JPS63197505A - Desorption liquid of group viii noble metallic complex adsorbed to adsorbent and desorbing method - Google Patents

Abstract

PURPOSE:To efficiently recover a group VIII noble metallic complex by bringing an adsorbent adsorbing the group VIII noble metallic complex into contact with desorption liquid consisting of a polar soln., organic base and organic phosphorus compd. CONSTITUTION:A group VIII noble metallic complex is adsorbed to an adsorbent by bringing organic liquid incorporating the group VIII noble metallic complex which has a ligand especially the ligand consisting of organic phosphorus compd. into contact with the adsorbent. After adsorption, the organic liquid stuck to the adsorbent is removed with a solvent. Then desorption liquid is flowed on the adsorbent and thereby the complex adsorbed thereto is desorbed. As the desorption liquid, a liquid having the composition consisting of a polar solvent, organic base and organic phosphorus compd. is used. Thereby the complex adsorbed to the adsorbent is efficiently eluted in the desorption liquid.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a desorption liquid and a desorption method for desorbing a group (I) noble metal complex adsorbed onto an adsorbent from said adsorbent.

BACKGROUND OF THE INVENTION Conventionally, a soluble complex of a Group I noble metal compound and an organic phosphorus compound has been used as a catalyst in the hydroformylation or hydrocarboxylation reaction of olefins.

Since the catalyst is uniformly dissolved in the reaction product, it is necessary to separate and recover the expensive catalyst and return it to the reaction system.

When the reaction product has a low boiling point, it is possible to separate the reaction product and the catalyst liquid by distillation and reuse the catalyst liquid in the next reaction.

However, in this reaction, various high-boiling byproducts are produced, so in order to avoid accumulation of high-boiling byproducts in the reaction system due to circulation of the catalyst liquid, high-boiling byproducts are removed from the reaction system by distillation. It is necessary. Since the removed high-boiling byproducts contain expensive Group III noble metals,
It is necessary to collect this efficiently.

However, at high temperatures of 150°C or higher, the above complex undergoes thermal deterioration and its catalytic activity decreases. requires a special activation treatment to activate the separated catalyst.

If the reaction product has a high boiling point, it can be removed by a method other than distillation, such as adsorption or extraction, in the same manner as above.
It is necessary to recover the Group noble metal complex or, in the case of distillation, to carry out a special activation treatment to activate the separated catalyst.

Conventionally, the following method has been proposed as a method for recovering a soluble complex of a group (I) noble metal compound and an organic phosphorus compound or a group (I) noble metal from a reaction solution used in the hydroformylation reaction of an olefin.

JP-A-49-121793 discloses that when an olefin such as butene is subjected to a hydroformylation reaction using a rhodium-tertiary phosphine complex catalyst, the low-boiling point portion is separated by distillation, and then rhodium is extracted from the high-boiling point distillation residue. - As a method for separating a tertiary phosphine complex catalyst, a mixture consisting of the catalyst and a high-boiling organic distillation residue is first brought into contact with an adsorbent typified by an alkaline earth metal silicate such as magnesium silicate, and then an aromatic A method is shown in which a hydrocarbon solvent is used to wash high-boiling organic distillation residues from the adsorbent, and a polar solvent containing a small amount of tertiary amine is used to elute the catalyst adsorbed on the adsorbent. .

Japanese Patent Publication No. 53-3993 discloses that in adsorbing and separating a group (I) noble metal from an organic liquid containing a group (I) noble metal complex using activated carbon, methanol is allowed to coexist in the organic liquid. . In this method, for example, propylene is subjected to a hydroformylation reaction in the presence of a rhodium-phosphorous compound complex catalyst, and then the aldehyde product is separated by distillation, and an organic liquid containing a high-boiling by-product and a catalyst is produced. When carrying out a hydroformylation reaction by charging rhodium into a reactor repeatedly as necessary, rhodium can be recovered from an organic liquid containing high-boiling byproducts and a catalyst by adding methanol and activated carbon to the organic liquid to remove the catalyst. This is done by adsorption. It is said that Group Ⅰ noble metals can be recovered from activated carbon after adsorption treatment by conventional methods such as roasting.

Japanese Patent Publication No. 53-3994 discloses the use of activated carbon that has been previously treated with nitric acid when adsorbing and separating group (III) noble metals from an organic liquid containing group (III) noble metal complexes using activated carbon. . In this method, for example, propylene is subjected to a hydroformylation reaction in the presence of a rhodium-phosphorus compound complex catalyst, and then the aldehyde product is separated by distillation, while the high-boiling by-products and the catalyst are separated. The organic liquid is added to the activated carbon treated with nitric acid, and methanol is further added to make the activated carbon treated with nitric acid adsorb rhodium. It is said that Group Ⅰ noble metals can be recovered from the nitric acid-treated activated carbon after adsorption treatment by conventional methods such as roasting.

Japanese Patent Publication No. 53-3995 describes the use of alkanes having 5 to 14 carbon atoms, alkenes having 6 to 14 carbon atoms, and methods for adsorbing and separating group Ⅰ noble metals from organic liquids containing complexes of group Ⅰ noble metals using activated carbon. , polyhydric alcohol having 2 to 6 carbon atoms,
It has been shown that Group 1 noble metals can be recovered by coexisting a compound selected from aliphatic carboxylic acids having 2 to 6 carbon atoms and dioxane. In this method, for example, propylene is subjected to a hydroformylation reaction in the presence of a rhodium-phosphorous compound complex catalyst, and then the aldehyde product is separated by distillation, and an organic liquid containing a high-boiling by-product and a catalyst is produced. When the hydroformylation reaction is carried out by charging the reactor repeatedly as necessary, rhodium can be recovered from the organic liquid containing the high-boiling by-products and the catalyst by adding the above-mentioned compound and activated carbon to the organic liquid. This is done by adsorbing the catalyst. It is said that Group Ⅰ noble metals can be recovered from activated carbon after adsorption treatment by conventional methods such as roasting.

JP-A-80-212233 discloses a method for separating and recovering rhodium by extraction with a complexing reagent from the product of oxo synthesis, in which a cationic, anionic or nonionic surfactant is dissolved in an aqueous solution of the complexing agent. A method of adding auxiliaries is shown.

E, J, Dufek and G, R, Li5t.
, Journal of the American
Oil Cbemist++' 5ociety,
54. 278-278 (1fl17?) describes a method of using an aqueous HCN solution containing triethanolamine as an extractant in extracting rhodium from hydroformylated vegetable oil or its ester.

J, P, Fr1edrich, G, R, Li5
t and V, E.

Sohng, Journal of the Ame
rican Oil Che1sts'5ociety
, 50.455-458 (1973), methyl oleate is subjected to a hydroformylation reaction in the presence of triphenyl phosphite and an activated rhodium catalyst supported on an alumina support, and then filtered to remove the filtration residue on the alumina support. The filtrate is distilled to separate the hydroformylated methyl stearate and the soluble rhodium catalyst, and the separated soluble rhodium catalyst is combined with the alumina support and calcined in a kiln. It has been shown that the catalyst on an alumina support activated by the method can be reused in the hydroformylation reaction.

Problems to be Solved by the Invention However, JP-A-49-12 uses an alkaline earth metal silicate such as magnesium silicate as a recovery adsorbent.
According to Publication No. 1793, the recovery rate of the catalyst is about 98.5%, but when the present inventors implemented this method, the adsorption properties of the catalyst were extremely poor, and once the catalyst was adsorbed, There was also a problem in that the elimination properties of the catalyst (soluble complex) were also poor.

Furthermore, when the activated carbon described in Japanese Patent Publication No. 53-3993 or Japanese Patent Publication No. 53-3995 is used as an adsorbent for recovery, the adsorption rate of the Group Ⅰ noble metal complex, which is the catalyst, to the activated carbon is low, and The recovery of Group I precious metals from activated carbon after adsorption treatment by roasting requires a high-temperature calcination process, the loss of the catalyst cannot be ignored, and the recovery of organic phosphorus compounds added as ligands is difficult. It is disadvantageous in that it is impossible to do so.

On the other hand, as an adsorbent for recovery,
When the nitric acid-treated activated carbon described in the publication is used, the adsorption rate of group (III) noble metal complexes is excellent, but recovery of group (III) noble metals from the activated carbon after adsorption treatment by roasting requires It is disadvantageous in that it requires a calcination step, that the loss of the catalyst is not negligible, and that the organic phosphorus compound added as a ligand cannot be recovered.

Journal of the America
n Oil Chemists'5ociety,
54.27!3-278 (11377) and Japanese Patent Application Publication No. 6
The extraction method described in Japanese Patent No. 0-212233 is difficult to adopt industrially because of the insufficient extraction rate of the catalyst and problems in handling HCN.

Journal of the A+5eric
an Oil Chemists'5ociety
, 50.455-458 (1973)) requires a high-temperature (600°C) calcination step, the recovery rate of the catalyst is about 98%, and the loss of the catalyst cannot be ignored. This method has not been industrially satisfactory because the organic phosphorus compound added as a ligand cannot be recovered, the organic phosphorus compound is mixed into the product, and the process is complicated.

The present inventors have been using various adsorbents (especially As a result, they discovered a composition of a desorption liquid and a desorption method that can almost quantitatively desorb the group Ⅰ noble metal compound complexes adsorbed on the adsorbent, and the present invention. I have reached the point where I have completed the .

Means for Solving the Problems The present invention provides a desorption liquid for desorbing a group (I) noble metal complex adsorbed on an adsorbent from the adsorbent, the desorption liquid comprising a polar solvent, ``A desorbed solution of group (I) noble metals adsorbed on an adsorbent characterized by comprising an organic base and an organic phosphorus compound.''

Further, the present invention provides a method for ``group Ⅰ noble metal complexes adsorbed on an adsorbent, which is characterized by contacting the group Ⅰ noble metal complex adsorbed with a desorption liquid consisting of a polar solvent, an organic base, and an organic phosphorus compound. The gist of this paper is ``Methods for desorption of precious metals from the Group.''

The present invention will be explained in detail below.

Examples of the adsorbent in the present invention include activated carbon adsorbents. Examples of the activated carbon-based adsorbent include (1) activated carbon, (2) oxidation-treated activated carbon, and (2) oxidation-treated activated carbon further supporting an organic phosphorus compound.

The activated carbon in (1) or the activated carbon before the oxidation treatment in (1) or (2) has a pore distribution with a pore diameter in the range of 20 to 300λ and a pore volume of 0.35 ml/g or more (that is,
It is desirable to use activated carbon whose pore diameter is 0.35 ml/g or more by integrating the pore volume of only pores in the range of 20 to 300 λ, and activated carbon that does not fall within this limit may be used as raw material. When used as a compound, the adsorption rate of group (I) noble metal complexes decreases.

The oxidation treatment method for activated carbon in I/or ■ is 1.
The following methods are adopted.

(a) Method of oxidizing with nitric acid Activated carbon is immersed in a nitric acid aqueous solution and stirred as necessary. The treatment temperature is usually set in the range from room temperature to the boiling point of the nitric acid aqueous solution, and may be cooled if necessary. The processing time is several minutes to several hours. The higher the nitric acid concentration, the lower the treatment temperature or the shorter the treatment time, and the lower the nitric acid concentration, the higher the treatment temperature or the longer treatment time.

Practical conditions are that the concentration of the nitric acid aqueous solution is about 10 to 60% by weight or more, the treatment temperature is room temperature to about 90° C. or more, and the treatment time is about 5 minutes to 3 hours or more. For example, when the nitric acid concentration is 60% by weight, the treatment is performed at room temperature for about 5 to 20 minutes, and when the nitric acid concentration is 10% by weight, the treatment is performed at 90° C. for about 3 hours.

After nitric acid treatment, wash with water to remove nitrate ions,
Further dry if necessary.

(b) Method of oxidizing with air or oxygen Activated carbon is oxidized by keeping it under high temperature conditions in air or an oxidized atmosphere. The oxidation temperature is usually 300 to 600°C, preferably 350 to 550°C in the case of air, and usually 200 to 45°C in the case of oxygen.
The temperature is selected from the range of 0°C, preferably from 250 to 400°C, and the treatment time is 0.5 to 2 hours.

Among the above oxidation methods, the nitric acid oxidation method is industrially most suitable, and the oxidation method using air or oxygen can also be employed industrially.

- In 1), phosphites or phosphines are used as the organic phosphorus compound supported on the oxidized activated carbon.

Examples of the phosphites include trimethyl phosphite, triethyl phosphite, tricyclohexyl phosphite, triphenyl phosphite, chlordiphenyl phosphite, and tetraphenylethylene diphosphite. Particularly suitable are triethyl phosphite and triphenyl phosphite.

Examples of phosphines include trimethylphosphine, triethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, chlordiethylphosphine, tris(ami/amyl)phosphine, tris(N,N-dimethylanilyl)phosphine, tris(〇- Examples include tolyl)phosphine, phenyldiisopropylphosphine, phenyldiamylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, chlordoxylylphosphine, and trianylylphosphine.

The amount of organic phosphorus compound supported on oxidized activated carbon is 0.
．． 01-5 mmol/g, especially 0.1-5 mmol/g
It is preferable to set the amount in the range of ol/H. If the amount of the organic phosphorus compound supported is too small, the desorption ability of Group II noble metal complex from the adsorbent will be insufficient, while if the amount supported is too large, the adsorbent will The adsorption ability of group Ⅰ noble metal complexes to the metal complex decreases.

Among the activated carbon-based adsorbents, the above-mentioned adsorbent (2), which is made by further supporting an organic phosphorus compound on oxidized activated carbon, is particularly preferred.

As the adsorbent in the present invention, in addition to the above-mentioned activated carbon-based adsorbent, an inorganic porous material-based adsorbent can also be used.

Examples of the inorganic porous material adsorbent include oxides, carbonates, silicates, and double salts of magnesium, calcium, strontium, barium, aluminum, silicon, titanium, zircon, and the like. Zeolites can also be used.

i Mutual 11 Adsorption of the group (I) noble metal complex onto the adsorbent is achieved by bringing an organic liquid containing the group (I) noble metal complex with a ligand, especially an organic phosphorus compound, into contact with the adsorbent. It will be done.

A Group Ⅰ noble metal complex having an organophosphorus compound as a ligand can be easily prepared from a Group Ⅰ noble metal compound and an organophosphorus compound such as phosphites or phosphines by a known complex formation method. . In this case, it may further contain a ligand other than the organic phosphorus compound, such as an acetylacetonate group, a cyclopentagenyl group, a carbonyl group, a carboxyl group, a halogen atom, or a hydrogen atom. It is also possible to form a complex by supplying a group (I) noble metal compound and an organic phosphorus compound to the reaction system.

Group III noble metal compounds used to form the complex include oxides, chlorides, bromides, fluorides, iodides, etc. of Group III noble metals such as ruthenium, rhodium, palladium, osmium, iridium, and platinum; nitrates, sulfur salts,
Examples include acetates, cyanides, hydrides, carbonyl complexes, and amine complexes. Among these, rhodium compounds are particularly important. Examples of rhodium compounds include rhodium oxide, rhodium nitrate, rhodium trichloride, rhodium acetate, rhodium sulfate, rhodium dicarbonyl chloride, and chlorpentaamino rhodium chloride.

The organic phosphorus compounds used to form the complex include the above-mentioned organic phosphorus compounds supported on the oxidized activated carbon, such as phosphites and phosphines, when using the activated carbon adsorbent described in (2) above. used. The organic phosphorus compound used to form the complex and the organic phosphorus compound supported on the oxidized activated carbon may be of the same type or different types, but it is more advantageous to use the same type of organic phosphorus compound.

Examples of organic liquids containing a Group Ⅰ noble metal complex with an organic phosphorus compound as a ligand include olefin hydroformylation reaction liquid, olefin hydrocarboxylation reaction liquid, and olefin, carbonyl compound, and aromatic compound hydrogenation reaction liquid. etc. can be mentioned. Among these, a reaction solution containing a hydroformylated higher fatty acid or an ester thereof obtained by a hydroformylation reaction of an olefin, particularly a higher unsaturated fatty acid or an ester thereof, is particularly important.

The above-mentioned adsorbent can be introduced into the organic liquid to adsorb the group (I) noble metal complex dissolved therein, and then separated from the organic liquid by means such as filtration or centrifugation.

However, industrially, a column is filled with this adsorbent, and an organic liquid such as a hydroformylation reaction solution is supplied to the column and brought into contact with this adsorbent, thereby adsorbing the group (I) noble metal complex. is desirable.

The organic liquid may be passed in either an upward flow or a downward flow, but an upward flow is more efficient because it is less likely to cause drift.

The higher the adsorption temperature in the adsorption step, the greater the amount of group (III) noble metal complex adsorbed, but if it is too high, the group (III) noble metal complex may deteriorate and the target product contained in the organic liquid may be altered. .

Usually it is set at room temperature to around 120°C.

After the Group 1 noble metal complex in the organic liquid introduced into the adsorption tower is adsorbed by the adsorbent, a solvent is flowed through the tower to remove the organic liquid remaining in the tower or attached to the adsorbent. As the solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and diethylbenzene, and aliphatic hydrocarbons such as heptane and hexane are used.

After removing the organic liquid, the desorbed liquid is passed through the column to desorb the group (I) noble metal complex adsorbed on the adsorbent. The desorption liquid is
Although it is preferable to introduce the organic liquid containing the group (I) noble metal complex in the direction of introduction in the previous adsorption operation, it is preferable to introduce the organic liquid in a countercurrent direction, but this is not necessarily the case.

In the present invention, this desorption liquid is composed of a polar solvent, an organic base, and an organic phosphorus compound.

Examples of polar solvents include ethers such as diethyl ether, tetrahydrofuran, and dioxane, ketones such as acetone, diethyl ketone, and methyl ethyl ketone, alcohols such as methanol, ethanol, and impropatol, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, etc. Polar solvents such as esters are suitable, especially ethers.

Amines are suitable as organic bases, such as ethylamine, propylamine, butylamine, diethylamine, trimethylamine, triethylamine, tributylamine, diisopropylethylamine, dicyclohexylethylamine, N-methylpyrrolidine, N-methylpiperidine, dimethylaniline, diethylaniline. etc. are used.

As the organic phosphorus compound, the phosphites or phosphines mentioned above are used.

The mixing amount of the organic base is about 0.05 to 5 to the polar solvent.
It is preferable to set it to about mol/fL. The amount of the organic phosphorus compound mixed is preferably about 0.01-1 mol/liter based on the polar solvent.

The amount of desorbed liquid is often about 3 to 15 times the amount of adsorbent packed in the column.

The temperature of the desorption operation using the desorption liquid is generally desirably higher, but in consideration of the boiling point and thermal efficiency of the desorption liquid, it is usually set at about room temperature to 50°C.

, Operation By the above desorption operation, the group (I) noble metal complex adsorbed on the adsorbent is efficiently eluted into the desorption liquid. In particular, when using the above adsorbent (■) as an adsorbent, it is almost quantitative (9
9.9% or more).

When the solvent in the desorbed solution after the desorption operation is distilled off, the Group (I) noble metal complex is recovered.

Since the recovered group (I) noble metal complex does not have a decrease in catalytic activity, it can be reused as it is in a reaction such as a hydroformylation reaction without any activation treatment. Also,
The adsorbent adsorbing the Group (I) noble metal complex described above can also be used as it is as a catalyst for the next reaction.

When using the adsorbent described in E.1 as an adsorbent, activated carbon with a specific pore distribution is selected, and
Because of the oxidation treatment, the number of adsorption active sites on the surface increases, improving the adsorption ability of group II noble metal complexes.Furthermore, since this oxidation treatment activated carbon is treated with an organic phosphorus compound, the surface of the activated carbon increases. Among the adsorption points, the activity is too strong and the
The portions that are difficult to desorb when adsorbing group noble metal complexes are controlled in advance by supporting an organic phosphorus compound. Therefore, when brought into contact with the desorption liquid of the present invention in this state,
The adsorbed Group I noble metal complex is almost quantitatively eluted into the desorption solution.

EXAMPLES Next, the present invention will be further explained with reference to examples. below"
"parts" and "%" are expressed on a weight basis.

Example 1 IL Nezutouou 1 Pore volume in the range of 20 to 300 pore diameters is 0.51 m
30 g of 60% nitric acid was added to 10 g of commercially available activated carbon (Diahope manufactured by Mitsubishi Chemical Industries, Ltd.) having a pore size distribution of 1/g, and the mixture was allowed to stand at room temperature for 15 minutes, with occasional stirring during this period. Next, the activated carbon is filtered out, thoroughly washed with water, and then heated to a temperature of 1.
Vacuum drying was performed at 20°C for 2 hours.

Next, this nitric acid-treated activated carbon was added to triphenylphosphine (
Reagent grade 1) 2J g (1 mmol/g for activated carbon
) and left at room temperature for 30 minutes, then taken out and vacuum-dried at room temperature for 2 hours.

As a result, an adsorbent for recovery of group (I) noble metal complexes was obtained.

Hydroformyl 100 parts of oleic acid, 0.0 parts of rhodium oxide in a high-pressure reactor
1 part, 0.5 part of triphenylphosphine, H2
/Co gas at a reaction temperature of 120°C: 60 kg/c
It was press-fitted so that the diameter was m'1□, and the reaction was carried out at 120°C for 4 hours.

The conversion rate and selectivity of the reaction from oleic acid to formylstearic acid were both 99% or more, and 100 gg/g of rhodium was dissolved in the reaction solution.

LatJLf! An adsorption tower (9 layers ■φ×300m■H) filled with 100g of the above hydroformylation reaction solution and 10g of the adsorbent obtained above.
The rhodium complex dissolved in the reaction solution was adsorbed by passing the solution through the bottom of the reactor. The temperature of the reaction solution was set to 100°C, and the space velocity was set to lhr.

Even after passing 100 g of the reaction solution, no rhodium was detected in the eluate.

The reaction solution in the adsorption tower was washed away by passing 50 g of toluene through the top of the adsorption tower. This effluent contained no rhodium.

Next, in order to desorb the rhodium complex adsorbed on the adsorbent, a desorption solution consisting of a mixture of 80 g of tetrahydrofuran, 20 g of n-butylamine, and triphenylphosphine Ig was passed through the top of the adsorption tower. The temperature of the desorption solution was set at 35°C.

When the amount of rhodium in the effluent in this desorption operation was measured, it was found that 9% of the rhodium used in the hydroformylation reaction.
It was found that more than 9.9% was recovered.

After removing the solvent from the effluent after the desorption operation under reduced pressure, the remaining liquid was used as a catalyst to carry out the hydroformylation reaction of oleic acid under the same temperature and pressure conditions as above. did.

Oleic acid was converted to formylstearic acid with both conversion rate and selectivity of 99% or more.

Example 2 The raw material activated carbon in Example 1 was air oxidized at 400° C. for 1 hour using a rotary crank to obtain an adsorbent for recovery of group (I) noble metal complexes.

Adsorption operation using this adsorbent under the same conditions as in Example 1,
Then, a desorption operation was performed.

When the amount of rhodium in the effluent from the desorption operation was measured, it was found to be 89. It was found that more than θ% was recovered.

Example 3 The same experiment as in Example 1 was repeated except that triphenylphosphine was replaced with triethylphosphite. That is, the treatment of nitric acid-treated activated carbon with an organic phosphorus compound was carried out using 1.8 g of triethylphosphite, the hydroformylation reaction was carried out by charging 0.32 parts of triethyl phosphite together with 0.012 parts of rhodium oxide, and the desorption As syneresis, 80 g of tetrahydrofuran, n-
Butylamine 20g and triethyl phosphite 0
．． 8g of the mixture was used.

When the amount of rhodium in the effluent from the desorption operation was measured, it was found that 88.9% or more of rhodium was recovered.

Comparative Examples 1 to 2 In Example 1, when only triethylphosphine was omitted from the composition of the desorbed liquid (Comparative Example 1), when triethylphosphine and n-butylamine were omitted (Comparative Example 2),
), the rhodium recovery rates were 85% and 30%, respectively.

Example 4 The same experiment as in Example 1 was repeated except that the nitric acid-treated activated carbon (not treated with triphenylphosphine) in Example 1 was used as the adsorbent. No rhodium was detected in the liquid extracted during the adsorption operation, confirming the excellent adsorption ability of the nitric acid-treated activated carbon.

When the amount of rhodium in the effluent during the desorption operation was measured, the recovery rate of rhodium was approximately 50%.

Comparative Examples 3 to 4 In Example 4, when only triethylphosphine was omitted from the desorbed liquid composition (Comparative Example 3), when triethylphosphine and n-butylamine were omitted (Comparative Example 4),
), the rhodium recovery rates were 40% and 20%, respectively.

Example 5 The same experiment as in Example 1 was repeated except that magnesium silicate having a particle size of 30 to 60 mesh was used as the adsorbent. When measuring the amount of rhodium in the eluate during adsorption operations,
It was found that approximately 50% of the rhodium had leaked out.

When measuring the amount of rhodium in the effluent during the desorption operation, the recovery rate of rhodium was about 40%, and in the end, the recovery rate of the catalyst used in the hydroformylation reaction was about 20% (50X
4G/100).

Comparative Examples 5 to 6 In Example 5, when only triethylphosphine was omitted from the desorbed liquid composition (Comparative Example 5), when triethylphosphine and n-butylamine were omitted (Comparative Example 6),
), the rhodium recovery rates were 15% and 5%, respectively.

Effects of the Invention According to the present invention, the group (I) noble metal complex adsorbed on the adsorbent is efficiently eluted into the desorption solution. In particular, when an oxidized activated carbon further supporting an organic phosphorus compound is used as an adsorbent, the group (I) noble metal complex is eluted almost quantitatively (Sa, S% or more).

Since the recovered group (III) noble metal complex does not reduce its catalytic activity, it can be reused as it is in reactions such as hydroformylation without any activation treatment. This method has great significance in the chemical industry because the compound does not mix with the target product.

Claims (1)

[Scope of Claims] 1. A desorption liquid for desorbing a Group VIII noble metal complex adsorbed on an adsorbent from the adsorbent, the desorption liquid comprising a polar solvent, an organic base and an organic phosphorus. A desorbed solution of Group VIII noble metals adsorbed on an adsorbent comprising a compound. 2. The mixing ratio of the organic base and organic phosphorus compound to 1 liter of polar solvent is 0.05 to 5 mol and 0.01 mol, respectively.
The desorption liquid according to claim 1, which has a concentration of ~1 mol. 3. The desorption solution according to claim 1, wherein the polar solvent is an ether, a ketone, an alcohol, or an ester. 4. The desorbing liquid according to claim 1, wherein the organic base is an amine. 5. The desorbing liquid according to claim 1, wherein the organic phosphorus compound is a phosphite or a phosphine. 6. Claim 1 in which the adsorbent is an activated carbon-based adsorbent
Desorption liquid as described in section. 7. Claim 6 in which the activated carbon-based adsorbent is activated carbon
Desorption liquid as described in section. 8. The desorption solution according to claim 6, wherein the activated carbon-based adsorbent is oxidized activated carbon. 9. The desorbing liquid according to claim 6, wherein the activated carbon adsorbent is made of oxidized activated carbon further supporting an organic phosphorus compound. 10. Activated carbon before oxidation treatment has a pore diameter of 20 to 300 Å
10. The desorbing liquid according to claim 8 or 9, which has a pore distribution with a pore volume in the range of 0.35 ml/g or more. 11. The desorption solution according to claim 8 or 9, wherein the oxidized activated carbon is obtained by nitric acid oxidation. 12. Claim 8, wherein the oxidized activated carbon is obtained by oxidation with air or oxygen at high temperatures.
The desorption liquid according to item 1 or item 9. 13. The desorption solution according to claim 9, wherein the amount of the organic phosphorus compound supported on the oxidized activated carbon is 0.01 to 5 mmol/g. 14. The desorbing liquid according to claim 1, wherein the adsorbent is an inorganic porous material-based adsorbent. 15. No. V adsorbed on an adsorbent characterized by contacting the adsorbent adsorbing the Group VIII noble metal complex with a desorption liquid consisting of a polar solvent, an organic base, and an organic phosphorus compound.
Method for desorption of Group III noble metals. 16. The desorption method according to claim 15, wherein the Group VIII noble metal complex has an organic phosphorus compound as a ligand. 17. The desorption method according to claim 15, wherein the Group VIII noble metal is rhodium. 18. Claim 1 in which the adsorbent is packed in a column
Desorption method described in Section 5.