SURFACE-MODIFIED CALCIUM CARBONATE AS CARRIER FOR TRANSITION METAL-BASED CATALYSTS

Abstract

The present invention relates to a catalyst system comprising a transition metal compound on a solid carrier which is a surface-reacted calcium carbonate. The invention further relates to a method for manufacturing said catalyst system and to its use in heterogeneous catalysis.

Claims

1. A catalyst system comprising a transition metal compound on a solid carrier, wherein the solid carrier is a surface-reacted calcium carbonate comprising ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC), and at least one water-insoluble calcium salt other than calcium carbonate, and wherein the surface-reacted calcium carbonate shows: (i) a specific surface area of from 15 to 200 m.sup.2/g measured using nitrogen and the BET method according to ISO 9277:2010; (ii) an intra-particle intruded specific pore volume in the range of from 0.1 to

2. 3 cm.sup.3/g calculated from mercury porosimetry measurement; and (iii) a ratio of the at least one water-insoluble calcium salt to calcite, aragonite and/or vaterite in the range of from 1:99 to 99:1 by weight.

2. The catalyst system according to claim 1, wherein the at least one water-insoluble calcium salt is selected from the group consisting of octacalcium phosphate, hydroxylapatite, chlorapatite, fluorapatite, carbonate apatite and mixtures thereof, preferably the at least one water-insoluble calcium salt is hydroxylapatite.

3. The catalyst system according to claim 1, wherein the ratio of the at least one water-insoluble calcium salt to calcite, aragonite and/or vaterite, preferably to calcite, is in the range of from 1:9 to 9:1, preferably from 1:7 to 8:1, more preferably from 1:5 to 7:1 and even more preferably from 1:4 to 7:1 by weight

4. The catalyst system according to claim 1, wherein the transition metal compound is selected from the group consisting of palladium compounds, platinum compounds, copper compounds and mixtures thereof

5. The catalyst system according to claim 1, wherein the transition metal compound is selected from the group consisting of elemental palladium, Pd(acac).sub.2, Na.sub.2PdCl.sub.4, Pd(OAc).sub.2, Pd(PPh.sub.3).sub.4, PdCl.sub.2(PPh.sub.3).sub.2, (dppf)PdCl.sub.2, (dppe)PdCl.sub.2, (dppp)PdCl.sub.2, (dppb)PdCl.sub.2, PdCl.sub.2, (C.sub.3H.sub.5PdCl).sub.2, bis(acetate)triphenylphosphine-palladium(II), Pd(dba).sub.2, Pd(H.sub.2NCH.sub.2CH.sub.2NH.sub.2)Cl.sub.2, elemental platinum, Na.sub.2PtCl.sub.6 Pt(acac).sub.2, Na.sub.2PtCl.sub.4, H.sub.2PtCl.sub.6, (NH.sub.4).sub.2[PtCl.sub.6], PtO.sub.2.H.sub.2O, PtCl.sub.4, elemental copper, Cu.sub.2O, Cu.sub.2S, copper(I)-thiophene-2-carboxylate, CuBr, CuCN, CuCl, CuF, CuI, CuH, CuSCN, CuBr.sub.2, CuCO.sub.3, CuCl.sub.2, CuF.sub.2, Cu(NO.sub.3).sub.2, Cu.sub.3(PO.sub.4).sub.2, CuO, CuO.sub.2, Cu(OH).sub.2, CuI.sub.2, CuS, CuSO.sub.4, Cu.sub.2(OAc).sub.4 and mixtures thereof, preferably the transition metal compound is selected from the group consisting of elemental palladium, Pd(acac).sub.2, Na.sub.2PdCl.sub.4, Pd(OAc).sub.2, Pd(PPh.sub.3).sub.4, PdCl.sub.2(PPh.sub.3).sub.2, (dppf)PdCl.sub.2, (dppe)PdCl.sub.2, (dppp)PdCl.sub.2, (dppb)PdCl.sub.2, PdCl.sub.2, (C.sub.3H.sub.5PdCl).sub.2, bis(acetate)-triphenylphosphine-palladium(II), Pd(dba).sub.2, Pd(H.sub.2NCH.sub.2CH.sub.2NH.sub.2)Cl.sub.2, elemental platinum, Na.sub.2PtCl.sub.6 Pt(acac).sub.2, Na.sub.2PtCl.sub.4, H.sub.2PtCl.sub.6, (NH.sub.4).sub.2[PtCl.sub.6], PtO.sub.2.H.sub.2O, PtCl.sub.4 and mixtures thereof.

6. The catalyst system according to claim 1, wherein the surface-reacted calcium carbonate has: (i) a specific surface area in the range of from 27 to 180 m.sup.2/g, preferably from 25 to 160 m.sup.2/g and more preferably from 30 to 150 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010; (ii) a d.sub.50(vol) in the range of from 1 to 75 ?m, preferably from 2 to 50 ?m, more preferably from 3 to 40 ?m, even more preferably from 4 to 30 ?m and most preferably from 5 to 15 ?m; (iii) a d.sub.98(vol) in the range of from 2 to 150 ?m, preferably from 4 to 100 ?m, more preferably from 6 to 80 ?m, even more preferably from 8 to 60 ?m and most preferably from 10 to 30 ?m; and/or (iv) an intra-particle intruded specific pore volume in the range of from 0.2 to 2.0 cm.sup.3/g, preferably from 0.4 to 1.8 cm.sup.3/g and most preferably from 0.6 to 1.6 cm.sup.3/g, calculated from mercury porosimetry measurement.

7. The catalyst system according to claim 1, wherein the catalyst system further comprises one or more reaction products obtained by reaction of the transition metal compound and the surface-reacted calcium carbonate.

8. The catalyst system according to claim 1, wherein the content of the transition metal compound and/or the one or more reaction products thereof is in the range of from 0.1 to 60 wt.-%, preferably from 0.1 to 30 wt.-%, more preferably 0.1 to 20 wt.-%, even more preferably from 0.1 to 10 wt.-% and most preferably from 0.2 to 5 wt.-%, based on the weight of the transition metal compound per total weight of the catalyst system.

9. A method for manufacturing a catalyst system comprising a transition metal compound on a solid carrier, the method comprising the following steps: (a) providing at least one surface-reacted calcium carbonate comprising ground natural calcium carbonate (GNCC) or precipitated calcium carbonate (PCC), and at least one water-insoluble calcium salt other than calcium carbonate; (b) providing at least one transition metal compound; and (c) contacting in a liquid medium, the surface-reacted calcium carbonate provided in step (a) and the transition metal compound provided in step (b) to obtain a mixture comprising surface-reacted calcium carbonate and a transition metal compound; wherein the surface-reacted calcium carbonate shows: (i) a specific surface area of from 15 to 200 m.sup.2/g measured using nitrogen and the BET method according to ISO 9277:2010; (ii) an intra-particle intruded specific pore volume in the range of from 0.1 to 2.3 cm.sup.3/g calculated from mercury porosimetry measurement; and (iii) a ratio of the at least one water-insoluble calcium salt to calcite, aragonite and/or vaterite in the range of from 1:99 to 99:1 by weight.

10. The method according to claim 9, wherein (i) the at least one surface-reacted calcium carbonate of step (a) is provided in a liquid medium in form of a suspension; and/or (ii) the at least one transition metal compound of step (b) is provided in a liquid medium in form of a solution or a suspension, preferably in form of a solution.

11. The method according to claim 9, wherein the method further comprises step (d) of removing at least part of the liquid medium contained in the mixture of step (c) by evaporation and/or filtration to obtain a concentrated mixture.

12. The method according to claim 9, wherein the method further comprises step (e) of thermally treating the mixture of step (c) or the concentrated mixture of step (d) at a temperature of below 400? C., preferably at a temperature in the range from 170? C. to 400? C., more preferably from 200? C. to 300? C., even more preferably from 250? C. to 310? C. and most preferably from 280? C. to 320? C.

13. The method according to claim 9, wherein the transition metal compound is selected from the group consisting of palladium compounds, platinum compounds, copper compounds and mixtures thereof

14. The method according to claim 9 wherein the transition metal compound is selected from the group consisting of elemental palladium, Pd(acac).sub.2, Na.sub.2PdCl.sub.4, Pd(OAc).sub.2, Pd(PPh.sub.3).sub.4, PdCl.sub.2(PPh.sub.3).sub.2, (dppf)PdCl.sub.2, (dppe)PdCl.sub.2, (dppp)PdCl.sub.2, (dppb)PdCl.sub.2, PdCl.sub.2, (C.sub.3H.sub.5PdCl).sub.2, bis(acetate)triphenylphosphine-palladium(II), Pd(dba).sub.2, Pd(H.sub.2NCH.sub.2CH.sub.2NH.sub.2)Cl.sub.2, elemental platinum, Na.sub.2PtCl.sub.6 Pt(acac).sub.2, Na.sub.2PtCl.sub.4, H.sub.2PtCl.sub.6, (NH.sub.4).sub.2[PtCl.sub.6], PtO.sub.2.H.sub.2O, PtCl.sub.4, elemental copper, Cu.sub.2O, Cu.sub.2S, copper(I)-thiophene-2-carboxylate, CuBr, CuCN, CuCl, CuF, CuI, CuH, CuSCN, CuBr.sub.2, CuCO.sub.3, CuCl.sub.2, CuF.sub.2, Cu(NO.sub.3).sub.2, Cu.sub.3(PO.sub.4).sub.2, CuO, CuO.sub.2, Cu(OH).sub.2, CuI.sub.2, CuS, CuSO.sub.4, Cu.sub.2(OAc).sub.4 and mixtures thereof, preferably the transition metal compound is selected from the group consisting of elemental palladium, Pd(acac).sub.2, Na.sub.2PdCl.sub.4, Pd(OAc).sub.2, Pd(PPh.sub.3).sub.4, PdCl.sub.2(PPh.sub.3).sub.2, (dppf)PdCl.sub.2, (dppe)PdC.sup.1.sub.2, (dppp)PdCl.sub.2, (dppb)PdCl.sub.2, PdCl.sub.2, (C.sub.3H.sub.5PdCl).sub.2, bis(acetate)triphenylphosphine-palladium(II), Pd(dba).sub.2, Pd(H.sub.2NCH.sub.2CH.sub.2NH.sub.2)Cl.sub.2, elemental platinum, Na.sub.2PtCl.sub.6 Pt(acac).sub.2, Na.sub.2PtCl.sub.4, H.sub.2PtCl.sub.6, (NH.sub.4).sub.2[PtCl.sub.6], PtO.sub.2.H.sub.2O, PtCl.sub.4 and mixtures thereof.

15. The method according to claim 9, wherein the liquid medium is a non-polar solvent, a polar solvent or a mixture thereof, preferably the non-polar solvent is selected from the group consisting of pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane and mixtures thereof and/or the polar solvent is selected from the group consisting of tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulphoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropanol, n-propanol, ethanol, methanol, acetic acid, water and mixtures thereof.

16. The method according to claim 9, wherein the transition metal compound is Na.sub.2PdCl.sub.4 and/or Na.sub.2PtCl.sub.4 and the liquid medium is a polar solvent, preferably water; and/or the transition metal compound is Pd(acac).sub.2 and/or Pt(acac).sub.2 and the liquid medium is a non-polar solvent, preferably toluene.

17. A catalyst system obtainable according to the method defined in claim 9.

18. Use of a catalyst system according to claim 1, in a process comprising the following steps: (a) providing one or more reactants; (b) providing said catalyst system; (c) subjecting the one or more reactants provided in step (a) to a chemical reaction in the presence of the catalyst system provided in step (b).

19. The use according to claim 18, wherein the process further comprises step (d) of recovering the catalyst system following the chemical reaction of step (c) and recycling the transition metal.

20. The use according to claim 18, wherein the chemical reaction in step (c) is selected from one or more of the following reaction types: hydrogenolyses, CC couplings and CC cross couplings, CN cross couplings, CO cross couplings, CS cross couplings, cycloaddition reactions, alkene hydrogenations and alkyne hydrogenations, allylic substitutions, reductions of nitro groups and hydrocarbonylations of aryl halides, preferably hydrogenolyses, CC couplings and CC cross couplings.

21. Use of a surface-reacted calcium carbonate as defined in claim 1 as carrier for transition metal-based catalysts.

22. Granules, mouldings or extrudates comprising a catalyst system according to claim 1.

Description

EXAMPLES

[0249] A) Analytical Methods

[0250] The parameters defined throughout the present application and determined in the following examples are based on the following measuring methods:

[0251] Solids Content

[0252] The suspension solids content (also known as dry weight) is determined using a Moisture Analyser MJ33 (Mettler-Toledo, Switzerland), with the following settings: drying temperature of 150? C., automatic switch off if the mass does not change more than 1 mg over a period of 30 s, standard drying of 5 g of suspension.

[0253] Particle size distribution of a particulate material The particle size of surface-reacted calcium carbonate herein is described as volume-based particle size distribution d.sub.x(vol). The volume determined median particle size d.sub.50(vol) and the volume determined top cut particle size d.sub.98(vol) were evaluated using a Malvern Mastersizer 2000 Laser Diffraction System (Malvern Instruments Plc., Great Britain). The d.sub.50(vol) or d.sub.98(vol) value indicates a diameter value such that 50% or 98% by volume, respectively, of the particles have a diameter of less than this value. The raw data obtained by the measurement was analyzed using the Mie theory, with a particle refractive index of 1.57 and an absorption index of 0.005. The methods and instruments are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments.

[0254] The particle size of particulate materials other than surface-reacted calcium carbonate is described herein as weight-based particle size distribution d.sub.x(vol). The weight determined median particle size d.sub.50(wt) was measured by the sedimentation method, which is an analysis of sedimentation behaviour in a gravimetric field. The measurement was made with a Sedigraph? 5100 or 5120 of Micromeritics

[0255] Instrument Corporation, USA. The method and the instrument are known to the skilled person and are commonly used to determine particle size distributions of fillers and pigments. The measurement was carried out in an aqueous solution of 0.1 wt.-% Na.sub.4P.sub.2O.sub.7. The samples were dispersed using a high speed stirrer and supersonicated.

[0256] Porosimetry

[0257] The specific pore volume is measured using a mercury intrusion porosimetry measurement using a Micromeritics Autopore V 9620 mercury porosimeter having a maximum applied pressure of mercury 414 MPa (60 000 psi), equivalent to a Laplace throat diameter of 0.004 ?m (?nm). The equilibration time used at each pressure step is 20 s. The sample material is sealed in a 3 cm.sup.3 chamber powder penetrometer for analysis. The data are corrected for mercury compression, penetrometer expansion and sample material compression using the software Pore-Comp (Gane, P. A. C., Kettle, J. P., Matthews, G. P. and Ridgway, C. J., Void Space Structure of Compressible Polymer Spheres and Consolidated Calcium Carbonate Paper-Coating Formulations, Industrial and Engineering Chemistry Research, 35(5), 1996, p 1753-1764.).

[0258] The total pore volume seen in the cumulative intrusion data can be separated into two regions with the intrusion data from 214 ?m down to about 1 to 4 ?m showing the coarse packing of the sample between any agglomerate structures contributing strongly. Below these diameters lies the fine interparticle packing of the particles themselves. If they also have intraparticle pores, then this region appears bimodal, and by taking the specific pore volume intruded by mercury into pores finer than the modal turning point, i.e. finer than the bimodal point of inflection, we thus define the specific intraparticle pore volume. The sum of these three regions gives the total overall pore volume of the powder, but depends strongly on the original sample compaction/settling of the powder at the coarse pore end of the distribution.

[0259] By taking the first derivative of the cumulative intrusion curve the pore size distributions based on equivalent Laplace diameter, inevitably including pore-shielding, are revealed. The differential curves clearly show the coarse agglomerate pore structure region, the interparticle pore region and the intraparticle pore region, if present. Knowing the intraparticle pore diameter range it is possible to subtract the remainder interparticle and interagglomerate pore volume from the total pore volume to deliver the desired pore volume of the internal pores alone in terms of the pore volume per unit mass (specific pore volume). The same principle of subtraction, of course, applies for isolating any of the other pore size regions of interest.

[0260] BET Specific Surface Area (SSA) of a Material

[0261] Throughout the present document, the specific surface area (in m.sup.2/g) of surface-reacted calcium carbonate or other materials is determined using the BET method (using nitrogen as adsorbing gas), which is well known to the skilled man (ISO 9277:2010). The total surface area (in m.sup.2) of the filler material is then obtained by multiplication of the specific surface area and the mass (in g) of treatment corresponding sample.

[0262] X-Ray Diffraction (XRD)

[0263] XRD experiments are performed on the samples using rotatable PMMA holder rings. Samples are analysed with a Bruker D8 Advance powder diffractometer obeying Bragg's law. This diffractometer consists of a 2.2 kW X-ray tube, a sample holder, a ?-?-goniometer, and a VANTEC-1 detector. Nickel-filtered Cu K? radiation is employed in all experiments. The profiles are chart recorded automatically using a scan speed of 0.7? per min in 24. The resulting powder diffraction pattern can easily be classified by mineral content using the DIFFRACsuite software packages EVA and SEARCH, based on reference patterns of the ICDD PDF 2 database.

[0264] Quantitative analysis of diffraction data refers to the determination of amounts of different phases in a multi-phase sample and has been performed using the DIFFRACsuite software package TOPAS. In detail, quantitative analysis allows to determine structural characteristics and phase proportions with quantifiable numerical precision from the experimental data itself. This involves modelling the full diffraction pattern using the Rietveld approach such that the calculated pattern(s) duplicates the experimental one.

[0265] HPLC Chromatography

[0266] Suzuki reaction: Samples were analysed on a Waters Symmetry Shield? column (RP-8, 3.5 ?M, 4.6?50 mM) using a Dionex P680 HPLC pump (1.0 ml.Math.min.sup.?1) equipped with a Dionex UVD3400 detector, a Dionex ASi-100 Autosampler (10 ?L injection), a Dionex TCC-100 HPLC column thermostat (40? C.) and a DG1210 degasser. A gradient of 0-100% of acetonitrile in an aqueous phase (0.1% formic acid and 5% acetonitrile in demineralised water) was used as eluent.

[0267] Hydrogenolysis reaction: Samples were analysed on a Waters Symmetry Shield? column (RP-8, 3.5 ?M, 4.6?50 mM) using a Dionex P680 HPLC pump (0.8 mL.Math.min-1) equipped with an ERC RefractoMax 520 detector, a Dionex ASi-100 Autosampler (10 ?L injection) and a Dionex TCC-100 HPLC column thermostat (70? C.). 5 mM H.sub.2SO.sub.4 (pH 1.5) in demineralised water was used as eluent.

[0268] B) Preparation of the Carriers (MCC)

[0269] SRCC1 (d.sub.50(vol)=4.4 ?m, d.sub.98(vol)=8.6 ?m, SSA=39.9 m.sup.2g.sup.?1)

[0270] SRCC1 was obtained by preparing 10 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground marble calcium carbonate from Hustadmarmor Norway having a mass based particle size distribution of 90% less than 2 ?m, as determined by sedimentation, such that a solids content of 15 wt.-%, based on the total weight of the aqueous suspension, is obtained. In addition, a solution was prepared containing 30 wt.-% phosphoric acid. Whilst mixing the slurry, 0.83 kg of the phosphoric acid solution was added to said suspension over a period of 10 min at a temperature of 70? C. Finally, after the addition of the phosphoric acid, the slurry was stirred for additional 5 min, before removing it from the vessel, filtering and drying.

[0271] SRCC2 (d.sub.50(vol)=8.3 ?m d.sub.98(vol)=19.5 ?m, SSA=74.4 m.sup.2g.sup.?1)

[0272] SRCC2 was obtained by preparing 10 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground marble calcium carbonate from Hustadmarmor Norway having a mass based particle size distribution of 90% less than 2 ?m, as determined by sedimentation, such that a solids content of 15 wt.-%, based on the total weight of the aqueous suspension, is obtained. In addition, a solution was prepared by blending diluted phosphoric acid and aluminium sulphate hexadecahydrate, wherein the phosphoric acid had a concentration of 30 wt.-% and the aluminium sulphate hexadecahydrate was dosed with a mass 5% that of the neat phosphoric acid. Whilst mixing the slurry, 1.7 kg of the phosphoric acid/aluminium sulphate solution was added to said suspension over a period of 10 min at a temperature of 70? C. Finally, after the addition of the phosphoric acid, the slurry was stirred for additional 5 min, before removing it from the vessel, filtering and drying.

[0273] SRCC3 (d.sub.50(vol)=8.2 ?m, d.sub.98(vol)=16.7 ?m, SSA=90.0 m.sup.2g.sup.?1)

[0274] SRCC3 was obtained by preparing 10 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground marble calcium carbonate from Hustadmarmor Norway having a mass based particle size distribution of 90% less than 2 ?m, as determined by sedimentation, such that a solids content of 10 wt.-%, based on the total weight of the aqueous suspension, is obtained. In addition, a solution was prepared by blending diluted phosphoric acid and citric acid, wherein the phosphoric acid had a concentration of 29 wt.-% and the citric acid was dosed with a mass 10% that of the neat phosphoric acid. Whilst mixing the slurry, 1.65 kg of the phosphoric acid/citric acid solution was added to said suspension over a period of 10 min at a temperature of 70? C. Finally, after the addition of the phosphoric acid, the slurry was stirred for additional 5 min, before removing it from the vessel, filtering and drying.

[0275] SRCC4 (d.sub.50(vol)=6.7 ?m, d.sub.98(vol)=12.9 ?m, SSA=146.5 m.sup.2g.sup.?1)

[0276] SRCC4 was obtained by preparing 101 of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground marble calcium carbonate from Hustadmarmor Norway having a mass based particle size distribution of 90% less than 2 ?m, as determined by sedimentation, such that a solids content of 10 wt.-%, based on the total weight of the aqueous suspension, is obtained. In addition, a solution was prepared containing 30 wt.-% phosphoric acid while another was prepared containing 5 wt.% citric acid. Whilst mixing the slurry, 1.60 kg of the phosphoric acid solution was added to said suspension over a period of 10 min at a temperature of 70? C. Additionally, starting 2 min after the start of phosphoric acid addition, 0.05 kg of the citric acid solution was also added to the slurry. Finally, after the addition of the phosphoric acid, the slurry was stirred for additional 5 min, before removing it from the vessel, filtering and drying.

[0277] SRCC5 (d.sub.50(vol)=7.1 ?m, d.sub.98(vol)=13.5 ?m, SSA=119.2 m.sup.2g.sup.?1)

[0278] SRCC5 was obtained by preparing 10 litres of an aqueous suspension of ground calcium carbonate in a mixing vessel by adjusting the solids content of a ground marble calcium carbonate from Hustadmarmor Norway having a mass based particle size distribution of 90% less than 2 ?m, as determined by sedimentation, such that a solids content of 10 wt.-%, based on the total weight of the aqueous suspension, is obtained. In addition, a solution was prepared containing 30 wt.-% phosphoric acid while another was prepared containing 5 wt.% citric acid. Whilst mixing the slurry, 1.60 kg of the phosphoric acid solution was added to said suspension over a period of 10 min at a temperature of 70? C. Additionally, starting 3 min after the start of phosphoric acid addition, 0.05 kg of the citric acid solution was also added to the slurry. Finally, after the addition of the phosphoric acid, the slurry was stirred for additional 5 min, before removing it from the vessel, filtering and drying.

TABLE-US-00001 TABLE 1 Quantitative Rietveld analysis (XRD) of the carriers (data normalised to 100% crystalline material). Mineral Formula SRCC1 SRCC2 SRCC3 SRCC4 SRCC5 Calcite CaCO.sub.3 74.5 50.6 17.7 14.7 16.9 Hydroxylapatite Ca.sub.5(OH)(PO.sub.4).sub.3 25.5 49.4 82.3 85.3 83.1 Total 100 100 100 100 100

TABLE-US-00002 TABLE 2 Hg Porosimetry of the carriers. SRCC1.sup.a SRCC2.sup.b SRCC3.sup.c SRCC4.sup.d SRCC5.sup.e Total intra particle 0.412 0.919 2.195 1.235 1.287 intruded specific pore volume [?m/cm.sup.3g.sup.?1] .sup.aFor the pore diameter range of 0.004 to 0.18 ?m .sup.bFor the pore diameter range of 0.004 to 0.32 ?m .sup.cFor the pore diameter range of 0.004 to 0.9 ?m .sup.dFor the pore diameter range of 0.004 to 0.51 ?m .sup.eFor the pore diameter range of 0.004 to 0.51 ?m

[0279] C) Preparation of the Catalysts

[0280] Method 1: Non-Aqueous Impregnation in Ethanol

[0281] A slurry of the carrier (0.5 g) is prepared in an organic solvent (20 ml) in which the metal salt is already dissolved. The slurry is then stirred (18 h) and filtered off, dried under vacuum at ambient temperature for 18 h. The procedure can be repeated one time to increase the catalyst loading.

[0282] Method 2: Non-Aqueous Impregnation in Toluene

[0283] A slurry of the carrier (2 g) is prepared in an organic solvent (25 ml) in which the metal salt is also dissolved. The solvent is then evaporated under constant agitation to impregnate the catalyst onto the carrier and to obtain a homogenous powder. The material is then dried under vacuum at ambient temperature for 18 h and calcinated at 300? C.

[0284] Method 3: Aqueous Impregnation

[0285] A water soluble salt of the metal is first dissolved in water (4 ml) and the pH is adjusted to 5.5 to 6 by using NaHCO.sub.3 (sat.). The solution is added to a slurry of the carrier (1.8-2.0 g) in water (8-12 ml). The mixture is heated to 70? C. for 30-90 min and then cooled to room temperature. The catalyst is filtered off, rinsed with water (3?4 ml), dried under vacuum at ambient temperature for 18 h and then calcinated at 300? C. for 3 h. The procedure can be repeated several times to increase the catalyst loading.

TABLE-US-00003 TABLE 3 Prepared catalysts (C1-C20) Ex. Support Metal Method Solvent Catalyst Number of No. used salt No. type amount.sup.a impregnations C1 SRCC1 Pd(acac).sub.2 2 Toluene 5 1 C2 SRCC2 Pd(acac).sub.2 2 Toluene 5 1 C3 SRCC3 Pd(acac).sub.2 2 Toluene 5 1 C4 SRCC4 Pd(acac).sub.2 2 Toluene 5 1 C5 SRCC5 Pd(acac).sub.2 2 Toluene 5 1 C6 SRCC1 Pt(acac).sub.2 2 Toluene 5 1 C7 SRCC2 Pt(acac).sub.2 2 Toluene 5 1 C8 SRCC3 Pt(acac).sub.2 2 Toluene 5 1 C9 SRCC4 Pt(acac).sub.2 2 Toluene 5 1 C10 SRCC5 Pt(acac).sub.2 2 Toluene 5 1 C11 SRCC1 Na.sub.2PdCl.sub.4 3 Water 5 1 (30 min) C12 SRCC2 Na.sub.2PdCl.sub.4 3 Water 5 1 (30 min) C13 SRCC3 Na.sub.2PdCl.sub.4 3 Water 5 1 (30 min) C14 SRCC4 Na.sub.2PdCl.sub.4 3 Water 5 1 (30 min) C15 SRCC5 Na.sub.2PdCl.sub.4 3 Water 5 1 (30 min) C16 SRCC1 Na.sub.2PtCl.sub.4 3 Water 5 2 (15 + 75 min) C17 SRCC2 Na.sub.2PtCl.sub.4 3 Water 5 2 (45 + 45 min) C18 SRCC3 Na.sub.2PtCl.sub.4 3 Water 5 2 (60 + 30 min) C19 SRCC4 Na.sub.2PtCl.sub.4 3 Water 5 2 (60 + 30 min) C20 SRCC5 Na.sub.2PtCl.sub.4 3 Water 5 1 (90 min) CE1 Palladium, 5% on calcium carbonate, unreduced, dry CE2 Platinum, 5% on calcium carbonate, unreduced, dry .sup.aCatalyst amount used for impregnation (wt.-% Pd or Pt)

[0286] Evaluation of Catalyst Loading:

[0287] The filtrate solution from aqueous impregnation C19 (SRCC4) was left standing until all soluble metal salt had precipitated as black material (i.e. until complete decolouration of the solution). The precipitate was weighed and the catalyst loading was calculated back from this value to be 4.6 wt.-% of Pt. The calculation was done from metallic platinum.

[0288] D) Application Examples

[0289] Suzuki reaction (Examples A1-A10, Comparative Examples CA1-CA5)

[0290] The coupling reaction between iodobenzene and phenylboronic acid was performed according to Letters in Organic Chemistry, 4, 2007, 13-15 with various catalysts loadings and catalysts type. In a typical reaction, 0.45 g of phenylboronic acid (1.5 equivalent, 3.7 mmol) was weighed into a 100 ml round bottom flask. Potassium carbonate (2.9 equivalent, 7.3 mmol, 1.0 g) was added to the mixture together with 80 mL solvent (ethanol 40% in water). The flask was closed with a septum, agitation was started and the flask was purged with a nitrogen flow. Iodobenzene (0.50 g, 2.5 mmol) was then added followed by the pre-weighed catalyst (in a closed vial). The nitrogen purge was continued for 10 to 15 min. Aliquots (ca 0.5 ml) were taken out of the mixture at regular intervals, extracted with 1 ml of heptane and analysed by HPLC using a UV diode array detector (238 nm). The conversion rate is summed up in Table 4.

[0291] At the end of the reaction, heptane was added to the reaction mixture and agitated for ca 15 min before transferring the contents to a 250 ml separation funnel and phases were separated and the organic phase was dried over Na.sub.2SO.sub.4 for ca 12 h and filtered. The clear organic layer was concentrated to dryness in a tared round bottom flask, using a rotary evaporator. The round bottom flask was weighed to determine the yield of the reaction. The aqueous layers from the extractions containing the catalyst were isolated by vacuum filtration using a fritted glass filter (porosity 3). The filter cake was washed with deionised water, ethanol, and heptane. The filters containing the filter cakes were placed in a vacuum oven and dried at 20? C. under full vacuum for >24 h. After drying the dried catalyst was collected from the filters and weighed into screw-cap glass vials to determine the recovered catalyst amount.

TABLE-US-00004 TABLE 4 comparison at similar catalyst loadings with a commercial supported catalyst. Example Catalyst Catalyst % conversion % conversion No. No. (mole-% Pd) after ca. 4 h.sup.a after ca. 7 h.sup.a CA1 CE1 1 47 87 A1 C11 1 71 93 A2 C14 1 96 >99 CA2 CE1 0.6 36 75 A3 C11 0.6 63 89 A4 C14 0.6 75 96 CA3 CE1 0.3 8 34 A5 C11 0.3 31 56 A6 C14 0.3 44 64 .sup.aBased on iodobenzene

[0292] The above Table 4 shows the improved efficiency of the catalysts prepared according to the invention over a commercial Pd/CaCO.sub.3 catalyst. The catalysts preparation can be found in table 3.

TABLE-US-00005 TABLE 5 recyclability of the catalysts. Example No. CA4 CA5 A7 A8 A9 A10 Catalyst No. CE1 CE1 C11 C11 C14 C14 Initial Catalyst amount 1 0.6 1 0.6 1 0.6 (mole-% Pd) % Pd on catalyst 4.96 4.96 n.a. n.a. 5.43 5.43 1.sup.st catalytic % conversion after ca. 4 h 47 36 71 63 96 75 cycle Yield 1.sup.st cycle [%] 95 95 95 98 98 98 % catalyst recovered 44 30 53 56 95 >100 % Pd on catalyst after n.a. n.a. 4.94 4.75 # 3.28 recovery 2.sup.nd Yield 2.sup.nd cycle [%] 85.sup.a 91.sup.a 93 # catalytic % catalyst recovered 15.sup.a 48.sup.a 82 # cycle % Pd on catalyst after 2.0.sup.a 4.0.sup.a 4.46 # recovery 3.sup.rd Yield 3.sup.rd cycle [%] # # 85 # catalytic % catalyst recovered # # 73 # cycle % Pd on catalyst after # # 3.7 # recovery .sup.aThe recovered catalyst from the 1.sup.st catalytic cycle (trials with 1% and 0.6% catalyst) were combined and used for the 2.sup.nd catalytic cycle. # The experiments were not conducted.

[0293] The above Table 5 shows the good efficiency of the recovered catalysts, and that they are easier to recover than the commercial catalyst from the commercial sample.

[0294] Hydrogenolysis of Glycerol (Examples A11-A21)

[0295] The reactions were performed according to Catalysis Communications, 13, 2011, 1-5. A mixture of the catalyst (5 mole-% active metal, relative to glycerol) and 20 ml glycerol in water (100 mM) was put under 40 bar hydrogen pressure and then heated to 200? C. for 18 hours while stirring at 800 rpm. After cooling to room temperature a sample was taken for analysis. The sample was filtered and mixed with an equal amount of 5 mM H.sub.2SO.sub.4. The catalyst was filtered off, rinsed with water (3?1 ml) and dried under vacuum. The reaction mixtures were analysed by HPLC to determine the amounts of starting material (glycerol) to and the 4 major reaction products; lactic acid (LA), 1,2-propanediol (12-PD), ethylene glycol (EG) and ethanol (EtOH). In all cases these compounds made up ?95% of the total peak area. Results are summarised in Table 6.

TABLE-US-00006 TABLE 6 Examples A11-20 and CA6 (hydrogenolysis of glycerol) Glyc- Example Catalyst Impregnation erol 12-PD EtOH EG LA No. No. method [%].sup.a [%].sup.a [%].sup.a [%].sup.a [%].sup.a CA6 CE2 76 15 6.5 1.9 1.5 A11 C6 Non-aqueous 28 55 5.7 11 1.0 A12 C7 Non-aqueous 31 19 47 2.9 0.5 A13 C8 Non-aqueous 39 28 26 6.5 0.4 A14 C9 Non-aqueous 30 26 38 5.1 0.4 A15 C10 Non-aqueous 28 51 11 7.8 1.6 A16 C16 Aqueous 47 34 9.6 8.4 0.9 A17 C17 Aqueous 37 49 7.0 6.5 1.0 A18 C18 Aqueous 46 36 11 6.8 0.6 A19 C19 Aqueous 45 43 5.9 5.4 0.9 A20 C20 Aqueous 31 35 27 6.5 0.7 .sup.aDetermined by HPLC analysis after reaction (peak area in % of total peaks area)

[0296] Table 6 shows that all catalysts according to the invention showed greater activity than the commercial catalyst used as comparative example.