (en) |
WO (1) | WO2000040531A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE112008000300T5 (en) | 2007-02-14 | 2010-01-14 | Instytut Ciezkiej Syntezy Organicznej "Blachownia" | Process for the production of bisphenol A |
WO2010062482A2 (en) * | 2008-10-28 | 2010-06-03 | Badger Licensing, Llc | Process for recovering phenol from a bpa waste stream |
WO2013157972A2 (en) | 2012-04-16 | 2013-10-24 | Instytut Ciężkiej Syntezy Organicznej "BLACHOWNIA" | Method of producing bisphenol a |
WO2014031019A1 (en) | 2012-08-23 | 2014-02-27 | Instytut Cieżkiej Syntezy Organicznej "Blachownia" | Method of transforming by-products in the process of synthesis of bisphenol a |
US20140121417A1 (en) * | 2012-10-29 | 2014-05-01 | Sabic Innovative Plastics Ip B.V. | Recovery of materials from a mother liquor residue |
WO2021054608A1 (en) * | 2019-09-16 | 2021-03-25 | 주식회사 엘지화학 | Method for decomposing phenolic by-products |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6620939B2 (en) * | 2001-09-18 | 2003-09-16 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
US6635788B1 (en) | 2002-12-20 | 2003-10-21 | General Electric Company | Process for manufacture of bisphenols |
US6858759B2 (en) * | 2002-12-20 | 2005-02-22 | General Electric Company | Process for manufacture of bisphenols |
DE102004032232A1 (en) * | 2004-07-02 | 2006-01-19 | Bayer Materialscience Ag | Process for the separation of phenol from phenol-containing streams from the preparation of bisphenol A |
KR20080077104A (en) * | 2005-10-07 | 2008-08-21 | 바져 라이센싱 엘엘씨 | Bisphenol-a plant yield enhancement |
JP5030472B2 (en) * | 2006-05-17 | 2012-09-19 | 出光興産株式会社 | Manufacturing method and manufacturing equipment of high purity bisphenol A |
US8044248B2 (en) * | 2008-04-03 | 2011-10-25 | Badger Licensing Llc | Treatment of bisphenol-A residue streams |
WO2020009705A1 (en) * | 2018-07-06 | 2020-01-09 | Badger Licensing Llc | Treatment of residual streams from the manufacture of bisphenols |
WO2020051186A1 (en) * | 2018-09-05 | 2020-03-12 | Badger Licensing Llc | Process for producing bisphenol-a |
CN112919720A (en) * | 2021-04-14 | 2021-06-08 | 陕西煤业化工集团神木天元化工有限公司 | Method for extracting dihydric phenol from wastewater |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4277628A (en) * | 1980-05-20 | 1981-07-07 | General Electric Company | Phenol recovery from bisphenol-A waste streams |
US4351966A (en) * | 1971-06-08 | 1982-09-28 | General Electric Company | Phenol recovery from bisphenol-A waste streams |
US5504251A (en) * | 1995-03-09 | 1996-04-02 | General Electric Company | Co-cracking of BPA and phenol process tars |
Family Cites Families (16)
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US3466337A (en) * | 1967-01-30 | 1969-09-09 | Dow Chemical Co | Regeneration of phenol from bisphenol a and byproducts |
US4424283A (en) * | 1979-12-13 | 1984-01-03 | General Electric Company | Catalyst for synthesizing bisphenol and method for making same |
US4346247A (en) * | 1979-12-13 | 1982-08-24 | General Electric Company | Method and catalyst for making bisphenol |
US4396728A (en) * | 1980-09-30 | 1983-08-02 | General Electric Company | Method and catalyst for making bisphenol |
US4327229A (en) * | 1981-01-19 | 1982-04-27 | General Electric Company | Recovery of bisphenol-A values |
US4337334A (en) * | 1981-02-10 | 1982-06-29 | Mitsui Toatsu Chemicals Inc. | Process for production of phenolic resin from bisphenol-A by-products |
US4400555A (en) * | 1981-10-06 | 1983-08-23 | General Electric Company | Ion exchange catalyzed bisphenol synethesis |
US4584416A (en) * | 1983-11-14 | 1986-04-22 | General Electric Company | Method and catalyst for making bisphenol |
US4766254A (en) * | 1987-10-05 | 1988-08-23 | General Electric Company | Method for maximizing yield and purity of bisphenol A |
US4847433A (en) * | 1988-05-23 | 1989-07-11 | General Electric Company | Process for preparing bisphenol-A |
US5315042A (en) * | 1993-03-22 | 1994-05-24 | General Electric Company | Use of partial acetone conversion for capacity increase and quality/yield improvement in the bisphenol-A reaction |
US5430199A (en) * | 1994-03-28 | 1995-07-04 | General Electric Company | Method for recovering phenol and xanthene values from bisphenol A tars |
US5672774A (en) * | 1995-10-24 | 1997-09-30 | General Electric Company | Phenol tar processing method |
DE19720540A1 (en) * | 1997-05-16 | 1998-11-19 | Bayer Ag | Process for processing mother liquors from bisphenol synthesis |
DE19720539A1 (en) * | 1997-05-16 | 1998-11-19 | Bayer Ag | Process for the continuous production of dihydroxydiarylalkanes |
DE19720541A1 (en) * | 1997-05-16 | 1998-11-19 | Bayer Ag | Process for the continuous production of dihydroxydiphenylalkanes |
-
1998
- 1998-12-30 US US09/222,980 patent/US6133486A/en not_active Expired - Lifetime
-
1999
- 1999-10-22 WO PCT/US1999/024872 patent/WO2000040531A1/en active IP Right Grant
- 1999-10-22 DE DE69914632T patent/DE69914632T2/en not_active Expired - Lifetime
- 1999-10-22 AT AT99956644T patent/ATE258908T1/en not_active IP Right Cessation
- 1999-10-22 CN CNB998152439A patent/CN1151108C/en not_active Expired - Fee Related
- 1999-10-22 EP EP99956644A patent/EP1140753B1/en not_active Expired - Lifetime
- 1999-10-22 JP JP2000592243A patent/JP2002534401A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4351966A (en) * | 1971-06-08 | 1982-09-28 | General Electric Company | Phenol recovery from bisphenol-A waste streams |
US4277628A (en) * | 1980-05-20 | 1981-07-07 | General Electric Company | Phenol recovery from bisphenol-A waste streams |
US5504251A (en) * | 1995-03-09 | 1996-04-02 | General Electric Company | Co-cracking of BPA and phenol process tars |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE112008000300T5 (en) | 2007-02-14 | 2010-01-14 | Instytut Ciezkiej Syntezy Organicznej "Blachownia" | Process for the production of bisphenol A |
WO2010062482A2 (en) * | 2008-10-28 | 2010-06-03 | Badger Licensing, Llc | Process for recovering phenol from a bpa waste stream |
WO2010062482A3 (en) * | 2008-10-28 | 2010-07-15 | Badger Licensing, Llc | Process for recovering phenol from a bpa waste stream |
US7858830B2 (en) | 2008-10-28 | 2010-12-28 | Badger Licensing Llc | Process for recovering phenol from a BPA waste stream |
CN102171172A (en) * | 2008-10-28 | 2011-08-31 | 巴杰许可有限责任公司 | Process for recovering phenol from a bpa waste stream |
WO2013157972A2 (en) | 2012-04-16 | 2013-10-24 | Instytut Ciężkiej Syntezy Organicznej "BLACHOWNIA" | Method of producing bisphenol a |
WO2014031019A1 (en) | 2012-08-23 | 2014-02-27 | Instytut Cieżkiej Syntezy Organicznej "Blachownia" | Method of transforming by-products in the process of synthesis of bisphenol a |
US20140121417A1 (en) * | 2012-10-29 | 2014-05-01 | Sabic Innovative Plastics Ip B.V. | Recovery of materials from a mother liquor residue |
US9732022B2 (en) * | 2012-10-29 | 2017-08-15 | Sabic Global Technologies B.V. | Recovery of materials from a mother liquor residue |
WO2021054608A1 (en) * | 2019-09-16 | 2021-03-25 | 주식회사 엘지화학 | Method for decomposing phenolic by-products |
US11414364B2 (en) | 2019-09-16 | 2022-08-16 | LG Chern, Ltd. | Method for decomposing phenolic by-products |
Also Published As
Publication number | Publication date |
---|---|
CN1151108C (en) | 2004-05-26 |
JP2002534401A (en) | 2002-10-15 |
ATE258908T1 (en) | 2004-02-15 |
US6133486A (en) | 2000-10-17 |
DE69914632T2 (en) | 2004-12-23 |
EP1140753B1 (en) | 2004-02-04 |
EP1140753A1 (en) | 2001-10-10 |
DE69914632D1 (en) | 2004-03-11 |
CN1332709A (en) | 2002-01-23 |
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