CN106000405A - Hierarchical porous supported nickel-based catalyst, preparation method and application - Google Patents
Hierarchical porous supported nickel-based catalyst, preparation method and application Download PDFInfo
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- CN106000405A CN106000405A CN201610316509.6A CN201610316509A CN106000405A CN 106000405 A CN106000405 A CN 106000405A CN 201610316509 A CN201610316509 A CN 201610316509A CN 106000405 A CN106000405 A CN 106000405A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 238000006057 reforming reaction Methods 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 68
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 238000011068 loading method Methods 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- 239000001569 carbon dioxide Substances 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 229910052756 noble gas Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 9
- 239000004480 active ingredient Substances 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 14
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 13
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 13
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000003570 air Substances 0.000 description 10
- 239000003345 natural gas Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013528 metallic particle Substances 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 108091006231 SLC7A2 Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical compound [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- -1 titanium dioxide Carbon methane Chemical compound 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/40—
-
- B01J35/615—
-
- B01J35/647—
-
- B01J35/657—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- 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
-
- 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
Abstract
The invention discloses a hierarchical porous supported nickel-based catalyst, a preparation method and application of the catalyst to a carbon dioxide methane reforming reaction. The hierarchical porous supported nickel-based catalyst is prepared from a carrier and an active ingredient dispersed on the carrier. The catalyst is characterized in that the carrier is selected from at least one of inorganic oxides and contains macropore with the average pore size larger than 50 nm and mesopore with the average pore size of 1 nm-50 nm, and nickel is adopted as the active ingredient. The hierarchical porous supported nickel-based catalyst is used for the carbon dioxide methane reforming reaction, has the excellent sintering resistance and carbon deposition resistance and has the important realistic significance on promoting industrialization of the carbon dioxide methane reforming reaction.
Description
Technical field
The application relates to a kind of multi-stage porous loading type nickel-based catalyst, preparation method and at carbon dioxide
Application in methane reforming reaction, belongs to petrochemical industry.
Background technology
Coal, oil and natural gas are three macrofossil energy resources.Rich coal resources in China, but closely
A little year coal mining and increasingly severe to the pollution of air, soil and groundwater during utilizing, limit
Make it to use in a large number.And China's oil reserves are few, it is necessary to rely on import, cause oil use cost
Higher.In recent years, along with China's shale gas ore reserves leaps into the front ranks of the world, the exploitation of natural gas
Increasingly being paid attention to, country has put into effect relevant policies and has encouraged the comprehensive high-efficiency of natural gas to utilize, natural gas
Efficiently utilize and rise to national strategy level.Natural gas is in addition to can be directly as fuel, and it is main
Wanting components methane can be the chemical products with high added value via synthesis gas Efficient Conversion, as produced
The ammonia of large-tonnage demand, methanol, it is possible to produce the intermediate of the liquid fuel such as alkene, aromatic hydrocarbons.
The method that current industrial production synthesis gas mainly uses natural gas to be raw material, mainly includes natural
Gas partial oxidation process and steam reforming.Gas by partial oxidation of natural method is a kind of method comparing power consumption,
Need to consume a large amount of oxygen or air as unstripped gas.If not using catalyst, reaction temperature is up to
1300～1400 DEG C.Even if use catalyst, catalytic bed temperature high about 900～1000 DEG C and
Reaction needs to carry out at high pressure (3.0MPa), and the high-temperature-resistant high-pressure-resistant of equipment is required harshness.Natural
In gas intermittent conversion steaming process, course of reaction maximum temperature is up to 1300 DEG C, and process consumes energy very much.Continuously
Although it is relatively low that steam converts observable index, but still the requirement to equipment high temperature high voltage resistant is higher.And not
Pipe is intermittent conversion or converts continuously, the corrosion meeting to equipment under the high temperature conditions of unstripped gas steam
Have influence on the service life of equipment, increase process costs.Generally there is reaction in these technical matters routes
Temperature is high, it is high to consume energy, the resistance to vapor corrosion of high-temperature-resistant high-pressure-resistant to equipment requires that the technology such as harshness are asked
Topic.Therefore, the commercial production of synthesis gas is had great importance by the production of exploitation anhydrous and oxygen-free technique.
In addition to methane steam reformation, methane portion oxidation, methane carbon dioxide reformation is nearer next
The synthesis gas production technology approach gradually received publicity.The advantage of methane carbon dioxide reformation route is such as
Under: (1) methane and carbon dioxide dry reforming process is without oxygen and water, relatively low to equipment requirements.(2)
H2/CO ratio is adjustable, is more suitable for follow-up F-T synthesis material rate；Reaction can be at 650 DEG C with enterprising
OK, energy consumption is relatively low.(3) feed carbon dioxide wide material sources, compare oxygen cheap.This technique
Process achieves carbon dioxide discharge-reduction while efficiently utilizing methane, have significant economic benefit and
Environmental benefit.How the end product that carbon dioxide is coal and downstream product efficiently utilizes, realize
The regeneration of carbon dioxide, turn waste into wealth be during Coal Clean efficiently utilizes very important content it
One.This process advan, in reducing the total amount of carbon dioxide in air, alleviates the environment that greenhouse gases cause
Pressure, reduces discharging for China and provides a kind of effective method.
Making inert methane and carbon dioxide molecule activation and be oriented conversion, exploitation has high living
Property, the low cost catalyst of high selectivity, high stability be crucial.Reforming methane with carbon dioxide is catalyzed
The active component of agent is mainly VIII group 4 transition metal, is divided into noble metal catalyst and non-precious metal catalyst
Two classes.Low and the expensive large-scale industrial application that is not suitable for of noble metal reserves, and measure the most inexpensive non-
Noble metal then has obvious cost advantage.Especially nickel-base catalyst be considered as industrial catalyst
Good candidate, widely studied by academia and industrial quarters for many years.Although nickel-base catalyst is in titanium dioxide
Carbon reforming methane generally has higher catalysis activity and selectivity, but the most easily burns
Knot, carbon deposit and inactivate, always hinder this chemical industry route to realize industrialized key technology bottleneck.Cause
This, develop the nickel-base catalyst of anti-carbon deposit and resistance to sintering to advancing the reaction of carbon dioxide methane dry reforming
Process of industrialization, it is achieved Resources of Carbon Dioxide utilizes has great environmental protection effect and economic benefit.
Mesoporous material is the catalyst carrier that in catalytic reaction, a class is important, and duct " interface confinement " imitates
Should contribute to preventing metallic particles from the migration of carrier surface and growing up, effectively improve Industrial Catalysis
The service life of agent.On the one hand, metal active centres is positioned at inside mesopore orbit, nano level duct
Provide limited space metallic particles, and limit its further agglomeration, prevent catalyst
Sinter and inactivate.On the other hand, porous material is generally of high-specific surface area, substantial amounts of Metal-Support
Interface is conducive to strengthening Metal-Support and interacts, and then increases the stability of metallic particles.But,
The duct of tradition mesoporous supports is the longest, makes duct internal resistance become big, will be unfavorable for that gas is in duct
Diffusion and mass transfer, cause formation of carbon.Chinese patent (CN104248959A) uses order mesoporous
Silicon dioxide is carrier, is prepared for the nickel-base catalyst of neodymium doping by the infusion process of cyclo-dextrin-modified,
In the long-time evaluation of methane reforming reaction by using carbon dioxide, stability is on a declining curve.Some documents are also
The nickel-base catalyst reporting mesoporous material load has preferable stability, although can be in the long period
The carbon dioxide inside kept relative stability and the conversion ratio of methane；But the transmission after reaction a period of time
Electronic Speculum or TPO result display catalyst form obvious carbon deposit, will badly influence catalyst longer
Application (the ACS Catal.2012,2:1331-1342 of time；Energy&Environment Science
2010,3:366-369；International Journal of Hydrogen energy 2012,37:
1454-14764).More than 700 DEG C carbon deposits are mainly derived from reducing side reaction of methane.Long-pending to eliminate
Charcoal, it is thus achieved that long life catalytic agent, it is necessary to improve the structure of porous carrier, improves gas and expands
Dissipating and mass transfer rate, the O* that the C* making methane decompose generation is produced by carbon dioxide decomposition in time reacts
Fall.
Therefore, the porous carrier of novel structure is developed, it is thus achieved that have excellent resistance to sintering and coking resistivity concurrently
Supported Nickel Catalyst, to promote methane reforming reaction by using carbon dioxide industrialization there is important showing
Sincere justice.
Summary of the invention
An aspect according to the application, it is provided that a kind of multi-stage porous loading type nickel-based catalyst, to solve
Existing loading type nickel-based catalyst easy-sintering and carbon deposit and problem of inactivating in pyroreaction.
Described multi-stage porous loading type nickel-based catalyst, including carrier and active group be dispersed on carrier
Point, it is characterised in that at least one in inorganic oxide of described carrier, described carrier comprises
Macropore and mesoporous；Described active component is nickel.
Described carrier comprises the mesoporous and two distinct types of pore passage structure of macropore.Compared to single
Tradition mesoporous supports, the mesopore orbit of this carrier contributes to the granule of fixing metal active constituent, can have
Effect metallic particles is avoided to sinter because of migration in catalytic reaction process.Macropore duct can be improved
The diffusion of medium and transfer rate, stop the formation of carbon deposit effectively.The cooperative effect of multiple hole can be same
Time solve high temperature sintering and carbon-collecting problem, extend catalyst life.Therefore, be provided simultaneously with mesoporous and big
The inorganic oxide of hole pore passage structure, all can be as the loading type nickel-based catalysis of herein described multi-stage porous
Carrier in agent, reaches to solve high temperature sintering and carbon-collecting problem, extends the effect of catalyst life.Excellent
Selection of land, at least one in described support selected from alumina, silicon oxide, titanium oxide, zirconium oxide.
Preferably, the average pore size of the macropore in described carrier is more than 50nm, mesoporous average pore size
For 1nm～50nm.It is further preferred that the average pore size of described macropore is 1 μm～2 μm；Given an account of
The average pore size in hole is 5nm～15nm.Preferably, the specific surface area of described carrier is 100m2/ g～350
m2/g。
The narrow diameter distribution of described active component nickel, is highly dispersed to be distributed in multi-stage porous carrier.Excellent
Selection of land, described in the particle diameter of active component nickel that is dispersed on carrier for being distributed between 5～100nm.Enter
One step preferably, described in the particle size range upper limit of active component nickel that is dispersed on carrier selected from 30nm,
35nm, 40nm, 45nm, 50nm, lower limit is selected from 5nm, 10nm, 15nm.The most excellent
Selection of land, described in the particle diameter of active component nickel that is dispersed on carrier be distributed between 10～30nm.
Described active component nickel weight/mass percentage composition in multi-stage porous loading type nickel-based catalyst is
2%～10%；Described active component nickel weight/mass percentage composition in multi-stage porous loading type nickel-based catalyst
In terms of the nickel element contained in multi-stage porous loading type nickel-based catalyst.Preferably, described active component nickel
The weight/mass percentage composition upper limit in multi-stage porous loading type nickel-based catalyst selected from 10%, 9%, 8%,
7%, 6%, 5%, 4.6%, 4.5%, 4.4%, lower limit is selected from 2%, 3%, 3.55%, 4%, 4.3%.
It is further preferred that the percent mass that described active component nickel is in multi-stage porous loading type nickel-based catalyst
Content is 3%～6%；Described active component nickel quality hundred in multi-stage porous loading type nickel-based catalyst
Divide content in terms of the nickel element contained in multi-stage porous loading type nickel-based catalyst.
Another aspect according to the application, it is provided that the preparation side of above-mentioned multi-stage porous loading type nickel-based catalyst
Method.Described method uses the ultrasonic assistant soakage-reducing process of improvement, with traditional impregnation-reduction method phase
Ratio, introduces ultrasonic link, is more beneficial for the dissolving of nickel compound containing and nickel element at multi-stage porous carrier hole
Diffusion in road, strengthens load efficiency and Metal-Support interacts.Before hydrogen reducing, catalyst
Roasting a period of time in air atmosphere, enhance the interaction between nickel and carrier.
The preparation method of any of the above-described multi-stage porous loading type nickel-based catalyst, it is characterised in that at least wrap
Include following steps:
A) carrier is placed in the solution containing nickel element, carries out ultrasonic immersing；
B) step a) gained solid is separated, vacuum drying, in air after roasting and hydrogen reducing,
Obtain described multi-stage porous loading type nickel-based catalyst.
Preferably, ultrasonic immersing described in step a) is that batch (-type) is ultrasonic, and total dip time is 24 little
Time～96 hours, the ultrasonic cumulative time is 2 hours～10 hours.It is further preferred that in step a)
Described ultrasonic immersing is that batch (-type) is ultrasonic, and total dip time is 36 hours～60 hours, ultrasonic accumulative time
Between be 2 hours～6 hours.It is further preferred that ultrasonic immersing is batch (-type) described in step a)
Ultrasonic, total dip time is 48 hours, and the ultrasonic cumulative time is 4 hours.
Those skilled in the art can select the supersonic frequency that batch (-type) is ultrasonic according to actual needs.Preferably
Ground, described supersonic frequency is 20KHz～100Hz.
The solution containing nickel element described in step a) is dissolved by nickel compound containing and obtains in a solvent.
Preferably, described nickel compound containing is in nickel acetate, nickel nitrate, nickel sulfate, nickel acetylacetonate
At least one；At least one in water, ethanol, acetone of described solvent.
Those skilled in the art can select suitably leaching according to specifically needing the amount of nickel-loaded on catalyst
Stain ratio and nickel element concentration.Nickel element concentration in solution containing nickel element can be at 0.01mol/L
Select between saturated solution.Preferably, the nickel element concentration in the described solution containing nickel element is
0.1mol/L～1mol/L.It is further preferred that the nickel element concentration in the described solution containing nickel element
For 0.25mol/L～0.75mol/L.Preferably, the consumption of the solution containing nickel element just floods carrier.
As a kind of embodiment, step b) described vacuum drying temperature is 60 DEG C～200 DEG C.Preferably
Ground, the described vacuum drying of step b) is to be vacuum dried 8 hours～10 hours at 60 DEG C～100 DEG C.
It is further preferred that the described vacuum drying of step b) is to be vacuum dried 8 hours at 60 DEG C～100 DEG C
～10 hours.It is further preferred that the described vacuum drying of step b) is to be vacuum dried at 80 DEG C
8 hours～10 hours.
As a kind of embodiment, in the described air of step b), roasting is with 1 DEG C/min～10 DEG C/min
Heating rate temperature is risen to a certain temperature between 300 DEG C～800 DEG C from room temperature, roasting be no less than 1
Hour.Preferably, in the described air of step b), roasting is the intensification speed with 1 DEG C/min～5 DEG C/min
Temperature is risen to a certain temperature between 500 DEG C～700 DEG C, roasting 2 hours～4 hours from room temperature by rate.Enter
One step preferably, in the described air of step b) roasting be the heating rate with 1 DEG C/min by temperature from
Room temperature rises to 600 DEG C, roasting 2 hours～4 hours.
As a kind of embodiment, hydrogen reducing described in step b) is with 5 DEG C/min～20 DEG C/min
Heating rate temperature is risen to a certain temperature between 600 DEG C～1000 DEG C from room temperature, at hydrogen or hydrogen
With reduction in the mixture of non-active gas no less than 1 hour；Hydrogen or hydrogen and non-active gas
The flow velocity of mixture is 20mL/min～80mL/min.Preferably, hydrogen reducing described in step b)
It is that temperature is risen between 800 DEG C～1000 DEG C by the heating rate with 5 DEG C/min～15 DEG C/min from room temperature
A certain temperature, in hydrogen, reduction was no less than 1 hour～2 hours；The flow velocity of hydrogen is
20mL/min～40mL/min.It is further preferred that hydrogen reducing described in step b) is with 10 DEG C
Temperature is risen to 900 DEG C from room temperature by the heating rate of/min, and in hydrogen, reduction was no less than 1 hour～2
Hour；The flow velocity of hydrogen is 20mL/min～40mL/min.Described non-active gas is selected from nitrogen, lazy
At least one in property gas.
Another aspect according to the application, it is provided that above-mentioned multi-stage porous loading type nickel-based catalyst is in titanium dioxide
Application in carbon methane reforming reaction, the most above-mentioned multi-stage porous loading type nickel-based catalyst is used for carbon dioxide
The method of methane reforming reaction preparing synthetic gas.Described multi-stage porous loading type nickel-based catalyst is used for titanium dioxide
Carbon methane reforming reaction does not occur sintering and carbon deposit, shows the high-temperature stability of excellence, can be used for
Manufacture synthesis gas, it is achieved carbon dioxide discharge-reduction and regeneration.
The method of described carbon dioxide methane reforming reaction preparing synthetic gas, it is characterised in that described contain
The raw material of methane and carbon dioxide contacts with catalyst, prepares synthesis gas；
Described catalyst any of the above-described multi-stage porous loading type nickel-based catalyst, according to any of the above-described method system
At least one in the standby multi-stage porous loading type nickel-based catalyst obtained.
Preferably, the described raw material containing methane and carbon dioxide reaction temperature 600 DEG C～850 DEG C,
Contact with described catalyst under conditions of reaction pressure 0.1MPa～0.5MPa, prepare synthesis gas；
In described unstripped gas, the molar ratio of methane and carbon dioxide is:
Methane: carbon dioxide=0.5～2.
Preferably, described carbon dioxide methane reforming reaction preparing synthetic gas is in using fixed bed reactors
Carry out.
The beneficial effect of the application includes but not limited to:
(1) multi-stage porous loading type nickel-based catalyst provided herein, with conventional mesoporous supports phase
Ratio, uses the carrier with multistage pore canal；Multi-stage porous carrier introduces macropore duct, adds medium
Diffusion and mass transfer rate.The cooperative effect of multi-stage porous makes herein described catalyst at high-temperature catalytic
Reaction has good anti-sintering and coking resistivity simultaneously.
(2) method for preparing catalyst provided herein, the ultrasonic assistant soakage of employing improvement-also
Former method.Compared with traditional impregnation-reduction method, introduce ultrasonic link, be more beneficial for nickel salt dissolving and
Nickel element diffusion in multi-stage porous carrier duct, strengthens load efficiency and Metal-Support interacts.
Before hydrogen reducing, catalyst is roasting a period of time in air atmosphere, enhances between ion and carrier
Interaction.
(3) the multi-stage porous loading type nickel-based catalyst that the application provides, as CO 2 reformation first
The high-temperature stable catalyst of alkane reaction, can manufacture synthesis gas, it is achieved carbon dioxide discharge-reduction and regeneration.
Under normal pressure, 800 DEG C of reaction conditions, the nickel-base catalyst of multi-stage porous alumina load has excellence concurrently
Anti-carbon deposit and sintering resistance energy, catalyst life is long, in 100 hours response time, carbon dioxide and
The conversion ratio of methane remains unchanged substantially.
Accompanying drawing explanation
Fig. 1 is that the scanning electron microscope of the carrier multi-stage porous aluminum oxide micro-sphere section employed in embodiment 1 shines
Sheet；A () is the stereoscan photograph of amplification 1100 times；B () is the scanning electricity of amplification 35000 times
Mirror figure.
Fig. 2 be in embodiment 2 sample CAT-1 for the chromatograph of methane reforming reaction by using carbon dioxide product
Testing result；A () is the result of thermal conductivity detector (TCD) TCD；B () is flame ionization detector FID
Result.
Fig. 3 is the stability test result of embodiment 3 sample CAT-1.
Fig. 4 is the transmission electron microscope photo before and after embodiment 3 sample CAT-1 reaction；A () is reaction before
The transmission electron microscope photo of sample CAT-1；B () is that sample CAT-1 is after 800 DEG C of reactions 102 hours
Transmission electron microscope photo.
Detailed description of the invention
Below in conjunction with embodiment in detail the application is described in detail, but the application is not limited to these embodiments.
Unless specifically stated otherwise, reagent used in the present embodiment and raw material all can be purchased by commercial sources
Buy.
In embodiment, the stereoscan photograph of sample uses FDAC S4800 type scanning electron microscopy
Mirror gathers；The transmission electron microscope photo of sample gathers on the F20 type transmission electron microscope of FEI Co..
In embodiment, carrier multi-stage porous aluminum oxide micro-sphere is from husky rope (Sasol) company, specific surface area
For 197.91m2/g；Macropore average pore size is 1.52 μm；Mesoporous average pore size is 9.80nm.Multistage
The stereoscan photograph of porous aluminum oxide microsphere section is as shown in Figure 1, it can be seen that multi-stage porous aluminium oxide
There are macropore and mesoporous two kinds of different ducts.
In embodiment, the Ultrasound Instrument used in ultrasonic immersing is that Kunshan Ultrasonic Instruments Co., Ltd. produces
KQ300ED type.
In embodiment, on catalyst, load capacity using plasma emission spectrum (ICP) of nickel is in method
Analyze on the Ultima 2 type instrument of HORIBA JY company of state and measure.
In embodiment, the product of carbon dioxide methane reforming reaction preparing synthetic gas detects in Shimadzu
Carry out on GC-2014 type chromatograph (TDX-01 post).
The preparation of embodiment 1 catalyst sample CAT-1～CAT-11 and sign
Take a certain amount of nickel salt and be dissolved in wiring solution-forming in 10ml ethanol, add 5g multi-stage porous aluminium oxide,
After ultrasonic immersing a period of time, it is filtered to remove solvent and unnecessary unabsorbed nickel salt.Nickel will have been adsorbed
After the aluminium oxide of ion is vacuum dried 8h at 80 DEG C, roasting in air atmosphere, last hydrogen reducing, obtains
Obtain described multi-stage porous loading type nickel-based catalyst.
ICP is used to measure the nickel content on described multi-stage porous loading type nickel-based catalyst.Employing transmission is swept
Retouch the particle size range of nickel granule on electron microscopic observation multi-stage porous loading type nickel-based catalyst.
Sample number into spectrum and specific experiment parameter, nickel element matter in multi-stage porous loading type nickel-based catalyst
The relation of the particle size range measuring percentage composition, nickel granule refers to table 1.
Table 1
Embodiment 2 catalyst reaction evaluation
Take 0.2g catalyst sample CAT-1 to be placed in the fixed bed reactors of internal diameter 1cm, carry out hydrogen
After gas reduces online, temperature is adjusted to reaction temperature.Gas is switched to CO2And CH4Gaseous mixture,
N2For internal standard.After reaction, gas enters each material concentration of gas chromatographic detection after cooling, calculates CO2
And CH4Conversion ratio.
Reaction condition and CO2And CH4The relation of conversion ratio is as shown in table 2.
When reaction condition is A, the chromatograph testing result of reaction end gas is as shown in Figure 2.Can be seen by figure
Going out, multi-stage porous loading type nickel-based catalyst provided herein has good selectivity, base in product
This is the main component of synthesis gas: hydrogen and carbon monoxide.
Table 2
CO2And CH4Conversion ratio use following equation to calculate respectively:
F in formulaCO2,inAnd FCO2,outIt is CO in unstripped gas and reaction end gas2Volume integral flow；FCH4, inAnd FCH4,outIt is CH in reactant and product respectively4Volume integral flow.
Under same reaction conditions, the reaction result of catalyst sample CAT-2～CAT-11 and CAT-1 class
Seemingly, according to the difference of method for preparing catalyst, CO2And CH4Conversion ratio become in the range of ± 10%
Change.
Embodiment 3 catalyst stability evaluation
Take 0.2g catalyst sample CAT-1 to be placed in the fixed bed reactors of internal diameter 1cm, implementing
Under the reaction condition A of example 2, carrying out catalyst stability evaluation, result is as shown in Figure 3.By Fig. 3
It can be seen that multi-stage porous loading type nickel-based catalyst provided herein, in normal pressure, 800 DEG C of reactions
Under the conditions of, there is the stability of excellence, in 100 hours response time, turning of carbon dioxide and methane
Rate remains unchanged substantially.
Transmission electron microscope photo before and after catalyst sample CAT-1 reaction is as shown in Figure 4.Fig. 4 (a) is
The transmission electron microscope photo of sample CAT-1 before reaction；Fig. 4 (b) is that sample CAT-1 is 800 DEG C of reactions
Transmission electron microscope photo after 102 hours.As seen from the figure, the active component nickel on catalyst sample
Granule before the reaction after be substantially not changed in, do not sinter；And at 102 hours catalytic reactions
Without formation of carbon in agent.
Under same reaction conditions, the catalyst stability evaluation knot of catalyst sample CAT-2～CAT-11
Fruit is similar with CAT-1, and in 100 hours response time, the conversion ratio of carbon dioxide and methane is tieed up substantially
Hold constant.Sample CAT-2～CAT-11 800 DEG C reaction 102 hours after transmission electron microscope photo with
Comparing result before reaction, similar with CAT-1, nickel granule does not sinter, without long-pending in catalyst
Charcoal is formed.
The above, be only several embodiments of the application, and the application not does any type of limit
System, although the application with preferred embodiment disclose as above, but and be not used to limit the application, any
Those skilled in the art, in the range of without departing from technical scheme, utilize above-mentioned taking off
The technology contents shown makes a little variation or modification is all equal to equivalence case study on implementation, belongs to technology
In aspects.
Claims (10)
1. a multi-stage porous loading type nickel-based catalyst, including carrier and the activity being dispersed on carrier
Component, it is characterised in that at least one in inorganic oxide of described carrier, described carrier bag
Containing macropore and mesoporous；Described active component is nickel.
Multi-stage porous loading type nickel-based catalyst the most according to claim 1, it is characterised in that
The average pore size of described macropore is more than 50nm, and described mesoporous average pore size is 1nm～50nm；
Preferably, the average pore size of described macropore is 1 μm～2 μm；
Preferably, described mesoporous average pore size is 5nm～15nm.
Multi-stage porous loading type nickel-based catalyst the most according to claim 1, it is characterised in that
The specific surface area of described carrier is 100m2/ g～350m2/g。
Multi-stage porous loading type nickel-based catalyst the most according to claim 1, it is characterised in that
The particle diameter of the described active component nickel being dispersed on carrier is for being distributed between 5～100nm；Preferably,
The particle diameter of the described active component nickel being dispersed on carrier is for being distributed between 10～30nm.
Multi-stage porous loading type nickel-based catalyst the most according to claim 1, it is characterised in that
Described active component nickel weight/mass percentage composition in multi-stage porous loading type nickel-based catalyst is
2%～10%；
Preferably, described active component nickel percent mass in multi-stage porous loading type nickel-based catalyst contains
Amount is 3%～6%；
Described active component nickel weight/mass percentage composition in multi-stage porous loading type nickel-based catalyst is with many
The nickel element meter contained in the loading type nickel-based catalyst of level hole.
6. the preparation side of the multi-stage porous loading type nickel-based catalyst described in any one of claim 1 to 5
Method, it is characterised in that at least comprise the following steps:
A) carrier is placed in the solution containing nickel element, carries out ultrasonic immersing；
B) step a) gained solid is separated, vacuum drying, in air after roasting and hydrogen reducing,
Obtain described multi-stage porous loading type nickel-based catalyst.
Method the most according to claim 6, it is characterised in that ultrasonic leaching described in step a)
Stain is that batch (-type) is ultrasonic, and total dip time is 24 hours～96 hours, and the ultrasonic cumulative time is 2 hours
～10 hours；
Preferably, ultrasonic immersing described in step a) is that batch (-type) is ultrasonic, and total dip time is 36 little
Time～60 hours, the ultrasonic cumulative time is 2 hours～6 hours.
Method the most according to claim 6, it is characterised in that the described vacuum drying of step b)
Temperature is 60 DEG C～200 DEG C；Preferably, the described vacuum drying of step b) is true at 60 DEG C～100 DEG C
Empty dry 8 hours～10 hours；
In the described air of step b) roasting be the heating rate with 1 DEG C/min～10 DEG C/min by temperature from
Room temperature rises to a certain temperature between 300 DEG C～800 DEG C, and roasting is no less than 1 hour；Preferably, step
B) in described air, roasting is temperature to be risen to from room temperature with the heating rate of 1 DEG C/min～5 DEG C/min
A certain temperature between 500 DEG C～700 DEG C, roasting 2 hours～4 hours；
Hydrogen reducing described in step b) be the heating rate with 5 DEG C/min～20 DEG C/min by temperature from
Room temperature rises to a certain temperature between 600 DEG C～1000 DEG C, in the mixing of hydrogen or hydrogen with non-active gas
In thing, reduction was no less than 1 hour；Hydrogen or hydrogen with the flow velocity of the mixture of non-active gas are
20mL/min～80mL/min；Preferably, hydrogen reducing described in step b) is with 5 DEG C/min～15 DEG C
Temperature is risen to a certain temperature between 800 DEG C～1000 DEG C from room temperature by the heating rate of/min, at hydrogen
Middle reduction is no less than 1 hour～2 hours；The flow velocity of hydrogen is 20mL/min～40mL/min；Described
At least one in nitrogen, noble gas of non-active gas.
9. the method for carbon dioxide methane reforming reaction preparing synthetic gas, it is characterised in that described contain
The raw material of methane and carbon dioxide contacts with catalyst, prepares synthesis gas；
Described catalyst is selected from the loading type nickel-based catalysis of multi-stage porous described in any one of claim 1 to 5
Agent, the multi-stage porous prepared according to method described in any one of claim 6 to 9 is loading type nickel-based urges
At least one in agent.
10. the method for carbon dioxide methane reforming reaction preparing synthetic gas, it is characterised in that described contain
The raw material of methane and carbon dioxide is in reaction temperature 600 DEG C～850 DEG C, reaction pressure 0.1MPa
～contact with described catalyst under conditions of 0.5MPa, prepare synthesis gas；
In described unstripped gas, the molar ratio of methane and carbon dioxide is:
Methane: carbon dioxide=0.5～2.
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| EP17795314.8A EP3456411A4 (en) | 2016-05-12 | 2017-03-15 | Catalyst, preparation method therefor and application thereof in preparation of syngas |
| PCT/CN2017/076793 WO2017193696A1 (en) | 2016-05-12 | 2017-03-15 | Catalyst, preparation method therefor and application thereof in preparation of syngas |
| US16/300,120 US11104575B2 (en) | 2016-05-12 | 2017-03-15 | Nanocatalysts, preparation methods and applications for reforming carbon dioxide and methane to syngas |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106799263A (en) * | 2017-03-03 | 2017-06-06 | 中国科学院上海高等研究院 | A kind of high intensity multistage pore catalyst for methane tri-reforming and preparation method thereof |
| CN106807375A (en) * | 2017-01-24 | 2017-06-09 | 中国科学院福建物质结构研究所 | A kind of catalyst, its preparation method and application |
| WO2017193696A1 (en) * | 2016-05-12 | 2017-11-16 | 中国科学院福建物质结构研究所 | Catalyst, preparation method therefor and application thereof in preparation of syngas |
| CN107626314A (en) * | 2017-10-18 | 2018-01-26 | 太原理工大学 | A kind of preparation method of the mesoporous Ni-based methanation catalyst of rule |
| CN109663593A (en) * | 2019-01-14 | 2019-04-23 | 宁夏大学 | A kind of diplopore nickel-base catalyst and preparation method thereof and the application in methane reforming with carbon dioxide |
| CN110252363A (en) * | 2019-06-25 | 2019-09-20 | 北京三聚环保新材料股份有限公司 | A kind of Ni-based methanation catalyst and preparation method thereof and application |
| CN112246245A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | Supported nickel-based catalyst and preparation method and application thereof |
| CN113368859A (en) * | 2021-04-16 | 2021-09-10 | 华南理工大学 | Nickel-zirconium co-doped mesoporous silica material and preparation method and application thereof |
| CN114570372A (en) * | 2022-03-29 | 2022-06-03 | 中国石油大学(华东) | Methane carbon dioxide dry reforming nickel-based catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450310A (en) * | 2007-12-07 | 2009-06-10 | 上海焦化有限公司 | Synthetic gas preparation catalyst through reforming natural gas and carbon dioxide |
| CN102380394A (en) * | 2010-08-31 | 2012-03-21 | 中国石油化工股份有限公司 | Catalyst for producing synthesis gas by reforming natural gas and carbon dioxide and preparation method thereof |
| CN103058138A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of synthesis gas |
| CN103706374A (en) * | 2013-12-30 | 2014-04-09 | 国家安全生产监督管理总局信息研究院 | Integrated methane oxidation catalyst for ventilation gas and preparation method of catalyst |
| CN104707614A (en) * | 2015-02-13 | 2015-06-17 | 上海交通大学 | Nickel/gamma-aluminum oxide nano catalyst and synthesis method thereof |
-
2016
- 2016-05-12 CN CN201610316509.6A patent/CN106000405B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450310A (en) * | 2007-12-07 | 2009-06-10 | 上海焦化有限公司 | Synthetic gas preparation catalyst through reforming natural gas and carbon dioxide |
| CN102380394A (en) * | 2010-08-31 | 2012-03-21 | 中国石油化工股份有限公司 | Catalyst for producing synthesis gas by reforming natural gas and carbon dioxide and preparation method thereof |
| CN103058138A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of synthesis gas |
| CN103706374A (en) * | 2013-12-30 | 2014-04-09 | 国家安全生产监督管理总局信息研究院 | Integrated methane oxidation catalyst for ventilation gas and preparation method of catalyst |
| CN104707614A (en) * | 2015-02-13 | 2015-06-17 | 上海交通大学 | Nickel/gamma-aluminum oxide nano catalyst and synthesis method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 李凝等: "Ni/ZrO2/Al2O3催化剂在CO2重整CH4反应中催化性能研究", 《化工技术与开发》 * |
| 杨华明: "《无机功能材料》", 31 May 2007, 化学工业出版社 * |
| 纪敏等: "Ni/γ-Al2O3,Ni/MgO,Ni/SiO2催化剂上甲烷与二氧化碳重整反应的研究", 《分子催化》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| US11104575B2 (en) | 2016-05-12 | 2021-08-31 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Science | Nanocatalysts, preparation methods and applications for reforming carbon dioxide and methane to syngas |
| CN106807375A (en) * | 2017-01-24 | 2017-06-09 | 中国科学院福建物质结构研究所 | A kind of catalyst, its preparation method and application |
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| CN107626314A (en) * | 2017-10-18 | 2018-01-26 | 太原理工大学 | A kind of preparation method of the mesoporous Ni-based methanation catalyst of rule |
| CN109663593A (en) * | 2019-01-14 | 2019-04-23 | 宁夏大学 | A kind of diplopore nickel-base catalyst and preparation method thereof and the application in methane reforming with carbon dioxide |
| CN109663593B (en) * | 2019-01-14 | 2021-03-30 | 宁夏大学 | Double-hole nickel-based catalyst, preparation method thereof and application thereof in methane and carbon dioxide reforming reaction |
| CN110252363A (en) * | 2019-06-25 | 2019-09-20 | 北京三聚环保新材料股份有限公司 | A kind of Ni-based methanation catalyst and preparation method thereof and application |
| CN112246245A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | Supported nickel-based catalyst and preparation method and application thereof |
| CN113368859A (en) * | 2021-04-16 | 2021-09-10 | 华南理工大学 | Nickel-zirconium co-doped mesoporous silica material and preparation method and application thereof |
| CN114570372A (en) * | 2022-03-29 | 2022-06-03 | 中国石油大学(华东) | Methane carbon dioxide dry reforming nickel-based catalyst and preparation method and application thereof |
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