TW574073B - Process for the recovery of rhodium - Google Patents

Description

574073 A7 B7 V. Description of the invention (彳) (Please read the notes on the back before filling out this page) This invention relates to self-contained rhodium / phosphite complex complexes, phosphorous acid decomposition products and high boiling points Method for recovering rhodium from organic reaction mixture of organic compounds. In addition, the invention also relates to the regeneration and recycling of germanium (germanium / phosphite form) thus separated. A method for producing an aldehyde by using a catalytic system composed of germanium and a lipophilic di-coordinate phosphite ligand to perform an aldolization reaction of an ethylenically unsaturated compound is disclosed. After the catalytic system is extracted into a non-polar solvent (such as hexane), the lipophilic catalyst is separated from the general non-lipophilic catalyst. The catalyst can be added to a non-polar solution or a process solvent and borrowed. Evaporation removes the non-polar solvent and recycles it to the aldolization reactor. The disadvantage of the conventional method is that the ligand decomposition products (for example, those generated by hydrolysis, oxidation, and / or thermal decomposition) are substantially extracted into the non-polar phase and therefore cannot be separated from the catalyst system. This results in an undesired continuous accumulation of ligand decomposition products in the reaction zone. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economics The purpose of this invention is to propose an improved and satisfactory method for separating and removing high-boiling organic compounds and decomposition products of phosphites. This method also contains rhodium / Germanium is recovered from an organic reaction mixture of a phosphite complex, a phosphite product, and a still-boiling organic compound. Furthermore, the object of the present invention is to propose a method for regenerating and recycling this separated rhodium-containing moiety (in the form of a germanium / phosphite complex complex). The first objective is achieved by: A) Aqueous oxidation and / or acid treatment of the organic reaction mixture. The paper size is CNS A4 (210X297 mm)--4-574073 A7 _____ B7 V. Description of the invention (2) Obtain an aqueous-polar organic two-phase mixture, B) Remove the aqueous phase, (please read the notes on the back before filling this page) C) lipophilic phosphine and / or lipophilic phosphorous acid A solution of the ester in a non-polar solvent is added to the organic phase. This solvent is incompatible with the polar organic phase to form a two-phase mixture. The two phases are rich in rhodium and lipophilic, phosphine and / or lipophilic phosphite Non-polar organic phase and polar organic phase rich in phosphite decomposition products and high-boiling organic compounds, or the polar organic phase is extracted with immiscible non-polar organic solvents to form a two-phase mixture. The two phases are rich in The non-polar organic phase and the germanium-rich polar organic phase of the phosphate ester decomposition product, D) The non-polar organic phase is separated from the polar organic phase. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, it was discovered that the ligand decomposition products and high boiling points can be separated from the organic mixture that also contains germanium / phosphite complex complexes. After that, germanium can be recycled and reused . An advantage of the present invention is that no or only a small amount of ligand decomposition products and high-boiling points accumulate in the aldehyde reaction zone. This is advantageous because the effective reactor volume and throughput have not been reduced. Another advantage of the method of the invention is that the activity and / or selectivity of the catalyst system is maintained for a longer period of time. This is because the decomposition products of the ligand will gradually passivate the catalyst. Continuous processes require high catalyst activity and / or selectivity over a long period of time. Another advantage of the present invention is that it can be used with the aldehyde / catalyst separation methods mentioned in WO-A-9 634687 and WO-A-9906345 to achieve the separation of high-boiling compounds from the catalyst recycle stream and Improved method of phosphite decomposition products. The purpose of the present invention is to propose a self-contained rhodium / non-lipophilic phosphite. The paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) q 574073 A7 B7 V. Description of the invention (3) (Please read the back first (Please fill in this page again for details) Method for recovering germanium from organic reaction mixture of ligand complex, non-lipophilic phosphite ligand decomposition products and high boiling point organic compounds, regeneration and recycling of this separated rhodium Part (germanium / non-lipophilic phosphite ligand complex morphology), which is achieved by: A) Aqueous oxidation and / or acid treatment of the organic reaction mixture to form an aqueous-polar organic two-phase mixture , B) Remove the aqueous phase, C) Add a solution of lipophilic phosphine and / or lipophilic phosphite in a non-polar solvent to the organic phase. This solvent and the polar organic phase are not mutually soluble to form a non-polar organic phase and a polar phase. Organic two-phase mixture, D) Separation of non-polar organic phase rich in rhodium and lipophilic phosphine and / or lipophilic phosphite from polar organic phase rich in phosphite decomposition products and high boiling point organic compounds / E ) Non-lipophilic phosphite ligands are added to the non-polar organic phase in a polar solution that is incompatible with the non-polar organic phase to form a non-polar organic and polar two-phase mixture. F) Separation of non-polar organic phase rich in lipophilic phosphine and / or lipophilic phosphite from polar organic phase rich in rhodium and non-lipophilic phosphite ligand complexes, and G) Polar organic phase circulation To the reactor. The purpose of the present invention is to propose a method for recovering rhodium from an organic reaction mixture containing a rhodium / lipophilic phosphite complex, a lipophilic phosphite decomposition product, and a high-boiling organic compound, and for separating the R h part (R h / lipophilic phosphite complex complex form.) Recycling This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-6-Consumer Consumption Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Print 574073 A 7 B7 V. Description of the invention (4) and recycling method, which is achieved by: A) Aqueous oxidation and / or acid treatment of the organic reaction mixture to form an aqueous polar organic two-phase mixture , B) the aqueous phase is removed, C) the polar organic phase is extracted with an immiscible non-polar organic solvent to form a two-phase mixture containing a non-polar organic phase rich in lipophilic phosphite decomposition products and rich in The polar organic phase of germanium, D) the non-polar organic phase is separated from the polar organic phase, E) the solution of lipophilic phosphite in a non-polar solvent is added to the polar organic phase. The organic phases are immiscible, forming a polar and non-polar organic two-phase mixture, F) separating the non-polar organic phase containing the germanium / lipophilic phosphite ligand complex from the polar organic phase, and G) the non-polar organic phase Recycle to reactor. Because rhodium is an extremely precious metal, efficient catalyst recovery is essential to the benefits of commercial rhodium-based catalytic processes. Therefore, it is often mentioned in the literature to recover and recycle germanium from different process streams. For example, in a commercial aldolization method using Rh in an organic reaction medium under the condition that an organophosphorus compound is used as a ligand, the Rh-based catalyst is efficiently separated from the product by distillation and allowed to react. Recycling. The Rh recycling process here usually includes: discharging a part of the organic reaction medium containing the catalyst and the aldehyde product from the aldolization zone in a continuous or intermittent manner, and at atmospheric, reduced or increased pressure (as the case may be) ), In a separate distillation zone, one or more stages of the discharged aldehyde product and other volatile substances are subjected to distillation treatment. R h This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) I ----- r — ------, 玎 ------ 0 (Please read the notes on the back first (Fill in this page again) 574073 A7 B7 V. Invention Description (5) (Please read the precautions on the back before filling out this page) The catalyst printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs remains undisturbed in the distillation residue of this distillation process Volatile state. Therefore, the 'Rh catalyst and the distillation residue can be easily recycled to the aldolization reaction zone. It is well known in the art that during the aldolization of olefin compounds, in addition to the aldehyde products that are reacted, by-products of high-boiling organic compounds are formed, such as 2-monohydroxybutyraldehyde, polymers, and so on. Therefore, when the Rh catalyst is recycled, high-boiling compounds will accumulate in the aldolization reaction zone. The accumulation of high-boiling substances has an adverse effect on the aldehyde process, as it reduces the effective volume of the reactor and the throughput. To avoid this problem, high-boiling products should be separated from the Rh catalyst recycle stream and removed at certain stages of the process. To achieve this, normally, a portion of the distillation residue containing the Rh catalyst is continuously discharged in a high boiling point scrubbing manner, or all or a portion of the distillation residue is periodically discharged from the catalyst recycle stream. When the catalyst is decomposed due to prolonged use or the catalyst is poisoned, causing passivation, it may also be necessary to discharge the main stream from the main catalyst recycle stream to regenerate the catalyst. Effective separation of Rh from this process stream, regeneration and recycling of Rh-organic phosphorus catalysts are also fundamentally beneficial to the economics of this method. Separation of Rh from high-boiling scrubbing products can be achieved in a variety of ways (such as adsorption, extraction, membrane filtration, etc.) that are known in the art. Organophosphorus ligands are mono-, di- or multi-coordinated phosphine derivatives (such as those described in EP-A 8 2 9 3 0 0), such Rh catalysts containing Rh part of the catalyst. Students are also shown in the literature. As mentioned above, a method for recovering Rh and reusing it from an aldehyde reaction mixture (including high-boiling scrubbing products) catalyzed by the Rh organic phosphorus system has been known. However, when the organophosphorus ligand is an organic bisphosphite compound, none of them can fully meet industrial applications. In this technique, the paper size of organic bi-Asian paper is applicable to the Chinese National Standard (CNS) A4 specification {210X297 mm) -8- 574073 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) Phosphate ester can As a ligand of the aldehyde-based catalyst based on Rh, such a catalyst has excellent activity and specific selectivity when it is used to produce an aldehyde through an olefin-formaldehyde reaction. For example, U S-A-4, 6 6 8, 6 5 1 and ϋ S-A-4, 7 6 9, 4 9 8 describe such aldehyde reactions. It has also been known that, compared with organic phosphines or organic bisphosphines, organic phosphites are extremely sensitive to the hydrolysis reaction of trace amounts of water and acids, and will form ligand decomposition products. The hydrolysis reaction of organic bisphosphite will generate, such as: phosphoric acid and mono-coordinated phosphite derivatives (such as oxidized phosphorous acid). Organic phosphites are also sensitive to decomposition by alcoholysis reactions with trace amounts of alcohol (derived from, for example, aldol dimerization or hydrogenation of aldehyde products). The details of such a decomposition reaction are described in, for example, U S-A-5 2 8 8 9 1 8. Therefore, the chemical stability and decomposition mode of the rh-organophosphite-based catalyst are different from those of the rh-organophosphine / bisphosphine-based catalyst. In commercial aldolization processes based on Rh-organic bisphosphite, the high-boiling by-products and ligand decomposition products of the aldolization reaction must be removed from the high-boiling scrub (secondary catalyst recycle stream) To avoid unwanted accumulation. This is why the Rh recovery method previously applied to the Rh-organophosphine / bisphosphine catalytic system cannot be fully applied to the Rh-organobisphosphite catalytic system. For example, U S-A-5 2 0 9 7 4 3 is targeted for the recovery of aldolization catalyst systems containing tris (trisubstituted phosphine) rhodium hydrocarbonyl complexes, trisubstituted phosphines and diphosphinones. There is no mention of removing ligand decomposition products. EP-A-8 2 9 3 00 describes a method in which a rhodium-containing liquid from a reactor is treated with an oxidizing agent in the presence of a recovery accelerator and an aqueous medium to obtain an rhodium-containing aqueous solution. In the next step, use this paper size to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ (Please read the precautions on the back before filling this page) 574073 A7 B7 V. Description of the invention (7) (Please first Read the notes on the back and fill in this page again.) The arylphosphine ligand extracts Rh into the organic phase. The main disadvantage of the method described in EP-A-8 2 9 3 0 0 using organic bisphosphites is that the carboxylic acid is present in the aqueous solution as a recovery accelerator, which acts as a hydrolysis catalyst and cannot be used with organic bisphosphonates. The re-extraction of phosphite is compatible. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Multiple patent cases describe a method for removing organic phosphite decomposition products from an aldehyde process or a method for recovering germanium. However, no one has proposed a complete and satisfactory procedure. For example, US-A-5 7 4 1 9 4 2, US-A-57 41944 λ US — A — 5744649, US — A-5786517 and US — A-5 8 7 4 6 4 0 describe the method of extraction with water Method for removing phosphorous acid decomposition products of organic bisphosphites from an aldehydeization process stream. However, no one method can remove other organic phosphite decomposition products (such as oxidized phosphorous acid) and high-boiling by-products simultaneously or continuously. The above patent case does not mention or suggest to separate Rh from the decomposition products of phosphite esters and commercial boiling point organic compounds in the organic reaction mixture by a multiple extraction method. In this multiple extraction method, at least one extraction step is on a lipophilic organic phosphorus compound. (Such as: mono-, bi- or multi-coordinated lipophilic organophosphine, mono-, bi- or multi-coordinated lipophilic organic phosphite). Organic mixtures containing germanium / non-lipophilic phosphite ligand complexes, such phosphites. Decomposition products of ligands and high-boiling organic compounds can be prepared by aldolization, among which ethylenically unsaturated compounds In the presence of a catalyst system containing rhodium and a multi-coordinated organic phosphite ligand, it is aldehyded into a linear aldehyde. Examples of such aldolization methods are described in W ◦ A-9733854 and WO — A-9819984. The paper size is adapted to the financial and household (CNS) A4 specifications (21GX297 mm) " ~~ -10 -574073 A7 B7 V. Description of Invention (8) This article is incorporated herein by reference. However, the present invention is not limited to a method for recovering germanium complexes from an organic mixture derived from such a specific aldehyde formation method. The method according to the present invention can be used for derivatization by aldehyde formation, hydrogenation, carbonylation or carboxylation reaction. Any of the catalysts in organic mixtures based on Rh-non-lipophilic or lipophilic organic phosphites. Organic mixtures containing germanium / non-lipophilic phosphite ligand complexes, decomposition products of such phosphite ligands, and high-boiling organic compounds can also be used, such as: W-A — 9 6 3 4 Obtained in the method described in 6 8 7. This bulletin describes the use of membrane filtration to separate aldehydes (formaldehyde reaction products) from Rh-organic bisphosphite complex catalysts and free organic bisphosphite complexes, and then to retain the germanium-containing catalyst.物 cycling. The disadvantage of this method is that the film retains all components whose molecular weight or size is similar to or higher than that of the Rh-organic biphosphite catalyst complex. Therefore, the molecular weight or size of the catalyst complex is similar to or higher than that of the ligand decomposition products and high-boiling organic compounds will be recycled with the catalyst, so that such ligand decomposition products and high-boiling organic compounds are continuously Accumulates in the catalyst recycle stream. This, in turn, leads to a reduction in the effective volume and throughput of the reactor. An organic mixture containing a rhodium / non-lipophilic phosphite ligand complex, a decomposition product of such a phosphite ligand, and a high-boiling organic compound is preferably prepared by the following method 1 in the method according to the present invention. Or method 2 processing. Method 1 refers to A) For papers containing germanium / non-lipophilic phosphite ligand complexes, this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before (Fill in this page) Order-I # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -11-574073 A7 B7 V. Description of the invention (9) Niu Yong's phosphonate acid η ligand decomposition products and high boiling point organic compounds The organic reaction mixture is subjected to aqueous oxidation and / or acid treatment to form an aqueous one-polar organic two-phase mixture, B) removing the aqueous phase and neutralizing the organic phase by washing or other processing methods as necessary, C ) Adding a solution of lipophilic phosphine and / or lipophilic phosphite in a non-polar solvent to the organic phase, this solvent is incompatible with the polar organic phase to form a non-polar organic and polar organic two-phase mixture, D) in step Before or after C, add a polar solvent to the polar organic phase as needed, E) optionally apply a reduction treatment to the organic two-phase mixture, F) separate the non-polar organic phase obtained after step E, G) as required After the process in step F was added to the solvent obtained in a non-polar organic phase, and optionally a non-polar organic phase from the nonpolar solvent was distilled off, the recirculated to the reactor. Method 2 refers to A) subjecting an organic reaction mixture containing a germanium / non-lipophilic phosphite ligand complex, a decomposition product of such a phosphite ligand, and a high-boiling organic compound to aqueous oxidation and / or Acid treatment to form an aqueous-polar organic toilet phase mixture, B) remove the water phase and neutralize the organic phase obtained by washing with water or other treatments as necessary, C) lipophilic phosphine and / or A solution of lipophilic phosphite in a non-polar solvent is added to the organic phase. This solvent is not compatible with the polar organic phase. It is soluble and suitable for paper sizes. National Standard (CNS) A4 (210X297 mm) ( (Please read the notes on the back before filling out this page)

1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 574073 A7 B7 V. Description of the invention (10) Form a non-polar organic and polar organic two-phase mixture, D) Before or after step C, add a polar solvent as needed In the polar organic phase obtained above to promote phase separation, E) before or after step C, if necessary, the organic two-phase mixture thus obtained is subjected to reduction treatment, F) the non-polar organic phase obtained after step E is separated G) Add a polar solution of non-lipophilic phosphite ligands, this solution is not compatible with the non-polar organic phase obtained in step F, Η) optionally apply a reduction treatment to the obtained organic two-phase mixture? I ) Separating the polar organic phase, J) After partially evaporating the solvent as needed, the polar organic phase obtained in step I is recycled to the reactor. Organic mixtures containing rhodium / lipophilic phosphite ligand complexes, decomposition products of such lipophilic phosphite ligands, and high-boiling organic compounds can be obtained by the aldolization reaction. When a catalyst system that coordinates a lipophilic organophosphite ligand exists, the ethylenically unsaturated compound is aldehyded into a linear aldehyde. An example of such an aldolization method is described in WO-A-9990 6 3 4 5 which is incorporated herein by reference. The so-called lipophilic ligand refers to the In a two-phase organic solvent system formed by a non-polar solvent, ligands substantially distributed in the non-polar phase. An example of a lipophilic phosphite ligand is a ligand of the structure [[P (〇R) (OR,) 〇] n R, '] m, where η is a paper standard that applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) (Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau Employee Consumer Cooperatives of the Ministry of Economic Affairs 574073 A7 B7 V. Invention Description (11) is an integer from 1 to 4, m is An integer of at least 1, wherein R, R, and R "are organic residues, which may be the same or different, and wherein r, R, and / or R" contain at least one C9 to C4. The lipid group is located at the tail end furthest away from the main ligand structure to make the ligand lipophilic. A preferred ligand is a two-coordinated organic ligand t P (OR) (〇R ') 〇] 2 R ″, which contains at least one C 9 to C. 4 Q lipid group on the backbone or linked to the ligand Structure. Examples of these types of ligands, methods of preparation, their specific properties, and possible aldehyde reactions are described in, for example: w〇-A -9 9 0 6 3 4 5, which are incorporated herein by reference. Reference: An organic mixture containing a germanium / lipophilic phosphite ligand complex, a decomposition product of such a phosphite ligand, and a high-boiling organic compound in accordance with Method 3 or Method 4 described below in accordance with the present invention Treatment is better. Method 3 refers to: A) The organic reaction mixture containing a germanium / lipophilic phosphite ligand complex, the decomposition products of such phosphite ligands, and high-boiling organic compounds is subjected to water Oxidation and / or acid treatment to form an aqueous-polar organic two-phase mixture, B) remove the water phase and neutralize the organic phase by washing with water or other processing methods as necessary, C) optionally polar organic Add a polar solvent to the phase, D) Non-miscible non-polar organic solvents Solvent to extract the organic phase, E) After removing the non-polar extract, add the lipophilic phosphite solution to the organic phase in a non-polar solvent that is incompatible with the polar organic solvent. ) A4 size (210X297 mm) (Please read the notes on the back before filling out this page) Order-I # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -14-574073 A7 B7 V. Description of the invention (12) (Please Read the precautions on the back before filling in this page) F) Before or after E, optionally apply a reduction treatment to the organic two-phase mixture, G) Separate the non-polar organic phase obtained after step F, Η) as appropriate A process solvent is added to the non-polar organic phase obtained in G, and the non-polar solvent in the non-polar organic phase is optionally evaporated, and then recycled back to the reactor. Method 4 refers to A) for rhodium / lipophilic phosphite compound An organic reaction mixture of a carboxyl complex, a decomposition product of such a phosphite ligand, and a high-boiling organic compound is subjected to aqueous oxidation and / or acid treatment to form an aqueous-polar organic two-phase mixture B) remove the water phase and neutralize the organic phase by water washing or other processing methods as necessary, C) add a polar solvent to the polar organic phase as appropriate, D) extract with a non-miscible non-polar organic solvent Organic phase, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs E) After removing the non-polar extract, add the non-lipophilic phosphite to the polar organic phase (which is optionally in a polar solvent), F) Before or after E, the polar organic phase is optionally subjected to reduction treatment, G) optionally, the program solvent is added to the polar organic phase obtained in F, and then recycled to the reactor. The present invention provides a method for recycling The method for improving the catalyst includes a regeneration process that completely or almost completely removes the ligand decomposition products and the catalyst. Although this paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) 574073 A7 B7 V. Description of the invention (13), for example, in method 1-2, step C can be performed before step B. The order of steps in the aforementioned method of the present invention is important. You can also skip the indicated selection steps. However, what is shown is a preferred sequence for performing the steps of Methods 1-4 and all of the optional steps described above. The steps of methods 1-4 can be repeated to improve the performance of the Rh-recovery method. In addition, any one of the methods 1 to 4 can be combined with any other to improve the performance in the Rh recovery method. In the following, this method will be described in more detail in accordance with the sequence of the aforementioned procedural steps. It is not intended to be limited to any particular theory, and it is believed that whether the phosphite is lipophilic or non-lipophilic, the oxidation and / or of methods 1-4 of the present invention In the acid treatment (step A), the phosphite ligands and optionally the phosphite ligands present in the germanium / ligand complex are decomposed into so-called ligand decomposition products. This oxidation treatment results in a two-phase mixture comprising an organic phase containing Rh and an oxidized phosphorus compound and an aqueous phase containing a relatively small amount of hydrolyzed phosphite. This oxidation treatment can be carried out with any suitable oxidant such as oxygen or an oxygen-containing gas. It is also possible to use oxidizing substances such as hypochlorite or peroxide compounds. The peroxide compound is an inorganic peroxide (such as: hydrogen peroxide) or an organic peroxide (such as: a third butylated peroxide). More preferably, an inorganic peroxide or hypochlorite is used as the oxidant in the aqueous solution. A more preferred oxidant is hypochlorite in an aqueous solution. The concentration of the liquid or solid oxidant in the aqueous phase can range from 0.01 to 60%, depending on the nature of the oxidant and the content of the organic phase that will oxidize as a result of processing. Preferably, the concentration of hypochlorite used is between 5 and 15%. Similarly, the volume of the water phase used in the oxidation treatment can be in all implementation scopes, such as: the paper size of the machine phase is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the note on the back first) (Fill in this page again)

、 1T -I # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-16- 574073 A7 B7 V. Description of the Invention (14) (Please read the precautions on the back before filling this page) 5 and 2 0 0 0 between. Preferably, the volume of the aqueous phase is equal to or lower than the organic phase used in the oxidation treatment. The ligand may be destroyed by acid treatment. Acid treatment results in a two-phase mixture consisting of an organic phase containing rh and an aqueous phase containing an acidic phosphorus compound. In the lipophilic ligand system (Methods 3 and 4), the organic phase contains substantial amounts of acidic and non-acidic lipophilic decomposition products. This acid treatment can be performed using inorganic acids (such as sulfuric acid, phosphoric acid or nitric acid) or organic acids (such as: sulfonic acid). In the best case, the corresponding test of the acid used will not strongly coordinate with the germanium atom, such as sulfuric acid, phosphoric acid or nitric acid. Sulfuric acid is more preferred. The acid concentration in the aqueous phase may be between 0.001 and 80%, depending on the nature of the acid and the content of the organic phase hydrolyzed by the acid treatment. Preferably, the amount of sulfuric acid is between 5 and 15%. Similarly, the volume of the water phase used in the acid treatment can be in all implementation ranges, such as between 5 and 2000 volumes of the organic phase. Preferably, the volume of the aqueous phase is equal to or lower than the organic phase used in the acid treatment. This oxidation and / or acid treatment in the Consumer Cooperative Printing Method 1-4 of the Intellectual Property Bureau of the Ministry of Economic Affairs is effective in completely or almost completely destroying non-lipophilic or lipophilic phosphite ligands (free and / or mismatched Ligands include those present in a partially decomposed form in the mixture to be treated in this method). Preferably, this hydration and / or acid treatment is carried out such that the amount of the undamaged phosphite ligand in the mixture of the destroyed ligand and germanium is lower than the phosphite at the beginning of the treatment. The ligand content is about 5%. Any technique already known to those skilled in the art (such as 3 1 P nuclear magnetic resonance spectroscopy (3 1 p -NM r) of inductively coupled plasma mass spectrometry (I c P -MS)) can be used to determine Coordination base. This paper scale is applicable to China National Standard (CNS) A4 (21GX297 mm) '574073 A7 B7 V. Description of the invention (15) The oxidation and / or acid treatment of methods 1-4 can be performed in a wide temperature range. The preferred processing range for this step is from about 200 t to about 120 ° C; the more preferred range is from 40 ° c to about 120 ° C. More specifically, the preferred temperature range for the oxidation treatment is normal temperature, and the preferred temperature for the acid treatment is between 80 ° C and 110 ° C. The pressure for performing the oxidation and / or acid treatment can be determined by the skilled person and depends on the reactants used. The preferred pressure for the oxidation and / or acid treatment is atmospheric pressure. The residence time in the oxidation and / or acid treatment may be between 1 minute and 5 hours and depends essentially on the application temperature. Preferably, the residence time is between 30 minutes and 2 hours. After the oxidation and / or acid treatment, the aqueous phase in the form of a waste liquid is removed from the oxidized or acid-treated organic phase. The resulting organic phase can be rinsed in one or several aqueous solutions. As mentioned above, water washing is an optional step in methods 1-4. Whether or not the water is washed depends on the nature and amount of the reactants used in the oxidation and / or acid treatment. The main purpose of water washing is to remove harmful residual oxidizing agents or acidic compounds (if any of these species are present) from the organic phase. However, this neutralization step can be achieved by means other than water washing if necessary, such as by contacting the organic phase with an appropriate soluble or insoluble solid scavenger. Similarly, soluble or insoluble liquids or gases can also be used for this purpose. For example, when using an acid treatment, it is believed that the use of a decanting step for neutralization with an aqueous alkaline solution will increase the efficiency of the Rh recovery method. Here, similarly good results are obtained using insoluble solid or liquid bases. Therefore, after acid treatment, neutralization of the organic phase can be performed by using aqueous or other heterogeneous bases. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T 574073 A7 B7 V. Description of the invention (16) The neutralization reaction can also be carried out by using solid, liquid or gaseous alkali (which is dissolved in the organic phase). Therefore, the nature of the base used for the neutralization reaction is not limited, and it can be selected by any skilled person. For example, inorganic bases (such as: sodium carbonate, sodium bicarbonate, ammonia, etc.) can be shaken in a heterogeneous or aqueous solution. Water-soluble amines or other organic bases can also be used in aqueous or other heterogeneous forms, including ion exchange resins. Preferably, if desired, aqueous or other heterogeneous forms are used in methods 1 and 4. Methods 2-3 have no preference for alkali. After the oxidation treatment, the neutralization reaction of the organic phase can be performed by using an aqueous solution of water and a reducing agent or other heterogeneous forms. This neutralization reaction can also be performed by using a solid, liquid or gaseous reducing agent which is soluble in the organic phase. There is no restriction on the nature of the reducing agent, which can be selected by those skilled in the art. For example, copper (I) and iron (I I) salts can be used in a heterogeneous form or in the form of an aqueous solution. Hydroquinone can also be used as an organic soluble reducing agent. Preferably, aqueous or other heterogeneous reducing agents are used in methods 1 and 4 when needed. Methods 2-3 have no particular preference for reducing agents. In methods 1 to 3, after the neutralization reaction in the aqueous or organic phase is removed, a lipophilic phosphine and / or phosphite ligand is added to the organic phase. Available lipophilic phosphite ligands are represented by the structure [[P (OR) (OR) 0] n R] m, where η is an integer from 1 to .4 and m is an integer at least 1, Where r, R, and R "are organic residues, which may be the same or different, and wherein R, R, and / or R" contains at least one C 9 to C. 4 lipid group as the main coordination The base structure is the furthest from the tail end to make the ligand lipophilic. The preferred coordination base is a two-coordination organic coordination base. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

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Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-19- 574073 A7 B7 V. Description of the invention (17) (Please read the notes on the back before filling this page) [P (OR) (OR ') 〇] 2 R ", Which contains at least one C9 to C4. The lipid group is located on the backbone or attached to the ligand structure. The types of these ligands, the method of preparation, their specific properties and possible aldolization reactions are described in examples such as: W〇— A — 9 9 0 6 3 4 5 is hereby incorporated by reference for reference. Preferably, in step C of method 1, the added lipophilic bisphosphite ligand is only located at the backbone Or the length of the lipid group attached to the non-lipophilic bisphosphite ligand (which was present in the organic mixture before processing) is different. In step E of Method 3, the bisphosphite ligand is The lipophilic bisphosphite ligands that are present in the organic mixture before processing are the same. Similarly, in step C of method 2, the lipophilic ligands are added to the organic phase. The lipophilic that can be used in this step Group ligands can be phosphine or phosphite derivatives' Expressed by [(PRR,) nR ”] @ or [[P (0 R) (OR,) 〇] nR”] m, where n is printed by the consumer property cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is an integer from 1 to 4. , M is an integer of at least 1, wherein R, R 'and R "are organic residues, which may be the same or different, and wherein R, R' and / or R" contains at least one C 9 to C 4 ϋ The lipid group is used as the farthest end from the main ligand structure, so that the ligand is lipophilic. The preferred ligand used in step C of method 2 is a lipophilic single coordination ligand whose structure is P (RR'R ") or P [(〇R) (〇R ') (〇R ,,)], wherein R, R' and R" are organic residues, which may be the same or different, and wherein R, R 'and / or R "contains at least one C9 to C4 (3 lipid group as the tail end furthest from the main ligand structure. The amount of this lipophilic ligand is effective to recover germanium (rhodium / The lipophilic ligand complex is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ 574073 A7 ————----_ __ V. Description of the invention (18) Form) In order to regenerate rhodium (germanium / ligand complex), the amount of ligand added in Step C of Step 1 and Step E of Method 3 is at least (please read the precautions on the back before filling (This page) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints 1 Molar complex / Mer germanium. It is better to use 1 to 10 Molar complex / Moor money. Use 1-4 Molar coordination Base / mole rhodium is more preferred. The amount of lipophilic ligand added in step C of method 2 is at least 2 moles / large rhodium. In this step, it is preferable to add 2 to 50 millimolar ligands / mole Rh. It is more preferable to add 2 to 15 millimolar ligands / Rh to step c of method 2. The lipophilic ligand can be added directly to the organic phase obtained in steps A-b of methods 1-3. It is preferred that the lipophilic ligand is dissolved in the extraction solvent. This solvent is incompatible with the organic phase obtained in Steps A-B of Method 1-3. The preferred extraction solvents for this purpose are alkanes, such as Kishiin, Isoocin, cyclohexane and the like. It is best to use a non-polar solvent such as hexane. Extraction 丨 depends on the partition coefficient of rhodium in the extraction solvent used. The extraction solvent J should be localized enough to allow two separate liquid phases to be present during the extraction period. Therefore, the 'extraction solvent can be used in all implementation ranges, for example, between 5 and 2000 vol% of the polar organic phase of steps A to B of Method 1 to 3. It is better to take a cereal volume similar to the organic phase obtained in steps A-B of methods 1-3. To facilitate phase separation in step F of methods 1-2, step D. and method G of method 3 and step D of method 4, add polar solvents as appropriate to steps A-B of methods 1-4 The resulting organic phase. This polar co-solvent can be added before or after adding the lipophilic phosphite or phosphine solution. The preferred auxiliary solvents here are highly polar solvents such as acetonitrile and dimethyl arylene. It is better to add acetonitrile. The amount of the polar auxiliary solvent can be changed within any paper size. The Chinese National Standard (CNS) A4 specification (210X297 mm) is applicable. -21-574073 Α7 Β7 V. Description of the invention (19) What is the actual range. The amount of the polar auxiliary solvent used is preferably not more than the amount of the organic phase obtained in Steps A to B of Method 1-4. In step E-1, step E, step 3-4, step F, and step 2 of step 2, the organic two-phase mixture obtained is preferably subjected to reduction treatment as appropriate. As shown, if necessary, a reduction treatment may be performed before adding a non-polar extraction solvent and a ligand. This reduction treatment is preferably performed after adding a ligand. In general, it is preferable to perform the reduction in steps 1 to 2 of the method, step F to the method 3 to 4 and step 2 of the method 2. Without wishing to be limited to any particular theory, Xianxin's use of reduction treatments in methods 1-4 will increase Rh recovery efficiency. Without wishing to be bound by theory, it is believed that in step A of method 1 to 4, the rhodium valence increases, and therefore the coordination properties of Rh are reduced. After the reduction treatment, the valence of Rh is reduced, so the coordination of Rh is improved. Because of these effects, it is possible to separate the destroyed ligand compound from Rh and regenerate the active Rh complex. The reduction treatment in method 1-12 step E, method 3-4 step F and method 2 step Η can be several kinds of agents (such as: hydrogen, inorganic compounds (such as: sodium borohydride), organic compounds (such as : Formaldehyde), hydrogen-containing gas (such as: synthesis gas (gas containing carbon monoxide and hydrogen))). Preferred is hydrogen or a hydrogen-containing gas. Particularly preferred is syngas. In a preferred case, the reduction. Reaction is carried out at a pressure between 0.1 · 10 MPa and a temperature of 20-Γ 50 ° C. The temperature is 60 ° C-100 ° C, and the pressure is 1-5 MPa. When syngas is used, C Η and Η 2 mole ratios are better than between 10: 1 and 1:10, and about 1: 1 is better. The residence time in the reduction process step can be between 5 minutes and .5 hours. This paper size is applicable to the Chinese National Standard (CNS) Α4 size (210X 297 mm) (Please read the precautions on the back before filling this page}-, 11 Φ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574073 A7 B7 V. The description of the invention (20), which basically depends on the application pressure and temperature. The residence time is between 10 minutes and 1 hour. A non-limiting example of possible reaction conditions for the reduction treatment is as follows: The germanium-containing solution obtained from the extraction step is heated for 1 hour under the conditions of 3 M Pa C 0 / Η 2, 100 t. Method 1-2 After the reduction step in step E, step F of method 3, and step ii of method 2, the polar phase and the non-polar phase are separated in step F of method 1-12, step G of method 3, and step I of method 2. The temperature used during these phase separations is usually between 0 ° C and 80 ° C. The pressure is usually between 0.1 · 0.5 MPa. Step 1 of Step 1 and Step 2 of Method 3 And step I of method 2 are preferably performed at 20 ° to 40 ° C under atmospheric pressure After phase separation, those rich in Rh are further processed in step G of method 1-2, step Η of method 3, and step J of method 2. As mentioned above, the steps of method 1-3 can be repeated to Improve the efficiency of the Rh recovery method. For example, after phase separation in step F of method 1-2 or step I of method 3, repeat step C of method 1-2 or step E of method 3 (in the extraction solvent Adding a new lipophilic ligand), it is possible to perform a new extraction step with or without reducing treatment. It is better to repeat this reduction treatment when repeating step 1 or step 2 of method 1 or step E of method 3. 〇In step D of method 3-4, the organic phase obtained after the acid or oxidation treatment is extracted with an extraction solvent. The purpose of the extraction is to remove the lipophilic subphase from the organic phase that is desired to be processed in step D of method 3 to step 4. Phosphate Ester Decomposition Product This paper size applies the Chinese National Standard (CNS) A4 specification (210X297) (please read the precautions on the back before filling this page), 11 Printed by the Consumer Cooperative of Intellectual Property Bureau of Ministry of Economic Affairs-23- 574073 Consumers of Intellectual Property Bureau, Ministry of Economic Affairs Cooperative printed A7 B7 V. Description of the invention (21). As for the extraction solvent, any non-polar solvent that is not miscible with the organic phase to be extracted can be used (as mentioned above, before extraction, step C-4 of method 3-4) Add a polar auxiliary solvent to the organic phase to help phase separation.) The preferred extraction solvent here is alkane or a mixture of alkane and arene, such as: hexane, ethane and toluene, isooctane, cyclohexane Mixtures and the like. It is best to use pure hexane or its concentrated solvent. It is also preferable to perform steps D and E of method 3 using the same immiscible solvent or solvent composition. The amount of extraction solvent used depends on the partition coefficient of the lipophilic phosphite decomposition products, which is related to the extraction solvent. The amount of extraction solvent should be high enough that two separate liquid phases are present during the extraction. Therefore, the extraction solvent can be used in all ranges, such as: 5 to 2000% by volume of the polar organic phase in steps A, B, or C of methods 3 to 4. The extraction solvent volume is preferably similar to the organic phase obtained in steps A, B, or C of Methods 3-4. This extraction can be performed with or without stirring. In the preferred case, the two-phase system obtained as in phase separation is stirred for at least 5 minutes. The temperature used during the extraction of steps 3-4 of step D is usually between 0 ° C and 80 ° C. The pressure is usually between 0.1 and 0.5 MPa. Steps 3 to 4 of Method 3 are preferably performed at 20 to 40 ° C and atmospheric pressure. In step G of method 2, non-lipophilic organic phosphite ligands and immiscible polar solvents are added to the non-polar organic phase obtained in the previous step. In a preferred case, the added non-lipophilic organic phosphite ligand is dissolved in a polar solvent, and the solvent is not compatible with the non-polar phase. In step E of method 4, a non-lipophilic organic phosphite ligand is optionally added in a polar solvent. In step G of method 2 and step E of method 4, the non-paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) I ------ ^ --- clothing ------ 、 玎 ------ 0 (Please read the notes on the back before filling this page} 574073 A7 B7 V. Description of the invention (22) (Please read the notes on the back before filling this page) Lipophilic ligands The added amount is preferably an amount effective to regenerate germanium (germanium / non-lipophilic ligand complex form). In order to regenerate germanium (rhodium / non-lipophilic ligand complex form), the method 2 The amount of the ligand added in step G and step E of method 4 is at least 1 mole ligand / mole germanium. It is preferable to add 1 to 10 mole ligand / mole germanium. The structure of the lipophilic phosphite ligand is [[[P (〇R) (〇R,) 〇] n] R ,,] m, where n is an integer from 1 to 4, and m is at least] _ An integer, wherein r, r, and R "are organic residues. A preferred coordination group is a bi-coordinated organic ligand P (〇R) (〇R ') 〇] 2 R". In a preferred case, Non-lipophilicity added in step G of method 2 Φ Phosphite ligands are the same as the non-lipophilic bisphosphite ligands that existed in the organic mixture prior to processing. In step E of method 4, it is preferred that the added non-lipophilic phosphites be coordinated The length of the lipid group differs only if it is located on the backbone or attached to a structure derived from a lipophilic bisphosphite ligand (which was present in the organic mixture before processing). The non-lipophilic property printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition to the ligand, a solvent is added in step G of method 2. As for the added solvent, it can be any polar solvent that is incompatible with the non-polar phase obtained in the previous step (step F of method 2). A good solvent is a polar solvent, such as an ester, aldehyde, or nitrile. It is better to use an aldehyde-ester (such as 5-methylmethylvalerate) or acetonitrile. The amount of this polar solvent depends on the distribution of the Rh-complex The coefficient depends on the extraction solvent. The amount of the polar solvent should be high enough to allow two paper sizes during the extraction period to apply the Chinese National Standard (CNS) A4 specification (210X297 mm) -25- 5 74073 A7

V. Invention Description (23) An isolated liquid phase exists. Therefore, the extraction solvent can be used in all practical ranges, such as: 5 to 2000% by volume of the polar organic phase in Step F of Method 2 ° The extraction solvent volume is preferably similar to the organic phase obtained in Step F of Method 2. Non-lipophilic ligands can be added alone or in a solvent in step E of method 4. As the solvent, any solvent which is incompatible with the polar phase obtained in the previous step (Method 4 Step D) can be used. Preferred solvents here are: toluene, ester, aldehyde or nitrile. More preferred are aldehyde-esters, such as 5-methylamidinofluorenyl valerate or toluene. In step G of method 1, step J of method 2, step Η of method 3, and step G of method 4, the regenerated Rh-ligand complex is recycled to the reactor. The organic mixture treated in the method of the present invention is usually continuously or intermittently removed from a hydrogenation reaction, an aldolization method or a carbonylation method using a catalyst based on Rh-di- or multi-coordinated phosphite. This mixture is removed from multiple points in the catalyst recycle stream. Although not the main object of the present invention, it is believed that the idea of the present invention can also be applied to the Rh / monocoordinated phosphite system. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The concentration of germanium complexes to be processed is not limited. This concentration is usually between 100 and 5000 p m rhodium. The concentration of the ligand decomposition products in the mixture to be processed may be from 0.01 to 1.0% by weight, and may contain high-boiling compounds such as: acetal condensation reaction products. The molar ratio of the content of P and rh in the mixture to be treated may be between 0 _ 〇 1: 1 and 100: 1. The P and Rh ratios in the mixture to be treated are preferably more than 20: 1. For the standard of this paper, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied. -26- 574073 Α7 Β7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Co-operative Cooperative 5. P and R in the mixture of invention description (24) Phosphorus compounds were added to h mole ratios below 2 to make P and Rh moles better. Here, for example, when the mixture to be treated is 20: 1, triphenylphosphine or phenylphenylphosphine) may be added to the mixture before the treatment. It has been found that the presence of an organic phosphine compound in the compound will enhance the present invention. When the ratio is 0: 1, the mixing ratio is lower than 20: 1, which is lower than the molar ratio of P and Rh. The invention is illustrated by the following non-limiting examples. In these examples, the Rh-recovery performance was tested with several different organic solvents. Approximately 10: 1 mixture of methyl-3-pentenoate and methyl-2-pentenoate was continuously aldehydeized with Rh-naphthol-3 based catalyst for 190 hours. The aldehydeization reactor yielded test solution A. The structure of R h -naphthol-3 is as follows:

naphthol-3 This aldolization reaction was performed at a temperature of 9 5 ° C, 5 bar, and a gas mixture of C0 / Η 2 = 1.1 / 1 by continuous introduction of methyl valerate and coordination based on naphthol-3 And tris (o-tolyl) phosphine in toluene as a make-up solution. The C 6 aldehyde product formed by vacuum distillation is continuously removed, and the catalyst is self-distilled (please read the precautions on the back before filling this page), 1T • 1 ^ This paper size is applicable to China National Standard (CNS) Α4 size (210 × 297 mm) ) -27- 574073 A7 B7 V. Description of the invention (25) The bottom of the state tube is circulated to the reactor which maintains about 240 ppm R h. After 190 hours of this aldolization reaction, the reactor contents were removed. After that, most of the toluene (solvent) and methyl pentenoate and about half of the C 6 -aldehyde were removed from the solution by vacuum distillation at 0.5 k P a and 105 ° C. The resulting yellow solution contained 6 7 2 ppm R h and 3 78 0 PP m P (measured by ICP), which are used in the following Rh recovery test, will be referred to as test solution A. Test solution A contains methyl 5-methylamylvalerate as the main component, and the remainder are aldehyde isomers and 13.7% high-boiling compounds (including aldol products of these aldehydes, measured by gas chromatography). ). As for the P content, 3 1 P-NMR and Η PLC indicate that there are free and coordinated naphthol-3 ligands and their decomposition products (eg, naphthol-3 — and dioxide) and a coordinated phosphite Decomposition products are present. An example of a decomposed naphthol-3 ligand and an undecomposed naphthol-3 ligand is 3: 1. In addition to some other minor monophosphite derivatives, this solution contains real mass of tris (o-tolyl) phosphine and its oxide (concentration of about 2.6% by weight). The inspection solution B was obtained in a manner similar to that described above for the test solution A, except that pure methyl 3-valerate was used instead of the methyl valerate mixture, which was continuously aldehydeized for 26 hours. Here, after the aldolization reaction, only methyl formaldehyde and unreacted methyl 3-valerate were removed from the reactor contents by vacuum distillation under conditions of 0.8 kPa and 100 ° C. The resulting yellow solution contained 2 3 4 ppm R h and 10 7 0 PP m P (determined by ICP), which was used in the following recovery test, which was referred to as the test solution B ° @ gas chromatography and found that: Test solution B except for aldehyde isomers and 5 · 〇 This paper size is applicable to China National Standards (CNS) A4 specifications (210 × 297 mm) (Please read the precautions on the back before filling this page) -Order-ΦMinistry of Economy Printed by the Consumer Cooperative of the Property Bureau -28- 574073 Α7 Β7 V. Description of the invention (26)% Isoboiling compounds (including the acid-alcohol products of these acids) In addition to 5'-methylmethylvalerate as the main component . As for the P content, 3 1 P -N M R and Η P L C showed similar compositions to the aforementioned test solution A. A part of the test solution B was subjected to vacuum distillation at 105 ° C and 0.5 kPa to obtain a test solution C. The obtained concentrated solution contained 6 8 2 P P m R h and 3 12 0 p P m P, and was used as a test solution in the Rh recovery test C. ° This test solution c contained about 14.5% high-boiling compounds. Test solution D was prepared in the following manner. 54 mg of Rh (co) 2 (acac) (acac = ethyl acetone) and 525 mg of F at — BINAP-2 suspended in N 2 in 2 ml of pure 5-methylformylvalerate In the ester. Fa t— B INAP — 2 with the following structure:

Thereafter, an additional 10 ml of methyl 5-methylamylvalerate containing 10% by weight of the aldol product of methyl 5-methylamylvalerate was added. To aid the dissolution of the lipophilic bisphosphite, 8 ml of methyl 3-valerate was added to the mixture, after which a clear yellow solution was formed. After that, the solution was at 100 bar under the conditions of 300 bar and C0 / Η 2 = 1/1. 〇 Autoclave for 1 hour. Cooling and this paper size apply Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page), 11 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives -29- 574073 A7 B7 V. Description of the invention (27) After the pressure of N 2 is released, the obtained solution is used as the test solution for the rh recovery test. This test solution D contained 4 9 4 p p m R h and 5 9 5 p P m P (measured by I C P). As for the p content, 3 1 p-N M R indicates that the presence of f a t-B I N A P for nearly 1 hour will coordinate with Rh in the HRh (C〇) 2 (f a t — B INAP — 2) complex. The remaining P content consists of uncoordinated f a t-B I N A P-2 and a small amount of its one and dioxide derivatives. Example 1 A reflux distillation tube was used, 30 ml (31.8 g) of test solution A and 40 ml of an aqueous solution containing 5% by weight sulfuric acid were heated in air at 100 ° C for 1 hour while stirring. Before, during and after heating, a two-phase mixture is present. After heating, the upper layer

20 ml of organic phase. The 3 1 P-N M R spectrum of the organic phase showed no coordinated or free bis- or monophosphite. The resulting organic phase was washed with 2 × 30 ml of a saturated aqueous sodium bicarbonate solution until gas evolution ceased. The aqueous lotion is combined with the first water. I C P analysis of the combined aqueous phase showed that the Rh content was less than 5 p p m, which was equivalent to less than 1.7% of the total Rh loss in the aqueous phase. After that, vacuum and nitrogen were applied 6 times to remove the gas in the organic phase. After that, 30 ml of degassed acetonitrile was added to the organic phase, and then 5 8 3 mg of f a t-BI N A P -2 (approximately 3 millimolar bisphosphite / mole 1 ^ 11) and 90 ml of hexane were added. The resulting mixture was autoclaved at 100 ° C for 1 hour at 30 bar and C0 / Η 2 = 1/1. After cooling and releasing pressure in Ν 2, the paper size of the autoclave is adapted to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order Φ Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives -30- 574073 Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ____B7_ V. Description of Invention (28) The resulting two-phase mixture was separated at room temperature from the almost colorless hexane phase. Thereafter, the residual polar phase (about 40 ml in volume) was rinsed with 30 ml of degassed hexane at room temperature. This hexane wash was combined with the first hexane extract. I c P analysis shows that the Rh remaining in the residual polar organic phase is lower than 15 P P m, which is equivalent to the rh loss in the polar organic phase not exceeding 2% of the total Rh. Therefore, the total efficiency of extracting Rh into hexane from test solution A is higher than or equal to 96%, which can be confirmed by the I C P R h analysis of the hexane phase sample of the compound. The 3 1 p-N M R spectrum obtained from the hexane solution showed that only the Rh complex in the form of H R h (Co) 2 (F a t — B I N A P-2) was considered to be a catalytically active species. About 2/3 of the added Fat-B I N A P-2 exists in an unaltered part, and part of it is decomposed into monophosphite (hydrolysis and oxidation). The hexane extract also showed a large amount of p- (o-tolyl) phosphine and its oxides, which were obviously not destroyed by the acid treatment, and therefore partly redistributed in the hexane extract. However, the concentration of this phosphine derivative remaining in the polar phase is at least 4 times higher than the concentration of this phosphine derivative in the hexane phase. G. C. analysis showed that approximately 85% and 15% of the high-boiling compounds were distributed in the residual polarity and the resulting hexane phase, respectively. The amount of high-boiling compounds removed with the aqueous phase was not determined. Example 1 demonstrates that Method 1 using acid treatment is an effective method for separating phosphite decomposition products and high-boiling compounds from Rh. Example 2 30 ml (30. 6 g) of test solution C contains 40 ml of this paper. The size of the paper is applicable to China National Standard (CNS) A4 specifications (210X297 mm) ~ (Please read the precautions on the back before filling this page ) > binding

• AW 574073 A7 B7 V. Description of the invention (29) (Please read the precautions on the back before filling out this page} 6 · 5% by weight sodium hypochlorite in water is gently stirred at room temperature in the air for 2 hours. Before treatment On, after, and after 'a two-phase mixture was present. To facilitate phase separation,' after processing ', 30 ml of toluene was added to the mixture. About 60 g of organic phase, which was on the upper layer during the separation period, was separated. Organic phase The 3 1 P-NMR spectrum shows that only a small amount of unbroken para (o-tolyl) phosphine exists. Most of the destroyed phosphite components are mostly converted to oxide derivatives. The resulting organic phase is 2 X 2 0 Wash with ml of saturated saline solution. The aqueous washing solution is combined with the first aqueous phase. IC analysis of the combined aqueous phase shows that the Rh content is less than 5 PP m 'This is equivalent to the Rh loss in the aqueous phase being lower than 1.9% of the total amount of Rh. After that, vacuum and nitrogen 6 times to remove the gas in the organic phase. Then, 25 ml of degassed acetonitrile was added to the organic phase, and then 390 mg of fat was added. -BINAP-2 (about 2 millimoles bisphosphite / mo Rh) and 35 ml of hexane. The resulting two-phase mixture was stirred under nitrogen for 5 minutes. Approximately 28 ml of the hexane phase was separated at the top. ICP analysis of this phase showed that 160 ppm Rh was extracted, which is equivalent to 19.3% R h. In this polar organic phase (approximately 90 ml) printed and separated by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, new 390 mg fat-BINAP — 2 and 70 ml were added again. Hexane. The resulting mixture (two-phase mixture) was autoclaved at 100 ° C for 1 hour at 30 bar, C0 / Η 2 = 1/1. After cooling and releasing the pressure at N 2, the autoclave was used. The resulting two-phase mixture was removed and the almost colorless hexane phase (64 ml) in the upper layer was separated at room temperature. ICP analysis of the hexane phase showed 270 ppm R h, and only 3 remained in the polar organic phase. 2 ppm R h. This is equivalent to the Rh extraction efficiency of the second extraction step. This paper standard is applicable to China National Standard (CNS) A4 (210X297 mm) ~ '574073 A7

V. Description of the invention (30) 7 1 · 6%. In the aforementioned hexane extraction method, a total of 9 1.0% Rh was extracted from the polar organic phase, and 7.1% Rh was left in the residual polar phase. (Please read the notes on the back before filling this page) The 3 ip-NMR spectrum of the second hexane extraction shows that only HR h (C 〇) 2 (fat — BINAP — 2) exists as the Rh complex 'Think of it as a catalytically active species. About 6 F a t-B I N A P-2 exists as an unaltered free ligand, and only 6% f a t — B I N A P-2 decomposes into a monophosphite. 3 1 p — Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. NMR shows that there are also some (o-tolyl) phosphine and its derivatives in the first and second hexane extracts. However, from 3 1 p-N M R, the concentration of the latter derivative in the residual polar phase is at least 4 times higher than that in the first and second extracts. The residual polar phase shows the presence of para (o-tolyl) phosphine and oxide derivatives of various phosphites. Hexane extraction was followed by G C analysis, which showed that approximately 87% and 13% of the high-boiling compounds were distributed in the residual polarity and the resulting hexane phase, respectively. The amount of high-boiling compounds removed with the aqueous phase was not determined. Example 2 demonstrates that method 1 using oxidation treatment is an effective method for separating phosphite decomposition products and high-boiling compounds from Rh, which also regenerates catalysts based on Rh-bisphosphite. In addition, Example 2 also confirmed the effect of the reduction treatment in the extraction method. Example 3 30 ml (30.2 g) of test solution B was gently stirred in 30 ml of an aqueous solution containing 6.5 wt% sodium hypochlorite at room temperature under air for 2 hours. A two-phase mixture was present during and after this treatment. To help this paper scale apply Chinese National Standard (CNS) A4 specifications (21 °, 〆297 mm) Γ33-574073 A7 B7 V. Description of the invention (31) After separation and processing, 6 ml of toluene is added to the mixture. Approximately 36 grams of organic phase were separated, which resided in the upper layer during the separation. The 3 1 P-N M R spectrum of this organic phase showed that all of the phosphine and phosphite components were mostly broken into oxide derivatives. The resulting organic phase was washed with 30 ml of water. The aqueous lotion is combined with the first water. The I C P analysis of the combined water phase showed that the Rh content was less than 5 p p m, which was equivalent to the Rh loss in the water phase being less than 4.0% of the total Rh content. After that, vacuum and nitrogen were applied 6 times to remove the gas in the organic phase. After that, 4 5 ml of degassed hexane was added to the organic phase, and then 600 mg of grease-like phosphine P (C 6 Η 4-ρ-10C12H25) 3 (approximately 10 mmol / mole) was added. Rh). The resulting two-phase mixture was stirred under nitrogen for 5 minutes. Separate approximately 5 2 mL of hexane phase from the top. I c ρ analysis of this phase showed that 15 p ρ R m was extracted, which is equivalent to 7% R h. The 3 1 P-N M R spectrum of the hexane phase showed that most of those present were uncoordinated lipid-like phosphine and a small amount of (o-tolyl) phosphine oxide. The 3 1 P-N M R spectrum of the polar phase showed that no grease-like phosphine derivatives were present, but there were a large number of various phosphite and o-tolyl phosphine oxide derivatives. After that, the separated hexane and the polar organic phase were mixed again, and after adding 100 ml of new greasy phosphine, the mixture was pressured at 100 ° C at 30 bar, C 0 / Η 2 = 1/1 Heat for 1 hour. After cooling and depressurizing under N 2, the resulting two-phase mixture was removed from the autoclave, and the upper red-brown anode phase (50 ml) was separated at room temperature. I C P analysis of the own phase showed 151 ppm R h, and only 28 ppm R h remained in the polar organic phase (20 ml). Compared with 7% obtained without reduction treatment, this is equivalent to the extraction step. Rh extraction (please read the precautions on the back before filling this page)

、 1T Printed by the Intellectual Property Bureau Employees ’Cooperatives of the Ministry of Economics This paper is printed to the Chinese National Standard Engine (CNS) A4 (210X297 mm) -34- Printed by the Intellectual Property Bureau ’s Employees’ Cooperatives of the Ministry of Economic Affairs 574073 A7 B7 (32) The output efficiency is 91%. The 3 1 p-N M R spectrum of the hexane extract showed that most of those present were grease-like phosphine oxides, and there were few complex and free grease-like phosphines. The 3 1 P-N M R spectra obtained from the organic phase showed no significant changes compared to similar spectra recorded before the reduction treatment. Thereafter, 30 ml of degassed hexane and 400 mg of unused fatty phosphine were added to the separated organic phase (16 ml). This mixture was autoclaved at 1000 ° C for 1 hour at 30 bar, C0 / Η 2 = 1/1. After cooling and depressurizing the N2, the autoclave was removed. The resulting two-phase mixture was separated and the upper red-brown hexane phase (32 ml) was separated at room temperature. I C P analysis of the own phase showed 10 ppm R h, and only 21 ppm R h remained in the polar organic phase (14 ml). This corresponds to an extraction efficiency of 96% of Rh including all extraction steps. The 3 1 P-N M R spectrum of the second Kojima extract showed that the presence of the test was mostly lipid-like phosphine oxide. The 3 1 P-N M R spectrum of the organic phase showed no significant change compared to similar spectra recorded before the reduction treatment. Then, under N 2, 30 ml of a mixture of 5-formamyl blue valeric acid methyl ester and its isomer was added to the first extract (4.4 halo), and then a two-phase mixture was obtained. (Approximately 46 ml of formaldehyde phase and 28 ml of own phase). Then, 2 1 mg of BI N A P-2 was added, and the mixture was stirred under N 2 for 5 minutes. The structure of B I N A P-2 is as follows: This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) Binding (please read the precautions on the back before filling this page) 35 574073 A7 B7 V. Description of the invention (33)

After the I c P of the aldehyde phase sample printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs showed that it contained only a minimum of Rh, the two-phase mixture was at 30 bar and C0 / Η 2 = 1/1 at 1 〇0 ° C autoclave for 1 hour. After cooling and depressurizing at N 2, the resulting two-phase mixture was removed from the autoclave and the lower yellow aldehyde phase (50 ml) and the internal phase (22 ml) were separated at room temperature. IC analysis of the polar organic phase showed 35 ppm Rh and 213 ppm Rh remained in the hexane phase. This corresponds to an efficiency of 38% for the extraction of the alkane phase into the aldehyde phase. The 3 1 P-N M R spectrum of the aldehyde phase showed that most of those present were uncoordinated B I N A P-2 without any decomposition products. In addition to B I N A P-2, some greasy phosphine oxides were also detected. However, the latter derivative has a much lower concentration than that measured in the hexane phase. Example 3 demonstrates that methods 1 and 2 using oxidation treatment are effective methods for separating phosphite decomposition products from Rh, and can also be used to regenerate catalysts based on Rh-bisphosphite. In addition, Example 3 also confirmed the effectiveness of the reduction treatment in the extraction method. Example 4 (Please read the precautions on the back before filling out this page) Poly · Paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 574073 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 _ V. Description of the invention (34) 31 ml (3.2.1 g) of test solution A is treated with 30 ml of an aqueous solution containing 6.5 wt% sodium hypochlorite under mild stirring 'at room temperature and in air 2 hour. During and after the treatment, a two-phase mixture was present. To help complete the oxidation reaction of the phosphine and phosphite components, another 15 ml of a 13% sodium hypochlorite solution was added, and the mixture was stirred for another 0.5 hours. The 3 1 P-N M R spectrum of the organic phase showed that only oxides were present, including para (o-tolyl) phosphine and various phosphites. After removing the aqueous light-colored solution on top during the separation period, the organic phase was washed with 2 x 2 5 ml of a dilute (2-3%) aqueous sodium bicarbonate solution. After washing with an aqueous solution, 28 ml of an organic phase was obtained. After that, the organic phase was degassed with 6 cycles of vacuum and nitrogen. Then, 20 ml of degassed acetonitrile was added to the organic phase, and then 35 ml of 367 mg of fatty phosphine P (C 6 Η 4 — ρ —〇ci 2 Η 2 5) 3 (about 2 mmol) was added. Ear P / Rh) in hexane / toluene = 4/1 mixture. The resulting two-phase mixture was stirred under nitrogen for 5 minutes. Then about 28 ml of a yellow hexane phase was separated from the top. A new portion of 367 mg of a greasy phosphine P (C6H4—p—〇c12H25) 3 in a hexane / toluene 4/1 mixture was added to the polar phase (53 ml). This two-phase mixture was autoclaved at 100 ° C for 1 hour at 30 bar, C0 / Η 2 = 1/1. After cooling and depressurizing at N 2, the resulting two-phase mixture was removed from the autoclave, and the upper red-brown hexane phase (29 ml) was separated at room temperature and combined with the first hexane extract. After that, add a new portion of 3,7 mg of greasy phosphine PC C6H4 — p — 〇Cl2H2 to the polar phase (: 5 4 ml) 5) 3 Yujiyuan / Toluene = 4/1隼 (CNS) A4 size (210X297 mm) 丨 Binding (please read the precautions on the back before filling this page) -37- 574073 A7 B7 V. Description of the invention (35) 30 ml of the solution in the mixture, then, 100 ° C, 30 bar, C. 〇 / Η 22 1/1 at 100. (: Performing reductive extraction. After cooling and depressurizing at N 2, the resulting two-phase mixture was removed from the autoclave, the red-brown hexane phase (30 ml) in the upper layer was separated at room temperature and extracted with the previous hexane The product was combined. In this way, 86 ml of a combined hexane extract containing 2 6 1 PP m R h was obtained. The residual organic phase (53 ml) contained 6 3 p P m R h, This corresponds to a total efficiency of the previous Rh extraction step of 85%. The 3 1 P-NMR of this hexane extract showed that most of the present were lipid-like phosphine oxides and some complex and free lipid-like phosphines. (This oxide content is partly derived from the 33% oxide originally present in the greasy phosphine starting material.) In addition to the greasy phosphine oxide, a small amount of other oxides, such as: three ( O-Tolyl) phosphine and various phosphites. However, the latter derivative is present in the residual polar phase in an amount approximately 10 times higher than that in the amalgamate phase. After that, 5-methylamylpentyl 30 ml of a mixture of methyl acetate and its isomers and 300 mg of B INA P-2 were added to the combined solution under nitrogen. In the alkane extract (84 ml). After this two-phase mixture, it was autoclaved at 1000 ° C for 1 hour at 1000, 30 bar, C0 / Η 22/1/1. Cooling After releasing the pressure from N 2, the obtained two-phase mixture was removed from the autoclave and the yellow aldehyde phase (41 ml) at the bottom was separated from the hexane phase (66 ml) at room temperature. ICP showed 9 6 ppm R h is present in the aldehyde phase, which corresponds to a total extraction efficiency of 27.5% in the subsequent extraction step. 3 1 P-NMR of this aldehyde phase shows that the presence of β INAP-2 is mostly uncoordinated β INAP — 2. Except for the coordinated B INAP — 2, there is a Chinese standard (CNS) A4 specification (210X297 mm) for this paper size (please read the precautions on the back before filling this page) > Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-38- 574073 A7 B7 V. About 10% of the invention description (36) BI NAP — 2 is a HRh (C0) 2 (BINAP-2) complex, which is considered to be It is a catalytically active species. On the other hand, some fat-like phosphine oxides and relatively A small amount of various phosphite oxides. After that, the isolated red-brown hospital extract was separated with 30 ml of new 5-methylmethylvalerate and its isomers and 300 mg of unused BI NAP-2 was circulated to the autoclave. The mixture was autoclaved at 100 ° C, 30 bar, C / H 2 = 1/1 for 0 · 5 hours . After cooling and depressurizing N 2, the resulting two-phase mixture was removed from the autoclave, and the upper red hexane phase (36 ml) was separated from the yellow aldehyde phase (60 ml) at room temperature. The second aldehyde extract was combined with the first. To make up for the loss of hexane entering the aldehyde phase, a new 30 ml hexane / toluene 4/1 mixture was added to the hexane phase, followed by a new 30 ml aldehyde and 300 Milligrams of BINAP-2 were recycled into the reactor. After heating at 10 Ot :, 30 bar, CO / H2 = 1/1 for 0.5 hours, the mixture was cooled and separated under n2. I C P showed 1 4 4 p p m R h in the resulting residual hexane phase (48 ml). The separated aldehyde extract was combined with the previous aldehyde extract to obtain 134 ml (13.1.4 g) of the aldehyde phase with a Rh content of 62 p p m. This corresponds to an rh extraction efficiency of 62% for the last three aldehyde extraction steps. The total efficiency of all extraction steps (including aqueous and separation extraction and recovery of Rh) is about 50.7%. G c analysis was performed with the combined aldehyde extract and the residual hexane phase obtained after repeated aldehyde extraction and the residual polar organic phase obtained after repeated extraction. G c analysis shows that the paper size is applicable to China National Standards (CNS) A4 specifications (210X297 mm) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -39- 574073 A7 B7____ 5. Description of the invention (37) It shows that the concentration of high-boiling substances in the aldehyde extractives of the compound and the residual phase in the compound are low. However, the concentration of high-boiling substances in the residual polar organic phase was 10 times higher than the former. Example 4 demonstrates that method 2 using oxidation treatment is an effective method for separating phosphite decomposition products and high-boiling compounds from Rh, and it can also be used to regenerate a catalyst based on Rh-bisphosphite. In addition, 'Example 4 also demonstrated that repeated use of the extraction step can improve Rh recovery efficiency. Example 5 41 ml (41.6 g) of test solution D was treated with 40 ml of an aqueous solution containing 6.5 wt% sodium hypochlorite under mild stirring at room temperature and in air for 2 hours. During and after the treatment, a two-phase mixture was present. Separate approximately 40 ml of the upper organic phase. The 3 1 P-N M R spectrum of this organic phase showed that, except for two other unidentified secondary oxide peaks, the majority were dioxide derivatives (80%) of f a t-β I NAP-2. The I C P of the separated water phase showed that 60 p P m R h and 18 p p m P existed, which is equivalent to 13.7% R h and 3.5% P lost to the water phase. Then, 20 ml of acetonitrile was added to the separated organic phase, and using a separatory funnel, the obtained polar mixture was extracted with 3 × 40 ml of air in air. During the multiple extractions, the amount of polar organic phase gradually decreased from about 57 grams to 52 grams. ICP analysis of all three hexane extracts showed that the rh content was less than 10 PP m 'This is equivalent to rh loss of each extraction step less than 1.2%. The P content in the second and third hexane extracts are 2 3 4, 1 7 3 and the paper size is applicable to China National Standard (CNS) A4 specifications (210X2 ?? i ^ ------ -40 -1— (Please read the notes on the back before filling out this page) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574073 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (38) p P m 〇 This is equivalent to the first, second, and third extractions of the hospital, respectively, to remove 25, 19. 5 and 1 · 7% of the initial P content. The initial Rh content of the three extractions consumed a total of 3 9%, and remove 58.7% of the initial P content. 50 ml of the obtained residual organic phase (containing 3 2 5 PP m R h and 179 ppm P) was filled with 6 cycles of vacuum, charged After degassing with nitrogen, 50 ml of degassed hexane was added to the organic phase, followed by 5 2 5 mg fat — Β INA Ρ — 2 (about 2.5 millimoles double Phosphate / mole Rh) and 35 ml of hexane. The resulting two-phase mixture was autoclaved at 100 ° C for 4 5 minutes at 30 bar, C0 / Η 2 = 1/1. Cooled and After depressurizing N 2, the obtained two-phase mixture was removed from the autoclave, and about 45 ml of an almost colorless hexane phase in the upper layer was separated at room temperature. The 3 1 P-NMR spectrum of this hexane phase showed only _ HRh (C〇) 2 (Fat — BINAP — 2) (Rh complex) is present and considered to be a catalytically active species. About 55% fat — BINAP-2 exists as an unaltered free ligand, only Fat-BINAP-2 decomposes into oxides. The separated polar organic phase is washed with fresh hexane under nitrogen at room temperature. This hexane washing solution is combined with the previously separated hexane. This fraction (6 5 · 9g) ICP analysis showed .2 3 8 ppm R h. The residual polar phase measured below 10 ppm. This is equivalent to extracting from polar phase into hexane when using fat — BINAP — 2. The extraction efficiency is 96.7% Rh. The total efficiency of all extraction steps (including aqueous and hexane extraction for separation and recovery of Rh) The efficiency is about 79.6%. Example 5 confirms that the Chinese paper standard (CNS) A4 specification (210X297 mm) is applied via oxygen paper. I ----- ~ 丨 ----- IT ------ 0 (Please read the notes on the back before filling out this page) -41-574073 A7 B7 V. Description of the Invention (39) Methods 3 and 4 are effective methods for separating lipophilic phosphite decomposition products. Example 5 also demonstrates that Method 3 is an effective method for regenerating a catalyst based on Rh-lipophilic bisphosphite.丨 Order (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -42-

Claims (1)

574073 A8 B8 C8 D8 Patent Application Scope -τγ- 14 _extinguish i Appendix II A: (Please read the precautions on the back before filling in this page) 0 9 0 1 1 7 1 2 0 Chinese Patent Application Scope Replacement without J-line after amendment Amended August 14, 19921. A method for recovering germanium from an organic reaction mixture containing a rhodium / phosphite complex, a phosphite decomposition product, and a high-boiling organic compound, characterized in that : A) Aqueous oxidation and / or acid treatment of the organic reaction mixture to obtain an aqueous-polar organic two-phase mixture containing an aqueous phase and an organic phase, B) removal of the aqueous phase, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs c) A solution of lipophilic phosphine and 7 or lipophilic phosphite in a non-polar solvent is added to the organic phase. This solvent is incompatible with the polar organic phase to form a two-phase mixture. The two phases are rich in germanium and hydrophilic Non-polar organic phase of fatty phosphine and / or lipophilic phosphite and polar organic phase rich in phosphite decomposition products and high-boiling organic compounds, or polar organic phase is immiscible non-polar organic solvent Extraction, form a two phase mixture, the two phases are phase rich in non-polar organic phosphite decomposition products and a rhodium-rich polar organic phase, D) a polar organic phase from the nonpolar organic phase was separated. 2 ・ As claimed in item 1 of the scope of patent application, it is used to recover from organic reaction mixtures containing rhodium / lipophilic phosphite complexes, non-lipophilic phosphite complexes, radical decomposition products and high-boiling organic compounds. The method of germanium, wherein, A) the organic reaction mixture is subjected to aqueous oxidation and / or acid treatment, and the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 574073 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 ___ D8 VI. Patent application scope Obtain an aqueous-polar organic two-phase mixture containing an aqueous phase and an organic phase, B) remove the aqueous phase, C) add a solution of lipophilic phosphite in a non-polar solvent to In the organic phase, the solvent and the polar organic phase are not miscible with each other to form a two-phase mixture. The two phases are a non-polar organic phase rich in rhodium and lipophilic phosphine and / or lipophilic phosphite, and a decomposition rich in phosphite. Polar organic phase of the product and high-boiling organic compounds, D) Non-polar organic phase is separated from the polar organic phase. 3. As claimed in item 1 of the scope of patent application, for recovering rhodium from an organic reaction mixture containing a germanium / lipophilic phosphite ligand complex, a lipophilic phosphite ligand decomposition product, and a high-boiling organic compound A method, wherein A) subjecting the organic reaction mixture to aqueous oxidation and / or acid treatment to obtain an aqueous-polar organic two-phase mixture comprising an aqueous phase and an organic phase, B) removing the aqueous phase, and C) polar organic phase without Extraction of miscible non-polar organic solvents to obtain a two-phase mixture containing a non-polar organic phase rich in lipophilic phosphite decomposition products and a polar organic phase rich in rhodium, D) separating non-polar organic phases from the polar organic phase Polar organic phase. 4 · A method for recovering germanium from an organic reaction mixture containing a germanium / non-lipophilic phosphite ligand complex, a decomposition product of non-lipophilic phosphite ligand, and a high boiling point organic compound, so as to separate it A method for regenerating and recycling the germanium-containing portion (R h / non-lipophilic phosphite ligand complex) in which: The wood paper scale is applicable to the Chinese standard (CNS) a4 ( 210X297 mm) (Please read the notes on the back before filling out this page) 2- 574073 A8 B8 C8 D8 VI. Patent Application Scope A) The organic reaction mixture is subjected to aqueous oxidation and / or sexual treatment to form an aqueous-polar organic two-phase mixture containing an aqueous phase and an organic phase (please read first Note on the back page, please fill in this page again) 5 B) Remove the aqueous phase, C) Add a solution of lipophilic phosphine and / or lipophilic phosphite in a non-polar solvent to the organic phase. This solvent is not compatible with the polar organic phase. Mutually soluble to form a non-polar organic phase and a polar organic two-phase mixture, D) Separation of rhodium and lipophilic phosphine and / or lipophilic phosphite from a polar organic phase rich in phosphite decomposition products and high-boiling organic compounds Non-polar organic phase, E) Non-lipophilic phosphite ligands are added to the non-polar organic phase in a polar solution that is incompatible with the non-polar organic phase to form a non-polar organic and polar two-phase mixture, F) self-rich Polar organic phase containing germanium and non-lipophilic phosphite ligand complex complex Separates non-polar organic phase rich in lipophilic phosphine and / or lipophilic phosphite, and G) The polar organic phase is recycled to the reaction DevicePrinted by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. An organic reaction for self-contained germanium / lipophilic phosphite ligand complexes, decomposition products of lipophilic phosphite ligands, and high-boiling organic compounds. Germanium is recovered from the mixture, and the separated germanium-containing portion (R h / lipophilic phosphite ligand complex complex) is regenerated and recycled. The method is characterized in that: A) the organic reaction mixture is subjected to Aqueous oxidation and / or acid treatment to form an aqueous-polar organic two-phase mixture containing an aqueous phase and an organic phase. This paper is sized for China National Standard (CNS) A4 (210X297 mm) -3- 574073 A8 B8 C8 D8 VI. Scope of patent application B) Remove the aqueous phase, (please read the precautions on the back before filling this page) C) The polar organic phase is extracted with immiscible non-polar organic solvents to form a two-phase mixture. The two phases The mixture contains a non-polar organic phase rich in lipophilic phosphite decomposition products and a germanium-rich polar organic phase, D) separating the non-polar organic phase from the polar organic phase, E) lipophilic phosphorous A solution of the ester in a non-polar solvent is added to the polar organic phase. This solvent is incompatible with the polar organic phase to form a polar and non-polar organic two-phase mixture. * F) Separation of rhodium / lipophilic phosphite from the polar organic phase The non-polar organic phase of the ligand complex, and: G) The non-polar organic phase is recycled to the reactor. 6. The method according to any one of claims 1 to 5, wherein the non-polar / polar organic two-phase mixture is subjected to reduction treatment. 7. The method according to any one of claims 1 to 5, wherein the reduction treatment is performed after adding a lipophilic ligand. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 8 · If the method of any one of claims 1, 3 and 4 of the scope of patent application, the reduction treatment is performed after adding non-lipophilic ligands. _ 9 · The method according to item 6 of the scope of patent application, in which synthesis gas is used for reduction treatment. 10. The method according to any one of claims 1 to 5, wherein the polar organic phase obtained in step A is neutralized. 1 1. The method according to any one of claims 1 to 5, wherein a polar solvent is added to the polar organic phase. This paper size applies to China National Standard (CNS) A4 (210X297 mm) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 574073 A8 B8 C8 ______ D8 VI. Application scope of patent 1 2. If the scope of application for patents is 1 to 5 The method according to any one of the preceding claims, wherein step A is carried out by treating the mixture with an oxidizing agent. 1 3. The method according to item 12 of the scope of patent application, wherein the oxidizing agent is hypochlorite in an aqueous solution. 1 4 _ The method of any one of claims 1 to 5 in the scope of patent application ′, wherein the solution is treated with a strong inorganic acid solution without coordination power, and the mixture is subjected to step A. 15 · The method according to item 14 of the scope of patent application, wherein the uncomplexed inorganic strong acid is sulfuric acid. 16 · The method according to item 4 of the scope of patent application, wherein the lipophilic mono-coordinating phosphite or phosphine ligand contains at least one C 9 -C 4 0 lipid group located at the end farthest from the backbone . 17. The method according to any one of claims 2 or 5, wherein the lipophilic di-coordinated phosphite ligand used has at least one 'C 9 -C 4. The lipid group is located on the backbone or attached to a bi-coordinating ligand structure. 18 • If the scope of the patent application: Li & 2 or 5 of any one of the methods of the above, wherein the lipophilic phosphite is formulated-dissolved in the extraction solvent. 109. As the scope of patent application 1 The method of 8 items, wherein the extraction solvent is a non-polar extraction solvent. 20. The method according to item 4 of the scope of patent application, wherein the added non-lipophilic bisphosphite ligand is the same as the non-lipophilic bisphosphite ligand present in the organic mixture to be treated. 2 1. If you apply for any of the items 2 or 5 in the scope of patent application (please read the precautions on the back before filling this page) This paper size is applicable to China National Standards (CNS) A4 (210X297 mm) -5- 574073 A8 B8 C8 ________D8 VI. Scope of patent application (please read the precautions on the back before filling this page) 'Among them' added The difference between the lipophilic bisphosphite ligand and the non-lipophilic bisphosphite ligand that was already present in the organic mixture prior to processing is only the length of the lipid group at the backbone or linking structure. 2 2 · The method according to any one of the claims 3 or 4 'wherein the added lipophilic diphosphite ligand and the lipophilic bisphosphite already present in the organic mixture before processing Ligands differ only in the length of the lipid group at the backbone or linker structure. 2 3 · The method according to any one of claims 1 to 5 in which the molar ratio of P to Rh in the organic mixture to be treated exceeds 2: 1 ° 2 4 · The claim in claims 1 to 5 The method according to any one of 5 items, wherein when the molar ratio of P to rh in the organic mixture to be treated is less than 20: 1, triphenylphosphine or ginseng (o-tolylphosphine) is added to the organic mixture. So that the molar numbers of p and Rh exceed 20: 1. 2 5 · The method according to any one of claims 1 to 5, wherein one or more steps are repeated. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 6 · If any one of the methods in the scope of patent applications 1 to 5 is applied, one or more methods are combined. 27. The method according to any one of claims 1 to 5 of the scope of the patent application, wherein the organic mixture to be treated is derived from an aldolization method, a hydrogenation method, a chemical method, or a carboxylation method. -6- This paper size adopts China National Standard (CNS) 8-4 (210x297 cm)