EP0000944A1 - Procédé de filtration pour la purification de polyols - Google Patents

Procédé de filtration pour la purification de polyols Download PDF

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Publication number
EP0000944A1
EP0000944A1 EP78100738A EP78100738A EP0000944A1 EP 0000944 A1 EP0000944 A1 EP 0000944A1 EP 78100738 A EP78100738 A EP 78100738A EP 78100738 A EP78100738 A EP 78100738A EP 0000944 A1 EP0000944 A1 EP 0000944A1
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EP
European Patent Office
Prior art keywords
solvent
polyol
filter
mixture
water
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.)
Withdrawn
Application number
EP78100738A
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German (de)
English (en)
Inventor
Joseph Francis Louvar
Michael Anthony Capraro
William Michael Herring
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
BASF Wyandotte Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US05/829,436 external-priority patent/US4137396A/en
Application filed by BASF Wyandotte Corp filed Critical BASF Wyandotte Corp
Publication of EP0000944A1 publication Critical patent/EP0000944A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying

Definitions

  • Polyoxyalkylene ether polyols hereinafter for convenience called polyols, are commonly used in the production of urethane polymers. These polyols are reacted with polyisocyanate in the presence of added catalyst and other materials to produce urethane polymers which may be
  • Pblyols as commercially prepared, contain in the crude form various impurities such as alkali metal hydroxide, or other metal salts which were employed as catalysts for the production of polyols.
  • the normal concentrations of catalysts range from 1700 to 4000 parts per million. It is desirable to reduce this to a level of about 5 parts per million or less.
  • the crude polyols without prior neutralization of the catalyst can be treated with a synthetic type adsorbent followed by filtration of the polyol.
  • a synthetic type adsorbent Present commercial practice involves mixing the polyol, adsorbert, water and optionally a filter aid then filtering off the polyol.
  • the resulting adsorbent contains an amount of polyol equal to at least its own weight.
  • the disposal of this spent adsorbent presents both ecological and safety problems.
  • the polyols are not biodegradable and disposal in a landfill is not desirable.
  • the wet adsorbent if allowed to remain exposed to the atmosphere, becomes pyrophoric and creates a safety hazard. The loss of polyol results in increased product costs.
  • U. S. Patent No. 3,433,816 teaches a process for separating mother liquor from a filter cake by employing a solvent.
  • the prior art does not teach a process for the employment of a solvent to remove a polyol from a filter cake of synthetic lauminum silicate without removal of the adsorbed catalyst.
  • the drawing illustrates a flow diagram of the polyol purification process, specifically the filtration cycle and the solvent reccvery system.
  • the improved process for the removal of residual catalysts from polyols involves the use of dry cake discharge type leaf filters with heel scavenging capabilities and the use of a solvent wash and recovery system wherein the entire system may be washed free of polyol.
  • valve 26 employing pump 28 and allowed to fill and overflow filter 24 with the excess flowing back to hold tank 6 through valves 30, 32, and 34 via lines 31, 33, 35 and 37.
  • valve 36 is opened and the mixture is cycled through filter 24 until sufficient filter cake is deposited on filter 24 to achieve a clear, catalyst free filtrate of the polyol.
  • the polyol is filtered through filter 24 and then transferred to flash stripper 38 via valves 36, 32, and 40 through lines 39, 41, 35 and 45 after valve 34 is closed.
  • the remaining filter heel which is that portion of the crude polyol batch which cannot be readily filtered through the leaf filter, is blown back to hold tank 6 through valves 42, 32, and 34 employing lines 47, 41, 43, 35, and 37 via nitrogen pressure through valves 44 and 30.
  • Valves 44, 30 and 40 are closed and the heel is then pumped through scavenger system 46 through valves 48 and 50 by means of pump 49 employing lines 27, 51, and 53 until a clarified heel is obtained.
  • the scavenger system 46 is one which is designed to purify the filter heel. It is generally a miniature version of a full scale leaf filter.
  • the clarified heel is then transferred to flash stripper 38 via valves 50, 32 and 40 and transfer lines 53, 43, 35, and 45 after valve 34 is closed.
  • Solvent from solvent decanter storage tank 12 is pumped through valve 52 via lines 13 and 55 washing out hold tank 6.
  • the washings are pumped through filter 24 via valve 26, transfer lines 25, 27 employing pump 28 and then circulated back to hold tank 6 via valves 36, 32, and 34 and through valves 42, 32 and 34 via transfer lines 41, 43, 35, and 37.
  • These washings are then circulated through scavenger system 46 via valves 48 and 50 using transfer lines 27, 51, and 53, then returned to flash stripper 38 via valves 50, 32 and 40 employing transfer lines 53, 43, 35 and 45 after valve 34 is closed.
  • Valve 36 is then opened.
  • Nitrogen gas 54 is passed through valves 44, 30, 36, 32 and 40 drying the filter cake and filter 24.
  • the vapors are carried to flash stripper 38 in a manner similar to the washings. Excess pressure in flash stripper 38 is relieved through relief valve 56.
  • the polyol in flash stripper 38 is then stripped of water and solvent, and transferred to polyol storage tank 58 via valve 60 through transfer line 57 employing pump 62.
  • Solvent and water are stripped from the polyol employing solvent recovery system 64 via valve 66 and transfer line 59.
  • the solvent is subsequently transferred to solvent recovery storage tank 12 via valve 68 and transfer line 61.
  • the dried tilter cake is then discharged from filter 24.
  • the impurities present in the polyol which must be removed are catalysts used in the preparation of the polyol.
  • These catalysts are generally alkali metal hydroxides or alkali metal alkoxides such as sodium hydroxide, potassium hydroxide, sodium alkoxide, potassium alkoxide, and so forth.
  • Additional catalysts which may be employed in the preparation of such polyols and which may be removed by the instant process include the hydroxides and alkoxides of lithium or rubidium and cesium.
  • the polyols purified in accordance with the present invention include those polyols prepared by condensing monomeric units such as ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof with active hydrogen compounds such as ethylene glycol, propylene glycol, water, dipropylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butarediol, hexanetriol, glycerol, trimethylolpropane, trimethylolethane, hydroquinone, pentaerythritol, alpha-methylglucoside, sorbitol, sucrose, ethylene diamine, diethylene triamine, toluene diamine, aniline, methylene dianiline; piperazine, triisopropanolamine, and bisphenol A wherein these polyols have a molecular weight range from about 300 to about 26,000.
  • polyols which are characterized as being essentially hydroxyl terminated polyether polyols which have the general formula: wherein R is an alkylene radical and n is an integer which in a preferred embodiment is sufficiently large that the compound, as a whole, has a molecular weight from about 300 to about 26,000.
  • R is an alkylene radical
  • n is an integer which in a preferred embodiment is sufficiently large that the compound, as a whole, has a molecular weight from about 300 to about 26,000.
  • R is an alkylene radical
  • n is an integer which in a preferred embodiment is sufficiently large that the compound, as a whole, has a molecular weight from about 300 to about 26,000.
  • R is an alkylene radical
  • n is an integer which in a preferred embodiment is sufficiently large that the compound, as a whole, has a molecular weight from about 300 to about 26,000.
  • R is an alkylene radical
  • n is an integer which in a preferred embodiment is sufficiently large that the compound, as a whole,
  • the polyols purified in accordance with this invention can contain arylene or cycloalkylene radicals together with the alkylene radicals.
  • the cyclic groups inserted in a polyether chain are preferably phenylene, naphthalene, or cyclohexylene radicals or those radicals containing alkyl or alkylene sub stituents as in the tolylene, phenylethylene or xylylene radicals.
  • the adsorbents which may be employed in the practice of this invention are those which will remove the alkaline catalysts.
  • Preferred are the synthetic magnesium silicate adsorbents. These synthetic adsorbents may be prepared by the reaction of a magnesium salt such as magnesium sulfate with sodium silicate. The resulting products can have particle sizes ranging from 5 to 500 microns with an average particle size of about 100-200 microns.
  • These adsorbents are sold under trademarks of "BRITE SORB” by Philadelphia Quartz Corporation, and "MAGNESOL” by Reagent Chemicals. The amount of adsorbent which can be employed depends on the concentration of catalyst present in the polyol.
  • amounts ranging from about 0.1 percent to about 5 percent by weight based on the weight of the polyol may be employed.
  • concentration of adsorbent ranges from about 1.0 percent to about 3.0 percent based on the weight of polyol. From an economical point of view it is preferable to use as little as possible of the adsorbent.
  • a filter aid may be employed in addition to the magnesium silicate adsorbent, however, this may not be necessary if the screen size on the leaf filter is sufficient to retain the magnesium silicate adsorbent. It is contemplated that any suitable leaf filter may be employed in the practice of this invention. It is especially desirable that the filter have internal heel scavenging capabilities, thus eliminating the need for an external scavenger system as was illustrated.
  • solvents which may be employed in the practice of this invention are the aliphatic, alicyclic, aromatic hydrocarbons, dialkyl ketones, dialkyl ethers, and halogenated hydrocarbons. These include the butanes, pentanes, hexanes, heptanes, octanes, nonanes, decanes, dodecanes, cyclcpentane, cyclohexane, methylcyclohexane, benzene.
  • the preferred solvents are the aliphatic, alicyclic and aromatic hydrocarbons. The solvents may be recycled through the process as many times as desired without any detrimental effects on the polyols.
  • the use of the solvents results in the recovery of additional polyol which previously was lost. Furthermore, the use of solvents improves the filtration rate due to a lower polyol viscosity. Additionally, the dry filter cake is readily removable from the filter screen leaving a clean surface which can be used for subsequent filtrations without washing the screen media.
  • the amount of solvent employed will depend upon the capacity of the equipment.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78100738A 1977-08-31 1978-08-24 Procédé de filtration pour la purification de polyols Withdrawn EP0000944A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US829436 1977-08-31
US05/829,436 US4137396A (en) 1976-09-24 1977-08-31 Filtration process for purifying polyols

Publications (1)

Publication Number Publication Date
EP0000944A1 true EP0000944A1 (fr) 1979-03-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100738A Withdrawn EP0000944A1 (fr) 1977-08-31 1978-08-24 Procédé de filtration pour la purification de polyols

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EP (1) EP0000944A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996011222A1 (fr) * 1994-10-07 1996-04-18 Basf Aktiengesellschaft Procede d'extraction des heteropolycomposes contenus dans des polyethers, polyesters et esters de polyether
US5824769A (en) * 1994-10-07 1998-10-20 Basf Aktiengesellschaft Polyether, polyester and polyether ester purification process
US5951829A (en) * 1994-10-07 1999-09-14 Basf Aktiengesellschaft Separation of heteropoly compounds from polyethers, polyesters and polyether esters
CN102887996A (zh) * 2011-07-19 2013-01-23 因温斯特技术公司 聚醚多元醇过滤中的聚合物回收方法
CN110325567A (zh) * 2017-01-25 2019-10-11 亨茨曼国际有限公司 生产聚醚多元醇的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU392078A1 (ru) * 1965-03-24 1973-07-27 , Т. М. Гриценко Способ очистки полиоксиалкилепполиолов
GB1369304A (en) * 1972-03-06 1974-10-02 Marles Kuhlmann Wyandotte Soc Purification of polyols
US4029879A (en) * 1975-11-17 1977-06-14 Basf Wyandotte Corporation Process for the removal of catalysts from polyether polyols employing water and adsorbent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU392078A1 (ru) * 1965-03-24 1973-07-27 , Т. М. Гриценко Способ очистки полиоксиалкилепполиолов
GB1369304A (en) * 1972-03-06 1974-10-02 Marles Kuhlmann Wyandotte Soc Purification of polyols
US4029879A (en) * 1975-11-17 1977-06-14 Basf Wyandotte Corporation Process for the removal of catalysts from polyether polyols employing water and adsorbent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 81, abstract no. 50462v, 1974, COLUMBUS, Ohio (USA) & SU-A-392 078 (SIMENIDO A.V. et al.) *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996011222A1 (fr) * 1994-10-07 1996-04-18 Basf Aktiengesellschaft Procede d'extraction des heteropolycomposes contenus dans des polyethers, polyesters et esters de polyether
US5741888A (en) * 1994-10-07 1998-04-21 Basf Aktiengesellschaft Removal of heteropoly compounds from polyethers, polyesters and polyether esters
US5824769A (en) * 1994-10-07 1998-10-20 Basf Aktiengesellschaft Polyether, polyester and polyether ester purification process
US5951829A (en) * 1994-10-07 1999-09-14 Basf Aktiengesellschaft Separation of heteropoly compounds from polyethers, polyesters and polyether esters
CN1071344C (zh) * 1994-10-07 2001-09-19 巴斯福股份公司 从聚醚、聚酯和聚醚酯中除去杂多化合物的方法
CN102887996A (zh) * 2011-07-19 2013-01-23 因温斯特技术公司 聚醚多元醇过滤中的聚合物回收方法
CN102887996B (zh) * 2011-07-19 2016-03-16 因温斯特技术公司 聚醚多元醇过滤中的聚合物回收方法
CN110325567A (zh) * 2017-01-25 2019-10-11 亨茨曼国际有限公司 生产聚醚多元醇的方法
CN110325567B (zh) * 2017-01-25 2022-02-11 亨茨曼国际有限公司 生产聚醚多元醇的方法

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Inventor name: CAPRARO, MICHAEL ANTHONY

Inventor name: HERRING, WILLIAM MICHAEL

Inventor name: LOUVAR, JOSEPH FRANCIS