GNCC and/or PCC 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 compound 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 compound as a catalyst and to granules mouldings or extrudates comprising the catalytic system.

Claims

1. A catalytic system comprising: at least one solid carrier and a transition metal compound on the at least one solid carrier, wherein the at least one solid carrier is a ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) and has a specific surface area of from 3 to 50 m.sup.2/g measured using nitrogen and the BET method according to ISO 9277:2010, wherein the ground natural calcium carbonate and/or precipitated calcium carbonate is not a surface-reacted calcium carbonate; and wherein the transition metal compound is selected from the group consisting of elemental Ni, elemental Ru, elemental Au, elemental Fe, elemental Cu, oxides of the foregoing transition metal compounds and mixtures thereof; and wherein the content of a transition metal species on the surface of the at least one 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 at least one solid carrier is precipitated calcium carbonate (PCC) and/or wherein the at least one solid carrier has: (i) a specific surface area in the range of from 5 to 40 m.sup.2/g; and/or (ii) a d.sub.50(wt) in the range of from 1 to 75 m; and/or (iii) a d.sub.98(wt) in the range of from 2 to 150 m.

3. The catalytic system according to claim 2, wherein the at least one solid carrier is precipitated calcium carbonate (PCC) and/or wherein the at least one solid carrier has: (i) a specific surface area in the range of 10 to 30 m.sup.2/g, measured using nitrogen and the BET method according to ISO 9277:2010; and/or (ii) a d.sub.50(wt) in the range of from 5 to 15 m; and/or (iii) a d.sub.98(wt) in the range of from 10 to 30 m.

4. The catalytic system according to claim 1, wherein the transition metal compound is selected from the group consisting of elemental Ni, NiO, Ni.sub.2O.sub.3, Ni.sub.3O.sub.4, elemental Ru, RuO.sub.2, Ru.sub.2O.sub.3, RuO.sub.4, elemental Au, Au.sub.2O, Au.sub.2O.sub.3, elemental Fe, FeO, FeO.sub.2, Fe.sub.2O.sub.3, Fe.sub.3O.sub.4, elemental Cu, CuO, Cu.sub.2O, CuO.sub.2, Cu.sub.2O.sub.3 and mixtures thereof.

5. The catalytic system according to claim 4, wherein the transition metal compound is selected from the group consisting of elemental Ru, RuO.sub.2, Ru.sub.2O.sub.3, RuO.sub.4 and mixtures thereof.

6. The catalytic system according to claim 1, wherein the catalytic system further comprises one or more reaction products obtained by reaction of the combination of transition metal compound and the solid carrier.

7. The catalytic system according to claim 1, wherein the content of the transition metal species on the surface of the solid carrier is in the range of from 0.25 to 25 wt. %, based on the dry weight of the solid carrier.

8. The catalytic system according to claim 7, wherein the content of the transition metal species on the surface of the solid carrier is in the range of from 2.5 to 5 wt. %, based on the dry weight of the solid carrier.

9. 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 in liquid or gas phase 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).

10. The method according to claim 9, wherein the process further comprises a step (D) of recovering and optionally recycling the catalytic system following the chemical reaction of step (C).

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

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

13. A method for manufacturing a catalytic system comprising at least one solid carrier and a transition metal compound on the solid carrier, the method comprising: (a) providing the at least one solid carrier, wherein the at least one solid carrier is ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) and has a specific surface area of from 3 to 50 m.sup.2/g measured using nitrogen and the BET method according to ISO 9277:2010, wherein the ground natural calcium carbonate and/or precipitated calcium carbonate is not a surface-reacted calcium carbonate; (b) providing at least one transition metal reagent comprising Ni ions, Ru ions, Au 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. to obtain the catalytic system comprising a transition metal compound on the at least one solid carrier, wherein the transition metal compound is selected from the group consisting of Ni oxides, Ru oxides, Au oxides, Fe oxides, Cu oxides and mixtures thereof.

14. The method according to claim 13, wherein the method further comprises a step (e) of reducing the calcined catalytic system obtained from step (d) under H2 atmosphere at a temperature between 100 C. and 500 C. to obtain the catalytic system comprising a transition metal compound on the at least one solid carrier, wherein the transition metal compound is selected from the group consisting of elemental Ni, elemental Ru, elemental Au, elemental Fe, elemental Cu, oxides of the foregoing transition metal compounds and mixtures thereof.

15. The method according to claim 13, wherein the calcining 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 270 C. and 480 C.

16. The method according to claim 13, 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; and optionally 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.

17. The method according to claim 16, 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.

18. The method according to claim 16, wherein the solvent is a non-polar solvent, a polar solvent or a mixture thereof, and wherein 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.

19. The method according to claim 18 wherein the solvent is water.

20. The method according to claim 13, 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, RuI.sub.3, RuF.sub.5, Ru(NO)(NO.sub.3).sub.3, HAuCl.sub.4, AuBr.sub.3, AuCl, AuCl.sub.3, Au(OH).sub.3, AuI, KAuCl.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.

Description

EXAMPLES

1. Measurement Methods

(1) The following measurement methods were used to evaluate the parameters given in the examples and claims.

(2) BET Specific Surface Area (SSA) of a Material

(3) 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.

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

(5) 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 % Na.sub.4P.sub.2O.sub.7. The samples were dispersed using a high speed stirrer and supersonicated.

(6) The processes and instruments are known to the skilled person and are commonly used to determine grain size of fillers and pigments.

(7) Powder X-Ray Diffraction (XRD)

(8) Powder X-Ray Diffraction (XRD) patterns were recorded on a Bruker D8-Advance X-ray powder diffractometer operated at an accelerating voltage of 40 kV and an emission current of 40 mA with Cu K radiation. Samples were scanned over the range of 10-70, step size of 0.014 and a time of 0.1 s par step. The setting of 10 mm divergence, fent primaire Soller 2.5 were used.

(9) Three types of catalysts were analysed: dried catalysts, calcined catalysts treated in static air and calcined catalysts treated in static air and reduced under H2 atmosphere.

(10) Two different protocols were applied to prepare the different types of catalysts for XRD analysis. Fresh catalysts and catalysts treated in static air were prepared under ambient atmosphere. Reduced catalysts were prepared in the glove box under inert atmosphere to avoid the oxidation of the metal species during the sample preparation.

(11) The samples were transferred, one by one, and analysed by XRD to avoid the oxidation of metal during sample transfer and analysis.

2. Material and Equipment

(12) Preparation of the Catalytic System

(13) The preparation of the catalysts was performed using Chemspeed Catimpreg workstation designed for automated parallel synthesis of catalysts by coprecipitation and impregnation. In the first stage, a precipitated calcium carbonate (PCC), that is commercial available and has a BET of 11.7 m.sup.2/g, a d.sub.50 of 1.52 m and a d.sub.98 of 6.16 m was dried overnight at 100 C., then distributed in the different glass reactors, followed by adding water into the carrier, then agitating the components at 600 RPM for 5 minutes. The different metal precursor solutions, prepared in water solvent, were added after on the solid carrier, followed by an agitation process at 600 RPM for 60 minutes. The catalysts 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 catalysts and the used metal salts used during the preparation procedure are described in the table below:

(14) TABLE-US-00001 Theoretical amount Name Metal salt of the elemental of the Used used for the metal in the final catalyst carrier preparation Producer Reference catalyst (wt %) Fe, 10%/PCC PCC Fe(NO.sub.3).sub.3 Sigma Aldrich 216828 10 Ni, 10%/PCC Ni(NO.sub.3).sub.2 Sigma Aldrich 72253 10 Cu, 10%/PCC Cu(NO.sub.3).sub.2 Sigma Aldrich 61194 10 Ru, 1%/PCC RuNO(NO.sub.3).sub.3 Alfa Aesar 12175 1 Au, 1%/PCC HAuCl.sub.4 Sigma Aldrich 520918 1

3. Example Data

(15) Characterization of the Catalytic Systems

(16) XRD measurements of the obtained catalytic systems were performed. X in the below table marks that the phase has been detected by XRD after drying but before calcination (dried), after calcination (calcined) and after calcination+reduction under hydrogen (reduced).

(17) TABLE-US-00002 Identification of the different phases analysed using XRD technique Sample Aragonite Calcite Fe.sub.2O.sub.3 Fe Ni(OH).sub.2 NiO Ni.sup.0 CuO Cu RuO.sub.2 Ru PCC X X Fe, 10%/PCC X X X calcined Fe, 10%/PCC X X X reduced Ni, 10%/PCC X X X dried Ni, 10%/PCC X X X calcined Ni, 10%/PCC X X X X reduced Cu, 10%/PCC X X X dried Cu, 10%/PCC X X X calcined Cu, 10%/PCC X X X reduced Ru, 1%/PCC X X dried Ru, 1%/PCC X X X calcined Ru, 1%/PCC X X X reduced
Catalytic Investigations

(18) The obtained catalysts were evaluated in three different type 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 reactors system.

(19) In a first step, the reactors were filled with the catalyst, 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.

(20) The performed reactivity tests are described in the table below:

(21) TABLE-US-00003 Pressure Temperature Time NaOH/Gly Atmosphere (bar) ( C.) (hours) 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 H2504 aqueous solution was used as the mobile phase. Products were analysed at a flow rate of 0.5 mL/min.

(22) The results obtained using the different catalysts under a reductive atmosphere are presented in the table below:

(23) TABLE-US-00004 Glycerol %.sup.a Used Experimental Glycerol/Metal conv. Lactic Carbon catalyst conditions molar ratio (%) acid 1,2-Propanediol Methanol Ethanol balance Fe, 10%/PCC 200 C., 6 hours, H.sub.2 30 bar, 106 4.6 1.7 0.0 0.0 0.0 97.1 NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 bar, 11.9 1.9 0.0 0.0 0.0 90.0 NaOH/Gly of 1.5 Ni, 10%/PCC 200 C., 6 hours, H.sub.2 30 bar, 107 100 41.7 23.6 15.8 7.0 93.1 NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 bar, 100 36.7 22.3 10.9 5.2 78.7 NaOH/Gly of 1.5 Cu, 10%/PCC 200 C., 6 hours, H.sub.2 30 bar, 105 6.0 3.1 0.0 0.0 0.0 97.2 NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 bar, 5.9 2.2 0.0 0.0 0.0 96.2 NaOH/Gly of 1.5 Ru, 1%/PCC 200 C., 6 hours, H.sub.2 30 bar, 1462 18.4 12.5 1.1 0.0 0.0 95.5 NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 bar, 23.9 16.9 1.5 0.0 0.0 94.6 NaOH/Gly of 1.5 Au, 1%/PCC 200 C., 6 hours, H.sub.2 30 bar, 1555 5.9 3.5 0.0 0.0 0.0 97.6 NaOH/Gly of 1.5 200 C., 12 hours, H.sub.2 30 bar, 7.7 4.2 0.0 0.0 0.0 96.5 NaOH/Gly of 1.5 .sup.aThe remaining products up to 100% are only detected but in limited amounts and, therefore, are not presented in this table.

(24) The results obtained using the different catalysts under an inert atmosphere are presented in the table below:

(25) TABLE-US-00005 Glycerol %.sup.a Used Experimental Glycerol/Metal conv. Lactic Carbon catalyst conditions molar ratio (%) acid 1,2-Propanediol Methanol Ethanol balance Fe, 10%/PCC 200 C., 6 hours, N.sub.2 30 bar, 106 3.8 1.9 0.0 0.0 0.0 98.0 NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 bar, 5.1 3.8 0.0 0.0 0.0 98.7 NaOH/Gly of 1.5 Ni, 10%/PCC 200 C., 6 hours, N.sub.2 30 bar, 107 100 47.7 11.5 9.8 4.4 78.6 NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 bar, 100 61.6 0.0 4.6 4.3 74.7 NaOH/Gly of 1.5 Cu, 10%/PCC 200 C., 6 hours, N.sub.2 30 bar, 105 4.5 2.4 0.0 0.0 0.0 98.1 NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 bar, 88.9 78.9 2.5 0.7 0.0 97.0 NaOH/Gly of 1.5 Ru, 1%/PCC 200 C., 6 hours, N.sub.2 30 bar, 1462 37.9 30.5 2.2 4.5 0.0 100.9 NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 bar, 74.4 69.0 2.4 0.7 0.0 102.4 NaOH/Gly of 1.5 Au, 1%/PCC 200 C., 6 hours, N.sub.2 30 bar, 1555 5.7 4.4 0.0 0.0 0.0 98.7 NaOH/Gly of 1.5 200 C., 12 hours, N.sub.2 30 bar, 14.3 10.9 0.0 0.0 0.0 96.8 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.

(26) The results obtained using the different catalysts under an oxidative atmosphere are presented in the table below:

(27) TABLE-US-00006 Glycerol %.sup.a Used Experimental Glycerol/Metal conv. Glyceric Glycolic Lactic Formic Carbon catalyst conditions molar ratio (%) acid acid acid acid 1,2-Propanediol balance Fe, 10%/PCC 100 C., 4 hours, 40% O.sub.2 at 17 106 6.8 0.2 1.7 2.3 0.9 0.0 98.3 bar, NaOH/Gly of 4 Ni, 10%/PCC 100 C., 4 hours, 40% O.sub.2 at 17 107 8.3 0.5 1.2 5.5 0.9 3.7 104.9 bar, NaOH/Gly of 4 Cu, 10%/PCC 100 C., 4 hours, 40% O.sub.2 at 17 105 5.1 0.3 1.3 2.7 0.9 0.0 100.1 bar, NaOH/Gly of 4 Ru, 1%/PCC 100 C., 4 hours, 40% O.sub.2 at 17 1462 3.1 0.3 1.0 3.1 0.9 0.0 102.3 bar, NaOH/Gly of 4 Au, 1%/PCC 100 C., 4 hours, 40% O.sub.2 at 17 1555 4.5 0.3 1.3 2.1 0.8 0.0 100.0 bar, NaOH/Gly of 4 .sup.aThe remaining products are only detected in limited amounts and, therefore, are not presented in this table.

(28) As can be seen from the above experimental data, by the inventive method it is possible to provide catalytic systems wherein the transition metal compound that is selected from the group consisting of elemental Ni, elemental Ru, elemental Au, elemental Fe, elemental Cu, oxides of the foregoing transition metal compounds and mixtures thereof is located on the solid carrier, which is a ground natural calcium carbonate (GNCC) and/or precipitated calcium carbonate (PCC) and has a specific surface area of from 3 to 50 m.sup.2/g measured using nitrogen and the BET method according to ISO 9277:2010. Furthermore, the inventive method is a cheap and simple production process which provides the inventive catalytic system.

(29) Additionally, as can be seen from the above experimental data the precipitated calcium carbonate is useful as carrier material for specific transition metal compounds in the catalysis. Furthermore, it can be seen that for 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.