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CN112547070B - Catalyst for preparing chlorotrifluoroethylene and preparation method thereof - Google Patents

Catalyst for preparing chlorotrifluoroethylene and preparation method thereof Download PDF

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CN112547070B
CN112547070B CN202011450384.9A CN202011450384A CN112547070B CN 112547070 B CN112547070 B CN 112547070B CN 202011450384 A CN202011450384 A CN 202011450384A CN 112547070 B CN112547070 B CN 112547070B
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catalyst
nickel alloy
sintered porous
porous copper
preparing
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CN112547070A (en
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李玲
马超峰
石能富
刘武灿
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Zhejiang Chemical Industry Research Institute Co Ltd
Zhejiang Lantian Environmental Protection Hi Tech Co Ltd
Sinochem Lantian Co Ltd
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Zhejiang Chemical Industry Research Institute Co Ltd
Zhejiang Lantian Environmental Protection Hi Tech Co Ltd
Sinochem Lantian Co Ltd
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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • 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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to a catalyst for preparing chlorotrifluoroethylene and a preparation method thereof. The catalyst carrier is sintered porous copper-nickel alloy, the active component is Pd, the loading capacity of the Pd active component is 0.1-5 wt%, the average pore diameter of the sintered porous copper-nickel alloy is 50-300nm, the sintered porous copper-nickel alloy is of a hollow structure, and the wall thickness is 0.5-25 mm. The catalyst prepared by the invention can be used for hydrodechlorination reaction, is particularly suitable for industrial large-scale production of chlorotrifluoroethylene by catalytic hydrodechlorination of trichlorotrifluoroethane, and has the advantages of long service life, high reliability and the like.

Description

Catalyst for preparing chlorotrifluoroethylene and preparation method thereof
Technical Field
The invention belongs to the field of fluorine chemical industry, and particularly relates to a catalyst for preparing chlorotrifluoroethylene and a preparation method thereof.
Background
The catalytic hydrogenation and dechlorination of the trifluorotrichloroethane is the most potential production process for preparing the chlorotrifluoroethylene, and has the advantages of environmental protection, continuous production and the like.
The existing catalyst for preparing trifluorochloroethylene mainly comprises a non-noble metal type and a noble metal type, and a catalyst carrier mainly comprises activated carbon and Al 2 O 3 And SiO 2 。
CN111013604A discloses a catalyst for catalytic hydrodechlorination, which is characterized by comprising an alloy catalyst, an auxiliary agent and a carrier, wherein the alloy catalyst takes element Ru as a main body, and any one or more of designated alloy elements Re, Ti, Cr, Ni, Al, Co, Cu, Nb, Ta, Ru, Pt or Ag is selected to form an alloy with Ru; the auxiliary agent is alkali metal or rare earth metal, and the carrier is an activated carbon carrier.
CN105944734B discloses a catalyst for preparing chlorotrifluoroethylene by catalytic hydrogenation and dechlorination of trifluorotrichloroethane, which comprises a first catalyst, a second catalyst, an auxiliary agent and a carrier, wherein the first catalyst is one of cobalt or rhodium, the dosage of the first catalyst is 0.1-15% of the total mass of the catalyst, the second catalyst is one of chromium or manganese, the dosage of the second catalyst is 0.5-22% of the total mass of the catalyst, the auxiliary agent is alkali metal potassium or rare earth metal rhenium, the dosage of the auxiliary agent is 0.1-5% of the total mass of the catalyst, and the carrier is SiO 2 And (3) a carrier.
EP0459463A discloses the influence of the properties of the support on the preparation of chlorotrifluoroethylene by catalytic hydrogenation, the conversion of chlorotrifluoroethane being below 50% when using alumina as support, which compares Pd-Hg/Al 2 O 3 The catalyst used in the former case was 1.3g, Pd loading was 0.5% and conversion was 54.7% and the catalyst used in the latter case was 0.6g, Pd loading was 2% and conversion was 63.9% of Pd-Hg/C activity.
US5089454 discloses that when activated carbon, alumina, titania and other material are used as carrier, one or more of alkali metal and alkali earth metal salt is used as assistant, and VIII metal is used as active component of catalyst, the reaction temperature is 200-300 deg.c, and the conversion rate of chlorotrifluoroethylene is over 40%.
CN1460549 discloses a catalyst for preparing chlorotrifluoroethylene and trifluoroethylene by catalytic hydrogenation and dechlorination of 1, 1, 2-trifluoro-2, 2, 1-trichloroethane, which is characterized in that noble metal palladium and metal copper are used as main active components, alkali metal lithium and rare earth metal or metal lanthanum are added as modifying additives, and coconut shell activated carbon is used as a carrier; the dosage of the noble metal palladium is 0.5 to 0.4 percent of the total weight of the catalyst; the dosage of the adopted metal copper is 1 to 12 percent of the total weight of the catalyst; the dosage of the adopted metal lithium is 0.2 to 2 percent of the total weight of the catalyst; the dosage of the rare earth metal or the metal lanthanum is 0.5 to 4 percent of the total weight of the catalyst. The conversion rate of raw materials can reach 100 percent, and the highest CTFE selectivity can reach 84.7 percent.
Existing activated carbon, Al 2 O 3 And SiO 2 Although these carriers have been used in large scale, they still have problems of poor strength, low stability, etc., and further improvement is required.
Disclosure of Invention
The invention aims to provide a catalyst for preparing chlorotrifluoroethylene, which has long service life and a preparation method thereof.
The technical scheme of the invention is as follows:
a catalyst for preparing chlorotrifluoroethylene, wherein a catalyst carrier is sintered porous copper-nickel alloy, an active component is Pd, the loading amount of the Pd active component is 0.1-5 wt%, preferably 0.1-2 wt%, and more preferably 0.5-1 wt%, the average pore diameter of the sintered porous copper-nickel alloy is 50-300nm, preferably 60-200nm, and more preferably 80-150nm, the sintered porous copper-nickel alloy is of a hollow structure, and the wall thickness of the sintered porous copper-nickel alloy is 0.5-25mm, preferably 1-20mm, and more preferably 2-10 mm.
The sintered porous copper-nickel alloy has a relatively uniform pore structure, and the pore volume of 50-300nm accounts for more than 80% of the total pore volume, preferably more than 85%.
The sintered porous copper-nickel alloy is a hollow cylinder, a hollow cube or a hollow cuboid.
The average particle diameter of the active component Pd is 5-30nm, preferably 6-10 nm.
Preferably, the hollow part of the sintered porous copper-nickel alloy is a through hole which penetrates through the hollow part up and down, and the diameter of the through hole is 0.1-10mm, preferably 2-8mm, and further preferably 4-6 mm.
Preferably, the sintered porous copper-nickel alloy is a hollow cylinder, and the height of the hollow cylinder is 5-50 mm.
Preferably, the sintered porous copper-nickel alloy is a hollow cube or a hollow cuboid, and the height of the sintered porous copper-nickel alloy is 5-50 mm.
The preparation method of the sintered porous copper-nickel alloy comprises the following steps: and sintering the nickel oxide powder and the copper oxide powder by a powder metallurgy method to prepare the sintered porous copper-nickel alloy.
Specifically, the average particle diameter of the nickel oxide powder is preferably 5 to 50nm, more preferably 10 to 30nm, and the average particle diameter of the copper oxide powder is preferably 5 to 50nm, more preferably 10 to 30 nm.
In one embodiment, a powder obtained by uniformly mixing nickel oxide and copper oxide is added to an aqueous solution of a dispersant and a binder to prepare a slurry, the slurry is granulated and molded, and the molded body is subjected to temperature programming and baking.
Preferably, the dispersant is low molecular weight sodium polyacrylate and the binder is polyvinyl alcohol. The dispersant of the invention has very excellent technical effect on inhibiting the agglomeration of nickel oxide powder and copper oxide powder.
Preferably, the dispersant is sodium polyacrylate with weight average molecular weight of 3000-4000 and the binder is polyvinyl alcohol with weight average molecular weight of 85000-95000.
Preferably, when the dispersant and the binder aqueous solution are prepared, the dispersant aqueous solution is prepared, then the binder is added, and the mixture is heated and uniformly mixed.
Preferably, when preparing the dispersant and the aqueous solution of the binder, firstly, the dispersant and the deionized water are mixed, stirred for 5-30min, the binder is added, heated to 60-80 ℃, stirred for 10-60min, and then cooled to room temperature.
Preferably, the mass ratio of the dispersing agent to the deionized water is 1: (10-100).
Preferably, the mass ratio of the binder to the deionized water is 1: (10-100).
Preferably, the nickel oxide and copper oxide uniformly mixed powder is added under stirring.
Preferably, the mass ratio of the nickel oxide to the copper oxide powder is (1-10): (1-10).
Preferably, the total proportion of nickel oxide powder and copper oxide powder in the resulting slurry is 60 to 80 wt%.
The slurry of the present invention can be granulated and formed by a granulation and forming method commonly used in the art.
Preferably, the temperature programming is carried out on the formed body, and during the roasting, the formed body is firstly programmed to the temperature of 300-500 ℃ in the nitrogen atmosphere, and then is switched to the 5% argon/hydrogen mixture atmosphere, and the temperature programming is carried out to the temperature of 800-1000 ℃ for roasting.
Preferably, the temperature of the formed body is programmed, and during the baking, the formed body is firstly heated to 300-500 ℃ at the speed of 5-20 ℃/min in the nitrogen atmosphere, the temperature is kept for 1-5 hours, then the formed body is switched to 5% argon/hydrogen mixture atmosphere, the temperature is heated to 800-1000 ℃ at the speed of 10-50 ℃/min, and the formed body is naturally cooled after the temperature is kept for 1-5 hours.
The sintered porous copper-nickel alloy prepared by the method is processed into required hollow cylinder, hollow cube, or hollow cuboid with regular shapes for standby.
The preparation method of the catalyst comprises the following steps:
(1) pretreating the sintered porous copper-nickel alloy;
(2) dipping active components on the pretreated sintered porous copper-nickel alloy;
(3) temperature programming and constant-temperature roasting.
The pretreatment in the step (1) comprises alkali washing, alcohol treatment, acid washing and/or liquid phase reduction.
Preferably, the above pretreatment steps are performed sequentially.
Preferably, the sintered porous copper-nickel alloy is sequentially subjected to four pretreatment steps of alkali washing, alcohol treatment, acid washing and liquid phase reduction, and deionized water is used for washing to be neutral after each step is finished.
Preferably, the alkaline washing is a treatment with a strong base containing an amino group. The strong base can be ammonia water, organic amine, etc. Preferably, the alkaline washing is immersion in 15-28 wt% ammonia solution for 5-30 min.
Preferably, the alcohol treatment is treatment with methanol, ethanol, isopropanol, or the like. Preferably, the alcohol treatment is immersion in ethanol for 5-30 min.
Preferably, the acid wash is a treatment with a strong acid that is non-oxidizing. The strong acid may be hydrochloric acid or the like. Preferably, the acid wash is a dip in a 10-30 wt% hydrochloric acid solution for 5-30 min.
Preferably, the liquid phase reduction is treatment with hydrazine hydrate, formaldehyde, or the like. Preferably, the liquid phase is reduced to 35-40 wt% formaldehyde solution for immersion for 5-30 min.
The pretreatment step of the invention can fully remove impurities on the surface of the sintered porous copper-nickel alloy and improve the bonding strength between the sintered porous copper-nickel alloy and the metal active component.
And (3) when active components are impregnated in the step (2), immersing the pretreated sintered porous copper-nickel alloy in an impregnating solution, performing ultrasonic treatment, controlling the temperature to be 10-80 ℃, preferably 40-60 ℃, enabling the impregnating solution to circularly flow on the inner side and the outer side of a cavity of the sintered porous copper-nickel alloy by using a liquid pump so as to achieve the purpose of uniform impregnation, wherein the time is 5-120min, preferably 30-60min, and washing the impregnated porous copper-nickel alloy to be neutral by using deionized water.
The impregnating solution comprises PdCl 2 、NaH 2 PO 2 ·H 2 O, hydrochloric acid (38 wt%), NH 3 ·H 2 O, ethylenediamine and water.
The pH of the impregnation solution is 7.5 to 11, preferably 9 to 10.
In the dipping solution of the invention, PdCl 2 Added according to the loading amount. NaH 2 PO 2 ·H 2 O is 2-15g/L, hydrochloric acid (38 wt%) is 1-10mL/L, NH 3 ·H 2 O is 10-200mL/L, and ethylenediamine is 5-50 mL/L.
In the present invention, ethylenediamine may be replaced with ammonium chloride, ammonium sulfate, etc.
In the step (3), the temperature is raised at a rate of 5-30 ℃/min, the constant-temperature roasting is carried out at 250-500 ℃ for 2-5 hours, and the atmosphere is hydrogen atmosphere. Preferably, the firing temperature may be 300-. And naturally cooling after roasting. The particle diameter of the active metal component Pd can be controlled within a desired average particle diameter range by performing the reduction roasting treatment at an appropriate temperature range and temperature rising rate.
Conventional Al is adopted in the prior art 2 O 3 And SiO 2 The supported catalyst prepared by the carriers has poor strength and is easy to pulverize,so that the acting force between the active component and the carrier is reduced, and the active component is easy to fall off and run off. The catalyst prepared by the method has high strength, the sintered porous copper-nickel alloy carrier has certain activity on hydrodechlorination reaction, the acting force between the active metal component and the sintered porous copper-nickel alloy carrier is strong, the active metal component is not easy to run off, and the catalyst has high stability.
The catalyst prepared by the invention can be used for hydrodechlorination reaction, is particularly suitable for industrial large-scale production of chlorotrifluoroethylene by catalytic hydrodechlorination of trichlorotrifluoroethane, and has the advantages of long service life, high reliability and the like.
Drawings
FIG. 1 is a schematic structural diagram of a hollow cylinder sintered porous Cu-Ni alloy in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1: preparation of sintered porous copper-nickel alloy
Mixing sodium polyacrylate with a weight-average molecular weight of 3500 and deionized water (the weight of sodium polyacrylate: the weight of water: 1: 50), stirring for 10min, adding polyvinyl alcohol with a weight-average molecular weight of 90000 (the weight of polyvinyl alcohol: the weight of water: 1: 20), heating to 80 ℃, stirring for 30min, cooling to room temperature, adding powder obtained by uniformly mixing nickel oxide powder with an average particle size of 10nm and copper oxide powder with an average particle size of 10nm (the weight of nickel oxide: the weight of copper oxide: 1) under stirring, and making slurry, wherein the total proportion of nickel oxide powder and copper oxide powder is 70 wt%.
And granulating and forming the slurry, heating the formed body to 400 ℃ at the speed of 10 ℃/min in a nitrogen atmosphere, keeping the temperature for 2 hours, switching to the 5% argon/hydrogen mixture atmosphere, heating to 1000 ℃ at the speed of 20 ℃/min, keeping the temperature for 3 hours, and then naturally cooling.
The pore diameter of the sintered porous copper-nickel alloy is measured by a nitrogen adsorption method, the pore volume of 50-300nm accounts for 85% of the total pore volume, and the average pore diameter is 122 nm.
The sintered porous cupronickel alloy was processed into a hollow cylindrical structure as shown in fig. 1. The diameter of a through hole which is vertically communicated with the hollow part is 5mm, the wall thickness is 5mm, and the height is 10mm for standby.
Example 2: preparation of the catalyst
The hollow cylindrical sintered porous copper-nickel alloy prepared in example 1 was subjected to pretreatment including alkali washing, alcohol treatment, acid washing, and liquid phase reduction in this order, and then the pretreated sintered porous copper-nickel alloy was impregnated with an active component. The above steps are all washed to be neutral by deionized water.
The alkali washing is to dip in 20 wt% ammonia water solution for 10min, the alcohol treatment is to dip in ethanol for 10min, the acid washing is to dip in 20 wt% hydrochloric acid solution for 10min, and the liquid phase reduction is to dip in 35 wt% formaldehyde water solution for 10 min.
When active components are impregnated, immersing the pretreated hollow cylindrical sintered porous copper-nickel alloy in an impregnating solution, performing ultrasonic treatment, controlling the temperature to be 60 ℃, and enabling the impregnating solution to circularly flow on the inner side and the outer side of a hollow cylindrical sintered porous copper-nickel alloy cavity by adopting a liquid pump so as to achieve the purpose of uniform impregnation, wherein the time is 60 min. And washing the mixture to be neutral by deionized water.
The components of the impregnating solution comprise PdCl 2 、NaH 2 PO 2 ·H 2 O, hydrochloric acid (38 wt%), NH 3 ·H 2 O, ethylenediamine and water, PdCl 2 Added according to the loading of 1 wt%, NaH 2 PO 2 ·H 2 O is 5g/L, hydrochloric acid (38 wt%) is 2mL/L, NH 3 ·H 2 O is 100mL/L, and ethylenediamine is 10 mL/L. The pH of the impregnation solution was 9.
Heating the hollow cylindrical sintered porous copper-nickel alloy impregnated with the active component to 350 ℃ at the speed of 10 ℃/min in a hydrogen atmosphere, keeping the temperature for 3 hours, and then naturally cooling.
The prepared catalyst is subjected to TEM characterization, and the average particle size of the active component Pd is 6.1 nm.
Example 3: preparation of the catalyst
The hollow cylindrical sintered porous copper-nickel alloy prepared in example 1 was subjected to pretreatment including alkali washing, acid washing, and liquid phase reduction in this order, and then the pretreated sintered porous copper-nickel alloy was impregnated with an active component. The above steps are all washed to be neutral by deionized water.
The alkali washing is to dip in 20 wt% ammonia water solution for 30min, the acid washing is to dip in 20 wt% hydrochloric acid solution for 20min, and the liquid phase is reduced to 35 wt% formaldehyde water solution for 20 min.
When active components are impregnated, immersing the pretreated hollow cylindrical sintered porous copper-nickel alloy in an impregnating solution, performing ultrasonic treatment, controlling the temperature to be 80 ℃, and enabling the impregnating solution to circularly flow on the inner side and the outer side of a hollow cylindrical sintered porous copper-nickel alloy cavity by adopting a liquid pump so as to achieve the purpose of uniform impregnation, wherein the time is 30 min. And washing the mixture to be neutral by deionized water.
The components of the impregnating solution comprise PdCl 2 、NaH 2 PO 2 ·H 2 O, hydrochloric acid (38 wt%), NH 3 ·H 2 O, ethylenediamine and water, PdCl 2 Added according to the loading of 0.5 weight percent, NaH 2 PO 2 ·H 2 O is 10g/L, hydrochloric acid (38 wt%) is 1mL/L, NH 3 ·H 2 O is 200mL/L, and ethylenediamine is 30 mL/L. The pH of the impregnation solution was 10.
Heating the hollow cylindrical sintered porous copper-nickel alloy impregnated with the active component to 400 ℃ at the speed of 20 ℃/min in a hydrogen atmosphere, keeping the temperature for 4 hours, and then naturally cooling.
The prepared catalyst is subjected to TEM characterization, and the average particle size of the active component Pd is 6.8 nm.
Comparative example 1
In contrast to example 2, the catalyst support was SiO 2 A specific surface area of 380m 2 Per g, pore volume 0.8cm 3 /g。
Example 4: enhanced dechlorination test
The catalysts of examples 2 and 3 and comparative example 1 were charged in a fixed bed reactor having an internal diameter of 10cm, and hydrogen and trichlorotrifluoroethane were fed at 250 ℃The molar ratio of the mixed gas consisting of the alkane is 1:1, and the space velocity is 300h -1 The hydrogenation product was analyzed by Agilent 7890A gas chromatography.
The results show that with the catalyst of example 2, the conversion is 100% and the chlorotrifluoroethylene selectivity is 97.56%. After 200 hours, the conversion was still 100%.
With the catalyst of example 3, the conversion was 100% and the chlorotrifluoroethylene selectivity was 97.27%. After 200 hours, the conversion was still 100%.
With the catalyst of comparative example 1, the conversion was 98.58% and the chlorotrifluoroethylene selectivity was 95.12%. After 200 hours, the conversion was 91.87%.

Claims (10)

1. A catalyst for preparing chlorotrifluoroethylene, characterized in that: the catalyst carrier is sintered porous copper-nickel alloy, the active component is Pd, the loading capacity of the Pd active component is 0.1-5 wt%, the average pore diameter of the sintered porous copper-nickel alloy is 50-300nm, the sintered porous copper-nickel alloy is of a hollow structure, and the wall thickness is 0.5-25 mm.
2. The catalyst of claim 1, wherein: the sintered porous copper-nickel alloy is a hollow cylinder, a hollow cube or a hollow cuboid.
3. The catalyst of claim 1, wherein: the average particle diameter of the active component Pd is 5-30 nm.
4. The catalyst of claim 1, wherein: the hollow part of the sintered porous copper-nickel alloy is a through hole which penetrates through the hollow part up and down, and the diameter of the through hole is 0.1-10 mm.
5. A process for preparing the catalyst of claim 1, wherein: the method comprises the following steps:
(1) pretreating the sintered porous copper-nickel alloy;
(2) dipping active components on the pretreated sintered porous copper-nickel alloy;
(3) temperature programming and constant-temperature roasting.
6. The method for preparing a catalyst according to claim 5, characterized in that: the pretreatment in the step (1) comprises alkali washing, alcohol treatment, acid washing and/or liquid phase reduction.
7. The method for preparing a catalyst according to claim 5, characterized in that: and (3) when active components are impregnated in the step (2), immersing the pretreated sintered porous copper-nickel alloy in an impregnating solution, performing ultrasonic treatment, controlling the temperature to be 10-80 ℃, enabling the impregnating solution to circularly flow on the inner side and the outer side of the sintered porous copper-nickel alloy cavity by adopting a liquid pump for 5-120min, and washing with deionized water to be neutral.
8. The method for preparing a catalyst according to claim 5, characterized in that: in the step (3), the temperature is raised at a rate of 5-30 ℃/min, the constant-temperature roasting is carried out at 250-500 ℃ for 2-5 hours, and the atmosphere is hydrogen atmosphere.
9. The method for preparing a catalyst according to claim 7, characterized in that: the impregnating solution comprises PdCl 2 、NaH 2 PO 2 ·H 2 O, 38 wt% hydrochloric acid, NH 3 ·H 2 O, ethylenediamine and water.
10. The method for preparing a catalyst according to claim 7 or 9, characterized in that: the pH of the impregnation liquid is 7.5-11.
CN202011450384.9A 2020-12-10 2020-12-10 Catalyst for preparing chlorotrifluoroethylene and preparation method thereof Active CN112547070B (en)

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