CN116116465B - Natural gas combustion-supporting catalyst and preparation method thereof - Google Patents

Natural gas combustion-supporting catalyst and preparation method thereof Download PDF

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CN116116465B
CN116116465B CN202310350741.1A CN202310350741A CN116116465B CN 116116465 B CN116116465 B CN 116116465B CN 202310350741 A CN202310350741 A CN 202310350741A CN 116116465 B CN116116465 B CN 116116465B
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CN116116465A (en
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高志强
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Kunshan Heng'an Industrial Gases Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/003—Additives for gaseous fuels
    • 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
    • B01J23/44—Palladium
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/04—Catalyst added to fuel stream to improve a reaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery

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Abstract

The application relates to the technical field of natural gas, in particular to a natural gas combustion-supporting catalyst and a preparation method thereof. The natural gas combustion-supporting catalyst comprises the following substances in parts by weight: 6-12 parts of methyl tertiary butyl ether; 8-15 parts of acetone; 10-15 parts of methanol; 15-20 parts of cyclopentane; 4.5 to 8.5 portions of light catalytic combustion-supporting particles; the light catalytic combustion-supporting particles comprise Pd/porous carrier catalytic particles. The composition of the natural gas combustion-supporting catalyst is optimized, the defect that the subsequent stability performance is reduced due to poor dispersion performance in the use process of single Pd/porous carrier catalytic particles is overcome, and meanwhile, oxygen sources are provided for natural gas combustion through continuous oxidation and reduction of the Pd/porous carrier catalytic particles in the use process, so that the natural gas is effectively supported, and a good combustion-supporting catalytic effect is realized.

Description

Natural gas combustion-supporting catalyst and preparation method thereof
Technical Field
The application relates to the technical field of natural gas, in particular to a natural gas combustion-supporting catalyst and a preparation method thereof.
Background
As an environment-friendly energy source, natural gas not only has the high-quality characteristic of low-temperature gas emission, but also generates less nitrogen oxides and sulfur oxides in the combustion process compared with coal and petroleum, and is a high-quality, high-efficiency and clean energy source. Nowadays, the number and variety of kilns, boilers, heating furnaces, incinerators, which use natural gas as fuel in industrial production in various industries are also increasing.
Since the main component in natural gas is methane, it is the hydrocarbon that is most difficult to deeply oxidize because it contains only four c—h bonds per methane molecule, which requires a catalyst with sufficiently efficient catalytic combustion activity. Although current catalyst materials are often catalytically treated with Pd complex catalysts.
In view of the above-mentioned related art, the inventors found that the stability of the Pd catalyst material produced by the existing ion exchange method is poor, and in the actual combustion-supporting natural gas process, the long-acting combustion-supporting is not possible and easy to deactivate, resulting in poor catalytic combustion-supporting effect.
Disclosure of Invention
In order to overcome the defect of poor stability of the catalytic combustion-supporting effect of the existing natural gas combustion-supporting catalyst, the application provides a purifying adsorbent and a method for purifying natural gas by applying the purifying adsorbent to pre-desulfurization.
In a first aspect, the present application provides a natural gas combustion-supporting catalyst, which adopts the following technical scheme:
the natural gas combustion-supporting catalyst comprises the following substances in parts by weight:
6-12 parts of methyl tertiary butyl ether;
8-15 parts of acetone;
10-15 parts of methanol;
15-20 parts of cyclopentane;
4.5 to 8.5 portions of light catalytic combustion-supporting particles;
the light catalytic combustion-supporting particles comprise Pd/porous carrier catalytic particles.
By adopting the technical scheme, the composition of the natural gas combustion-supporting catalyst is optimized, on one hand, as the methyl tertiary butyl ether, the acetone, the methanol and the cyclopentane adopted by the technical scheme can form a good dispersion system in the natural gas, the defect that the subsequent stability performance is reduced due to poor dispersion performance in the use process of single Pd/porous carrier catalytic particles is overcome, and the subsequent effect on the natural gas combustion-supporting catalysis is ensured; on the other hand, according to the technical scheme, pd/porous carrier catalytic particles are adopted for further catalytic treatment, and because the Pd/porous carrier catalytic particles prepared by the method are catalytic particles formed by coating Pd on the surface of the porous carrier, the Pd/porous carrier catalytic particles are continuously oxidized and reduced in the use process, and an oxygen source is provided for natural gas combustion, so that the natural gas is effectively combured, and a good combustion-supporting catalytic effect is realized.
Preferably, the porous carrier catalytic particles are porous ZrO 2 Particulate or porous Al 2 O 3 And (3) particles.
Through adopting above-mentioned technical scheme, the porous carrier catalytic particle's of this application optimization composition selects zirconia or alumina to be the main part, because alumina and zirconia also have good stability and life under high temperature environment, has effectively improved the stability and the durability in the combustion-supporting catalyst of natural gas use. Meanwhile, the porous structure adopted by the application can load more catalytic active substances under the condition of the same volume, so that the combustion-supporting catalytic effect of the natural gas is further improved.
Preferably, the porous carrier catalytic particles are porous grade ZrO 2 The porous support catalyzesThe particles are prepared by adopting the following scheme:
placing polyoxyethylene lauryl ether and polyoxyethylene polyoxypropylene segmented copolymer into deionized water, stirring and mixing, continuously adding nitric acid and zirconium n-propoxide, stirring and mixing after the addition is completed, and collecting emulsion;
taking emulsion, carrying out hydrothermal reaction, filtering, collecting filter cakes, calcining, grinding and sieving to obtain the porous ZrO 2 。
By adopting the technical scheme, the application optimizes the porous carrier catalytic particles to be porous ZrO 2 Compared with the traditional catalyst, the porous structure prepared by the method has the advantages that the porous structure has more active centers and stronger adsorption and mass transfer capacity by utilizing the high specific surface area and the high pore volume of the porous material, so that the catalytic activity of the porous structure is improved, and the catalytic combustion-supporting effect on natural gas is improved. Meanwhile, the multistage pore structure can improve the structural strength of the single-pore-diameter catalyst carrier, so that the durability and the stability of the single-pore-diameter catalyst carrier are further improved in the actual use process.
The porous carrier catalytic particle is also doped with Ba element, and the porous carrier catalytic particle doped with Ba element is prepared by adopting the following scheme:
placing polyoxyethylene lauryl ether and polyoxyethylene polyoxypropylene segmented copolymer into deionized water, stirring and mixing, continuously adding nitric acid, barium nitrate and zirconium n-propoxide, stirring and mixing after the addition is completed, and collecting emulsion;
taking emulsion, carrying out hydrothermal reaction, filtering, collecting filter cakes, calcining, grinding and sieving to obtain the porous carrier catalytic particles doped with Ba element.
By adopting the technical scheme, the composition of the porous carrier catalytic particles is further optimized, and the addition of the Ba element in the porous carrier catalytic particles enables the active ingredient PdO particles to be enlarged and simultaneously improves the reduction temperature, so that more stable PdO active species are formed, and the combustion-supporting catalytic effect of the combustion-supporting catalyst material is improved; on the other hand, the porous carrier is stabilized by adding the Ba element, so that the phase change of crystals at high temperature is prevented, and the high surface area of the carrier is maintained, thereby ensuring that the catalyst material has good catalytic stability.
In a second aspect, the present application provides a method for preparing a natural gas combustion-supporting catalyst, including the following preparation steps:
taking porous carrier catalytic particles for preheating treatment for standby;
heating palladium chloride in nitrogen atmosphere until the palladium chloride sublimates to form mixed gas;
purging the spare porous carrier catalytic particles with the mixed gas, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting reaction particles;
placing the reaction particles in reducing gas, preserving heat, standing and cooling to room temperature, grinding and sieving, heating again, calcining with oxygen enriched, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Through adopting above-mentioned technical scheme, this application has optimized the technical scheme of the combustion-supporting catalyst of preparation natural gas, and this application abandons traditional hydrothermal cladding's technical scheme, sweeps the deposit cladding through adopting high temperature sublimated gas, not only makes more active element of cladding in the hole in the porous catalyst support body, sweeps the cladding structure that the deposit cladding formed simultaneously and is more stable and durable than traditional hydrothermal cladding structure to make the combustion-supporting catalyst of natural gas of this application preparation have good catalytic performance and stability.
Preferably, the preheating treatment is to heat up the porous carrier catalytic particles to 450-500 ℃, keep the temperature for 0.5h, and then stand and cool to 350-400 ℃.
The volume ratio of the nitrogen to the palladium chloride gas in the mixed gas is 4.5-6.5: 0.5 to 0.8.
The nitrogen purging rate is 450-500 mL/min.
The reducing gas includes any one of carbon monoxide and hydrogen.
By adopting the technical scheme, the parameters for preparing the natural gas combustion-supporting catalyst are further optimized, so that active elements and catalytic elements in the natural gas combustion-supporting catalyst are coated more stably, and the catalytic stability of the natural gas combustion-supporting catalyst is further improved.
In summary, the present application has the following beneficial effects:
firstly, the composition of the natural gas combustion-supporting catalyst is optimized, on one hand, as the methyl tertiary butyl ether, the acetone, the methanol and the cyclopentane adopted in the technical scheme of the application can form a good dispersion system in the natural gas, the defect that the subsequent stability performance is reduced due to poor dispersion performance in the use process of single Pd/porous carrier catalytic particles is overcome, and the subsequent effect on the natural gas combustion-supporting catalysis is ensured; on the other hand, according to the technical scheme, pd/porous carrier catalytic particles are adopted for further catalytic treatment, and oxygen sources are provided for natural gas combustion through continuous oxidation and reduction of the Pd/porous carrier catalytic particles in the use process, so that the natural gas is effectively combured, and a good combustion-supporting catalytic effect is achieved.
Secondly, the composition of the porous carrier catalytic particles is further optimized, and by adding Ba element into the porous carrier catalytic particles, on one hand, the addition of the Ba element enlarges the active ingredient PdO particles, and meanwhile, the reduction temperature is increased, so that more stable PdO active species are formed, and the combustion-supporting catalytic effect of the combustion-supporting catalyst material is improved; on the other hand, the porous carrier is stabilized by adding the Ba element, so that the phase change of crystals at high temperature is prevented, and the high surface area of the carrier is maintained, thereby ensuring that the catalyst material has good catalytic stability.
Thirdly, this application has optimized the technical scheme of the combustion-supporting catalyst of preparation natural gas, and this application abandons traditional hydrothermal cladding's technical scheme, sweeps the deposit cladding through adopting high temperature sublimated gas, not only makes more active elements of cladding in the hole in the porous catalyst support, sweeps the cladding structure that the deposit cladding formed simultaneously and is more stable and durable than traditional hydrothermal cladding structure to make the combustion-supporting catalyst of natural gas of this application preparation have good catalytic performance and stability.
Fourth, this application has optimized porous carrier catalytic particle and has been porous grade ZrO2, compares in traditional catalyst and sees, the porous grade structure of this application preparation, utilizes the high specific surface area of multistage pore material and pore volume, makes it have more active center, stronger absorption and mass transfer ability to in order to improve its catalytic activity, thereby improved the catalytic combustion-supporting effect to natural gas. Meanwhile, the multistage pore structure can improve the structural strength of the single-pore-diameter catalyst carrier, so that the durability and the stability of the single-pore-diameter catalyst carrier are further improved in the actual use process.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs conventional purity used in the field of industrial purity or polyimide foam foaming.
All raw materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
All processes of the present invention, the abbreviations of which are conventional in the art, are each well-defined in the art of their relevant use, and the skilled artisan will be able to understand the conventional process steps thereof based on the abbreviations.
Preparation example
Preparation example 1
Porous support catalytic particle 1:
400g of polyoxyethylene lauryl ether and 300g of polyoxyethylene polyoxypropylene segmented copolymer are placed in 10kg of deionized water, stirred and mixed, 200g of 0.8mol/L nitric acid and 1kg of zirconium n-propoxide are continuously added, and after the addition is completed, the mixture is stirred and mixed, and emulsion is collected;
taking emulsion, placing the emulsion at 85 ℃ for hydrothermal reaction, filtering and collecting a filter cake, calcining at 500 ℃ for 5 hours, grinding and sieving to obtain the porous carrier catalytic particles 1.
Preparation example 2
Porous carrier catalytic particles 2:
450g of polyoxyethylene lauryl ether and 350g of polyoxyethylene polyoxypropylene segmented copolymer are placed in 10kg of deionized water, stirred and mixed, 250g of 0.8mol/L nitric acid and 1kg of zirconium n-propoxide are continuously added, and after the addition is completed, the mixture is stirred and mixed, and emulsion is collected;
taking emulsion, placing the emulsion at 87 ℃ for hydrothermal reaction, filtering and collecting a filter cake, calcining at 550 ℃ for 5 hours, grinding and sieving to obtain the porous carrier catalytic particles 2.
Preparation example 3
Porous carrier catalytic particles 3:
placing 500g of polyoxyethylene lauryl ether and 400g of polyoxyethylene polyoxypropylene segmented copolymer into 10kg of deionized water, stirring and mixing, continuously adding 300g of 0.8mol/L nitric acid and 1kg of zirconium n-propoxide, stirring and mixing after the addition is completed, and collecting emulsion;
taking emulsion, placing the emulsion in 90 ℃ for hydrothermal reaction, filtering and collecting a filter cake, calcining the filter cake at 600 ℃ for 6 hours, grinding and sieving the filter cake, and obtaining the porous carrier catalytic particles 3.
Preparation example 4
Porous carrier catalytic particles 4:
400g of polyoxyethylene lauryl ether and 300g of polyoxyethylene polyoxypropylene segmented copolymer are placed in 10kg of deionized water, stirred and mixed, 200g of 1.5mol/L barium nitrate and 1kg of zirconium n-propoxide are continuously added, and after the addition is completed, the mixture is stirred and mixed, and emulsion is collected;
taking emulsion, placing the emulsion at 85 ℃ for hydrothermal reaction, filtering and collecting a filter cake, calcining at 500 ℃ for 5 hours, grinding and sieving to obtain the porous carrier catalytic particles 4.
Preparation example 5
Porous carrier catalytic particles 5:
450g of polyoxyethylene lauryl ether and 350g of polyoxyethylene polyoxypropylene segmented copolymer are placed in 10kg of deionized water, stirred and mixed, 250g of 1.8mol/L barium nitrate and 1kg of zirconium n-propoxide are continuously added, and after the addition is completed, the mixture is stirred and mixed, and emulsion is collected;
taking emulsion, placing the emulsion at 87 ℃ for hydrothermal reaction, filtering and collecting a filter cake, calcining at 550 ℃ for 5 hours, grinding and sieving to obtain the porous carrier catalytic particles 5.
Preparation example 6
Porous carrier catalytic particles 6:
placing 500g of polyoxyethylene lauryl ether and 400g of polyoxyethylene polyoxypropylene segmented copolymer into 10kg of deionized water, stirring and mixing, continuously adding 300g of 2.0mol/L barium nitrate and 1kg of zirconium n-propoxide, stirring and mixing after the addition is completed, and collecting emulsion;
taking emulsion, placing the emulsion in 90 ℃ for hydrothermal reaction, filtering and collecting a filter cake, calcining the filter cake at 600 ℃ for 6 hours, grinding and sieving the filter cake, and obtaining the porous carrier catalytic particles 6.
Examples
Example 1
A natural gas combustion-supporting catalyst comprises 6 parts of methyl tertiary butyl ether, 8 parts of acetone, 10 parts of methanol, 15 parts of cyclopentane and 4.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating porous alumina to 450 ℃, preserving heat for 0.5h, and standing and cooling to 350 ℃ for later use;
taking palladium chloride, heating to 650 ℃ in nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 4.5:0.5 mixed gas;
selecting at 350 ℃, purging the spare porous carrier catalytic particles with mixed gas, controlling the purging rate to be 450mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 600 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Example 2
A natural gas combustion-supporting catalyst comprises 9 parts of methyl tertiary butyl ether, 12 parts of acetone, 12 parts of methanol, 17 parts of cyclopentane and 6.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating porous alumina to 475 ℃, preserving heat for 0.5h, and standing and cooling to 375 ℃ for later use;
taking palladium chloride, heating to 675 ℃ in a nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 5.5:0.65 mixed gas;
selecting at 375 ℃, purging the standby porous carrier catalytic particles with mixed gas, controlling the purging rate to 475mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 625 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Example 3
A natural gas combustion-supporting catalyst, which comprises 12 parts of methyl tertiary butyl ether, 15 parts of acetone, 15 parts of methanol, 20 parts of cyclopentane and 8.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating porous alumina to 500 ℃, preserving heat for 0.5h, and standing and cooling to 400 ℃ for later use;
taking palladium chloride, heating to 700 ℃ in nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 6.5:0.8 of a mixed gas;
selecting at 400 ℃, purging the spare porous carrier catalytic particles with mixed gas, controlling the purging rate to be 500mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 650 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Example 4
A natural gas combustion-supporting catalyst comprises 6 parts of methyl tertiary butyl ether, 8 parts of acetone, 10 parts of methanol, 15 parts of cyclopentane and 4.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating the porous carrier catalytic particles 1 to 450 ℃, preserving heat for 0.5h, and standing and cooling to 350 ℃ for later use;
taking palladium chloride, heating to 650 ℃ in nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 4.5:0.5 mixed gas;
selecting at 350 ℃, purging the spare porous carrier catalytic particles with mixed gas, controlling the purging rate to be 450mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 600 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Example 5
A natural gas combustion-supporting catalyst comprises 6 parts of methyl tertiary butyl ether, 8 parts of acetone, 10 parts of methanol, 15 parts of cyclopentane and 4.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating the porous carrier catalytic particles 2 to 450 ℃, preserving heat for 0.5h, and standing and cooling to 350 ℃ for later use;
taking palladium chloride, heating to 650 ℃ in nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 4.5:0.5 mixed gas;
selecting at 350 ℃, purging the spare porous carrier catalytic particles with mixed gas, controlling the purging rate to be 450mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 600 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Example 6
A natural gas combustion-supporting catalyst comprises 6 parts of methyl tertiary butyl ether, 8 parts of acetone, 10 parts of methanol, 15 parts of cyclopentane and 4.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating the porous carrier catalytic particles 3 to 450 ℃, preserving heat for 0.5h, and standing and cooling to 350 ℃ for later use;
taking palladium chloride, heating to 650 ℃ in nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 4.5:0.5 mixed gas;
selecting at 350 ℃, purging the spare porous carrier catalytic particles with mixed gas, controlling the purging rate to be 450mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 600 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Example 7
A natural gas combustion-supporting catalyst comprises 6 parts of methyl tertiary butyl ether, 8 parts of acetone, 10 parts of methanol, 15 parts of cyclopentane and 4.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating the porous carrier catalytic particles 4 to 450 ℃, preserving heat for 0.5h, and standing and cooling to 350 ℃ for later use;
taking palladium chloride, heating to 650 ℃ in nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 4.5:0.5 mixed gas;
selecting at 350 ℃, purging the spare porous carrier catalytic particles with mixed gas, controlling the purging rate to be 450mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 600 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Example 8
A natural gas combustion-supporting catalyst comprises 6 parts of methyl tertiary butyl ether, 8 parts of acetone, 10 parts of methanol, 15 parts of cyclopentane and 4.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating the porous carrier catalytic particles 5 to 450 ℃, preserving heat for 0.5h, and standing and cooling to 350 ℃ for later use;
taking palladium chloride, heating to 650 ℃ in nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 4.5:0.5 mixed gas;
selecting at 350 ℃, purging the spare porous carrier catalytic particles with mixed gas, controlling the purging rate to be 450mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 600 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Example 9
A natural gas combustion-supporting catalyst comprises 6 parts of methyl tertiary butyl ether, 8 parts of acetone, 10 parts of methanol, 15 parts of cyclopentane and 4.5 parts of light catalytic combustion-supporting particles.
The natural gas combustion-supporting catalyst is prepared by adopting the following scheme:
heating the porous carrier catalytic particles 6 to 450 ℃, preserving heat for 0.5h, and standing and cooling to 350 ℃ for later use;
taking palladium chloride, heating to 650 ℃ in nitrogen atmosphere, and preserving heat for 1h, wherein the volume ratio of the collected nitrogen to the palladium chloride gas is 4.5:0.5 mixed gas;
selecting at 350 ℃, purging the spare porous carrier catalytic particles with mixed gas, controlling the purging rate to be 450mL/min, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting the reaction particles;
placing the reaction particles in CO gas, carrying out heat preservation treatment at 600 ℃, standing and cooling to room temperature, grinding and sieving, heating again, carrying out oxygen-enriched calcination, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
Comparative example
Comparative example 1
In comparison with example 1, no light catalytic combustion-supporting particles were added in comparative example 1.
Performance test
The catalysts prepared in examples 1 to 9 were tested for catalytic durability by the following method:
catalytic durability performance: accurately weighing 2g, putting into a quartz tube reactor, and fixing two ends by quartz cotton.
The composition of the reaction gas is as follows: 0.5% CH 4 、8.0%O 2 And 91.5% N 2 The gas flow rate during the test is 30 mL/min -1 . The temperature of the catalyst is increased to 250 ℃ from the room temperature through the setting of a temperature controller. The gas components before and after the reaction were detected by Echrom A90 gas chromatography equipped with a FID detector. For each sample, a methane combustion performance test was performed using the dry reaction gas during the first 24 hours, and then 5.0vol% steam was introduced into the reaction gas. After 30min of stabilization, the first injection was started and this condition was continued for 6h. After 6h the water vapour was removed until the reaction time was 36 hours. The activity was measured and the catalyst activity was evaluated from the methane conversion, namely:
CH 4 percent conversion = (CH 4 Inlet-CH 4 Exit)/CH 4 X100% (CH) 4 Enter, CH 4 The output refers to the methane concentration before and after the reaction of the mixed gas respectively); the test results are shown in table 1 below:
as can be seen by combining the data of examples 1-3 and comparative example 1, the composition of the natural gas combustion-supporting catalyst is optimized, on one hand, the methyl tertiary butyl ether, the acetone, the methanol and the cyclopentane adopted in the technical scheme of the application can form a good dispersion system in the natural gas, so that the defect that the subsequent stability performance is reduced due to poor dispersion performance in the use process of single Pd/porous carrier catalytic particles is overcome, and the subsequent effect on the natural gas combustion-supporting catalysis is ensured; on the other hand, according to the technical scheme, pd/porous carrier catalytic particles are adopted for further catalytic treatment, and oxygen sources are provided for natural gas combustion through continuous oxidation and reduction of the Pd/porous carrier catalytic particles in the use process, so that the natural gas is effectively combured, and a good combustion-supporting catalytic effect is achieved.
Further, as can be seen from the data of examples 1 to 9, the composition of the porous carrier catalytic particles is further optimized, and by adding the Ba element into the porous carrier catalytic particles, on one hand, the addition of the Ba element enlarges the PdO particles as an active ingredient, and simultaneously increases the reduction temperature, thereby forming more stable PdO active species, and further improving the combustion-supporting catalytic effect of the combustion-supporting catalyst material; on the other hand, the porous carrier is stabilized by adding the Ba element, so that the phase change of crystals at high temperature is prevented, and the high surface area of the carrier is maintained, thereby ensuring that the catalyst material has good catalytic stability.
Meanwhile, the technical scheme for preparing the natural gas combustion-supporting catalyst is optimized, the technical scheme of traditional hydrothermal cladding is abandoned, and the high-temperature sublimated gas is adopted for sweeping, depositing and cladding, so that more active elements are clad in the pores of the porous catalyst carrier, and meanwhile, a cladding structure formed by sweeping, depositing and cladding is more stable and durable than a traditional hydrothermal cladding structure, so that the natural gas combustion-supporting catalyst prepared by the method has good catalytic performance and stability.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (6)

1. The natural gas combustion-supporting catalyst is characterized by comprising the following substances in parts by weight:
6-12 parts of methyl tertiary butyl ether;
8-15 parts of acetone;
10-15 parts of methanol;
15-20 parts of cyclopentane;
4.5 to 8.5 portions of light catalytic combustion-supporting particles;
the light catalytic combustion-supporting particles comprise Pd/porous carrier catalytic particles; the porous carrier catalytic particles are porous-grade ZrO doped with Ba element 2 Catalytic particles of porous-grade ZrO doped with Ba element 2 The catalytic particles are prepared by adopting the following scheme:
placing polyoxyethylene lauryl ether and polyoxyethylene polyoxypropylene segmented copolymer into deionized water, stirring and mixing, continuously adding nitric acid, barium nitrate and zirconium n-propoxide, stirring and mixing after the addition is completed, and collecting emulsion;
taking emulsion, carrying out hydrothermal reaction, filtering, collecting filter cakes, calcining, grinding and sieving to obtain the porous ZrO doped with Ba element 2 Catalytic particles.
2. The method for preparing the natural gas combustion-supporting catalyst according to claim 1, comprising the following preparation steps:
taking porous carrier catalytic particles for preheating treatment for standby;
heating palladium chloride in nitrogen atmosphere until the palladium chloride sublimates to form mixed gas;
purging the spare porous carrier catalytic particles with the mixed gas, standing and cooling to room temperature after purging is completed, grinding and sieving, and collecting reaction particles;
placing the reaction particles in reducing gas, preserving heat, standing and cooling to room temperature, grinding and sieving, heating again, calcining with oxygen enriched, standing and cooling to room temperature, and collecting light catalytic combustion-supporting particles;
and stirring and mixing the light catalytic combustion-supporting particles, methyl tertiary butyl ether, acetone, methanol and cyclopentane, performing vacuum ultrasonic dispersion, and collecting a suspension to obtain the natural gas combustion-supporting catalyst.
3. The method for preparing a natural gas combustion-supporting catalyst according to claim 2, wherein the preheating treatment is to raise the temperature of the porous carrier catalytic particles to 450-500 ℃, keep the temperature for 0.5h, and then cool the porous carrier catalytic particles to 350-400 ℃ by standing.
4. The method for preparing a natural gas combustion-supporting catalyst according to claim 2, wherein the volume ratio of nitrogen to palladium chloride gas in the mixed gas is 4.5-6.5: 0.5 to 0.8.
5. The method for preparing a natural gas combustion-supporting catalyst according to claim 4, wherein the nitrogen purging rate is 450-500 mL/min.
6. The method for preparing a natural gas combustion-supporting catalyst as set forth in claim 4, wherein the reducing gas comprises any one of carbon monoxide and hydrogen.
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