Surface-modified calcium carbonate as carrier for transition metal-based catalysts

Patent metadata

Field	Value
Publication number	US-10875014-B2
Application number	US-201716307819-A
Country	US
Kind code	B2
Filing date	Jul 17, 2017
Priority date	Jul 25, 2016
Publication date	Dec 29, 2020
Grant date	Dec 29, 2020

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.

First claim

The invention claimed is:

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

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.

3. The catalyst system according to claim 1 , wherein the ratio of the at least one water-insoluble calcium salt to the calcium carbonate is in the range of from 1:9 to 9:1by 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) 2 , Na 2 PdCl 4 , Pd(OAc) 2 , Pd(PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 , (dppf)PdCl 2 , (dppe)PdCl 2 , (dppp)PdCl 2 , (dppb)PdCl 2 , PdCl 2 , (C 3 H 5 PdCl) 2 , bis(acetate)triphenyl-phosphine-palladium(II), Pd(dba) 2 , Pd(H 2 NCH 2 CH 2 NH 2 )Cl 2 , elemental platinum, Na 2 PtCl 6 Pt(acac) 2 , Na 2 PtCl 4 , H 2 PtCl 6 , (NH 4 ) 2 [PtCl 6 ], PtO 2 H 2 O, PtCl 4 , elemental copper, Cu 2 O, Cu 2 S, copper(I)-thiophene-2-carboxylate, CuBr, CuCN, CuCl, CuF, Cul, CuH, CuSCN, CuBr 2 , CuCO 3 , CuCl 2 , CuF 2 , Cu(NO 3 ) 2 , Cu 3 (PO 4 ) 2 , CuO, CuO 2 , Cu(OH) 2 , CuI 2 , CuS, CuSO 4 , Cu 2 (OAc) 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 2 /g, measured using nitrogen and the BET method according to ISO 9277:2010;
(ii) a d 50 (vol) in the range of from 1 to 75 μm;
(iii) a d 98 (vol) in the range of from 2 to 150 μm; and/or
(iv) an intra-particle intruded specific pore volume in the range of from 0.2 to 2.0 cm 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.-%, based on the weight of the transition metal compound per total weight of the catalyst system.

9. A carrier for transition metal-based catalysts comprising a catalyst system according to claim 1 .

10. Granules, mouldings or extrudates comprising the catalyst system according to claim 1 .

11. A method for manufacturing a catalyst system comprising a transition metal compound on a solid carrier, the method comprising:
(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 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 3 /g calculated from mercury porosimetry measurement; and
(iii) a ratio of the at least one water-insoluble calcium salt to calcium carbonate in the range of from 1:99 to 99:1 by weight. wherein the calcium carbonate comprises calcite, aragonite, and/or vaterite.

12. The method according to claim 11 , 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.

13. The method according to claim 11 , 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 or filtration to obtain a concentrated mixture.

14. The method according to claim 11 , 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.

15. The method according to claim 11 , wherein the transition metal compound is selected from the group consisting of palladium compounds, platinum compounds, copper compounds and mixtures thereof.

16. The method according to claim 11 wherein the transition metal compound is selected from the group consisting of elemental palladium, Pd(acac) 2 , Na 2 PdCl 4 , Pd(OAc) 2 , Pd(PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 , (dppf)PdCl 2 , (dppe)PdCl 2 , (dppp)PdCl 2 , (dppb)PdCl 2 , PdCl 2 , (C 3 H 5 PdCl) 2 , bis(acetate)triphenylphosphine-palladium(II), Pd(dba) 2 , Pd(H 2 NCH 2 CH 2 NH 2 )Cl 2 , elemental platinum, Na 2 PtCl 6 Pt(acac) 2 , Na 2 PtCl 4 , H 2 PtCl 6 , (NH 4 ) 2 [PtCl 6 ], PtO 2 H 2 O, PtCl 4 , elemental copper, Cu 2 O, Cu 2 S, copper(I)-thiophene-2-carboxylate, CuBr, CuCN, CuCI, CuF, Cul, CuH, CuSCN, CuBr 2 , CuCO 3 , CuCl 2 , CuF 2 , Cu(NO 3 ) 2 , Cu 3 (PO 4 ) 2 , CuO, CuO 2 , Cu(OH) 2 , Cul 2 , CuS, CuSO 4 , Cu 2 (OAc) 4 and mixtures thereof.

17. The method according to claim 11 wherein the liquid medium is a non-polar solvent, a polar solvent or a mixture thereof.

18. The method according to claim 11 , wherein the transition metal compound is Na 2 PdCl 4 and/or Na 2 PtCl 4 and the liquid medium is a polar solvent.

19. A catalyst system obtained according to the method of claim 11 .

20. A method of using 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 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 3 /g calculated from mercury porosimetry measurement; and
(iii) a ratio of the at least one water-insoluble calcium salt to calcium carbonate in the range of from 1:99 to 99:1 by weight, wherein the calcium carbonate comprises calcite, a

Assignees

• Omya Int Ag

Inventors

• Gane Patrick A C
• Rentsch Samuel
• Welker Matthias

Classifications

• B01J2235/15

  X-ray diffraction · CPC title

• C07C29/60

  by elimination of -OH groups, e.g. by dehydration (C07C29/34 takes precedence) · CPC title

• C07C1/32

  starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen · CPC title

• C07B37/04

  Substitution · CPC title

• B01J37/0201

  Impregnation · CPC title