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Title:
VALORIZATION OF SYNGAS VIA FORMALDEHYDE – HYDROFORMYLATION OF FORMALDEHYDE USING HETEROGENIZED ORGANOMETALLIC COMPLEXES OF GROUP VIII METALS
Document Type and Number:
WIPO Patent Application WO/2019/123055
Kind Code:
A1
Abstract:
Disclosed is a process and catalyst for the production of glycolaldehyde from mixtures of formaldehyde, carbon monoxide, and hydrogen. The process disclosed herein employs a heterogenized catalyst complex for the production of glycolaldehyde with high levels of formaldehyde conversion. The heterogenized catalyst complexes can be recovered in relatively high amounts as compared to other glycolaldehyde-production catalysts.

Inventors:
DIWAKAR, Makarand (Sabic R&T Pvt. Ltd, Plot # 81-85 Chikkadunnasandra,Off Sarjapur-Attibele Road, Bangalore 5, 562125, IN)
NAMBOOTHIRI, Rakesh Kesavan (Sabic R&T Pvt. Ltd, Plot # 81-85 Chikkadunnasandra,Off Sarjapur-Attibele Road, Bangalore 5, 562125, IN)
DESHPANDE, Raj (Sabic R&T Pvt. Ltd, Plot # 81-85 Chikkadunnasandra,Off Sarjapur-Attibele Road, Bangalore 5, 562125, IN)
Application Number:
IB2018/059420
Publication Date:
June 27, 2019
Filing Date:
November 28, 2018
Export Citation:
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Assignee:
SABIC GLOBAL TECHNOLOGIES B.V. (Plasticslaan 1, 4612 PX Bergen OP Zoom, 4612 PX, NL)
International Classes:
B01J23/58; C07C45/68; C07C47/19
Domestic Patent References:
WO2012108973A12012-08-16
Foreign References:
US20080081931A12008-04-03
EP0046680A11982-03-03
Other References:
None
Download PDF:
Claims:
CLAIMS

1. A process for production of glycolaldehyde, said process comprising:

heating a mixture of H2, CO, CH20, and a heterogenized catalyst in the presence of an organic solvent;

catalytically reacting the mixture under conditions favorable to the formation of glycolaldehyde;

wherein the heterogenized catalyst comprises a heterogeneous metal-ligand complex comprising a Group VIII metal and a non-Group VIII metal salt deposited on a support material.

2. The process of claim 1, wherein the non-Group VIII metal salt is a salt of alkaline earth metal.

3. The process of either of claims 1 or 2, wherein the H2 and CO are provided in a H2:CO ratio ranging from 0.5:1 to 2:1.

4. The process of either of claims 1 or 2, wherein the support material is an organic, inorganic, or polymeric material.

5. The process of either of claims 1 or 2, wherein the CH20 is provided by monomeric formaldehyde, paraformaldehyde, trioxane, or other source that contains or is capable of generating a formaldehyde monomer.

6. A process for the conversion of a mixture of H2, CO, and CH20 into a product stream comprising glycolaldehyde, said process comprising: a) preparing a first pre-catalyst material comprising a non-Group VIII metal salt on a support material by mixing a support material and a non-Group VIII metal salt in a liquid followed by removal of the liquid to achieve deposition of said salt on said support material; b) preparing a mixture of the first pre-catalyst material and a Group VIII metal compound in a liquid, and removing the liquid to give a heterogenized metal-ligand catalyst complex including a non-Group VIII metal salt; and c) contacting a mixture of the catalyst complex, H2, CO, and CH20 in the presence of an organic solvent under conditions to effect the production of glycolaldehyde with greater than 15% formaldehyde conversion.

7. The process of claim 6, wherein the first pre-catalyst material non-Group VIII metal salt reacts with the Group VIII metal compound to form a complex that is insoluble in the liquid.

8. The process of claim 6 or 7, wherein the conditions to effect the production of glycolaldehyde comprise a reactor pressure ranging from 500 to 2100 psig.

9. The process of either of claims 6 or 7, wherein the conditions to effect the production of glycolaldehyde comprise a reaction temperature ranging from 50 °C to 150 °C.

10. The process of either of claims 6 or 7, wherein the conditions to effect the production of glycolaldehyde comprise a reaction duration ranging from 1 to 10 hours.

11. The process of either of claims 6 or 7, wherein the H2 and CO are provided in a H2:CO ratio ranging from 0.5:1 to 2:1.

12. A method of preparing a catalyst complex for conversion of H2, CO, and

CH20 into glycolaldehyde, said method comprising: a) preparing a solution of a non-Group VIII metal salt and a support material in a first solvent, and removing the first solvent to provide the support material loaded with the non- Group VIII metal salt; and b) preparing a solution of the support material loaded with the non-Group VIII metal salt and an organo-rhodium composition in a second solvent, and removing the second solvent to provide the support material loaded with a non-Group VIII metal salt and organo- rhodium compound as a catalyst complex; wherein said first and second solvents are essentially free of N,N-dihexylbutyramide.

13. The method of claim 12, wherein the first pre-catalyst material non-Group VIII metal salt reacts with the Group VIII metal compound to form a complex that is insoluble in the second solvent.

14. The method of claim 12 or 13, wherein the non-Group VIII metal salt is a salt of an alkaline earth metal.

15. The method of either of claims 12 to 13, wherein the organo-rhodium compound comprises a phosphine ligand.

16. The method of either of claims 12 to 13, wherein the support material is an organic, inorganic, or polymeric material.

Description:
VALORIZATION OF SYNGAS VIA FORMALDEHYDE - HYDROFORMYLATION OF FORMALDEHYDE USING HETEROGENIZED ORGANOMETALLIC COMPLEXES OF GROUP VIII METALS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application Serial No. 62/608,799, filed December 21, 2017, the entire contents of which are hereby incorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0002] The present invention provides a process and catalyst for the production of glycolaldehyde from mixtures of H 2 , CO, and formaldehyde.

B. Description of Related Art

[0003] Glycolaldehyde is an important chemical due to the presence of two reactive groups on the molecule. Glycolaldehyde has various applications in the food industry, for example, as a cross-linking agent for proteinaceous materials such as sausage casings. Another use is as a browning promoter during the cooking of foods. Glycolaldehyde promotes the Maillard reaction that occurs between protein amines and reducing sugar ketones or aldehydes during the carmelization process. As an intermediate in organic synthesis, glycolaldehyde is used for the preparation of serine.

[0004] Glycolaldehyde is particularly useful as an intermediate in the production of chemicals having a variety of applications. Glycolaldehyde can be used to produce ethylene glycol by a catalytic hydrogenation process. Ethylene glycol is a valuable commercial chemical with a wide variety of uses, e.g., as a coolant and antifreeze, monomer for polyester production, solvent, and an intermediate for production of commercial chemicals.

[0005] Glycolaldehyde can be converted to glycolic acid (an important alpha-hydroxy acid) and glycolic acid esters. Glycolic acid is used in the textile industry as a dyeing and tanning agent, in food processing as a flavoring agent and preservative, and in the pharmaceutical industry as a skin care agent. Glycolic acid is often included in emulsion polymers, solvents, and inks and paints to improve flow properties and impart gloss. Glycolic acid is also useful as a synthetic organic intermediate in a range of reactions including redox reactions, esterifications, and long-chain polymerizations. Glycolic acid is used as a monomer in the preparation of polyglycolic acid and other biocompatible copolymers such as poly(lactic-co-glycolic acid), PLGA.

[0006] One method for the production of glycolaldehyde involves dihydroxymaleic acid as a starting material. However, this method is ill-suited to large-scale production and is impractical for industrial usage. Accordingly, several alternative methods and processes for production of glycolaldehyde are found in the prior art. Glycolaldehyde may be produced from the pyrolysis of ligno-cellulosic materials, however, the yields form these cellulosic feedstocks is small. Another production method involves the vapor-phase conversion of ethylene glycol to glycolaldehyde. This method suffers from low conversion, low yields, and high byproduct concentrations.

[0007] The primary method for the preparation of glycolaldehyde involves hydroformylation of formaldehyde. Current methods employ organometallic complexes of rhodium as catalysts under homogeneous reaction conditions. In these processes, separation of the glycolaldehyde product from the catalyst is difficult, as the catalyst, starting material, and product are present in the same phase. Distillation or extraction techniques are typically employed in order to separate the catalyst from the reaction mixture. These techniques are challenging as the catalyst can decompose during distillation, or may leach out during the extraction process. Both distillation and extraction may result in the loss of valuable transition metal catalysts.

[0008] Overall, there is an ongoing need for improved method for producing glycolaldehyde from inexpensive feedstocks such as CO and H 2 . Improved catalyst systems may be used to circumvent the current loss-inducing catalyst collection processes and improve process economics.

SUMMARY OF THE INVENTION

[0009] A discovery has been made that provides a solution to some of the problems discussed above. The solution is premised on the use of heterogenized organometallic complexes of Group VIII metal, particularly rhodium as catalysts for the hydroformylation of formaldehyde to synthesize glycolaldehyde. The heterogenized catalyst complexes may be separated from reaction mixtures by simple filtration and or settling techniques. In contrast to conventional distillation or extraction catalyst recovery methods, the presently disclosed heterogenized catalyst complexes may be recovered in higher amounts, with lower risk of catalyst loss or decomposition. Notably, the high-recovery heterogenized catalyst complexes of the present invention improve process economics by allowing higher proportions of catalyst to be recycled.

[0010] In a particular aspect of the present invention, a process for the production of glycolaldehyde is described. The process can include heating a mixture of H 2 , CO, CH 2 0, and a heterogenized catalyst in the presence of an organic solvent and catalytically reacting the mixture under conditions favorable to the formation of glycolaldehyde. In some aspects, the heterogenized catalyst comprises a heterogeneous metal-ligand complex comprising a Group VIII metal and a non-Group VIII metal salt. The heterogeneous metal-ligand complex may be deposited on a support material that may be an organic, inorganic or polymeric material.

[0011] In some aspects of the invention, a process for the conversion of a mixture of H 2 , CO, and CH 2 0 into a product stream comprising glycolaldehyde is described. The process includes a step of preparing a first pre-catalyst material comprising a non-Group VIII metal salt on a support material by mixing a support material and a non-Group VIII metal salt in a liquid followed by removal of the liquid to achieve deposition of said salt on said support material. The first pre-catalyst material is mixed with a Group VIII metal compound in a liquid. The liquid may be selected from the group consisting of alcohols, water, ethers, aromatic hydrocarbons, aliphatic hydrocarbons, N-monosubstituted or N,N-disubstituted formamides, acetamides, propionamides, butyramides, higher amides, aromatic amides. A higher amide is an amide in which a Cs or larger group is attached to the amide nitrogen atom through a carbon atom. In particular embodiments, the liquid is dimethylacetamide. In some aspects, N,N-dihexylbutyramide is not employed. The liquid may then be removed to give a heterogenized metal-ligand catalyst complex including a non-Group VIII metal salt. Liquid removal may be accomplished by techniques known to those of skill in the art, including but not limited to evaporation, distillation, decanting, filtration, rotary evaporation, and the like. The process further includes the step of contacting a mixture of the heterogenized metal- ligand catalyst complex, H 2 , CO, and CH 2 0 in the presence of an organic solvent under conditions to effect the production of glycolaldehyde. The conversion of formaldehyde may be greater than 10%, preferably greater than 15%, more preferably greater than 20%.

[0012] In some aspects of the disclosure, a method for preparing a catalyst complex for conversion of H 2 , CO, and CH 2 0 into glycolaldehyde is described. The method comprises the steps of preparing a solution of a non-Group VIII metal salt and a support material in a first solvent, and removing the first solvent to provide the support material loaded with the non-Group VIII metal salt, preparing a solution of the support material loaded with the non- Group VIII metal salt and an organo-rhodium composition in a second solvent, and removing the second solvent to provide the support material loaded with a non-Group VIII metal salt and organo-rhodium compound as a catalyst complex. In some aspects, the non-Group VIII metal salt and organo-rhodium compound chemically react to provide the catalyst complex, which may be insoluble in the second solvent. In some embodiments, the organo-rhodium compound comprises a phosphine ligand, preferably a phosphine-sulfonate ligand, more preferably a triphenylphosphine trisulfonate ligand. In some aspects, the first and second solvents are essentially free of N,N-dihexylbutyramide.

[0013] The following includes definitions of various terms and phrases used throughout this specification. The term“ligand,” as used herein, is intended to have its commonly accepted meaning as would be understood by persons having ordinary skill in the art, that is a molecule, atom, ion, or group of atoms that is bound or capable of binding to a central atom as a complex or coordination compound. The term“hydroformylation,” as used herein, also is understood to have its commonly accepted meaning of a catalytic process in which hydrogen and carbon monoxide are reacted with formaldehyde resulting in the net addition of CO and H 2 to the formaldehyde. The term“formaldehyde,” as used herein, is intended to include monomeric formaldehyde and any formaldehyde source that is readily converted to formaldehyde under the conditions of the hydroformylation reaction. For example, “formaldehyde,” as used herein, would include formaldehyde in its monomeric form as well as its various acetals, hemiacetals, and low molecular weight oligomers such as, for example, paraformaldehyde and trioxane. Similarly, the term“glycolaldehyde,” is intended to include 2-hydroxy-acetaldehyde and any derivatives thereof such as, for example, acetals, ethers, hemiacetals, oligomers, and hydrogenated products, that may be produced from glycolaldehyde under hydroformylation reaction conditions. [0014] The terms“about” or“approximately” are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%. The terms “wt.%”, “vol.%”, or“mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or total moles of a material, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt.% of component. The term“substantially” and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%.

[0015] The use of the words“a” or“an” when used in conjunction with any of the terms “comprising,”“including,”“containing,” or“having” in the claims, or the specification, may mean“one,” but it is also consistent with the meaning of“one or more,”“at least one,” and “one or more than one.” The words“comprising” (and any form of comprising, such as “comprise” and“comprises”),“having” (and any form of having, such as“have” and“has”), “including” (and any form of including, such as“includes” and“include”) or“containing” (and any form of containing, such as“contains” and“contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0016] The methods of the present invention can“comprise,”“consist essentially of,” or “consist of’ particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase“consisting essentially of,” in one non limiting aspect, a basic and novel characteristic of the methods of the present invention are their abilities to efficiently produce glycolaldehyde from mixtures of H 2 , CO, and CH 2 0.

[0017] Other objects, features and advantages of the present invention will become apparent from the following detailed description and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein. DETAILED DESCRIPTION OF THE INVENTION

[0018] The catalysts that are currently employed in the production of glycolaldehyde suffer from potential decomposition and/or loss during reaction work-up and catalyst recovery. The processes disclosed herein address this problem by providing heterogenized catalyst complexes that are amenable to less wasteful catalyst recovery techniques. The heterogenized catalyst complexes of the present invention may be recovered by simple filtration or settling/decanting processes. These techniques are associated with higher catalyst recovery. The increase in catalyst recovery is associated with improved process economics because a higher proportion of catalyst may be recovered and re-used.

[0019] The presently disclosed catalysts are based on heterogenized organometallic complexes of Group VIII metal and a non-Group VIII metal as catalysts for the hydroformylation of formaldehyde to synthesize glycolaldehyde. During the synthesis of the heterogenized organometallic complexes, the first pre-catalyst material non-Group VIII metal salt reacts with the Group VIII metal compound to form a complex that is insoluble in the liquid, in some aspects. In a particular aspect of the invention, the Group VIII metal is rhodium. In some aspects, the heterogeneous metal-ligand complex further comprises a phosphine ligand coordinated to the Group VIII metal, the non-Group VIII metal, or both the Group VIII metal and the non-Group VIII metal. Mono- or bi-dentate phosphate ligands in which the phosphorus moiety has the general formula PR 3 , where R = alkyl, aryl, H, halide, or sulfonic acid are contemplated. In some aspects, the ligand comprises a sulfonate group. The sulfonate ligand may partially or fully react with the non-Group VIII metal to provide a catalyst complex in which the at least a portion of the sulfonate ligand is complex or bound to the Group VIII metal, the non-Group VIII metal, or both. In a particular aspect, the ligand is a triphenylphosphine trisulfonate salt. In some aspects, the catalyst does not include a phosphine- amine ligand. The non-Group VIII metal salt may be the salt of an alkaline metal, an alkaline earth metal, or at least one transition metal of Columns 4-7 and 9-12 of the Periodic Table. In a preferred aspect, the non-Group VIII metal is an alkaline earth metal, preferably barium.

[0020] In some embodiments, the heterogenized organometallic complex support material is an organic, inorganic, or polymeric material. A preferred support material is carbon. In some aspects, conditions to effect the production of glycolaldehyde comprise a reaction or reactor temperature ranging from 50 °C to 150 °C, preferably from 75 °C to 125 °C, more preferably from 80 °C to 120 °C. The CH2O may be sourced or provided by monomeric formaldehyde, paraformaldehyde, trioxane, or other source that contains or is capable of generating a formaldehyde monomer. Formaldehyde sources include but are not limited to paraformaldehyde, methylal, formalin solutions, polyoxymethylenes, and trioxane. In a particular aspect, the CH2O is provided as a formalin solution. The production of glycolaldehyde may be performed at a reactor pressure ranging from 500 to 2100 psig, preferably from 650 to 1100 psig, more preferably from 800 to 900 psig. Fb and CO may be provided to the reactor in a Fb:CO ratio ranging from 0.5:1 to 2:1, preferably from 0.75:1 to 1.5:1, more preferably from 0.8:1 to 1.2:1. In some aspects, the Fb and CO are provided in the form of syngas. The glycolaldehyde production reaction duration may range from 1 to 10 hours, preferably from 2 to 5 hours, more preferably from 2.5 to 3.5 hours. The glycolaldehyde production reaction may be performed in a liquid phase, in some embodiments. When performed in a liquid phase one or more solvents may be employed. In a particular aspect, a liquid phase glycolaldehyde production reaction is performed in a N,N- dimethylacetamide solvent.

EXAMPLES

[0021] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Example 1

Heterogenized Catalyst Production

[0022] Preparation of 15% Ba(N0 3 ) 2 -loaded carbon: A 250 ml round bottom flask was charged with 1.5 g Ba(N0 3 ) 2 and 50 ml of distilled water. The mixture was stirred until a clear solution was obtained. 9 g activated charcoal was added to the solution and stirred for 10 minutes. The water was distilled out using rotary evaporator and the remaining solid was dried under vacuum to obtain 15% Ba(N0 3 ) 2 loaded carbon (w/w).

[0023] Preparation of TPPTS-Ba-loaded carbon: A 250 ml round bottom flask was charged with 1.01 g triphenylphosphinetrisulfonate sodium salt and 50 ml of distilled water. The mixture was stirred until a clear solution was obtained. 5 g of 15% Ba(N0 3 ) 2 -loaded carbon prepared above was added to the solution and stirred for 15 hours. The mixture was filtered through a Buchner funnel under vacuum. The filtered solid was dried under vacuum to obtain the TPPTS-Ba loaded carbon.

[0024] Preparation of Rh-TPPTS-Ba-loaded carbon: A 250 ml round bottom flask was charged with 0.0535 g (RhCODCl) 2 and 50 ml of dimethylacetamide. The mixture was stirred until a clear solution was obtained. 5 g TPPTS-Ba loaded carbon was added to the solution and stirred for 6 hours. The mixture was filtered through a Buchner funnel under vacuum. The filtered solid was dried under vacuum to obtain the catalyst complex Rh- TPPTS-Ba loaded carbon, (Rh-TPPTS/C).

Example 2

Hydroformylation Experiment

[0025] A 60 ml PARR reactor was charged with 1.0 g Rh-TPPTS/C catalyst, 19.5 ml (17.93 g) dimethylacetamide solvent, and 0.5 ml (0.456 g) of formalin solution (37% aqueous formaldehyde, catalyst: substrate ratio of 1:200). 780 psig of 1:1 CO:H 2 gas was added to the reactor and the reactor was heated to 100 °C. Heating was stopped after 3 hours and the reactor was allowed to cool overnight. The reactor was allowed to vent gases during the overnight cooling period. The formaldehyde conversion for this reaction was 17.79%, with a glycolaldehyde selectivity of 72.45%. The catalyst was recovered by filtration, washed with reaction solvent, then washed with acetone.

[0026] In the context of the present invention, embodiments 1-16 are described. Embodiment 1 is a process for the production of glycolaldehyde. The process includes heating a mixture of H 2 , CO, CH 2 0, and a heterogenized catalyst in the presence of an organic solvent, and catalytically reacting the mixture under conditions favorable to the formation of glycolaldehyde. The heterogenized catalyst of embodiment 1 comprises a heterogeneous metal-ligand complex comprising a Group VIII metal and a non-Group VIII metal salt deposited on a support material. Embodiment 2 is the process of embodiment 1, wherein the non-Group VIII metal salt is a salt of alkaline earth metal. Embodiment 3 is the process of embodiment 1 or 2, wherein the H 2 and CO are provided in a H 2 :CO ratio ranging from 0.5:1 to 2:1. Embodiment 4 is the process of any of embodiments 1 to 3, wherein the support material is an organic, inorganic, or polymeric material. Embodiment 5 is the process of any of embodiments 1 to 4, wherein the CH 2 0 is provided by monomeric formaldehyde, paraformaldehyde, trioxane, or other source that contains or is capable of generating a formaldehyde monomer.

[0027] Embodiment 6 is a process for the conversion of a mixture of H 2 , CO, and CH 2 0 into a product stream comprising glycolaldehyde. The process includes: a) preparing a first pre-catalyst material comprising a non-Group VIII metal salt on a support material by mixing a support material and a non-Group VIII metal salt in a liquid followed by removal of the liquid to achieve deposition of said salt on said support material, b) preparing a mixture of the first pre-catalyst material and a Group VIII metal compound in a liquid, and removing the liquid to give a heterogenized metal-ligand catalyst complex including a non-Group VIII metal salt, and c) contacting a mixture of the catalyst complex, H 2 , CO, and CH 2 0 in the presence of an organic solvent under conditions to effect the production of glycolaldehyde with greater than 15% formaldehyde conversion. Embodiment 7 is the process of embodiment 6, wherein the first pre-catalyst material non-Group VIII metal salt reacts with the Group VIII metal compound to form a complex that is insoluble in the liquid. Embodiment 8 is the process of embodiment 6 or 7, wherein the conditions to effect the production of glycolaldehyde comprise a reactor pressure ranging from 500 to 2100 psig. Embodiment 9 is the process of any of embodiments 6 to 8, wherein the conditions to effect the production of glycolaldehyde comprise a reaction temperature ranging from 50 °C to 150 °C. Embodiment 10 is the process of any of embodiments 6 to 9, wherein the conditions to effect the production of glycolaldehyde comprise a reaction duration ranging from 1 to 10 hours. Embodiment 11 is the process of any of embodiments 6 to 10, wherein the H 2 and CO are provided in a H 2 :CO ratio ranging from 0.5:1 to 2:1.

[0028] Embodiment 12 is a method of preparing a catalyst complex for conversion of H ¾ CO, and CH 2 0 into glycolaldehyde. The method includes: a) preparing a solution of a non- Group VIII metal salt and a support material in a first solvent, and removing the first solvent to provide the support material loaded with the non-Group VIII metal salt, and b) preparing a solution of the support material loaded with the non-Group VIII metal salt and an organo- rhodium composition in a second solvent, and removing the second solvent to provide the support material loaded with a non-Group VIII metal salt and organo -rhodium compound as a catalyst complex. The first and second solvents of embodiment 1 are essentially free of N,N- dihexylbutyramide. Embodiment 13 is the method of embodiment 12, wherein the first pre catalyst material non-Group VIII metal salt reacts with the Group VIII metal compound to form a complex that is insoluble in the second solvent. Embodiment 14 is the method of embodiment 12 or 13, wherein the non-Group VIII metal salt is a salt of an alkaline earth metal. Embodiment 15 is the method of any of embodiments 12 to 14, wherein the organo- rhodium compound comprises a phosphine ligand. Embodiment is the method of any of embodiments 12 to 15, wherein the support material is an organic, inorganic, or polymeric material.