SRCC AS A CATALYTIC CARRIER FOR METAL SPECIES

Abstract

The present invention refers to a catalytic system comprising a transition metal compound on a solid carrier, wherein the content of the transition metal element on the surface of the solid carrier is from 0.1 to 30 wt.-%, based on the dry weight of the solid carrier. Furthermore, the present invention refers to a method for manufacturing the catalytic system, the use of the inventive catalytic system in a chemical reaction, the use of a solid carrier loaded with a transition metal as a catalyst and to granules mouldings or extrudates comprising the catalytic system.

Claims

1. A catalytic system comprising a transition metal compound on a solid carrier, wherein a) the solid carrier is a surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and one or more H.sub.3O.sup.+ ion donors, wherein the carbon dioxide is formed in situ by the H.sub.3O.sup.+ ion donors treatment and/or is supplied from an external source; and b) wherein the transition metal compound is selected from the group consisting of elemental Ni, elemental Ru, elemental Au, elemental Pd, elemental Pt, elemental Fe, elemental Cu and mixtures thereof; and wherein the content of the transition metal element on the surface of the solid carrier is from 0.1 to 30 wt.-%, based on the dry weight of the solid carrier.

2. The catalytic system according to claim 1, wherein the natural ground calcium carbonate is selected from the group consisting of marble, chalk, limestone, and mixtures thereof, or the precipitated calcium carbonate is selected from the group consisting of precipitated calcium carbonates having an aragonitic, vateritic or calcitic crystal form, and mixtures thereof.

3. The catalytic system according to claim 1, wherein the at least one H.sub.3O.sup.+ ion donor is selected from the group consisting of hydrochloric acid, sulphuric acid, sulphurous acid, phosphoric acid, citric acid, oxalic acid, an acidic salt, acetic acid, formic acid, and mixtures thereof,

4. The catalytic system according to claim 1, wherein the solid carrier has: (i) a volume median particle size d.sub.50 from 0.1 to 75 m, (ii) a volume top cut particle size d.sub.98 from 0.2 to 150 m, and/or (iii) a specific surface area of from 10 m.sup.2/g to 200 m.sup.2/g, measured using nitrogen and the BET method.

5. The catalytic system according to claim 1, wherein the transition metal compound is preferably selected from the group consisting of elemental Ni, elemental Ru, elemental Au, elemental Fe, elemental Cu and mixtures thereof and most preferably is selected from the group consisting of elemental Ni, elemental Ru, elemental Au and mixtures thereof.

6. The catalytic system according to claim 1, wherein the content of the transition metal element on the surface of the solid carrier is in the range of from 0.25 to 25 wt. %, preferably from 0.5 to 20 wt. %, more preferably 1 to 15 wt. %, even more preferably from 2 to 10 wt. % and most preferably from 2.5 to 5 wt. %, based on the dry weight of the solid carrier.

7. A method for manufacturing a catalytic system comprising a transition metal compound on a solid carrier, the method comprising the following steps: (a) providing at least one solid carrier, wherein the solid carrier is a surface-reacted calcium carbonate, wherein the surface-reacted calcium carbonate is a reaction product of natural ground calcium carbonate or precipitated calcium carbonate with carbon dioxide and one or more H.sub.3O.sup.+ ion donors, wherein the carbon dioxide is formed in situ by the H.sub.3O.sup.+ ion donors treatment and/or is supplied from an external source; (b) providing at least one transition metal reagent comprising Ni ions, Ru ions, Au ions, Pd ions, Pt ions, Fe ions, Cu ions and mixtures thereof in such an amount that the amount of said ions is from 0.1 to 30 wt.-%, based on the dry weight of the solid carrier; (c) contacting the at least one solid carrier provided in step (a) and the transition metal reagent provided in step (b) to obtain a mixture comprising a solid carrier and a transition metal reagent; and (d) calcining the mixture of step (c) at a temperature between 250 C. and 500 C.; and (e) reducing the calcined catalytic system obtained from step (d) under H.sub.2 atmosphere at a temperature between 100 C. and 500 C. for obtaining a catalytic system comprising a transition metal compound on the solid carrier, wherein the transition metal compound is selected from the group consisting of elemental Ni, elemental Ru, elemental Au, elemental Pd, elemental Pt, elemental Fe, elemental Cu and mixtures thereof.

8. The method according to claim 7, wherein the calcination step (d) is performed (i) under air, N.sub.2 atmosphere, Ar atmosphere, O.sub.2 atmosphere or mixtures thereof and/or (ii) at a temperature between 275 C. and 475 C.

9. The method according to claim 7, wherein the method further comprises a step of (f) providing a solvent and contacting the at least one solid carrier provided in step (a) and/or the transition metal reagent provided in step (b) before or during step (c) in any order, wherein the solvent is a non-polar solvent, a polar solvent or a mixture thereof.

10. The method according to claim 9, wherein the method further comprises a step of (g) removing at least part of the solvent after step (c) and before step (d) by evaporation and/or filtration and/or centrifugation and/or spray drying to obtain a concentrated mixture.

11. The method according to claim 9, wherein the method further comprises step (h) of thermally treating the mixture of step (c) or the concentrated mixture of step (g) at a temperature between 25 C. and 200 C.

12. The method according to claim 7, wherein the transition metal reagent is selected from the group consisting of (NH.sub.4).sub.2Ni(SO.sub.4).sub.2, Ni(OCOCH.sub.3).sub.2, NiBr.sub.2, NiCl.sub.2, NiF.sub.2, Ni(OH).sub.2, NiI.sub.2, Ni(NO.sub.3).sub.2, Ni(ClO.sub.4).sub.2, Ni(SO.sub.3NH.sub.2).sub.2, NiSO.sub.4, K.sub.2Ni(H.sub.2IO.sub.6).sub.2, K.sub.2Ni(CN).sub.4, [Ru(NH.sub.3).sub.6]Cl.sub.2, [Ru(NH.sub.3).sub.6]Cl.sub.3, [Ru(NH.sub.3).sub.5Cl]Cl.sub.2, RuCl.sub.3, Ru(NO)(NO.sub.3), RuI.sub.3, RuF.sub.5, HAuCl.sub.4, AuBr.sub.3, AuCl, AuCl.sub.3, Au(OH).sub.3, Aul, KAuCl.sub.4, Pd(NO.sub.3).sub.2, 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, Na.sub.2PtCl.sub.6Pt(acac).sub.2, Na.sub.2PtCl.sub.4, H.sub.2PtCl.sub.6, (NH.sub.4).sub.2[PtCl.sub.6], PtO.sub.2.Math.H.sub.2O, PtCl.sub.4, Pt(NO.sub.3).sub.4, 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, Cu(OH).sub.2, CuI.sub.2, CuS, CuSO.sub.4, Cu.sub.2(OAc).sub.4, (NH.sub.4).sub.2Fe(SO.sub.4).sub.2, FeBr.sub.2, FeBr.sub.3, FeCl.sub.2, FeCl.sub.3, FeF.sub.2, FeF.sub.3, FeI.sub.2, Fe(NO.sub.3).sub.3, FeC.sub.2O.sub.4, Fe.sub.2(C.sub.2O.sub.4).sub.3, Fe(ClO.sub.4).sub.2, FePO.sub.4, FeSO.sub.4, Fe(BF.sub.4).sub.2, K.sub.4Fe(CN).sub.6 and mixtures thereof.

13. A method of using a catalytic system according to claim 1 in a process comprising: (A) providing one or more reactants; (B) providing said catalytic system ; (C) subjecting the one or more reactants provided in step (A) to a chemical reaction under air, O.sub.2 atmosphere, H.sub.2 atmosphere, or inert atmosphere at a temperature between 75 and 300 C. in the presence of the catalytic system provided in step (B).

14. The method according to claim 13, wherein the process further comprises step (D) of recovering and optionally recycling the catalytic system following the chemical reaction of step (C).

15. A catalyst comprising the catalyst system according to claim 1.

16. Granules, mouldings or extrudates comprising the catalytic system according to claim 1.

17. The catalytic system according to claim 3, wherein the at least one H.sub.3O.sup.+ ion donor is phosphoric acid.

18. The catalytic system according to claim 4, wherein the solid carrier has: (i) a volume median particle size d.sub.50 from 1.5 to 15 m, and (ii) a volume top cut particle size d.sub.98 from 3 to 30 m, and (iii) a specific surface area of from 30 m.sup.2/g to 100 m.sup.2/g, measured using nitrogen and the BET method.

19. The method according to claim 9 wherein the solvent is water.

20. The method according to claim 12 wherein the transition metal reagent is selected from the group consisting of Ni(NO.sub.3).sub.2, RuNO(NO.sub.3), HAuCl.sub.4, Fe(NO.sub.3).sub.3, Cu(NO.sub.3).sub.2, Pd(NO.sub.3).sub.2, and Pt(NO.sub.3).sub.4.

Description

EXAMPLES

1. Measurement Methods

[0294] The following measurement methods were used to evaluate the parameters given in the examples and claims.

BET Specific Surface Area (SSA) of a Material

[0295] The BET specific surface area was measured via the BET process according to ISO 9277:2010 using nitrogen, following conditioning of the sample by heating at 250 C. for a period of 30 minutes. Prior to such measurements, the sample was filtered, rinsed and dried at 110 C. in an oven for at least 12 hours.

Particle Size Distribution (Volume % Particles with a Diameter<X), d.sub.50 Value (Volume Median Grain Diameter) and d.sub.98 Value of a Particulate Material:

[0296] Volume median grain diameter d50 was evaluated using a Malvern Mastersizer 2000 Laser Diffraction System. The d50 or d98 value, measured using a Malvern Mastersizer 2000 Laser Diffraction System, 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 are analysed using the Mie theory, with a particle refractive index of 1.57 and an absorption index of 0.005.

[0297] The weight median grain diameter is determined by the sedimentation method, which is an analysis of sedimentation behaviour in a gravimetric field. The measurement is made with a Sedigraph 5100, Micromeritics Instrument Corporation. The method and the instrument are known to the skilled person and are commonly used to determine grain size of fillers and pigments. The measurement is carried out in an aqueous solution of 0.1 wt % Na4P2O7. The samples were dispersed using a high speed stirrer and supersonicated.

[0298] The processes and instruments are known to the skilled person and are commonly used to determine grain size of fillers and pigments.

Porosity/Pore Volume

[0299] The porosity or pore volume is measured using a Micromeritics Autopore IV 9500 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 seconds. The sample material is sealed in a 5 ml 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, p1753-1764.).

X-Ray Photoelectron Spectroscopy (XPS) Measurements

[0300] The X-ray photoelectron spectroscopy (XPS) experiments were carried out in a Kratos AXIS Ultra DLD spectrometer using a monochromatic Al K radiation (hv=1486.6 eV) operating at 225 W (15 mA, 15 kV). Instrument base pressure was 41010 Torr. The instrument work function was calibrated to give an Au 4f7/2 metallic gold binding energy (BE) of 83.96 eV. The spectrometer dispersion was adjusted to give a binding energy (BE) of 932.62 eV for metallic Cu 2p3/2. The Kratos charge neutralizer system was used for all analyses. Charge neutralization was deemed to have been fully achieved by monitoring the C is signal for adventitious carbon. For each sample, a general survey spectrum was recorded within a binding energy range from 1200 to 5 eV with a 160 eV pass energy, a 1 eV step and a 1 s dwell time. High-resolution core level spectra were obtained using an analysis area of 300 m700 m and a 20 eV pass energy. This pass energy corresponds to Ag 3d5/2 Full Width at Half Maximum (FWHM) of 0.48 eV. Core level spectra were recorded with a 0.1 eV step and a 150 ms dwell time. The instrument detection limit is around 0.1 atomic % at the surface.

[0301] Spectra were analysed using CasaXPS software (version 2.3.16). Gaussian (70%)-Lorentzian (30%) profiles were used for each component except for metallic component for which asymmetrical Lorentzian profiles were used. For each sample, a single peak ascribed to alkyl type carbon (CC, CH), was fitted to the main peak of the C is spectrum for adventitious carbon. A second peak was added and was constrained to be 1.5 eV above the main peak. This higher BE peak is ascribed to alcohol (COH) and/or ester (COC) functionality. All spectra have been charge corrected to give the adventitious C is spectral component (CC, CH) a BE of 284.8 eV. Quantification was performed after the subtraction of a standard Shirley background for all spectra. After a background removal for each spectrum, a relative atomic quantification of the chemical elements present at the surface can be estimated.

2. Material and Equipment

Preparation of Surface-Reacted Calcium Carbonate (SRCC) Powder

[0302] (d.sub.50=5.5 m, d.sub.98=10.6 m, SSA=141.5 m.sup.2g.sup.1)

[0303] SRCC 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 wet ground marble calcium carbonate, containing polyacrylate dispersant added in the grinding process, from Omya Hustadmarmor AS having a mass based particle size distribution with 90 w/w % of the particles finer than 2 m, as determined by sedimentation, such that a solids content of 16 wt %, based on the total weight of the aqueous suspension, is obtained.

[0304] Whilst mixing the slurry, 3 kg of an aqueous solution containing 30 wt % phosphoric acid was added to said suspension over a period of 10 minutes at a temperature of 70 C. Two minutes after the start of the phosphoric acid solution addition, 0.36 kg of an aqueous solution containing 25 wt% citric acid was added to said suspension over a period of 0.5 minutes. After the addition of the two solutions, the slurry was stirred for an additional 5 minutes, before removing it from the vessel and drying.

Preparation of the Catalytic System

[0305] The preparation of the catalytic system was performed using Chemspeed Catimpreg workstation designed for automated parallel synthesis of catalysts by coprecipitation and impregnation. In the first stage, a SRCC of 141.5 m.sup.2/g as prepared above was dried overnight at 100 C., then distributed in the different glass reactors, followed by adding water into the SRCC, agitating the components at 600 RPM for 5 minutes. The different metal precursor solutions, prepared in water solvent, were added after on the carrier, followed by an agitation process at 600 RPM for 60 minutes. The catalytic systems were next dried at 90 C. under vacuum (950 mbar) over 6 hours. A calcination step under static air was performed at 400 C. for 3 hours, followed by a reduction under a hydrogen flow at 350 C. for 3 hours. The obtained catalytic systems and the used metal salts used during the preparation procedure are described in the table below:

TABLE-US-00001 Theoretical amount of the elemental Name of Metal salt metal in the the Used used for the final catalytic BET catalyst carrier preparation Producer Reference system (wt %) (m.sup.2/g) Fe, SRCC Fe(NO.sub.3).sub.3 Sigma 216828 10 51.5 10%/SRCC Aldrich Ni, Ni(NO.sub.3).sub.2 Sigma 72253 10 61.8 10%/SRCC Aldrich Cu, Cu(NO.sub.3).sub.2 Sigma 61194 10 57.5 10%/SRCC Aldrich Ru, RuNO(NO.sub.3).sub.3 Alfa Aesar 12175 1 116.5 1%/SRCC Pd, Pd(NO.sub.3).sub.2 Sigma 380040 1 1%/SRCC Aldrich Pt, Pt(NO.sub.3).sub.4 Alfa Aesar H37737 1 1%/SRCC Au, HAuCl.sub.4 Sigma 520918 1 118.3 1%/SRCC Aldrich

3. Example Data

Characterization of the Catalytic Systems

[0306] XPS measurements of the obtained catalytic systems were performed. The relative atomic percent concentration for samples after calcination and after calcination +reduction under hydrogen flow are given in the table below:

TABLE-US-00002 Sample O Ca P Cu Fe Ni Pd Pt Au Ru Cu, 10%/SRCC calcined 67.1 18.4 11.5 3.0 Cu, 10%/SRCC 66.8 19.9 11.9 1.5 calcined + reduced Fe, 10%/SRCC calcined 70.2 16.7 8.6 4.5 Fe, 10%/SRCC calcined + 65.6 19.7 11.9 2.8 reduced Ni, 10%/SRCC calcined 69.9 16.5 8.5 5.1 Ni, 10%/SRCC 65.7 19.6 11.9 2.8 calcined + reduced Pd, 1%/SRCC calcined 72.7 18.5 8.7 <0.5 Pd, 1%/SRCC calcined + 67.6 20.8 11.6 <0.5 reduced Pt, 1%/SRCC calcined 72.9 18.2 8.8 <0.5 Pt, 1%/SRCC calcined + 67.2 20.5 12.1 <0.5 reduced Au, 1%/SRCC calcined 71.9 18.9 9.3 <0.5 Au, 1%/SRCC calcined + 66.9 20.7 12.3 <0.5 reduced Ru, 1%/SRCC calcined 73.8 17.4 8.6 <0.5 Ru, 1%/SRCC calcined + 69.2 19.6 11.0 <0.5 reduced

[0307] An identification of the metal species and their oxidation state, on the surface of the catalytic systems is presented in the below table. These remarks are extracted from the measured XPS data and show the difference occurring on the catalytic systems after calcination and after calcination+reduction.

TABLE-US-00003 Sample Metals core level spectra Cu, 10%/SRCC Cu 2p spectrum presents a complex structure and is decomposed into calcined several components. The spectral envelope and decomposition is consistent with the presence of copper oxide in its +2 oxidation state. Cu, 10%/SRCC Cu 2p spectrum presents a different spectral envelope. It can be calcined + decomposed into a mixture of copper oxide in its 2+ oxidation state and a reduced reduced copper. The study of the Cu L3M4, 5M4, 5 Auger peak, and the calculation of the modified Auger parameter allows to identify the reduced species as copper oxide in its 1+ oxidation state. However, the oxidation state of +1 is obtained due to the oxidation of the elemental Cu on the surface of the solid carrier under air, occurred during the sample transfer step to the XPS device. Fe, 10%/SRCC Fe 2p spectrum presents a complex structure and is decomposed into calcined several components. The spectral envelope and decomposition is consistent with a mixture of iron oxides, with both Fe2+ and Fe3+ states. Fe, 10%/SRCC Fe 2p spectrum presents again a complex structure corresponding to a calcined + mixture of Fe2+ and Fe3+ states. However, an additional component at reduced lower BE (BE = 708.9 eV) is found and corresponds to the presence of metallic iron. Ni, 10%/SRCC Ni 2p spectrum presents a complex structure and is decomposed into calcined several components. The spectral envelope and decomposition is consistent with a mixture of nickel oxide and hydroxide. Ni, 10%/SRCC Ni 2p spectrum presents again a complex structure corresponding to a calcined + mixture of nickel oxide and hydroxide. However, an additional component reduced at lower BE (BE = 851.9 eV) is found and corresponds to the presence of metallic nickel. Pd, 1%/SRCC Pd 3d spectrum presents only one component (i.e. one doublet peak). The calcined binding energy for the main peak (corresponding to the Pd 3d5/2 orbital) is 336.6 eV. This BE is consistent with the presence of palladium oxide in its 2+ oxidation state. Pd, 1%/SRCC Pd 3d spectrum presents only one component (i.e. one doublet peak). The calcined + binding energy for the main peak (corresponding to the Pd 3d5/2 orbital) is reduced 335.0 eV. This BE is consistent with the presence of metallic palladium. Pt, 1%/SRCC Pt 4f spectrum presents two components (i.e. two doublet peaks). Both calcined doublet peaks are symmetrical. The binding energy (BE) for the main peaks (corresponding to the Pt 4f7/2 orbital) are 72.4 eV and 74.2 eV. These BE are consistent with the presence of a mixture of platinum oxides, with both platinum divalent state and platinum tetravalent state. Pt, 1%/SRCC Pt 4f spectrum presents only one component (i.e. one doublet peak). The calcined + doublet peak is asymmetrical at high binding energy. The binding energy reduced for the main peak (corresponding to the Pt 4f7/2 orbital) is 70.3 eV. This BE along with the asymmetry of the peaks is consistent with the presence of metallic platinum. Au, 1%/SRCC Due to the low amount of gold at the surface of the samples (below 0.5%) calcined as compared to the percentage of calcium, and the weak chemical shift of Au, 1%/SRCC gold in its different oxidation states, it is not possible to conclude on the calcined + oxidation state of the gold. reduced Ru, 1%/SRCC Ru 3d spectrum presents only one component (i.e. one doublet peak). The calcined binding energy for the main peak (corresponding to the Ru 3d5/2 orbital) is 280.7 eV. This BE is consistent with the presence of ruthenium oxide in its 4+ oxidation state. Ru, 1%/SRCC Ru 3d spectrum presents only one component (i.e. one doublet peak). The calcined + binding energy for the main peak (corresponding to the Ru 3d5/2 orbital) reduced is 279.9 eV eV. This BE is consistent with the presence of metallic ruthenium.

Catalytic Investigations

[0308] The obtained catalytic systems were evaluated in three different types of chemical transformations, using glycerol as a starting molecule. Glycerol chemical transformations were performed under hydrogen or inert atmosphere (nitrogen) or oxygen atmospheres. The procedure was performed using a Screening Pressure Reactor (SPR) from Unchained Labs, which is an automated high-throughput reactor system.

[0309] In a first step, the reactors were filled with the catalytic system, glycerol and sodium hydroxide reagents. The reactors were next purged with nitrogen while mixing its contents, to eliminate air. Then the required atmosphere was replaced, followed by heating the reactors to the desired temperatures. The performed reactivity tests are described in the table below:

TABLE-US-00004 Atmosphere Pressure (bar) Temperature ( C.) Time (hours) NaOH/Gly molar ratio H.sub.2 30 200 6 1.5 12 N.sub.2 30 200 6 12 40% O.sub.2/60% N.sub.2 7.5 80 4 4
For the identification of the products obtained during the catalytic reaction, HPLC-UV liquid chromatograph from Shimadzu equipped with UV detector SPD-20A (=210 nm), pumps LC-30AD coupled with Waytt Refractive Index (RI) detector (Optilab T-rEX) were used for the qualitative and quantitative analysis of the products. A calibration of all the potentially obtained products was performed, for a precise quantification. HPLC analysis were carried out using a LC column Bio-Rad Aminex HPX-87H, operated at 60 C. A 0.01N H2SO4 aqueous solution was used as the mobile phase. Products were analysed at a flow rate of 0.5 mL/min.

[0310] The results obtained using the different catalytic systems under a reductive

[0311] atmosphere are presented in the table below:

TABLE-US-00005 Used Glycerol % catalytic Experimental Glycerol/Metal conv. Lactic system conditions molar ratio (%) acid 1,2-Popanediol Methanol Ethanol Carbon balance Fe, 10%/ 200C., 6 hours, H.sub.2 30 106 4.3 1.8 0.0 0.0 0.0 97.5 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 5.6 2.0 0.0 0.0 0.0 96.4 bar, NaOH/Gly of 1.5 Ni, 10%/ 200 C., 6 hours, H.sub.2 30 107 100 52.6 7.8 9.3 4.9 77.9 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 100 49.7 6.9 10.2 6.1 75.4 bar, NaOH/Gly of 1.5 Cu, 10%/ 200 C., 6 hours, H.sub.2 30 105 37.6 29.1 3.2 0.0 0.0 95.4 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, 55.7 39.5 6.2 0.0 0.0 91.1 H.sub.2 30 bar, NaOH/Gly of 1.5 Ru, 1%/ 200 C., 6 hours, H.sub.2 30 1462 26.2 22.4 0.0 0.0 0.0 96.3 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 29.8 25.1 0.0 0.0 0.0 95.4 bar, NaOH/Gly of 1.5 Pd, 1%/ 200 C., 6 hours, H.sub.2 30 1534 4.4 1.7 0.0 0.0 0.0 97.3 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 5.9 2.1 0.0 0.0 0.0 96.1 bar, NaOH/Gly of 1.5 Pt, 1%/ 200 C., 6 hours, H.sub.2 30 1539 61.9 52.5 0.7 2.7 0.0 95.1 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 100 82.2 2.6 4.7 0.0 91.9 bar, NaOH/Gly of 1.5 Au, 1%/ 200 C., 6 hours, H.sub.2 30 1555 5.7 2.5 0.0 0.0 0.0 96.8 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 8.2 3.8 0.0 0.0 0.0 95.7 bar, NaOH/Gly of 1.5 .sup.aThe remaining products up to 100% are only detected in limited amounts and, therefore, are not presented in this table.

[0312] The results obtained using the different catalytic systems under an inert

[0313] atmosphere are presented in the table below:

TABLE-US-00006 Used Glycerol % catalytic Experimental Glycerol/Metal conv. Lactic 1,2- system conditions molar ratio (%) acid Propanediol Methanol Ethanol Carbon balance Fe, 10%/ 200 C., 6 hours, N.sub.2 30 106 6.6 3.9 0.0 0.0 0.0 97.4 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 6.5 4.1 0.0 0.0 0.0 97.7 bar, NaOH/Gly of 1.5 Ni, 10%/ 200 C., 6 hours, N.sub.2 30 107 100 59.9 2.2 12.5 5.5 83.1 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, N2 30 100 69.7 1.9 0.8 2.3 78.9 bar, NaOH/Gly of 1.5 Cu, 10%/ 200 C., 6 hours, N.sub.2 30 105 97.6 72.3 7.0 3.8 0.0 88.6 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 100 88.3 1.8 0.0 0.0 96.0 bar, NaOH/Gly of 1.5 Ru, 1%/ 200 C., 6 hours, N.sub.2 30 1462 54.8 47.4 0.4 0.0 0.0 94.5 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 90.6 86.9 1.0 0.0 0.6 101.8 bar, NaOH/Gly of 1.5 Pd, 1%/ 200 C., 6 hours, N.sub.2 30 1534 4.6 2.8 0.0 0.0 0.0 98.5 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 8.6 5.4 0.0 0.0 0.0 96.9 bar, NaOH/Gly of 1.5 Pt, 1 %/ 200 C., 6 hours, N.sub.2 30 1539 100 82.4 0.0 0.0 0.0 83.7 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 100 89.5 0.0 0.0 0.0 92.5 bar, NaOH/Gly of 1.5 Au, 1%/ 200 C., 6 hours, N.sub.2 30 1555 10.5 7.7 0.0 0.0 0.0 97.6 SRCC bar, NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 7.0 5.6 0.0 0.0 0.0 98.8 bar, NaOH/Gly of 1.5 .sup.aThe remaining products up to 100% are only detected in limited amounts and, therefore, and are not presented in this table.

[0314] The results obtained using the different catalytic systems under an oxidative atmosphere are presented in the table below:

TABLE-US-00007 Used Glycerol % catalytic Experimental Glycerol/Metal molar conv Glyceric Glycolic Lactic Formic Carbon system conditions ratio (%) acid acid acid acid 1,2-Propanediol balance Fe, 10%/ 100 C., 4 hours, 40% O.sub.2 at 106 5.6 0.2 1.8 2.2 1.0 0.0 99.6 SRCC 17 bar, NaOH/Gly of 4 Ni,10%/ 100 C., 4 hours, 40% O.sub.2 at 107 4.9 0.1 1.3 5.6 0.8 0.0 103.0 SRCC 17 bar, NaOH/Gly of 4 Cu, 10%/ 100 C., 4 hours, 40% O.sub.2 at 105 5.3 1.1 1.1 2.1 0.8 0.0 100.0 SRCC 17 bar, NaOH/Gly of 4 Ru, 1%/ 100 C., 4 hours, 40% O.sub.2 at 1462 5.6 0.0 0.0 0.0 0.1 0.0 94.5 SRCC 17 bar, NaOH/Gly of 4 Pd, 1%/ 100 C., 4 hours, 40% O.sub.2 at 153 10.5 1.2 1.9 6.5 1.7 0.0 101.1 SRCC 17 bar, NaOH/Gly of 4 Pt, 1%/ 100 C., 4 hours, 40% O.sub.2 at 1539 13.0 1.9 2.2 7.3 1.8 0.0 100.7 SRCC 17 bar, NaOH/Gly of 4 Au, 1%/ 100 C., 4 hours, 40% O.sub.2 at 1555 4.2 0.4 1.4 2.0 0.9 0.0 100.8 SRCC 17 bar, NaOH/Gly of 4 .sup.aThe remaining products are only detected in limited amounts and, therefore are not presented in this table.

[0315] As can be seen from the above data by the inventive method it is possible to provide a catalytic system wherein the transition metal compound that is selected from the group consisting of elemental Ni, elemental Ru, elemental Au, elemental Pd, elemental Pt, elemental Fe, elemental Cu and mixtures thereof is located on the solid carrier, which is a surface-reacted calcium carbonate. Furthermore, the inventive method is a cheap and simple production process which provides the inventive catalytic system.

[0316] As can be seen from the above experimental data the surface-reacted calcium carbonate is useful due to its specific surface properties as carrier material for specific elemental transition metal compounds in the catalysis. Furthermore, it can be seen that with the inventive catalytic system high catalytic activities, for example high glycerol transformation under inert atmosphere, hydrogen or oxygen were achieved as well as a targeted selectivity to a well-defined product, namely lactic acid.