Activated carbon with a special finishing, production and use thereof

Patent metadata

Field	Value
Publication number	US-9566575-B2
Application number	US-201414782649-A
Country	US
Kind code	B2
Filing date	Mar 11, 2014
Priority date	Apr 6, 2013
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

The invention relates to a method for producing activated carbon provided and/or impregnated with a metal-organic framework substance (MOF material), the activated carbon being in particular in the form of discrete activated carbon particles, and preferably for producing an activated carbon with a reactive and/or catalytic action. The metal-organic framework substance is produced in situ in the pores and/or in the pore system of the activated carbon, starting from at least one metal precursor compound (MP) containing a metal and at least one ligand precursor (LP).

First claim

What is claimed is:

1. A process for producing an activated carbon in the form of discrete particles of activated carbon comprising a porous system with a multitude of pores, which activated carbon is provided with catalytic properties via impregnation of the activated carbon particles with at least one metal-organic framework substance (MOF material);
wherein the metal-organic framework substance is produced in situ in the pores of the activated carbon from at least one metal precursor (MP) compound, which comprises at least one metal, and from at least one ligand precursor (LP),
wherein the metal precursor (MP) compound and the ligand precursor (LP) are introduced into the pores of the activated carbon, wherein the metal precursor (MP) compound and ligand precursor (LP) are each used, conjointly or separately from each other, in the form of at least one aqueous, aqueous-alcoholic or alcoholic solution or dispersion, wherein introducing the metal precursor (MP) compound and the ligand precursor (LP), conjointly or separately from each other, into the pores the activated carbon is effected by a step of impregnating the activated carbon with the at least one solution or dispersion of the metal precursor (MP) compound and of the ligand precursor (LP),
wherein introducing the metal precursor (MP) compound and the ligand precursor (LP) is followed by at least a step of drying the activated carbon until the solvent or dispersant is at least essentially completely removed from the pores of the activated carbon, wherein the drying is carried out at temperatures in the range from 0° C. to 50° C.,
wherein the steps of introducing the metal precursor (MP) compound and the ligand precursor (LP) and of drying the activated carbon are followed by at least one thermal post-treatment to convert the metal precursor (MP) compound together with the ligand precursor (LP) into a metal-organic framework substance (MOF-material), wherein the thermal post-treatment is carried out at a temperature in the range from 50° C. to 500° C., and wherein the metal-organic framework substance (MOF material) is present in crystalline form, wherein the particles of the metal-organic framework substance (MOF material) have an average particle size in the range from 0.1 nm to 500 nm.

2. The process as claimed in claim 1
wherein the metal, in particular metal atom, of the metal precursor (MP) compound is selected from the group of Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi, preferably selected from the group of Zn, Cu, Ni, Pd, Pt, Ru, Fe, Mn, Ag, Al and Co, preferably selected from the group of Cu, Fe, Co, Zn, Mn, Al and Ag, more preferably selected from the group of Cu, Fe, Al and Zn.

3. The process as claimed in claim 1 ,
wherein the ligand precursor (LP) is employed in the form of an at least bidentate or bridging organic ligand precursor (LP).

4. The process as claimed in claim 1 ,
wherein the ligand precursor (LP) includes at least one functional group capable of forming, in respect of one metal, wherein the functional group of the ligand precursor (LP) includes at least one heteroatom from the group consisting of N, O, S, B, P, Si and Al.

5. The process as claimed in claim 1 ,
wherein the ligand precursor (LP) is selected from at least dibasic organic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, their salts and combinations, comprising each at least one heteroatom, identical or different, from the group consisting of N, O, S, B, P, Si and Al.

6. The process as claimed in claim 1 ,
wherein the activated carbon is formed from granular or spherical activated carbon having particle sizes in the range from 0.001 mm to 3 mm.

7. The process as claimed in claim 1 ,
wherein the activated carbon has a specific BET surface area in the range from 500 m 2 /g to 4000 m 2 /g and a Gurvich total pore volume in the range from 0.50 cm 3 /g to 2.0 cm 3 /g.

8. The process as claimed in claim 1 ,
wherein the activated carbon has a bursting pressure of at least 5 newtons per particle.

9. The process as claimed in claim 1 ,
wherein the activated carbon has an adsorption volume V ads in the range from 250 cm 3 /g to 3000 cm 3 /g and a total porosity in the range from 10% to 80%, based on the particle volume of the activated carbon.

10. The process as claimed in claim 1 ,
wherein the step of drying is effected under reduced pressure and at temperatures in the range from 5° C. to 40° C., and
wherein the thermal post-treatment is carried out at a temperature in the range from 50° C. to 400° C.

11. The process as claimed in claim 1 , wherein a further step of activating the metal-organic framework substance (MOF material) is carried out.

12. The process as claimed in claim 11 ,
wherein the further step of activating the metal-organic framework substance (MOF material) is carried out by subjecting the activated carbon provided with the metal-organic framework substance (MOF material) to a heat activation treatment at temperatures in the range from 90° C. to 300° C. under an at least essentially nonreactive or oxidizing atmosphere.

13. The process as claimed in claim 1 ,
wherein the metal precursor (MP) compound and the ligand precursor (LP) are employed in the form of a conjoint solution or dispersion comprising the metal precursor (MP) compound and the ligand precursor (LP),
wherein the solution or dispersion comprising the metal precursor (MP) compound and the ligand precursor (LP) is obtained by mixing a first solution or dispersion comprising the metal precursor (MP) compound and a second solution or dispersion comprising the ligand precursor (LP).

14. The process as claimed in claim 1 ,
wherein the metal precursor (MP) compound and the ligand precursor (LP) are employed in the form of separate solutions or dispersions,
wherein introducing the metal precursor (MP) compound and the ligand precursor (LP) into the pores of the activated carbon is effected by successively impregnating the activated carbon with the separate solutions or dispersions of the metal precursor (MP) compound on the one hand and of the ligand precursor (LP) on the other hand.

15. An activated carbon in the form of discrete particles of activated carbon comprising a porous system with a multitude of pores, which activated carbon is provided with catalytic properties via impregnation of the activated carbon particles with at least one metal-organic framework substance (MOF material),
wherein the metal-organic framework substance (MOF material) is present in crystalline form, wherein the particles of the metal-organic framework substance (MOF material) have an average particle size in the range from 0.1 nm to 500 nm.

16. The activated carbon as claimed in claim 15 ,
wherein the activated carbon is obtained by producing the metal-organic framework substance (MOF material) in situ in the pores of the activated carbon from at least one metal precursor (MP) compound, which comprises at least one metal, and at least one ligand precursor (LP).

17. The activated carbon as claimed in claim 15 ,
wherein the activated carbon is obtained by a process as claimed in claim 1 .

18. The activated carbon as claimed in claim 15 ,
wherein the metal-organic framework substance (MOF material) has a crystallinity in the range from 10% to 99.5%, based on the metal-organic framework substance (MOF material), and
wherein the activated carbon comprises the metal-organic framework subs

Assignees

• Bluecher Gmbh
• Univ Dresden Tech
• Bluecher Gmbh
• Univ Dresden Tech

Inventors

• Bohringer Bertram
• Eckle Ilsebill
• Kaskel Stefan
• Lohe Martin R

Classifications

• B01J23/74

  Iron group metals · CPC title

• B01J20/3236

  containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts · CPC title

• B01J20/3204

  Inorganic carriers, supports or substrates · CPC title

• B01J20/28069

  Pore volume, e.g. total pore volume, mesopore volume, micropore volume · CPC title

• B01J20/226

  Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF] (preparation of metal complexes containing carboxylic acid moieties C07C51/418; MOF's per se C07F) · CPC title