CA2080478A1 - Process for catalyst recovery - Google Patents
Process for catalyst recoveryInfo
- Publication number
- CA2080478A1 CA2080478A1 CA002080478A CA2080478A CA2080478A1 CA 2080478 A1 CA2080478 A1 CA 2080478A1 CA 002080478 A CA002080478 A CA 002080478A CA 2080478 A CA2080478 A CA 2080478A CA 2080478 A1 CA2080478 A1 CA 2080478A1
- Authority
- CA
- Canada
- Prior art keywords
- process according
- cross
- flow filtration
- filtration
- ether
- 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.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
Abstract
Process for the recovery of catalyst in the production of ether carboxylic acids by catalytic oxidation with a suspended ether catalyst in which the reaction mixture is subjected to cross-flow filtration.
Description
~O 91/16294 - 1 - PCT/EP91/00649 - Description 2 ~ 8 0 4 7 8 Process for catalys-t reco~ery The present invention relat~s to ~ process for the recovery of catalyst in the preparation of ether-car--boxylic acids by catalytic oxidakion of the correspondingether alcohols with oxygen on suspended noble me~al catalysts~
The catalytic oxidation of ether alcohols according ~o the general equation Pk/C
R(OC~32CH2 )nOCH2CH2(~
has long been known and i5 described for example in German Patent 2,936,123 and European Patent 206,054~
However, as the molar mass of the radical R increases, the separation and thus the complete recovery ancl recy-cling of the noble metal catalyst becomes problematicO
Thus in German Patent 3,446,561, on ~age 4, a laborious four-stage method is described to xestrict the losses of noble metal. An essential processing disad~antage of this procedure lies in the fact that the reaction mixture;
prior to the filtra~ion, i~ diluted with 1-10 times -tha amount of acetone, which must -then be remov~d again by distillation, purified and recycled. The noble metal contents of 1-4 ppm, which can ultimat~ly be obtained in the product, are also relatively high and lead to a gradual decrease in the acti~ity of the catalyst. Over-all, this entail~ a sexious sconomic disadvantage.
The object was therefore to develop an indus^trially and economically acceptable process for ca~alyst recove~y.
The sub~ec~ of the presen~ i~venkion is a process for-the recovery of catalysk in the prepara~ion of e~hsr-car-boxylic acids by catalytic ox:idation using a susp~ndecl catalyst, characterized in that the reaction mixture is ~O 91/16294 - 2 -2 ~ ~ O ~ ~J 3 PCT/F.P9ltoo649 ~,..
. ..;
subjected to a cross-flow filtration.
Preferred ether-carboxylic acids are-those of the formul~
R--( OC~I2C~I2 ) nOC~I2COOH
in which R is a linear or branched alkyl radical of 1 to S about 24 carbon atoms, an aryl radical, such as for example a phenyl, naphthyl or biphenyl radical, addition~
ally an alkyl(Cl-C24)aryl radical, the aryl radical being for example a phenyl, naph~hyl or biphenyl radical, or an arylalkyl radical, f~r example a benzyl rzdical/ and n is a number from 0 to about 24. The abovementioned aryl radicals can be substituted.
In the cross-flow filtration, the catalyst-con-taining reaction mixture is pumped at a high overflow velocity tangentially ~o the membrane surface through -~he filter elemen-t, the filtrate being withdrawn perpendicular to the direction o~ flow through the membrane layer, as described in de~tail in ULLMANN's Encyclopedla of Industrial Chemistry, 5th Editiont Vol. B2, p. 10-54.
Tu~e-shaped ilter element~ having a membrane layer on the inner ~ide of ~he tubes are par~icularly suitc~hle.
Preferred membrane and support material is ~ -Al203 and ZrO2; however, plastic and carbon elemen.ts can also be used. Membrane and support can be composed of different materials. The necessa~y pore sizes are expediently in the ultrafiltration range, for example b~we~n abou~ 1 and about 200 nmO A suitable appara-tus is descr:;bed i~
th~ ex~mple (cf. in this con~ext also Figure 1 on page 7).
The cro~s-flow 1Eil~ration according ~o thP inven~io:n can be pe.rformed at tamperat~res from about ~0 -to c~bout 150~C~
It has proved ~o ~e advan~ageou~ to carry out ~he :Eilt ration at temperatures from c~bout 50 -to c~bout 100C, :in particular at tempera~ure~ ~rom abou~ 60 to abou-t 80C
W~ 91/1~294 - 3 - PC'~ P91/00~9 A pressure drop must of course prevail hetween the Eront side and the rear side of the membrane, ~o that the reaction solution can be moved -through.
A solubilizer used in the oxidation can -facilitate filt~
ration. Solubilizers without hydroxyl groups are suit~
able. Glycol ether~ without hydroxyl groups are particu~
larly suitable, in particular diethylene glycol dime-thyl ether.
A brief hydrogen treatment after the oxidation lS
completed at the reaction temperature (about 50 to about 100C) has proved to be advantageous, -to precipi-ta-te an~
dissolved and colloidal noble metal traces, so -that filter elements with somewhat larger pores can be used.
Apar-t from hydrogen Eormaldehyde, ~or example, can also be used as reducing agent.
Surprisingly, the problems of filtration (blockage, losses of noble metals) are solved by the process accord~
ing to the invention without the need for expenst~e measures, such as for example clilution with a solventO
The example below ~erves to illustrate the proce~
according to the invention wi-thou-t restricting it theretoO
Example A reaction sol~tion Erom the catalytic o~ida-tion f comprising 25 % by weight of ether carboxylic acids of the formula R-(OCH2C~23nOC~2COO~ having linaar alkyl group~
R having a distribution of C12 to C14 and a mean value of n = 4 and also 45 % by weight of diethylene ylycoL
dimethyl ether~ 25 % by weight of water and 5 ~ by weight of a suspended commercial cataly~t (5 % by weigh-t o-~platin~n on acti~ated charcoal) is txeated for 30 minutes at 70C with hydrocJen in a bubbl~ column and then sub-jec-ted to a cross-Elow Eil-tration.
~O 91/16294 2 ~ 8 ~ ~ 7 8 PCT~Epgl,00~49 The filter element is composed of a ZrO2 tube (diametQr:
7 mm, length: 250 mm), the inner side of ~hich is composed o~ a membrane layer having pore sizes of 35 nm ( 1O-a m) . An apparatus is used, which corresponds to the accompanyiny drawing (cf. Figure 1 on page 7)O The reaction solution is pumped thxough ~he filter elemen~
(B) situated in a housing (A) at a linear flow velocity of 5 m/s. A pressure P1 o~ 3 bar is established a~ a temperature of 70C. A fil-trate flow of 2.5 l/h is obtained. The catalyst is concentrated to a solids content of approxLmately 30% by weightj this concentrate is returned to the catalytic oxidation.
After separation of the diglycol dimethyl ether and ~ater from the filtrate by distillation, the mixture of ether-15 carboxylic acids is obtained as a clear, p~le producthaving a residual ~lantity o~ platinum of less than 0.5 ppm.
Comparison example The reaction solution described in -the above ex~mple i5 repeatedly filtered on a suction fil-ter wi-th insertsd filter paper (for quantita-tive analysis). The filter paper must be changed frequently because of blockage. A
cloudy filtrate is obtained, which after work-up according to the example yields a dark, cloudy produc-~
having a platinum content of 36 ppm.
The catalytic oxidation of ether alcohols according ~o the general equation Pk/C
R(OC~32CH2 )nOCH2CH2(~
has long been known and i5 described for example in German Patent 2,936,123 and European Patent 206,054~
However, as the molar mass of the radical R increases, the separation and thus the complete recovery ancl recy-cling of the noble metal catalyst becomes problematicO
Thus in German Patent 3,446,561, on ~age 4, a laborious four-stage method is described to xestrict the losses of noble metal. An essential processing disad~antage of this procedure lies in the fact that the reaction mixture;
prior to the filtra~ion, i~ diluted with 1-10 times -tha amount of acetone, which must -then be remov~d again by distillation, purified and recycled. The noble metal contents of 1-4 ppm, which can ultimat~ly be obtained in the product, are also relatively high and lead to a gradual decrease in the acti~ity of the catalyst. Over-all, this entail~ a sexious sconomic disadvantage.
The object was therefore to develop an indus^trially and economically acceptable process for ca~alyst recove~y.
The sub~ec~ of the presen~ i~venkion is a process for-the recovery of catalysk in the prepara~ion of e~hsr-car-boxylic acids by catalytic ox:idation using a susp~ndecl catalyst, characterized in that the reaction mixture is ~O 91/16294 - 2 -2 ~ ~ O ~ ~J 3 PCT/F.P9ltoo649 ~,..
. ..;
subjected to a cross-flow filtration.
Preferred ether-carboxylic acids are-those of the formul~
R--( OC~I2C~I2 ) nOC~I2COOH
in which R is a linear or branched alkyl radical of 1 to S about 24 carbon atoms, an aryl radical, such as for example a phenyl, naphthyl or biphenyl radical, addition~
ally an alkyl(Cl-C24)aryl radical, the aryl radical being for example a phenyl, naph~hyl or biphenyl radical, or an arylalkyl radical, f~r example a benzyl rzdical/ and n is a number from 0 to about 24. The abovementioned aryl radicals can be substituted.
In the cross-flow filtration, the catalyst-con-taining reaction mixture is pumped at a high overflow velocity tangentially ~o the membrane surface through -~he filter elemen-t, the filtrate being withdrawn perpendicular to the direction o~ flow through the membrane layer, as described in de~tail in ULLMANN's Encyclopedla of Industrial Chemistry, 5th Editiont Vol. B2, p. 10-54.
Tu~e-shaped ilter element~ having a membrane layer on the inner ~ide of ~he tubes are par~icularly suitc~hle.
Preferred membrane and support material is ~ -Al203 and ZrO2; however, plastic and carbon elemen.ts can also be used. Membrane and support can be composed of different materials. The necessa~y pore sizes are expediently in the ultrafiltration range, for example b~we~n abou~ 1 and about 200 nmO A suitable appara-tus is descr:;bed i~
th~ ex~mple (cf. in this con~ext also Figure 1 on page 7).
The cro~s-flow 1Eil~ration according ~o thP inven~io:n can be pe.rformed at tamperat~res from about ~0 -to c~bout 150~C~
It has proved ~o ~e advan~ageou~ to carry out ~he :Eilt ration at temperatures from c~bout 50 -to c~bout 100C, :in particular at tempera~ure~ ~rom abou~ 60 to abou-t 80C
W~ 91/1~294 - 3 - PC'~ P91/00~9 A pressure drop must of course prevail hetween the Eront side and the rear side of the membrane, ~o that the reaction solution can be moved -through.
A solubilizer used in the oxidation can -facilitate filt~
ration. Solubilizers without hydroxyl groups are suit~
able. Glycol ether~ without hydroxyl groups are particu~
larly suitable, in particular diethylene glycol dime-thyl ether.
A brief hydrogen treatment after the oxidation lS
completed at the reaction temperature (about 50 to about 100C) has proved to be advantageous, -to precipi-ta-te an~
dissolved and colloidal noble metal traces, so -that filter elements with somewhat larger pores can be used.
Apar-t from hydrogen Eormaldehyde, ~or example, can also be used as reducing agent.
Surprisingly, the problems of filtration (blockage, losses of noble metals) are solved by the process accord~
ing to the invention without the need for expenst~e measures, such as for example clilution with a solventO
The example below ~erves to illustrate the proce~
according to the invention wi-thou-t restricting it theretoO
Example A reaction sol~tion Erom the catalytic o~ida-tion f comprising 25 % by weight of ether carboxylic acids of the formula R-(OCH2C~23nOC~2COO~ having linaar alkyl group~
R having a distribution of C12 to C14 and a mean value of n = 4 and also 45 % by weight of diethylene ylycoL
dimethyl ether~ 25 % by weight of water and 5 ~ by weight of a suspended commercial cataly~t (5 % by weigh-t o-~platin~n on acti~ated charcoal) is txeated for 30 minutes at 70C with hydrocJen in a bubbl~ column and then sub-jec-ted to a cross-Elow Eil-tration.
~O 91/16294 2 ~ 8 ~ ~ 7 8 PCT~Epgl,00~49 The filter element is composed of a ZrO2 tube (diametQr:
7 mm, length: 250 mm), the inner side of ~hich is composed o~ a membrane layer having pore sizes of 35 nm ( 1O-a m) . An apparatus is used, which corresponds to the accompanyiny drawing (cf. Figure 1 on page 7)O The reaction solution is pumped thxough ~he filter elemen~
(B) situated in a housing (A) at a linear flow velocity of 5 m/s. A pressure P1 o~ 3 bar is established a~ a temperature of 70C. A fil-trate flow of 2.5 l/h is obtained. The catalyst is concentrated to a solids content of approxLmately 30% by weightj this concentrate is returned to the catalytic oxidation.
After separation of the diglycol dimethyl ether and ~ater from the filtrate by distillation, the mixture of ether-15 carboxylic acids is obtained as a clear, p~le producthaving a residual ~lantity o~ platinum of less than 0.5 ppm.
Comparison example The reaction solution described in -the above ex~mple i5 repeatedly filtered on a suction fil-ter wi-th insertsd filter paper (for quantita-tive analysis). The filter paper must be changed frequently because of blockage. A
cloudy filtrate is obtained, which after work-up according to the example yields a dark, cloudy produc-~
having a platinum content of 36 ppm.
Claims (12)
1. Process for the recovery of catalyst in the pre-paration of ether-carboxylic acids by catalytic oxidation using a suspended catalyst, characterized in that the reaction mixture is subjected to a cross-flow filtration.
2. Process according to Claim 1, characterized in that the ether-carboxylic acids are those of the formula R-(OCH2CH2)nOCH2COOH
in which R is a linear or branched alkyl radical having 1 to about 24 carbon atoms, an aryl, alkyl-aryl or arylalkyl radical unsubstituted or sub-stituted at the aromatic nucleus and n is a number from 0 to about 24.
in which R is a linear or branched alkyl radical having 1 to about 24 carbon atoms, an aryl, alkyl-aryl or arylalkyl radical unsubstituted or sub-stituted at the aromatic nucleus and n is a number from 0 to about 24.
3. Process according to at least one of Claims 1 and 2, characterized in that the filter element in the cross-flow filtration is composed of ceramic material and/or carbon.
4. Process according to at least one of Claims 1 to 3, characterized in that the filter element in the cross-flow filtration is composed of ZrO2 and/or .alpha.-A1203.
5. Process according to at least one of Claims 1 to 4, characterized in that the filtration is carried out at temperatures from about 20 to about 150°C.
6. Process according to at least one of Claims 1 to 5, characterized in that the filtration is carried out at temperatures from about 50 to about l00°C.
7. Process according to at least one of Claims l to 6, characterized in that the filtration is carried out at temperatures from about 60 to about 80°C.
8. Process according to at least one of Claims 1 to 7, characterized in that the cross-flow filtration is performed in the presence of a solubilizer without hydroxyl groups.
9. Process according to at least one of Claims 1 to 8, characterized in that the cross-flow filtration is performed in the presence of a glycol ether without hydroxyl groups.
10. Process according to at least one of Claims 1 to 9, characterized in that the cross-flow filtration is performed in the presence of diethylene glycol dimethyl ether.
11. Process according to at least one of Claims 1 to 10, characterized in that the reaction mixture, prior to the cross-flow filtration, is treated with hydrogen at temperatures from about 50 to about 100°C.
12. Process according to at least one of Claims 1 to 10, characterized in that the reaction mixture is treated with a reducing agent, preferably with hydrogen or formaldehyde.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4012128A DE4012128A1 (en) | 1990-04-14 | 1990-04-14 | METHOD FOR RECOVERY CATALYST |
| DEP4012128.3 | 1990-04-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2080478A1 true CA2080478A1 (en) | 1991-10-15 |
Family
ID=6404451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002080478A Abandoned CA2080478A1 (en) | 1990-04-14 | 1991-04-05 | Process for catalyst recovery |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0524985B1 (en) |
| JP (1) | JP3249115B2 (en) |
| AT (1) | ATE125248T1 (en) |
| CA (1) | CA2080478A1 (en) |
| DE (2) | DE4012128A1 (en) |
| DK (1) | DK0524985T3 (en) |
| ES (1) | ES2077222T3 (en) |
| GR (1) | GR3017113T3 (en) |
| WO (1) | WO1991016294A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2520563A1 (en) * | 2009-12-28 | 2012-11-07 | Kao Corporation | Method for producing polyoxyalkylene alkyl ether carboxylic acid and salt thereof |
| US9555374B2 (en) | 2009-04-29 | 2017-01-31 | Basf Se | Method for conditioning catalysts by means of membrane filtration |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT408544B (en) * | 1996-02-12 | 2001-12-27 | Oebs Gmbh | METHOD FOR TREATING POLLUTED ALKALINE AQUEOUS CLEANING SOLUTIONS |
| FR2749191B1 (en) * | 1996-06-04 | 1998-07-17 | Rhone Poulenc Fibres | METHOD FOR FILTERING A THREE-PHASE REACTION MIXTURE |
| US5885452A (en) * | 1997-05-28 | 1999-03-23 | Koteskey; Gary L. | Effluent filtering apparatus |
| DE19727715A1 (en) * | 1997-06-30 | 1999-01-07 | Basf Ag | Process for the preparation of 1,4-butanediol |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2757800A (en) * | 1953-01-23 | 1956-08-07 | Joseph B Kucera | Strainer device |
| DE2936123A1 (en) * | 1979-09-07 | 1981-04-02 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING ALKOXY ACETIC ACIDS |
| US4861471A (en) * | 1987-03-20 | 1989-08-29 | Toshiba Ceramics Co., Ltd. | Activated sludge treatment apparatus |
-
1990
- 1990-04-14 DE DE4012128A patent/DE4012128A1/en not_active Withdrawn
-
1991
- 1991-04-05 DE DE59106051T patent/DE59106051D1/en not_active Expired - Lifetime
- 1991-04-05 AT AT91907141T patent/ATE125248T1/en not_active IP Right Cessation
- 1991-04-05 CA CA002080478A patent/CA2080478A1/en not_active Abandoned
- 1991-04-05 JP JP50684791A patent/JP3249115B2/en not_active Expired - Fee Related
- 1991-04-05 WO PCT/EP1991/000649 patent/WO1991016294A1/en active IP Right Grant
- 1991-04-05 ES ES91907141T patent/ES2077222T3/en not_active Expired - Lifetime
- 1991-04-05 DK DK91907141.5T patent/DK0524985T3/en active
- 1991-04-05 EP EP91907141A patent/EP0524985B1/en not_active Expired - Lifetime
-
1995
- 1995-08-11 GR GR950402227T patent/GR3017113T3/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9555374B2 (en) | 2009-04-29 | 2017-01-31 | Basf Se | Method for conditioning catalysts by means of membrane filtration |
| EP2520563A1 (en) * | 2009-12-28 | 2012-11-07 | Kao Corporation | Method for producing polyoxyalkylene alkyl ether carboxylic acid and salt thereof |
| EP2520563A4 (en) * | 2009-12-28 | 2013-09-11 | Kao Corp | Method for producing polyoxyalkylene alkyl ether carboxylic acid and salt thereof |
| US8940933B2 (en) | 2009-12-28 | 2015-01-27 | Kao Corporation | Method for producing polyoxyalkylene alkyl ether carboxylic acid and salt thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05508800A (en) | 1993-12-09 |
| JP3249115B2 (en) | 2002-01-21 |
| EP0524985B1 (en) | 1995-07-19 |
| EP0524985A1 (en) | 1993-02-03 |
| GR3017113T3 (en) | 1995-11-30 |
| ATE125248T1 (en) | 1995-08-15 |
| ES2077222T3 (en) | 1995-11-16 |
| DE59106051D1 (en) | 1995-08-24 |
| DE4012128A1 (en) | 1991-10-17 |
| WO1991016294A1 (en) | 1991-10-31 |
| DK0524985T3 (en) | 1995-11-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |