Machine for processing aqueous solution of spent rhodium hydroforming catalyst

专利摘要:
A water-soluble salt of a carboxylic acid having 7 to 22 carbon atoms is added to the solution, the latter is treated at 50 to 200 DEG C with an oxidising agent and the rhodium precipitated as a water- insoluble compound is separated off.
公开号:SU1498380A3
申请号:SU874202996
申请日:1987-07-24
公开日:1989-07-30
发明作者:Бекстен Лудгер；Купис Дитер
申请人:Рурхеми Аг (Фирма)；
IPC主号:

专利说明:

The invention relates to a process for the treatment of a WATNRGS noble-metal spent catalyst solution, in particular, a method for processing a water-based spent rhodium catalyst solution, KOTOpbtfi can be applied in petrochemical industry, in particular in the hydroformylation process.
The purpose of the invention is to reduce rhodium losses by using the soluble carboxylic sodium salt Cg., J as the carboxylic acid salt, taken in excess in terms of, and treating the solution after mixing with an oxidizing agent at 100 ° (:: and pH 4.5-7 ,eight.
Example 1. 300 I aqueous solution of the working catalyst hydP formJ J Ip () Mon tava, wt.%:
Na j - Triphenylphosphine trisulfonate (TFFTS) Na - Triphenylphosphine oxide trisulfonate (TFFTS)
Na 2 - Triphenylphosphine disulfonate (TFFDS) Na 2 -Triphenylphosphipoxide disulfonate (TFFODS)
On I - Triphenylphosphine - sulfide disulfonate (TFFSDS)
NO - Benzene sulphonate (LC)
The rest of the salts (dry BcinecTBO obtained by evaporation by sudden iiomi, 8
45 0.14
0.50
0.02
0.97 5.12

CO OQ CO
00
 cm
pressure under pressure and
p 2.25 kPa)
Rhodium135 ppm
mixed with 18.53 g of an aqueous solution of sodium 2-ethylhexanoate (65.8% by weight of a solution of sodium salt). i The resulting solution is oxidized in a glass autoclave at a pressure of 0.4–1. 45 kPa and a pH of 6.4 by Introduce jg NIN 150 liters of air. The reaction is completed after 2 hours. Then the contents of the auto-cool are cooled. An oily layer is formed, which is separated by extraction of 60 g of toluene a5
re-extraction of 50 g of toluene. 7.5% of the rhodium discharged in the initial solution remains in the aqueous solution.
Example 2. In a 1-liter glass automaton with a capacity of 1 l, 300 g of an aqueous solution of the spent catalyst of the following composition are fed, wt.%;
TFFTS0,22
TFFOTS1,72,
Na J - Triphenylphosphine Sulfide Trisulfonate
(TFFSTS)
Tfffs
25
Tffods
BS
Salt residue
Rhodium
0.03
0.01
0.48
0.92
7.19
165 chumpn,
thirty
n
jg l a5
 .
20 -
98380
ri (L5.8% by weight of paei Bopa sodium salt). With stirring, heated to 100 ° (after which the oxidation is carried out by introducing oxygen at a pressure of 0, b MCH and pH value b, 3. The oxidation is completed after 4 hours. Then cooled and extracted with toluene as in example 2. In an aqueous solution 4.8% rhodium contained in the stock solution,
Example 4. Example 3 is repeated, with the difference that in addition to; uTBOpy 2-sodium hexanoate was added an additional 5 g of 2-ethylhexanoic acid. At the same time, the oxidation is carried out at 100 ° C and RP of medium 6.0 for 2 hours. Then it is cooled and extracted in Example 2.
In the aqueous solution, 4.7 / o of the rhodium contained in the initial solution remains.
Note .J p s 5 a-d. 300 g of an aqueous solution of 1) trabptan catalyst composition, wt.%:
25
thirty
Tfts
TFFOTS
TFFSTS
Tfffs
Tffods
TFFSDS
BS
Salt residue
Rhodium
3.13 2.0
0.02
0.2
0.42
0.02
0.55
2.33
174 h / mp
40
8.0 g of an aqueous solution of 2-ethylhexano is mixed with those indicated in Table 1 of sodium (65.81 by weight of the sodium salt solution) and 5.0 g of 2-ethylhexanoic acid. With stirring, heated to 100 ° C, after which the oxidation is carried out by the addition of hydrogen peroxide. In this case, 10 g of hydrogen peroxide (30% by mass) is added over a period of 5 minutes and the mixture is allowed to react at a setting pressure. The oxidation, which is carried out at RP of medium 6.0, is completed dg after 30 minutes.
The contents of the glass autoclave are cooled and the aqueous solution is first mixed with 60 g of toluene, shaken, and after separation of the toluene phase, 50 g of toluene are extracted again. After separation of the toluene phase in the aqueous solution, 6.2% of the rhodium contained in the stock solution remains.
Example 3. 300 g of an aqueous solution of a spent catalyst used in Example 2 and 8.0 g of a solution of 2-ethylhexanoate, sodium 35, were used in a 1 liter glass autoclave.
and sodium hydroxide and is fed into a caravan with a capacity of 1 liter, heated under stirring, after which oxidation is carried out by supplying air at a pressure of 0.4 given in table 1 of the pDy. The amount of air supplied is also given in table 1. Acid finished after 4 hours.
The contents of the glass. Auto-recycle is processed analogously to an example.
The amount of rhodium remaining in the aqueous extraction solution is listed in Table 1.
Comparative Example 1 is carried out using a water-soluble carboxylic acid salt having less than 8 carbon atoms. Repeat example 56 with the difference that 19.53 g of n-С -acids and 3.0 g of NaOn are used with an amount of air of 248 l. The pH value is 5.2. The birth content in one hundred water is 31.2%.
50
55
0
mixed with specified in table.1 g
5 quantities of carboxylic acid
and sodium hydroxide and is fed into a 1 liter glass autodruck, heated with stirring, before oxidation is carried out by supplying air at a pressure of 0.4 MPa and the RP value of the medium given in Table 1. The amount of air supplied is also given in table 1. The oxidation is completed after 4 hours.
The contents of the glass autoclave are processed as in Example 1.
The amount of rhodium remaining in the aqueous solution after extraction is given in Table 1.
Comparative Example 1 is carried out using a water soluble carboxylic acid salt having less than 8 carbon atoms. Example 56 is repeated, with the difference that 19.53 g of n-C-acid and 3.0 g of NaOn are used with an air quantity of 248 l. The pH value is 5.2. The birth content in waste water is 31.2%.
0
five

Examples 6 a-g, 300 g of an aqueous solution of spent hydroformylation catalyst of the following composition, wt.%:
1, 70 1.73 0.04 0.38 0.03 0.55 4.23
124 ppm, listed in Table.
salts
colifTFTS
TFFOTS
Tfffs
Tffods
TFFSDS
BS
Remainder
Rhodium
mixed with sodium 2-ethylhexanoate (65.8% by weight of the sodium salt solution) and fed into a 1 liter glass autoclave. By adding sodium hydroxide or sulfuric acid, the pH value given in Table 2 is adjusted, which is maintained during oxidation. After stirring, it is dissolved at 100 ° C and 0.45 MPa by the addition of 150 liters of air. The reaction is completed within 2 hours. An oily layer is formed, and the liquid in Example 1 is separated by extraction with toluene.
The amount of rhodium remaining in one solution after extraction is given in Table 2.
Example 7. 300 g of an aqueous solution of the spent catalyst are distilled in order to remove the existing organic products. The distillation is carried out at normal pressure. At a temperature in the upper part, 78.3 g of product (26.1% by weight of the aqueous solution) are withdrawn.
The remainder of the distillation is supplemented with water to 300 g, and it is processed in the manner described in examples 6 a-d.




Example 11 (comparative) Oxidation is carried out at a pH of 4.5 and 8,

R -
ten
15
20
Example 6a is repeated with the fact that the oxidation is carried out at a pH value of 4.3 or 8.7. G. This is the birth content in waste water is 26 and 33.5%, respectively
Thus, as follows from the presented data, according to the invention, at least 90% of the rhodium contained in it can be recovered from the aqueous solution of the spent catalyst.
The organic phase can be used without further processing directly as a component of the catalyst system. In addition, it is also possible that the rhodium carboxylate that is retained in an organic solvent is extracted by treatment with phosphine ligand-containing solutions and the resulting extract is used as a catalyst solution.

权利要求:
Claims (1)
[1]
25g Formula of Invention
A method for processing an aqueous solution of spent rhodium catalyst hydroformylation, comprising mixing the spent aqueous solution of catalyst containing a complex rhodium compound with a salt of carboxylic acid and separating the product containing rhodium by extracting a water-insoluble organic solvent, characterized in that water-soluble carboxylic acid salt, the sodium salt of carboxylic acid is used as the salt of carboxylic acid
Cj.j, for mixing, an excess of carboxylic acid salt in terms of rhodium is taken, and after mixing, the solution is worked up with an oxidizing agent at a pH of 4.5-7.8,
Hydroformylation of diieobutylene and subsequent oxidation is obtained.
Get 1 by formalization of tetrapropylene and subsequent oxidation
table 2
A.5 5.8 6.2 6.6 6.9
U, A5
14.45
14.45
13.8
13.8
Editor M. Medoluzhenko
Compiled by N.Putov Tehred M.Didyk
Order 4461/58
Circulation 486
VNIIPI State Committee for Inventions and Discoveries at the State Committee for Science and Technology of the USSR 1P035, Moscow, Zh-35, 4/5 Rauschskaya Emb.
T a about face 1
9.6
6.2 6.1 7.7 6.7
Proofreader M.Iojo
Subscription

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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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DE19863626536|DE3626536A1|1986-08-06|1986-08-06|METHOD FOR RECOVERING RHODIUM FROM AQUEOUS SOLUTIONS CONTAINING RHODIUM COMPLEX COMPOUNDS|

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