CN112275293B - Preparation method and reforming method of catalyst for low-carbon alkane reforming hydrogen production and application of catalyst - Google Patents
Preparation method and reforming method of catalyst for low-carbon alkane reforming hydrogen production and application of catalyst Download PDFInfo
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- CN112275293B CN112275293B CN202010927717.6A CN202010927717A CN112275293B CN 112275293 B CN112275293 B CN 112275293B CN 202010927717 A CN202010927717 A CN 202010927717A CN 112275293 B CN112275293 B CN 112275293B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000001257 hydrogen Substances 0.000 title claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 238000002407 reforming Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000004005 microsphere Substances 0.000 claims description 31
- 239000000741 silica gel Substances 0.000 claims description 31
- 229910002027 silica gel Inorganic materials 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 24
- 229910003294 NiMo Inorganic materials 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 42
- 239000001569 carbon dioxide Substances 0.000 abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 abstract description 20
- 239000011593 sulfur Substances 0.000 abstract description 20
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000003345 natural gas Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J1/00—Production of fuel gases by carburetting air or other gases without pyrolysis
- C10J1/20—Carburetting gases other than air
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method and a reforming method of a catalyst for preparing hydrogen by reforming low-carbon alkane and application thereof. The preparation method comprises the following steps: with Ni (NH) 3 ) 6 Cl 2 ·6H 2 Preparation of Ni/SiO by O 2 Then add (NH) 4 ) 6 Mo 7 O 24 ·4H 2 And O aqueous solution. The invention further discloses a method for preparing hydrogen and carbon monoxide by catalytic reforming of low-carbon alkane and carbon dioxide. The beneficial effects of the invention are as follows: the sulfur resistance of the catalyst can be enhanced; the treatment method is simple; has important energy and environmental protection significance; the catalyst is used for preparing hydrogen by reforming low-carbon alkane in a sulfur-containing atmosphere, and has the advantages of catalytic reforming of the low-carbon alkane and carbon dioxide in the sulfur-containing atmosphere, high conversion rate of the low-carbon alkane and the carbon dioxide up to more than 90%, high sulfur resistance, and good application prospect.
Description
Technical Field
The invention relates to the technical field of energy functional materials, in particular to a preparation and reforming method of a catalyst for preparing hydrogen and carbon monoxide by reforming low-carbon alkane in sulfur-containing gas and carbon dioxide, and application thereof.
Background
With the consumption of non-renewable energy sources and the annual increase of environmental protection requirements, the development, utilization and research of various renewable energy sources in various countries around the world are also in depth. Natural gas, which uses low-carbon alkane as a main component, is expected to be extremely high in quality as an energy source with the advantages of economy, safety, environmental protection and the like, is widely available in coal seam gas (natural gas existing in coal seams and associated mineral resources of coal), shale gas (natural gas extracted from shale layers) and combustible ice (natural gas hydrate) besides being obtained from conventional natural gas resources. Carbon dioxide is a main cause of greenhouse effect, widely exists in the atmosphere, can be used as a reactant source of the reaction, and is beneficial to improving the energy utilization efficiency and protecting the environment. The invention is studied in the direction of converting light alkanes and carbon dioxide into synthesis gas (CO and H) by using catalytic reforming technology 2 ) Conversion of light alkanes and carbon dioxide to synthesis gas (CO and H) 2 ) The product can be used as a clean energy source, more importantly, the synthesis gas can be further converted into liquid fuel or other chemicals, so that the product has wide energy utilization value, however, 35 percent of natural gas fields worldwide contain 1 to 15mol percent of acid gas molecules (mainly H 2 S), which has become a major challenge for the processing and utilization of natural gas.
Catalyst technology commonly used in downstream flue gas capture (HGD) is susceptible to sulfiding deactivation, even at very low H 2 S concentration can poison the catalyst, at 35%Natural gas field contains H 2 In the context of S, the widely used Claus process is for H 2 S has a degree of removal of 90-98%, which requires us to explore a new way to cope with H present in the reaction 2 S gas.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and provides a preparation method of a catalyst for preparing hydrogen by reforming low-carbon alkane; the sulfur resistance of the catalyst is improved from the aspects of resource utilization and environmental protection, the dry reforming reaction of low-carbon alkane and carbon dioxide can be efficiently carried out, hydrogen sulfide in the catalyst can be effectively absorbed and decomposed, the problem of environmental pollution is solved, and the catalyst can be regenerated by a roasting method.
It is another object of the present invention to provide a method for regenerating the catalyst for the reformation of light alkane to produce hydrogen.
A third object of the present invention is to provide the use of the catalyst for the reformation of light alkane to produce hydrogen.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a method for preparing a catalyst for low-carbon alkane reforming hydrogen production, which comprises the following steps:
(1) According to 0.23178-2.3178g Ni (NH) 3 ) 6 Cl 2 ·6H 2 Ratio of O dissolved in 1-10ml deionized water to dissolve Ni (NH) 3 ) 6 Cl 2 ·6H 2 O is dissolved in deionized water, and ammonia water is used for adjusting the pH value to 9-11; adding 1-5g SiO 2 Stirring the carrier for 2-10min, and treating with ultrasonic wave with frequency of 40-60kHz for 5-15min; standing for 8-10h, drying in an oven at 100-200deg.C for 8-12h, calcining in a muffle furnace at 400-600deg.C for 1-3h, and cooling to room temperature to obtain Ni/SiO catalyst 2 。
(2) According to 0.1-0.5g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 The ratio of O dissolved in 1-10ml deionized water will (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in deionized water, and then Ni/SiO obtained in (1) is added 2 Stirring for 2-10min, and then performing ultrasonic treatment at 40-60kHz for 10Standing for 8-10h, drying in 100-200deg.C oven for 8-12h, calcining in 400-600deg.C muffle furnace for 1-3h, and cooling to room temperature to obtain NiMo/SiO catalyst 2 。
Preferably, the preparation method of the catalyst for preparing hydrogen by reforming low-carbon alkane comprises the following steps:
(1) 0.91g of Ni (NH) 3 ) 6 Cl 2 ·6H 2 Dissolving O in 3.5ml deionized water, and regulating pH value to 9-11 with ammonia water; 2g of SiO are added 2 Carrying out ultrasonic treatment for 10min after stirring for 5min; standing for 9h, drying in an oven at 11 ℃ for 10h, roasting in a muffle furnace at 550 ℃ for 3h, and cooling to room temperature to obtain the catalyst Ni/SiO 2 。
(2) 0.46g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 3.5ml of deionized water, and then Ni/SiO obtained in (1) was added 2 Stirring for 5min, performing ultrasonic treatment for 10min, standing for 10h, drying in a 110 ℃ oven for 12h, roasting in a 550 ℃ muffle furnace for 3h, and cooling to room temperature to obtain the catalyst NiMo/SiO 2 。
The SiO is 2 The carrier is that microsphere silica gel is put into acid liquor to be soaked for 8-10 hours; washing the obtained microsphere silica gel with deionized water, drying in 100-200deg.C oven for 8-12 hr, roasting in 400-600deg.C muffle furnace for 1-3 hr, and naturally cooling to room temperature to obtain SiO 2 A carrier.
The microsphere silica gel is screened by using a 40-60 mesh sieve, so that the particle size of the microsphere silica gel is uniform.
In order to make the catalyst NiMo/SiO 2 Has the highest catalytic activity and is used for preparing the catalyst NiMo/SiO 2 The activation treatment is carried out, and comprises the following steps: niMo/SiO 2 Placed in a fixed bed reactor, continuously introducing 10% of H 2 Under the Ar condition, the temperature is increased from 30 ℃ to 300-600 ℃ for 0-30min to carry out deep steady state reduction, and then the temperature is continuously increased to 700 ℃ for 1-3h (10 ℃/min) to carry out final reduction.
A method for regenerating a catalyst for the reformation of light alkane to produce hydrogen, comprising the steps of: will beNiMo/SiO 2 Placed in a fixed bed reactor, continuously introducing 10% of H 2 Under the Ar condition, the temperature is increased from 30 ℃ to 300-600 ℃ for 0-30min to carry out deep steady state reduction, and then the temperature is continuously increased to 700 ℃ for 1-3h (10 ℃/min) to carry out final reduction.
Wherein the temperature rise range is 10 ℃/min.
A method for preparing hydrogen and carbon monoxide by catalytic reforming, comprising the following catalytic reforming reaction conditions based on the catalyst for preparing hydrogen by reforming low-carbon alkane:
(1) The catalytic reforming temperature is 600-800 ℃;
(2) The flow rate of the reaction gas of catalytic reforming/the mass of the catalyst are as follows
40-60(cm 3 ·min -1 )/0.2g;
(3) Reaction gas C x H 2x+2 (x is a natural number less than 4), CO 2 、H 2 The concentration of S is: 10-49.9vol%, 10-1000ppm.
The treatment process adopted by the invention can effectively improve the sulfur resistance of the catalyst; the catalyst may be in the presence of 100ppmH 2 S is used for catalytically reforming low-carbon alkane and carbon dioxide in the atmosphere, the conversion rate of the low-carbon alkane and the carbon dioxide can reach more than 90 percent, and H 2 The CO is stabilized at about 1.2, H 2 The removal rate of S can reach 99%, so that the utilization rate of resources can be improved, the pollution problem is safely and effectively solved, the method is stable and efficient, and the method has a good application prospect.
In general, compared with the prior art, the invention has the following beneficial effects:
(1) The activity is high: the catalyst is used for preparing hydrogen and carbon dioxide by catalytic reforming of low-carbon alkane and carbon dioxide in sulfur-containing gas, when the catalyst is carried out at 700 ℃, the conversion rate of the low-carbon alkane and the carbon dioxide can reach more than 90%, and H is 2 The CO is stabilized at about 1.2, H 2 The removal rate of S can reach 99 percent, and the method has good application prospect;
(2) The sulfur resistance of the catalyst is improved: the sulfur resistance of the catalyst can be doubled or even more;
(3) The operation is simple and the cost is low: only 10% H was used during the whole treatment 2 The Ar treatment method is very simple, and the required requirement can be met only by raising the temperature to a certain intermediate temperature in the pretreatment process to perform deep steady-state reduction.
Drawings
FIG. 1 is a XRD pattern of the catalysts prepared in examples 1, 2, 3 and 4 at different times during the reaction;
FIG. 2 shows the catalyst pair reactant CH prepared in examples 1, 2, 3, 4 4 Is a conversion map of (2);
FIG. 3 shows the catalyst pair reactant CO prepared in examples 1, 2, 3, 4 2 Is a conversion map of (2);
FIG. 4 shows the catalyst pair product H prepared in examples 1, 2, 3, 4 2 Ratio graph of/CO.
Detailed Description
In order to make the technical solution of the present invention more clear, the following detailed description will be given with examples, but the content of the present invention is not limited to the scope of the following embodiments.
Example 1
A method for preparing a catalyst for low-carbon alkane reforming hydrogen production, which comprises the following steps:
(1) Screening the microsphere silica gel by using a 40-mesh sieve to ensure that the microsphere silica gel has uniform particle size; placing the screened microsphere silica gel into a nitric acid solution with the concentration of 34% to be soaked for 9 hours; washing the obtained microsphere silica gel with deionized water, drying in a 110 ℃ oven for 12h, roasting in a 550 ℃ muffle furnace for 3h, and naturally cooling to room temperature to obtain SiO 2 A carrier;
(2) 0.91g of Ni (NH) 3 ) 6 Cl 2 ·6H 2 O was dissolved in 3.5ml of deionized water, pH was adjusted to 11 with ammonia, and then 2g of SiO was added 2 The carrier is stirred for 5min, then is ultrasonically treated for 10min at 41kHz, is placed for 9h, is put into a baking oven at 110 ℃ for drying for 12h, is put into a muffle furnace at 550 ℃ for baking for 3h, and is cooled to room temperature, thus obtaining the catalyst Ni/SiO 2 ;
(3) 0.46g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in 3.5mI deionized water, then adding the Ni/SiO obtained in (2) 2 Stirring for 5min, ultrasonic treating at 41kHz for 10min, standing for 10 hr, drying in 110 deg.C oven for 12 hr, roasting in 550 deg.C muffle furnace for 3 hr, and cooling to room temperature to obtain NiMo/SiO catalyst 2; And the catalyst NiMo/SiO 2 XRD characterization is carried out, the result is shown in figure 1 (Fresh), the XRD pattern of the sample shows that the main components in the sample are NiO and MoO 3 。
A method for preparing hydrogen and carbon monoxide by catalytic reforming, which uses the catalyst obtained in the step (3) for the catalytic reforming of low-carbon alkane and carbon dioxide in sulfur-containing gas, and comprises the following reaction conditions: the total flow rate was 50cm 3 /min,CH 4 、CO 2 And H 2 S concentration was 30vol%, 30vol% and 100ppm, respectively; the catalyst was used in an amount of 0.4g at 700℃under reaction conditions. The reaction was started after the gases were mixed well, with samples taken at 20min intervals (total reaction time 240 min). And measuring CH with a gas chromatograph FID, TCD, FPD 4 、CO 2 、H 2 S、H 2 And the concentration of CO and the conversion rate thereof were calculated, and as a result, as shown in fig. 2 to 4 (Fresh), the catalytic reaction initial activity of the sample was 81% and the activity was reduced to half in 80 minutes, and the stability was poor and the effect was poor, compared with the catalysts in other examples.
Example 2
A method for preparing a catalyst for low-carbon alkane reforming hydrogen production, which comprises the following steps:
(1) Screening the microsphere silica gel by using a 60-mesh sieve to ensure that the microsphere silica gel has uniform particle size; placing the screened microsphere silica gel into a nitric acid solution with the concentration of 34% to be soaked for 9 hours; washing the obtained microsphere silica gel with deionized water, drying in a 180 ℃ oven for 12h, roasting in a 500 ℃ muffle furnace for 3h, and naturally cooling to room temperature to obtain SiO 2 A carrier;
(2) 0.91g of Ni (NH) 3 ) 6 Cl 2 ·6H 2 O was dissolved in 3.5ml of deionized water, pH was adjusted to 10 with ammonia, and then 2g of SiO was added 2 The carrier is stirred for 5min, then is ultrasonically treated for 8min at 50kHz, is placed for 9h, is placed into a baking oven at 120 ℃ for drying for 10h, and is placed into a horse at 500 DEG CRoasting in a furfurer for 2h, and cooling to room temperature to obtain the catalyst Ni/SiO 2 ;
(3) 0.46g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 3.5ml of deionized water, and then Ni/SiO obtained in (2) was added 2 Stirring for 5min, performing ultrasonic treatment for 10min, standing for 8h, drying in a 130 ℃ oven for 12h, roasting in a 500 ℃ muffle furnace for 3h, and cooling to room temperature to obtain the catalyst NiMo/SiO 2 。
The catalyst NiMo/SiO is prepared newly 2 The activation treatment is carried out, and comprises the following steps: catalyst NiMo/SiO 2 Placed in a fixed bed reactor, continuously introducing 10% of H 2 Under the condition of Ar, the temperature is increased from 30 ℃ to 700 ℃ and stays for 1h (the heating amplitude is 10 ℃/min) for reduction. XRD characterization of the reduced material is carried out, and the result is shown in figure 1 (30-700), the XRD pattern of the sample shows that the main components in the sample are Ni and Ni 3 Mo, with a small amount of Ni 3 Mo is present but Ni compared to the catalysts in examples 3 and 4 3 Mo and Ni 3 The phase difference of Mo is not obvious.
The method for preparing hydrogen and carbon monoxide by catalytic reforming uses the obtained catalyst for the catalytic reforming of low-carbon alkane and carbon dioxide in sulfur-containing gas, and the reaction conditions are as follows: the total flow rate was 50cm 3 /min,CH 4 、CO 2 And H 2 S concentration was 30vol%, 30vol% and 100ppm, respectively; the catalyst was used in an amount of 0.2g at 700℃under reaction conditions. The reaction was started after the gases were mixed well, with samples taken at 20min intervals (total reaction time 240 min). And measuring CH with a gas chromatograph FID, TCD, FPD 4 、CO 2 、H 2 S、H 2 And the concentration of CO, and the conversion rate thereof were calculated, and as a result, as shown in FIGS. 2 to 4 (30 to 700), the initial activity of the catalytic reaction was 85%, and the activity was reduced to half by more than 100 minutes, and the stability was improved, as compared with example 1.
Example 3
A method for preparing a catalyst for low-carbon alkane reforming hydrogen production, which comprises the following steps:
(1) Make the following stepsScreening the microsphere silica gel by a 50-mesh sieve to unify the particle size of the microsphere silica gel; placing the screened microsphere silica gel into a nitric acid solution with the concentration of 34% to be soaked for 9 hours; washing the obtained microsphere silica gel with deionized water, drying in a 110 ℃ oven for 12h, roasting in a 550 ℃ muffle furnace for 3h, and naturally cooling to room temperature to obtain SiO 2 A carrier;
(2) 0.91g of Ni (NH) 3 ) 6 Cl 2 ·6H 2 O was dissolved in 3.5ml of deionized water, pH was adjusted to 11 with ammonia, and then 2g of SiO was added 2 The carrier is stirred for 5min, then is ultrasonically treated for 10min at 50kHz, is placed for 9h, is put into a baking oven at 110 ℃ for drying for 12h, is put into a muffle furnace at 550 ℃ for baking for 3h, and is cooled to room temperature, thus obtaining the catalyst Ni/SiO 2 ;
(3) 0.46g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 3.5ml of deionized water, and then Ni/SiO obtained in (2) was added 2 Stirring for 5min, ultrasonic treating at 40kHz for 10min, standing for 8 hr, drying in 110 deg.C oven for 12 hr, roasting in 550 deg.C muffle furnace for 3 hr, and cooling to room temperature to obtain NiMo/SiO catalyst 2 。
The catalyst NiMo/SiO is prepared newly 2 The activation treatment is carried out, and comprises the following steps: niMo/SiO 2 Placed in a fixed bed reactor, continuously introducing 10% of H 2 Under Ar condition, heating from 30deg.C to 400deg.C, standing for 30min for deep steady state reduction, then continuously heating to 700deg.C, standing for 1h (10deg.C/min) for final reduction, and XRD characterizing the material, wherein the result is shown in figure 1 (30-400-700), and the XRD pattern of the sample shows that the main components in the sample are Ni and Ni 3 Mo, with a small amount of Ni 3 Mo is present, ni compared to the catalysts in examples 2 and 4 3 Mo and Ni 3 The crystal phase of Mo is best and quite obvious.
The method for preparing hydrogen and carbon monoxide by catalytic reforming uses the obtained catalyst for the catalytic reforming of low-carbon alkane and carbon dioxide in sulfur-containing gas, and the reaction conditions are as follows: the total flow rate was 55cm 3 /min,CH 4 、CO 2 And H 2 S concentration was 30vol%, 30vol% and 100ppm, respectively; at 700 DEG CUnder the reaction conditions, the catalyst amount was 0.2g. The reaction was started after the gases were mixed well, with samples taken at 20min intervals (total reaction time 240 min). And measuring CH by using gas chromatograph FID, TCD and FPD 4 、CO 2 、H 2 S、H 2 And the concentration of CO, and the conversion rate thereof were calculated, and the results are shown in FIGS. 2-4 ((30-400-700), the initial catalytic activity of the catalyst was 90%, and the stability was optimal.
Example 4
A method for preparing a catalyst for low-carbon alkane reforming hydrogen production, which comprises the following steps:
(1) Screening the microsphere silica gel by using a 55-mesh sieve to ensure that the microsphere silica gel has uniform particle size; placing the screened microsphere silica gel into a nitric acid solution with the concentration of 34% to be soaked for 9.5 hours; washing the obtained microsphere silica gel with deionized water, drying in a 110 ℃ oven for 12h, roasting in a 550 ℃ muffle furnace for 3h, and naturally cooling to room temperature to obtain SiO 2 A carrier;
(2) 0.91g of Ni (NH) 3 ) 6 Cl 2 ·6H 2 O was dissolved in 3.5ml of deionized water, pH was adjusted to 10 with ammonia, and then 2g of SiO was added 2 The carrier is stirred for 5min, then ultrasonic is carried out at 45kHz for 10min, then the carrier is placed for 9.5h, then is put into a baking oven at 110 ℃ for drying for 12h, is put into a muffle furnace at 550 ℃ for baking for 3h, and is cooled to room temperature, thus obtaining the catalyst Ni/SiO 2 ;
(3) 0.46g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 3.5ml of deionized water, and then Ni/SiO obtained in (2) was added 2 Stirring for 5min, ultrasonic treating at 40kHz for 10min, standing for 8-10 hr, drying in 110 deg.C oven for 12 hr, roasting in 550 deg.C muffle furnace for 3 hr, and cooling to room temperature to obtain NiMo/SiO catalyst 2 。
The catalyst NiMo/SiO is prepared newly 2 The activation treatment is carried out, and comprises the following steps: niMo/SiO 2 Placed in a fixed bed reactor, continuously introducing 10% of H 2 Under Ar condition, heating from 30deg.C to 600deg.C for 30min for deep steady state reduction, then continuously heating to 700deg.C for 1h (10deg.C/min) for final reduction, and subjecting the material toXRD characterization, the result is shown in figure 1 (30-600-700), and the main components in the sample are Ni and Ni 3 Mo, with a small amount of Ni 3 Mo is present as compared to Ni of example 3 3 Mo and Ni 3 Mo has a poorer crystalline phase but still better crystalline phase than in example 2. .
The method for preparing hydrogen and carbon monoxide by catalytic reforming uses the obtained catalyst for the catalytic reforming of low-carbon alkane and carbon dioxide in sulfur-containing gas, and the reaction conditions are as follows: the total flow rate is 45cm 3 /min,CH 4 、CO 2 And H 2 S concentration was 30vol%, 30vol% and 100ppm, respectively; the catalyst was used in an amount of 0.4g at 700℃under reaction conditions. The reaction was started after the gases were mixed well, with samples taken at 20min intervals (total reaction time 240 min). And measuring CH with a gas chromatograph FID, TCD, FPD 4 、CO 2 、H 2 S、H 2 And the concentration of CO, and the conversion rate and the like are calculated, and the results are shown in the figures 2-4 (30-600-700), wherein the initial activity of the catalytic reaction of the catalyst is 87%, the reaction activity is reduced by half by 100 minutes, and the stability is improved slightly.
Example 5
A method for preparing a catalyst for low-carbon alkane reforming hydrogen production, which comprises the following steps:
(1) Screening the microsphere silica gel by using a 50-mesh sieve to ensure that the microsphere silica gel has uniform particle size; placing the screened microsphere silica gel into a nitric acid solution with the concentration of 34% to be soaked for 9 hours; washing the obtained microsphere silica gel with deionized water, drying in a 110 ℃ oven for 12h, roasting in a 550 ℃ muffle furnace for 3h, and naturally cooling to room temperature to obtain SiO 2 A carrier;
(2) 2.31g of Ni (NH) 3 ) 6 Cl 2 ·6H 2 O was dissolved in 3.5ml of deionized water, pH was adjusted to 10 with ammonia, and then 2g of SiO was added 2 The carrier is stirred for 5min, then ultrasonic is carried out at 45kHz for 10min, then the carrier is placed for 9.5h, then is put into a baking oven at 110 ℃ for drying for 12h, is put into a muffle furnace at 550 ℃ for baking for 3h, and is cooled to room temperature, thus obtaining the catalyst Ni/SiO 2 ;
(3) 0.5g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 3.5mlAdding the Ni/SiO obtained in the step (2) into ionized water 2 Stirring for 5min, ultrasonic treating at 40kHz for 10min, standing for 8-10 hr, drying in 110 deg.C oven for 12 hr, roasting in 550 deg.C muffle furnace for 3 hr, and cooling to room temperature to obtain NiMo/SiO catalyst 2 。
The catalyst NiMo/SiO is prepared newly 2 The activation treatment is carried out, and comprises the following steps: niMo/SiO 2 Placed in a fixed bed reactor, continuously introducing 10% of H 2 Under the Ar condition, the temperature is increased from 30 ℃ to 600 ℃ for 30min to carry out deep steady-state reduction, and then the temperature is continuously increased to 700 ℃ for 1h (10 ℃/min) to carry out final reduction.
The method for preparing hydrogen and carbon monoxide by catalytic reforming uses the obtained catalyst for the catalytic reforming of low-carbon alkane and carbon dioxide in sulfur-containing gas, and the reaction conditions are as follows: the total flow rate was 56cm 3 /min,C 2 H 6 、CO 2 And H 2 S concentration was 30vol%, 30vol% and 100ppm, respectively; the catalyst was used in an amount of 0.4g at 700℃under reaction conditions. The reaction was started after the gases were mixed well, with samples taken at 20min intervals (total reaction time 240 min). And measuring C with a gas chromatograph FID, TCD, FPD 2 H 6 、CO 2 、H 2 S、H 2 And the concentration of CO and calculate the conversion thereof, etc.
Example 6
A method for preparing a catalyst for low-carbon alkane reforming hydrogen production, which comprises the following steps:
(1) Screening the microsphere silica gel by using a 50-mesh sieve to ensure that the microsphere silica gel has uniform particle size; placing the screened microsphere silica gel into a nitric acid solution with the concentration of 34% to be soaked for 9 hours; washing the obtained microsphere silica gel with deionized water, drying in a 110 ℃ oven for 12h, roasting in a 550 ℃ muffle furnace for 3h, and naturally cooling to room temperature to obtain SiO 2 A carrier;
(2) 0.23g of Ni (NH) 3 ) 6 Cl 2 ·6H 2 O was dissolved in 3.5ml of deionized water, pH was adjusted to 10 with ammonia, and then 2g of SiO was added 2 The carrier is stirred for 5min, then is ultrasonically treated for 10min at 45kHz, then is placed for 9.5h and is put into a baking oven at 110 ℃ for dryingDrying for 12 hours, then placing the catalyst into a muffle furnace at 550 ℃ for roasting for 3 hours, and cooling to room temperature to obtain the catalyst Ni/SiO 2 ;
(3) 0.1g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 3.5ml of deionized water, and then Ni/SiO obtained in (2) was added 2 Stirring for 5min, ultrasonic treating at 40kHz for 10min, standing for 8-10 hr, drying in 110 deg.C oven for 12 hr, roasting in 550 deg.C muffle furnace for 3 hr, and cooling to room temperature to obtain NiMo/SiO catalyst 2 。
The catalyst NiMo/SiO is prepared newly 2 The activation treatment is carried out, and comprises the following steps: niMo/SiO 2 Placed in a fixed bed reactor, continuously introducing 10% of H 2 Under the Ar condition, the temperature is increased from 30 ℃ to 600 ℃ for 30min to carry out deep steady-state reduction, and then the temperature is continuously increased to 700 ℃ for 1h (10 ℃/min) to carry out final reduction.
The method for preparing hydrogen and carbon monoxide by catalytic reforming uses the obtained catalyst for the catalytic reforming of low-carbon alkane and carbon dioxide in sulfur-containing gas, and the reaction conditions are as follows: the total flow rate was 52cm 3 /min,C 3 H 8 、CO 2 And H 2 S concentration was 30vol%, 30vol% and 100ppm, respectively; the catalyst was used in an amount of 0.4g at 700℃under reaction conditions. The reaction was started after the gases were mixed well, with samples taken at 20min intervals (total reaction time 240 min). And measuring C with a gas chromatograph FID, TCD, FPD 3 H 8 、CO 2 、H 2 S、H 2 And the concentration of CO and calculate the conversion thereof, etc.
The invention can enhance the sulfur resistance of the catalyst; the treatment method is simple; has important energy and environmental protection significance; the catalyst is used for preparing hydrogen by reforming low-carbon alkane in a sulfur-containing atmosphere, and has the advantages of catalytic reforming of the low-carbon alkane and carbon dioxide in the sulfur-containing atmosphere, high conversion rate of the low-carbon alkane and the carbon dioxide up to more than 90%, high sulfur resistance, and good application prospect.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, i.e., the invention is not limited to the specific embodiments described herein, but is to be accorded the full scope of the claims.
Claims (7)
1. A method for preparing a catalyst for preparing hydrogen by reforming low-carbon alkane, which is characterized by comprising the following steps:
(1) According to 0.23178-2.3178g Ni (NH) 3 ) 6 Cl 2 ·6H 2 Ratio of O dissolved in 1-10ml deionized water to dissolve Ni (NH) 3 ) 6 Cl 2 ·6H 2 O is dissolved in deionized water, and ammonia water is used for adjusting the pH value to 9-11; adding 1-5g SiO 2 Stirring the carrier for 2-10min, and treating with ultrasonic wave with frequency of 40-60kHz for 5-15min; standing for 8-10h, drying in oven at 100-200deg.C for 8-12h, calcining in muffle furnace at 400-600deg.C for 1-3h, and cooling to room temperature to obtain Ni/SiO 2 ;
(2) According to 0.1-0.5g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 The ratio of O dissolved in 1-10ml deionized water will (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is dissolved in deionized water, and then Ni/SiO obtained in (1) is added 2 Stirring for 2-10min, ultrasonic treating at 40-60kHz for 10min, standing for 8-10 hr, drying in 100-200deg.C oven for 8-12 hr, roasting in 400-600deg.C muffle furnace for 1-3 hr, and cooling to room temperature to obtain NiMo/SiO catalyst 2 ;
(3) NiMo/SiO 2 The activation treatment is carried out, and comprises the following steps: niMo/SiO 2 Placed in a fixed bed reactor, continuously introducing 10% of H 2 Under the Ar condition, the temperature is increased from 30 ℃ to 300-600 ℃ for 30min to carry out deep steady state reduction, and then the temperature is continuously increased to 700 ℃ for 1-3h to carry out final reduction.
2. The method for preparing the catalyst for preparing hydrogen by reforming low-carbon alkane according to claim 1, comprising the following steps:
(1) 0.91g of Ni (NH) 3 ) 6 Cl 2 ·6H 2 O was dissolved in 3.5ml to be removedRegulating pH value to 9-11 with ammonia water in the sub water; 2g of SiO are added 2 Carrying out ultrasonic treatment for 10min after stirring for 5min; standing for 9h, drying in oven at 110deg.C for 10h, calcining in muffle furnace at 550deg.C for 3h, and cooling to room temperature to obtain Ni/SiO 2 ;
(2) 0.46g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O was dissolved in 3.5ml of deionized water, and then Ni/SiO obtained in (1) was added 2 Stirring for 5min, performing ultrasonic treatment for 10min, standing for 10h, drying in a 110 ℃ oven for 12h, roasting in a 550 ℃ muffle furnace for 3h, and cooling to room temperature to obtain the catalyst NiMo/SiO 2 。
3. The method for preparing a catalyst for reforming of light alkane to produce hydrogen according to claim 1 or 2, wherein the SiO 2 The preparation method of the carrier comprises soaking microsphere silica gel in acid solution for 8-10 hr; washing the soaked microsphere silica gel with deionized water, drying in a 100-200deg.C oven for 8-12h, roasting in a 400-600deg.C muffle furnace for 1-3h, and naturally cooling to room temperature.
4. A method for preparing a catalyst for the reformation of light alkane to produce hydrogen as claimed in claim 3, wherein the microsphere silica gel is screened using a 40-60 mesh screen.
5. A method for regenerating a catalyst for the reformation of light alkane to produce hydrogen, comprising the steps of: placing a catalyst prepared by a preparation method of the catalyst for preparing hydrogen by reforming light alkane as claimed in claim 4 in a fixed bed reactor, and continuously introducing 10% H 2 Under the Ar condition, the temperature is increased from 30 ℃ to 300-600 ℃ for 30min for deep steady reduction, and then the temperature is continuously increased to 700 ℃ for 1-3h.
6. The method for regenerating a catalyst for use in the reformation of lower alkane to produce hydrogen as claimed in claim 5, wherein the temperature is raised to a value of 10 ℃/min while continuing to raise the temperature to 700 ℃.
7. A method for preparing hydrogen and carbon monoxide by catalytic reforming, characterized in that the catalytic reforming reaction conditions of the catalyst prepared by the preparation method based on the catalyst for preparing hydrogen by reforming light alkane according to claim 4 comprise:
(1) The catalytic reforming temperature is 600-800 ℃;
(2) The flow rate of the reaction gas for catalytic reforming/the mass of the catalyst is 40-60 (cm) 3 ·min -1 )/0.2g;
(3) Reaction gas C x H 2x+2 、CO 2 And H 2 The concentration of S is: 10 to 49.9vol%,
10-49.9vol% and 10-1000ppm, wherein x is a natural number less than 4.
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