CN112973688B - Ion exchange resin-based loaded metal carbon pellet and preparation method thereof - Google Patents

Ion exchange resin-based loaded metal carbon pellet and preparation method thereof Download PDF

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CN112973688B
CN112973688B CN201911284862.0A CN201911284862A CN112973688B CN 112973688 B CN112973688 B CN 112973688B CN 201911284862 A CN201911284862 A CN 201911284862A CN 112973688 B CN112973688 B CN 112973688B
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exchange resin
ion exchange
silicon oxide
metal
carbon
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CN112973688A (en
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徐金铭
王婧
樊斯斯
李阳
黄延强
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel

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Abstract

The invention discloses a preparation method for preparing a loaded metal carbon pellet by using ion exchange resin, which comprises the steps of simultaneously carrying out ion exchange on silicate and an anionic metal complex for the anion exchange resin, then pyrolyzing at high temperature to obtain a composite material of carbon, silicon oxide and metal, and removing silicon oxide material components in the composite material to obtain the loaded metal carbon pellet with high specific surface area. The preparation method has the advantages of simple process, good metal dispersibility, large specific surface area, high strength and wide application prospect in the field of catalysis.

Description

Ion exchange resin-based loaded metal carbon pellet and preparation method thereof
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of an ion exchange resin-based loaded metal carbon pellet.
Background
The porous carbon material has developed pores, high thermal stability and acid and alkali corrosion resistance, and is an excellent catalyst carrier. The metal-supported activated carbon carrier can be obtained by a method such as immersing activated carbon in an aqueous solution of a metal salt, and the performance of the activated carbon carrier to be surface-oxidized for uniform dispersion is determined by the pore structure and the surface chemical structure. Therefore, the activated carbon is prepared by performing processes such as oxidation pretreatment on the surface of the activated carbon, and then performing processes such as impregnation, drying and reduction.
The ion exchange resin based porous carbon pellet has smooth surface, controllable particle size, high strength, no slag loss during use and convenient use. At present, the process of preparing the porous carbon material from the ion exchange resin is all subjected to the processes of pre-crosslinking, pyrolysis and activation. The high molecules in the ion exchange resin have a certain degree of crosslinking, but in the carbonization process, most of the ion exchange resins have insufficient degree of crosslinking, and are easy to deform and adhere in the subsequent pyrolysis process, so that the ion exchange resin needs to be crosslinked in advance by methods such as air pre-oxidation or concentrated sulfuric acid treatment. The pyrolyzed ion exchange resin needs to undergo an activation process in which molecules of an activating substance react with carbon to etch away a part of the carbon and increase the specific surface area, which results in a low yield of carbon material from the ion exchange resin. In chinese patent applications CN201711295470.5 and CN201711294620.0, we provide a method for preparing ion exchange resin-based porous carbon material, which comprises the steps of firstly performing ion exchange on anion exchange resin with alkaline silicate, then pyrolyzing at high temperature to obtain a composite material of carbon and silicon oxide, and then removing silicon oxide material components in the composite material to obtain the carbon material with high specific surface area.
The method is further developed, silicate and an anionic metal complex are added into an ion exchange solution at the same time, silicate and anionic metal complex ions are exchanged in anion exchange resin or amphoteric ion exchange resin at the same time, then the composite material of carbon, silicon oxide and metal is obtained by pyrolysis at high temperature, and silicon oxide material components in the composite material are removed to obtain the metal-loaded carbon spheres. In the high-temperature pyrolysis process, metal ions are reduced to zero-valent metal, and after silicon oxide is removed, pore channels are opened, and the specific surface area is high. When the ion exchange resin of silicate and anionic metal complex is pyrolyzed at high temperature, metal ions are limited in the framework of silicon oxide and carbon, sintering and growth of metal particles during roasting are inhibited, and the obtained metal nanoparticles have small particle size and high dispersity. The preparation method has the advantages of simple process, good metal dispersibility, large specific surface area, high strength and wide application prospect in the field of catalysis.
Disclosure of Invention
The invention aims to provide a preparation method of an ion exchange resin-based loaded metal carbon pellet, which has a simple process, avoids an impregnation process in a catalyst preparation process, and has small metal particles and high dispersity.
The purpose of the invention can be realized by the following technical scheme.
1. A preparation method of an ion exchange resin-based loaded metal carbon pellet comprises the following specific steps:
(a) simultaneously carrying out ion exchange on the ion exchange resin by using silicate and an anionic metal complex solution;
(b) pyrolyzing the ion exchange resin containing silicate radical and anionic metal complex at high temperature to obtain the composite material of carbon, silicon oxide and metal;
(c) and removing the silicon oxide material component in the composite material to obtain the loaded metal carbon pellet.
The ion exchange resin in the step (a) is one or more of anion exchange resin or amphoteric ion exchange resin, and the amphoteric ion exchange resin refers to an ion exchange resin containing both anion and cation exchange groups.
In the step (a), the anion exchange resin and the amphoteric ion exchange resin contain one or more than two of quaternary ammonium groups, primary amine functional groups, secondary amine functional groups, tertiary amine functional groups or quaternary phosphonium functional groups.
The silicate in the step (a) is soluble alkali metal silicate, and the mass concentration of the silicate and the anionic metal complex solution is 0.5 to 30 percent.
In the step (a), the metal is one or more of Fe, Co, Ni, Cu, Zn, Mn, Ru, Rh, Pt, Pd, Au, Ag and Ir.
The anionic ligand in the anionic metal complex in the step (a) is Cl - (chloride ion), CN - (cyanate radical), SCN - (thiocyanate) and EDTA 4- One or more than two of (ethylene diamine tetraacetic acid).
In the step (a), after ion exchange, the mass ratio of the silicon dioxide to the ion exchange resin is 0.1 to 4.5; the mass ratio of metal to ion exchange resin is 0.001 to 0.5.
The pyrolysis temperature in the above step (b) is 600 to 1200 ℃ for 0.2 to 12 hours.
In the step (c), the silica is removed by reacting the silica with a solution of a silica removing agent which is one or more of alkali metal hydroxide, alkali metal salt, hydrofluoric acid, alkali metal fluoride and ammonium fluoride.
In the step (c), the mass concentration of the silicon oxide removing reagent solution is 1 to 95 percent; the mass ratio of the agent for removing silicon oxide to silicon oxide is 1.2 to 90.
In the step (c), the reaction for removing the silica reagent is carried out at a temperature of 15 to 200 ℃ for 0.2 to 24 hours.
The specific surface area of the metal-loaded carbon-loaded pellets prepared by the method is 100 to 2000m 2 /g。
The specific anion exchange resin can be one or more than two of D201, Amberlite IRA-900, Lewatit MP-500, Diaion PA 308, D301, Lewatit MP-60, Diaion WA-30, Duolite A305, AH-89 x 77 II, Zerolite MPH and D345;
the amphoteric ion exchange resin can be one or more of Lewatit TP-260, Diaion AMP03 and Retardion 11A 8.
The preparation method has the advantages of simple process, good metal dispersibility, large specific surface area, high strength and wide application prospect in the field of catalysis.
Drawings
FIG. 1 is a photograph of the metal-loaded carbon pellet obtained in example 1 of the present invention.
FIG. 2 is an X-ray diffraction (XRD) pattern of the supported metal carbon pellet obtained in example 1 according to the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Loading Amberlite IRA-900 macroporous strongly basic ion exchange resin in ion exchange column, and adding 0.5M Na 2 SiO 3 And performing ion exchange with 0.025M solution of sodium copper ethylenediamine tetraacetate, filtering, drying, and obtaining light blue resin particles, which indicates that the anion of copper ethylenediamine tetraacetate is exchanged on the resin particles. The samples were placed in a tube furnace, N 2 Atmosphere(s)And heating to 600 ℃ at the speed of 2 ℃/min, preserving heat for 3h, and carbonizing the sample to obtain the composite material of carbon, silicon oxide and copper. HF with the mass concentration of 5% (soaking for 2 hours) is used for removing silicon oxide in the carbon, silicon oxide and copper composite material to obtain the globular carbon-supported copper catalyst, and the BET specific surface area is 1495m 2 (ii) in terms of/g. The photograph is shown in FIG. 1. The XRD of the sample is shown in fig. 2, with only two broad peaks of amorphous carbon and no copper diffraction peaks, indicating very small copper particles and high degree of dispersion.
Example 2
Loading D301 macroporous strong basic ion exchange resin in ion exchange column, and adding 1.0M Na 2 SiO 3 And 0.1M K 3 [Fe(CN) 6 ]The solution was ion-exchanged, filtered and dried, and the resin particles were yellow in color, indicating [ Fe (CN) ] 6 ] 3- The anions are exchanged onto the resin particles. And (3) putting the sample in a tubular furnace, heating to 700 ℃ at a speed of 5 ℃/min in the He atmosphere, preserving heat for 3h, and carbonizing the sample to obtain the composite material of carbon, silicon oxide and iron. And (3) removing the silicon oxide in the carbon, silicon oxide and iron composite material by using a 2M NaOH solution (soaking for 24 hours) to obtain the globular carbon-supported iron catalyst.
Example 3
Loading D301 macroporous strong basic ion exchange resin in ion exchange column, and adding 0.3M Na 2 SiO 3 And 0.05M K 4 [Ni(SCN) 6 The solution was ion exchanged, filtered and dried, and the resin particles were pale green, indicating [ Ni (SCN) 6 ] 4- The anions are exchanged onto the resin particles. The samples were placed in a tube furnace, N 2 And (3) heating to 600 ℃ at the temperature of 3 ℃/min in the atmosphere, preserving the heat for 3 hours, and carbonizing the sample to obtain the composite material of the carbon, the silicon oxide and the nickel. And (3) removing silicon oxide in the carbon, silicon oxide and nickel composite material by using a 2M NaF solution (soaking for 12 hours) to obtain the globular carbon-supported nickel catalyst.
Example 4
Loading 717 microporous strong-base ion exchange resin in ion exchange column, and adding 0.5M Na 2 SiO 3 And 0.05M Na 2 PtCl 6 The solution was ion exchanged, filtered and dried, and the resin particles were pale orange. Placing the sample inIn a tube furnace, N 2 And (3) heating to 800 ℃ at the temperature of 3 ℃/min in the atmosphere, preserving the heat for 3h, and carbonizing the sample to obtain the composite material of carbon, silicon oxide and platinum. And (3) removing silicon oxide in the carbon, silicon oxide and nickel composite material by using an HF (soaking for 6 hours) solution with the mass concentration of 5% to obtain the globular carbon-supported platinum catalyst.
Example 5
Loading 717 microporous strong-base ion exchange resin in ion exchange column, and adding 0.5M Na 2 SiO 3 And 0.05M K4[ Ru (CN) 6 ]The solution is ion exchanged, filtered and dried. The samples were placed in a tube furnace, N 2 And (3) heating to 700 ℃ at a speed of 3 ℃/min under the atmosphere, preserving heat for 3h, and carbonizing the sample to obtain the composite material of carbon, silicon oxide and ruthenium. And (3) removing silicon oxide in the carbon, silicon oxide and ruthenium composite material by using an HF solution with the mass concentration of 5% (soaking for 8 hours) to obtain the globular carbon-supported ruthenium catalyst.

Claims (6)

1. A preparation method of an ion exchange resin based loaded metal carbon pellet is characterized by comprising the following steps:
(a) simultaneously carrying out ion exchange on the ion exchange resin by using silicate and an anionic metal complex solution;
(b) pyrolyzing the ion exchange resin containing silicate radicals and anionic metal complexes at high temperature to obtain a composite material of carbon, silicon oxide and metal, wherein the pyrolysis temperature is 600-1200 ℃, and the pyrolysis time is 0.2-12 hours;
(c) removing silicon oxide material components in the composite material to obtain loaded metal carbon balls;
the ion exchange resin is one or more than two of anion exchange resin or amphoteric ion exchange resin, and the anion exchange resin and the amphoteric ion exchange resin contain one or more than two of quaternary ammonium group, primary amine, secondary amine, tertiary amine or quaternary phosphonium group functional groups;
the specific surface area of the metal-loaded carbon pellets is 100 to 2000m 2 Between/g.
2. The method of claim 1, wherein: the amphoteric ion exchange resin refers to an ion exchange resin containing both anion-and cation-exchangeable groups.
3. The method of claim 1, wherein: the silicate is soluble alkali metal silicate, and the total mass concentration of the silicate and the anionic metal complex solution is 0.5 to 30 percent; the mass ratio of the silicate to the anionic metal complex is 0.01 to 1;
the alkali metal is one or more than two of Li, Na, K, Rb and Cs.
4. The method of claim 1, wherein:
the metal in the anionic metal complex is one or more than two of Fe, Co, Ni, Cu, Zn, Mn, Ru, Rh, Pt, Pd, Au, Ag and Ir;
the anionic ligand in the anionic metal complex is Cl - (chloride ion), CN - (cyanate radical), SCN - (thiocyanate) and EDTA 4- (ethylenediaminetetraacetic acid radical) and (III) one or more of them.
5. The method of claim 1, wherein: removing silicon oxide by reacting silicon oxide with a reagent solution for removing silicon oxide containing one or more of alkali metal hydroxide, alkali metal salt, hydrofluoric acid, alkali metal fluoride and ammonium fluoride;
the mass concentration of the silicon oxide removing reagent solution is 1 to 95 percent; the mass ratio of the silicon oxide removing agent to the silicon oxide is 1.2 to 90.
6. The method of claim 5, wherein: the reaction for removing the silica reagent is carried out at a temperature of 15 to 200 ℃ for 0.2 to 24 hours.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130006765A (en) * 2011-06-23 2013-01-18 인하대학교 산학협력단 Method for preparing porous carbons for electronic double layer capacitor using ion exchange resins
CN102992306A (en) * 2012-11-14 2013-03-27 中山大学 Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof
CN105126833A (en) * 2015-07-28 2015-12-09 浙江工业大学 Ruthenium-carbon catalyst and its use in acetylene hydrochlorination preparation of vinyl chloride
CN109896513A (en) * 2017-12-08 2019-06-18 中国科学院大连化学物理研究所 A kind of preparation method of ion exchange resin base porous carbon material
CN110280240A (en) * 2019-07-10 2019-09-27 东华理工大学 A kind of carbon nanosheet supported precious metal nano-particle catalyst and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130006765A (en) * 2011-06-23 2013-01-18 인하대학교 산학협력단 Method for preparing porous carbons for electronic double layer capacitor using ion exchange resins
CN102992306A (en) * 2012-11-14 2013-03-27 中山大学 Graphitized carbon with high specific surface area and hierarchical pores and preparation method thereof
CN105126833A (en) * 2015-07-28 2015-12-09 浙江工业大学 Ruthenium-carbon catalyst and its use in acetylene hydrochlorination preparation of vinyl chloride
CN109896513A (en) * 2017-12-08 2019-06-18 中国科学院大连化学物理研究所 A kind of preparation method of ion exchange resin base porous carbon material
CN110280240A (en) * 2019-07-10 2019-09-27 东华理工大学 A kind of carbon nanosheet supported precious metal nano-particle catalyst and its preparation method and application

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