Method of recovering hydroforming catalyst containing rhodium and phosphines with sulfoacid groups

专利摘要:

公开号:SU1232150A3
申请号:SU833643951
申请日:1983-09-21
公开日:1986-05-15
发明作者:Гертнер Родерих；Корнильс Бой；Бекстен Людгер；Купис Дитер
申请人:Рурхеми Аг (Фирма)；
IPC主号:

专利说明:

The invention relates to a method for recovering a rhodium-containing hydroformylation catalyst, in particular to a method for recovering a water-soluble hydroformylation catalyst containing rhodium and phosphines with sulfate groups and an aqueous solution of the spent catalyst, and can be used in the petrochemical industry.
The purpose of the invention is to increase the degree of catalyst recovery.
Example 1.100 g of an aqueous solution of spent catalyst containing per kg 0.155 g of rhodium, 0.160 g of iron, 9.0 g of sodium tripothenate triphenylphosphine (TSTFF), 22.0 g of sodium tripothenate sodium triphenylphosphine (TSTOTPP), 2.0 g of sodium tryurfonate Triphenylfoeofine sulfide (TSCTFP), 4.0 g of sodium dioxid triphenylphosphine (DMTPP), is treated by shaking 17.04 g of extractant in 82.96 g of toluene by dissolving 100 of triisooctylamine in 900 g of toluene.
Example 3. Example 1 is repeated, with the difference that 100 g of water
5 of the spent catalyst solution are acidified with 49.2 g of a 40% silver bottle. The resulting acidified solution is further treated as in Example 2,
 About Example 4. Example 1 is repeated. The difference is that 100 g of the aqueous solution of the spent catalyst is acidified with 20.2 g of 10% sulfuric acid followed by 6-K, applied by extraction, applied at each stage. a solution of 16.54 g ecetragent in 60 g of tol ol. The extractant is prepared by dissolving 100 g of tri-n-octylamine 900 g of toluene.
20 Example 5. Example 1 is repeated, with the difference that 100 g of an aqueous solution of the spent catalyst is acidified with 20.2 g of 10% silver on the next 6 times eq.
la for 30 min. Eketragent is applied with 25, applied at each stage
It is prepared by dissolving 100 g of triisooctylamine and 30 g of sulfur cell acid in 900 g of toluene, using amine as an etagent, and it is used in an amount of 0.25 mole n equivalent of sulfonate. In the separation of the toluene phase, the ecetraction is repeated five more times using the same ecologically and toluene,
In a three-necked flask enabenced by a discharge valve in the bottom, organic phases separately mix e 0, .1 n. aqueous sodium hydrocate until the pH of the medium is at least 8, and mixing is carried out at the same time and intensively stirred. Then, the aqueous phases, the content of the recovered catalyst, are separated from the organic phases, before which they can be used again in the hydroformylation in the next phase, diluted with water.
Example 2 Example 1 is repeated. The difference is that 100 g of the aqueous solution of the spent catalyst shows 39.3 g of 10% green billet with a 6-fold extraction process, using 16.54 g of the ecologically agent in each stage. 60 g of toluene (0.25 mol per equivalent of eulfoquel group). Eketragent
prepared by dissolving 100 g of triisooctylamine in 900 g of toluene.
Example 3. Example 1 is repeated, with the difference that 100 g of water
the spent catalyst solution is acidified with 49.2 g of 40% ferric acid. The acidified solution obtained in this way is further treated as in Example 2.
Example 4. Example 1 is repeated. The difference is that 100 g of an aqueous solution of a spent catalyst is acidified with 20.2 g of 10% sulfuric acid, followed by 6-k, and applied at each stage. a solution of 16.54 g ecetragent in 60 g of toluene. The extractant is prepared by dissolving 100 g of tri-n-octylamine in 900 g of toluene.
Example 5. Example 1 is repeated, with the difference that 100 g of the aqueous solution of the spent catalyst is acidified with 20.2 g of 10% green billet of the next 6-fold exposure 5
0
a solution of t6.54 g of zetaragent in 60 g of toluene (the Eketragent is prepared by dissolving 38.1 g of tri-n-hekeyl-amine in 461.9 g of toluene), Amount 0 of the amine ecological agent used in Kacheetva corresponds to 0.25 mol of amine per equivalent of sulfonate at each stage of extraction.
Example 6. Example 1 is repeated with the difference that 100 g of the aqueous solution of the spent catalyst is acidified with 20.2 g of 10% sulfur. A 6-fold extraction was applied using a solution of 16.54 g of the ecologic agent in 60 g of toluene on each etiadia (the ecologic agent is prepared by treating 34.14 g of di-2-ethylhexylanin in 465.86 g of toluene). The amount of amine used as an ecology agent corresponds to 0.25 mol per equivalent of sulfonate at each stage of eetraction.
The results of examples 1-6 evedy in table. 1. They show that the correlation of the added kielta to the existing sulfonate groups only slightly influences the effect of extracg and, in examples 1-6, the degree of recuperation of parents is 5-5 96.5-98 , 5%, and the degree of recovery of foefin TSTFF - 99.5 100% (foefin TSTOTP, TSCTPP and DSOTPP are impurities).
five
0
Example 7. 100 g of an aqueous solution of the spent catalyst of composition specified in Example 1 are mixed with 20.2 g of 10% sulfuric acid. The solution of the catalyst acidified with sulfuric acid is subjected to a triple extraction using, at the first stage, a solution of 7.54 g of extractant in 70 g of toluene (0.25 moamine per equivalent of sulfonate); in the second stage, a solution of 7.54 g of extrint in 70 g of toluene (0.25 mol per equivalent of sulfonate) f per third stage of a solution of 15.08 g of extractant in 70 g of toluene (0.50 mol of amine per equivalent of sulfonate).
The extractant used was prepared from 61.88 g of isotridecylamine and 438.12 g of toluene.
The resulting toluene solutions (extracts) are separately mixed with 1N, sodium hydroxide solution until the pH of the medium is equal to t2.0.
The results of the experiment are summarized in table 2
The degree of recovery of rhodium is 95.6%, and the degree of recovery of phosphine TSTFF is 100%.
Example 8 Example 1 is repeated, with the difference that 100 g of an aqueous solution of spent catalyst containing 345 mg of rhodium, 27.0 mg of iron, 19.2 g of TSTFF, 38.0 g of TSOTPP, 0,7 g of TSCTPPP, 2, per kg, per kg 0 g of sodium disulfonate triphenylphosphine DCTFP, 7.7 g DSOTFP, acidified with 6 g concentrated sulfuric acid (1.5 mol per mol of the sulfonic acid group) or 3 g of acetic acid (1.3 mol per mol of the sulfonic acid group), followed by extraction 100 g of isotridecylamine solution in toluene. The resulting organic phase is treated with 1N, sodium hydroxide solution until the pH of the medium is reached, Rabbi12.
The results of the experiments are summarized in table.
The degree of recovery of rhodium is 98.3%, and the degree of recovery of phosphine TSTFF - 98.4 - 100%.
Example 9. Example 8 is repeated, with the difference that 10.0 g of the aqueous solution of the spent catalyst is acidified with 3 to acetic acid (1.3 mol per mole of sulphate acid) and then extracted with 100 g of a solution of isooctylamine in toluene.
5 nd to a t5
20
.25
zo up to 5
.
50
55
The results of the experiment are summarized in table 4.
The degree of recovery of rhodium is 98%, and the degree of recovery of phosphine TSTFF - 100%.
Example 10. Example 8 is repeated, with the difference that isotridecyl amine is used as a solution in n-butanol after acidification with acetic acid in an amount of 1.3 mol per mole of sulfonic acid groups. The results of the experiment are summarized in table. 5. The degree of recovery of rhodium is 96.7%, and the degree of recovery of phosphine TSTFF -. 99%.
Example 11. Example 8 is repeated with the difference that di-n-hexylamine is used as a solution in diethyl ether after acidification. acetic acid. The results of the experiment. are summarized in table. 6. The degree of recovery of rhodium is 98%, and the degree of recovery of phosphine TSTFF - 99%.
Example 12. Example 8 is repeated, with the difference that isonoylamine is used as a solution in a hydrocarbon fraction with a bp. 140-17b s (density at 12 ° С is 0.757 g / l, n 1.420, contains unbranched, branched and cyclic naschatyennye hydrocarbons with the number of carbon atoms from 7 to 10) after acidification with acetic acid, taken in an amount of 1.3 mol per mole sulfonic acid groups, the pH of which is adjusted to pH 12 using sodium hydroxide.
The results of the experiment are summarized in table 7.
The degree of recovery of rhodium is 96.3%, and the steppe of recovery of phosphine TSTFF is 98.4%.
Example 13. Example 8 is repeated with the difference that tri-n-hexylamine is used as a solution in cyclohexane (Test I) xylene (Test C) and 2-ethylhexanol (Test III) after acidification with acetic acid, the organic phase being treated with 0, 1 n. sodium hydroxide solution until the pH of the medium is 8.
The results of experiments I-III are summarized in table. eight.
At the same time, the degree of rhodium recovery is 96.8-97.2, and the degree of phosphine recovery is 96.9 - 98.4%.
As amine salt | Spent catalyst solution f
Recovered after extraction and treatment with water and sodium hydroxide solution, the salt of rhodium in water solution after addition to 100 g; ..one
I.Table2
1st stage extract (25% extraction
amine theory)
2nd stage extract (extraction of 25% of amine theory)
3rd stage extract (extraction of 50% of amine theory)
Table 1
6.5 0.60
0.11
0.08
10.5 0.25
0.24
0.12
22.3 0.05
0.65 0.10 0.18
The solution after extraction (114.6 g)
Combined toluene solutions after triple extraction
After treatment with sodium hydroxide solution and addition to 100 g.
Table 3





225
114
6.0
and 313

and 24.6

5, 4
Acidification with sulfuric acid 3.1 1.50 0.25
5.8 0.39
1.13
261.1 0.03 2.42 Acidification with acetic acid
39 1.90 0.65
3.5 0.02
1.21
227.5
1.94
After treatment with sodium hydroxide solution and addition to 100 g.
Continued that bl.2
118.6
1.20 0.10 0.07
2.1
0.18 0.3.1
1.13
.0.29
0.07 0.02 0.17
0.21
0.43
1.21
.0.17.
1.94
0.07
0.27
Acidification with acetic acid
a) first stage extract
170
16.5 1.67
(extraction of 100% amine theory)
b) second stage extract
102
12.0 0.25
(extraction of 50% of amine theory)
c) third stage extract
66.1
6.3


6.9
235.2
 After treatment with sodium hydroxide solution and addition to 100 g.
Table 5


, 6
38,8
After treatment with sodium hydroxide and supplement to 100 g.
Table A
0.1
0.18 -0.39
0.65
0.11
0.95
0.11
2,1 €
0.07
0.09
1.85
0.62
0.21
0.42



315.2 38.6 1.88
22,8
3.80.02
Solution after
extraction
(91 g) 7.0
227.6 0.02
After treatment with sodium hydroxide solution and addition to 100 g.



312 38.6 1.87
20.2 3.6
0.02
12.8 227.8 0.03
Treatment with sodium hydroxide and supplements up to 100 g.
0.64
0.21 0.40
1.22
0.19
1,940.07
Oj28
Table 7
0.64
0.21 0.42
0.02
1.20
0.18
1.96 0.07
0.27
.
314
21.5 3.5
38.1, 1.87 0.63
0.02 1.20
9.5
313.5
l 21.1
10; 4

313.2
20.8
11.6
38
3.5
228.5
38
3.4
228.6
1.86 0.62
0.02 1.20
0.04
0.02
0.05
1.97
1.84 0.60
1.20
j, 00
228.1 1.97 0.03 0.07
0.07
0.07
 After treatment with sodium hydroxide and supplement to 100. g.
0.21
0.42
0.02 1.20
0.17
0.28
1.86 0.62
0.21
0.42
0.02 1.20
0.17
0.04
1.97
0.07
0.28
1.84 0.60
0.21
0.40
1.20
j, 00
0.07
0.17 O.Zb

权利要求:
Claims (2)
[1]
1. METHOD FOR RECOVERY OF A HYDROFORMILIZATION CATALYST CONTAINING RHODY AND PHOSPHINS WITH SULFURIC-ACID GROUPS, from an aqueous solution of spent catalyst by multistage extraction using acid, an aliphatic amine and an organic solvent, characterized in that sulfur is added to increase the degree of acetic acid, taken in an amount of 1.1-10 mol per 1 mol of sulfonic acid group, and subjected to a 2-6-step extraction with a solution of an aliphatic amine, selected and from the group containing triisooctylamine, tri-n-octylamine, tri-n-hexylamine, di-n-hexylamine, isononylamine, di-2-ethylhexylamine, isotridecylamine, in an organic solvent selected from the group containing n-butanol, 2-ethylhexanol , diethyl ether, hydrocarbon fraction with so Kip. 140-170 ° C, cyclohexane, toluene and xylene, when 0.25 to 1.0 mol of the indicated amine is added at each extraction stage to the equivalent of sulfonic acid group, followed by processing of 0.1-1 N organic phases obtained during extraction. an aqueous solution of sodium hydroxide until a pH of 8-12 is reached and the aqueous phase is separated.
[2]
2. The method according to p. 1, characterized in that the acid used for acidification is added in the form of a salt of the specified amine.
SU 1232150 A5 ’1232150

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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DE19823235029|DE3235029A1|1982-09-22|1982-09-22|METHOD FOR RECOVERY OF WATER-SOLUBLE, RHODIUM-CONTAINING HYDROFORMYLATION CATALYSTS|

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