WO2006002788A1 - Verfahren zur abtrennung von phenol aus phenolhaltigen strömen aus der herstellung von bisphenol a - Google Patents
Verfahren zur abtrennung von phenol aus phenolhaltigen strömen aus der herstellung von bisphenol a Download PDFInfo
- Publication number
- WO2006002788A1 WO2006002788A1 PCT/EP2005/006603 EP2005006603W WO2006002788A1 WO 2006002788 A1 WO2006002788 A1 WO 2006002788A1 EP 2005006603 W EP2005006603 W EP 2005006603W WO 2006002788 A1 WO2006002788 A1 WO 2006002788A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phenol
- stream
- bisphenol
- residence time
- distillation column
- Prior art date
Links
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
- C07C37/68—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
-
- 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
-
- 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
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
- C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
Definitions
- Bisphenols as condensation products of phenols and carbonyl compounds are starting materials or intermediates for the preparation of a large number of commercial products. Of particular industrial importance is the condensation product of the reaction between phenol and acetone, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A, BPA).
- BPA serves as a starting material for the production of various polymeric materials such as, for example, polyarylates, polyetherimides, polysulfones and modified phenol-formaldehyde resins. Preferred fields of application are in the production of epoxy resins and polycarbonates.
- the selectivity of the reaction as well as the long-term stability of the catalyst is significantly influenced by the quality of the raw materials phenol and acetone used.
- BPA as a raw material for high-grade plastics such as polycarbonate therefore very high purity requirements of the Grund ⁇ used substances Phenol and acetone provided.
- purities of> 99.95% by weight for phenol and> 99.90% by weight for acetone with simultaneously low impurity levels (S ⁇ 0.5 ppm, Fe ⁇ 1 ppm) are typically positive for achieving high product purities and to minimize catalyst deactivation.
- EP-A-876 319 describes that commercial phenol is freed from interfering impurities by treatment with molecular sieve and thus ensures better usability in a process for producing BPA becomes.
- EP-A-680 913 describes the use of modified acidic ion exchangers for the removal of hydroxyacetone from phenol for BPA synthesis.
- a product mixture is formed which, in addition to unreacted phenol and optionally acetone, primarily contains BPA and water.
- typical by-products of the condensation reaction occur, for example 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane (o, p-BPA), substituted indanes, hydroxyphenylindanols, hydroxyphenylchromans, substituted xanthenes and higher condensed compounds having three or more phenyl rings in the molecular skeleton.
- the adduct crystals obtained in this way typically have a purity of> 99% by weight BPA based on BPA and the secondary components with a phenol content of about 40% by weight, based on the total adduct crystal amount.
- suitable solutions which typically contain one or more components from the group of acetone, water, phenol, BPA and Maukom ⁇ components, the adduct crystals can be freed from superficially adhering impurities.
- the Zusam ⁇ composition of the mother liquor at this point and thus the composition of the outfeed subset typically consists of 70 to 90 wt .-% phenol, 3 to 15 wt .-% BPA and 3 to 15 wt .-% minor components and isomers, the were formed in the reaction. Since ultimately only the last-mentioned proportion of secondary components has to be removed from the process, the discharged quantity is subjected to further work-up steps in order to minimize material losses.
- a portion of the BPA contained in the recirculated amount is recovered by distilling off part of the phenol from the withdrawn partial stream - A -
- a filtrate consisting of typically 60 to 90% by weight of phenol, 3 to 12% by weight of BPA and 3 to 18% by weight of secondary components is obtained. From this filtrate, the phenol contained is typically distilled off to ⁇ 10 wt .-% residual content and the resulting residual resin containing ⁇ 10 wt .-% phenol, 14 to 80 wt .-% BPA, 20 to 86 wt .-% secondary components of disposal fed.
- the invention relates to a process for the continuous separation of phenol from a partial stream produced in the production of bisphenol A containing 40 to 90 wt .-% of phenol, 5 to 40% by weight of bisphenol A and 5 to 40% by weight of secondary components which are formed in the reaction of phenol and acetone to give bisphenol A,
- the phenol distilled off in step b) preferably has a purity of> 99.8% by weight.
- the technical problem is solved by acid-catalyzed cleavage of the exit stream in a residence time vessel and continuous separation of the phenol via a vacuum column with high separation capacity.
- FIG. 1 shows a preferred embodiment of the method according to the invention.
- Another partial stream 8 of the bottom product is fed to a residence time tank 11.
- the acid-catalyzed isomerization takes place. sierang and cleavage of BPA and minor components to form phenol.
- the cleavage is accelerated by the addition of suitable acids (stream 12) through a metering unit 13.
- the phenol-containing effluent 14 of the residence time vessel 11 is combined with the recirculated substream 1 and thus returned to the distillation unit 2 for the recovery of phenol.
- the process is operated continuously and reaches an equilibrium state after a short time.
- the partial stream 1 fed out from the process for producing bisphenol A can be any product stream from a process for producing BPA which contains the following components: 40 to 90% by weight of phenol, 5 to 40% by weight of bisphenol A and 5 to 40% by weight of secondary components which are obtained in the reaction of phenol and acetone to give bisphenol A:
- Partial stream 1 is preferably a recycled partial stream from a BPA production process with suspension crystallization and solid-liquid separation, wherein a partial stream of the filtrate is removed from the solid-liquid separation for the purpose of discharging by-products in the direction of the process according to the invention for the separation of phenol.
- this partial stream 1 is passed through an additional rearrangement unit before being fed into the distillation column 2, whereby a portion of the BPA contained in the filtrate is recovered by treatment with acidic ion exchanger, followed by partial distilling off of phenol, crystallization and solid-liquid separation and fed to the main process becomes.
- the filtrate of the solid-liquid separation of the rearrangement unit serves as the feed stream 1 of the distillation column. 2
- the distillation column 2 must have at least 5 theoretical plates, preferably at least 10 theoretical plates, to separate other mecanicsie ⁇ dender components such as For example, to allow isopropenylphenol and to ensure a purification of the resulting phenol to a purity of> 99.8 wt .-% at the top of the column.
- the distillation is preferably operated at an absolute pressure at the top of the column of 70 to 200 mbar, preferably 90 to 120 mbar.
- the residence time tank 11 must be designed in such a way that an average hydrodynamic residence time of the circulation stream 8 of at least 2 hours, preferably at least 4 hours, is set in order to achieve an effective and as complete as possible cleavage of BPA and by-products.
- the residence time reactor can in this case be operated completely filled in upflow or downflow or in a position-controlled manner.
- the isomerization and the associated cleavage in the residence time vessel 11 in step d) is carried out in the presence of an acidic catalyst.
- acidic catalyst (stream 12) for the cleavage in step d) can in principle a variety of strongly acidic heavy or non-volatile Brönsted acids are used, including phosphoric acid or its higher condensates, sulfuric acid, alkanesulfonic acids with> 4 carbon atoms in the alkane chain, aromatic Sulfonic acids, arylalkane sulfonic acids or phosphonium acids.
- heterogeneous cleavage catalysts such as, for example, strongly acidic aluminum oxide, supported Lewis acids, acidic zeolites or other clays or polystyrrolesulfonic acids.
- the metering unit 13 is omitted and the heterogeneous catalyst is introduced by a suitable retaining structure in the residence time tank 11 and replaced if necessary.
- metering can be effected as stream 12 via the metering unit 13 into the circulation stream of the bottoms product of the distillation column 2.
- the metering can also take place in the input stream 8 into the residence time container 11 or into the output stream 14 out of the residence time container 11.
- the metering can also be carried out in the partial stream 1 in the distillation column 2.
- the metering is in the circulation stream of the bottom product of the distillation column 2 of the column.
- X is the mass fraction of phenol in substream 1
- c for effective cleavage is between 0.001% and 2%, preferably between 0.005 and 1%, more preferably between 0.01 and 0.2%.
- the temperature in the residence time vessel 11 must be> 190 ° C., preferably> 200 ° C., for effective isomerization and cleavage.
- the heat input in a preferred embodiment takes place directly through the evaporator 7 of the distillation column 2. This means that the input stream 8 into the residence time vessel 11 is not heated by a separate heat exchanger and the bottom of the column 2 and the dwell tank 11 are operated at the same temperature.
- composition (without phenol content) in all examples and comparative examples is: p, p-BPA 35-40% by weight, o, p-BPA 9 to 12% by weight, hydroxyphenyl-substituted indanes 15 to 19% by weight. %, hydroxyphenyl-substituted chromans 18 to 22% by weight, trisphenol 3 to 5% by weight, other constituents 9 to 12% by weight. This corresponds to a typical composition of a feed stream from a bisphenol A production plant.
- Table 1 shows the purity C (5) and the mass flow M (5) of the phenol stream 5 obtained at the top of the column for the various conditions on which Examples 1 to 7 are based.
- the column 2 used has 20 theoretical plates and was operated with a reflux ratio of about 0.6 and with the pressures that set in setting the temperature T (I l) at the bottom of the column 2 in the thermodynamic equilibrium.
- the temperature in the residence time container 11 is equal to the temperature at the bottom of the column 2.
- the values indicated relate to equilibrium conditions which occur after a few hours when the column is operated continuously.
- the cleavage in the residence time vessel 11 is assisted by the addition of sulfuric acid.
- Comparative Example 7 is carried out with the already in Examples 1 to 5 Column 2, but the residence time 11 is bypassed, so that no residence time for cleavage is available. As a result, despite the addition of sulfuric acid, no high yield of phenol Y in the phenol stream 5 is realized.
- T (11) temperature in the residence time container 11
- M (8) mass flow of bottom product through the residence time vessel 11
- ⁇ (l 1) hydrodynamic residence time in the residence time vessel (11).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007518497A JP2008504320A (ja) | 2004-07-02 | 2005-06-18 | ビスフェノールaの調製によるフェノール含有ストリームからフェノールを分離するためのプロセス |
EP05756999.8A EP1765752B1 (de) | 2004-07-02 | 2005-06-18 | Verfahren zur abtrennung von phenol aus phenolhaltigen strömen aus der herstellung von bisphenol a |
CN2005800225273A CN1980876B (zh) | 2004-07-02 | 2005-06-18 | 从制备双酚a的含苯酚流中分离苯酚的方法 |
ES05756999.8T ES2550008T3 (es) | 2004-07-02 | 2005-06-18 | Procedimiento para la separación de fenol a partir de corrientes que contienen fenol a partir de la producción de bisfenol A |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004032232.5 | 2004-07-02 | ||
DE102004032232A DE102004032232A1 (de) | 2004-07-02 | 2004-07-02 | Verfahren zur Abtrennung von Phenol aus phenolhaltigen Strömen aus der Herstellung von Bisphenol A |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006002788A1 true WO2006002788A1 (de) | 2006-01-12 |
Family
ID=35063346
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/006603 WO2006002788A1 (de) | 2004-07-02 | 2005-06-18 | Verfahren zur abtrennung von phenol aus phenolhaltigen strömen aus der herstellung von bisphenol a |
Country Status (9)
Country | Link |
---|---|
US (1) | US7301056B2 (de) |
EP (1) | EP1765752B1 (de) |
JP (1) | JP2008504320A (de) |
KR (1) | KR20070028473A (de) |
CN (1) | CN1980876B (de) |
DE (1) | DE102004032232A1 (de) |
ES (1) | ES2550008T3 (de) |
RU (1) | RU2401255C2 (de) |
WO (1) | WO2006002788A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7858830B2 (en) * | 2008-10-28 | 2010-12-28 | Badger Licensing Llc | Process for recovering phenol from a BPA waste stream |
US8431749B2 (en) | 2011-06-06 | 2013-04-30 | Badger Licensing Llc | Recovery of phenol and acetone from bisphenol-A streams |
TWI557103B (zh) | 2011-06-06 | 2016-11-11 | 貝吉特許有限責任公司 | 雙酚-a殘留物流份之處理 |
CN104056464B (zh) * | 2014-07-02 | 2015-08-05 | 南通星辰合成材料有限公司 | 以蒸汽喷射与液环真空泵实现双酚a汽提单元真空的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0680913A1 (de) | 1994-05-02 | 1995-11-08 | Ferag AG | Verfahren und Vorrichtung zum Speichern von Zuschnitten |
EP0758637A1 (de) * | 1995-08-14 | 1997-02-19 | Bayer Ag | Verfahren zur Reinigung von Bisphenol-A |
EP0812815A2 (de) | 1996-06-13 | 1997-12-17 | General Electric Company | Verfahren zur Herstellung von Bisphenol |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6015648B2 (ja) * | 1980-09-29 | 1985-04-20 | アイシン化工株式会社 | シエルモ−ルド用樹脂の製造方法 |
US6133486A (en) * | 1998-12-30 | 2000-10-17 | General Electric Company | Phenol recovery from BPA process waste streams |
-
2004
- 2004-07-02 DE DE102004032232A patent/DE102004032232A1/de not_active Withdrawn
-
2005
- 2005-06-18 ES ES05756999.8T patent/ES2550008T3/es active Active
- 2005-06-18 JP JP2007518497A patent/JP2008504320A/ja not_active Withdrawn
- 2005-06-18 EP EP05756999.8A patent/EP1765752B1/de active Active
- 2005-06-18 WO PCT/EP2005/006603 patent/WO2006002788A1/de active Application Filing
- 2005-06-18 CN CN2005800225273A patent/CN1980876B/zh not_active Expired - Fee Related
- 2005-06-18 RU RU2007103892/04A patent/RU2401255C2/ru not_active IP Right Cessation
- 2005-06-18 KR KR1020067027776A patent/KR20070028473A/ko not_active Application Discontinuation
- 2005-06-28 US US11/168,025 patent/US7301056B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0680913A1 (de) | 1994-05-02 | 1995-11-08 | Ferag AG | Verfahren und Vorrichtung zum Speichern von Zuschnitten |
EP0758637A1 (de) * | 1995-08-14 | 1997-02-19 | Bayer Ag | Verfahren zur Reinigung von Bisphenol-A |
EP0812815A2 (de) | 1996-06-13 | 1997-12-17 | General Electric Company | Verfahren zur Herstellung von Bisphenol |
Also Published As
Publication number | Publication date |
---|---|
JP2008504320A (ja) | 2008-02-14 |
DE102004032232A1 (de) | 2006-01-19 |
RU2007103892A (ru) | 2008-08-10 |
EP1765752A1 (de) | 2007-03-28 |
CN1980876B (zh) | 2010-12-01 |
US20060004234A1 (en) | 2006-01-05 |
ES2550008T3 (es) | 2015-11-03 |
CN1980876A (zh) | 2007-06-13 |
EP1765752B1 (de) | 2015-08-26 |
KR20070028473A (ko) | 2007-03-12 |
US7301056B2 (en) | 2007-11-27 |
RU2401255C2 (ru) | 2010-10-10 |
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