CN102151570A - Methane-carbon dioxide reforming reactive catalyst and preparation method thereof - Google Patents
Methane-carbon dioxide reforming reactive catalyst and preparation method thereof Download PDFInfo
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- CN102151570A CN102151570A CN2011100482833A CN201110048283A CN102151570A CN 102151570 A CN102151570 A CN 102151570A CN 2011100482833 A CN2011100482833 A CN 2011100482833A CN 201110048283 A CN201110048283 A CN 201110048283A CN 102151570 A CN102151570 A CN 102151570A
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- oxide
- methane
- metal oxides
- nitrate
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 title abstract 3
- 238000002407 reforming Methods 0.000 title abstract 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 36
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- 238000006057 reforming reaction Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002114 nanocomposite Substances 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 230000029087 digestion Effects 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012702 metal oxide precursor Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 235000011147 magnesium chloride Nutrition 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 2
- 229910001630 radium chloride Inorganic materials 0.000 claims description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000008246 gaseous mixture Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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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
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Abstract
The invention discloses a methane-carbon dioxide reforming reactive catalyst and a preparation method thereof. The methane-carbon dioxide reforming reactive catalyst is a nanometer composite oxide with a mesoporous structure, formed by taking a carrier metal oxide as a substrate and taking another auxiliary metal oxide and an active metal oxide as disperse phases. The catalyst has the advantages of strong catalytic activity, high stability and good anti-carbon performance.
Description
Technical field
The present invention relates to a kind of methane-CO 2 reforming reaction Catalysts and its preparation method, belong to the chemical catalyst preparing technical field.
Background technology
Along with gas chemical industry's development, the huge natural gas of reserves replaces oil to become the important chemical raw material trend that will be inevitable.The direct utilization of methane at present still has a segment distance apart from industrialization, so the indirect utilization of methane, promptly prepares the route that is converted into other products behind the synthesis gas again by methane and has obtained paying close attention to widely.Prepare synthesis gas by methane several by way of in, methane-CO 2 reformation (CDR) has unique advantage, on the one hand, this process has huge economic benefit with the chemicals that a large amount of methane that exist of occurring in nature and carbon dioxide transform into high added value; On the other hand, this process has been utilized carbon dioxide and two kinds of greenhouse gases of methane simultaneously, has certain environmental benefit; At last, by the synthesis gas that the CDR process has obtained having lower hydrogen/carbon monoxide mol ratio, this is very beneficial for the commercial Application in downstream.At present, research emphasis and focus that CDR is reacted concentrate on raising catalyst stability aspect, and this mainly is because this course of reaction carbon distribution is serious, thereby causes the rapid inactivation of catalyst, and this also is the main cause that hinders the CDR process industrialization.
The metallic catalyst that is used for methane reforming reaction mainly contains rhodium, ruthenium, palladium, nickel.The catalytic activity of different metal pair reactions has bigger difference.But in methane-CO 2 reforming reaction process, because reactive metal easy-sintering formation at high temperature carbon distribution, a large amount of carbon distributions that catalyst surface forms have covered the activated centre, thereby cause catalysqt deactivation.The modulation of auxiliary agent can strengthen the stability of catalyst to a certain extent; On the other hand, there are some researches show that grain diameter can effectively suppress the generation of carbon distribution process less than the metallic particles of certain size, thereby make catalyst have good anti-carbon performance.Therefore, carrier and auxiliary agent metal oxides that reactive metal and heat endurance is high combine, and form the nano composite oxide with meso-hole structure, can improve the stability and the anti-carbon performance of catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of methane-CO 2 reforming reaction Catalysts and its preparation method.
The catalyst of the present invention's preparation is a kind of inorganic mesoporous material with high thermal stability, and the aperture is at 4 ~ 20nm.Based on the high catalytic activity of reactive metal, under the high-temperature pressure condition, can efficiently methane and carbon dioxide be converted into synthesis gas to methane-CO 2 reforming reaction; The meso-hole structure that catalyst has makes catalyst possess excellent catalytic activity and stability in high-temperature reaction process to the limit threshold effect and the metal-oxide strong interaction of metal nanoparticle.
A kind of methane provided by the invention-CO 2 reforming reaction catalyst is matrix with the carrier metal oxide, is decentralized photo with auxiliary agent metal oxides and reactive metal oxides, the nano composite oxide with meso-hole structure of formation.
Further, the mol ratio of described reactive metal oxides, described auxiliary agent metal oxides and described carrier metal oxide is 1:0.05 ~ 3:1 ~ 100.
Further, aforesaid carrier metal oxide is a zirconia.
Aforesaid auxiliary agent metal oxides be in magnesia, calcium oxide or the lanthana one or more.
Aforesaid reactive metal oxides be in palladium oxide, ruthenium-oxide, rhodium oxide, platinum oxide, nickel oxide, cobalt oxide or the di-iron trioxide one or more.
Further, the aperture of described nano composite oxide meso-hole structure is 4 ~ 20nm.
The present invention adopts sol-gel process to prepare methane-CO 2 reforming reaction catalyst, may further comprise the steps:
(1) will contain the soluble compound of reactive metal oxides precursor, the soluble compound of auxiliary agent metal oxides precursor mixes for 1:0.05 ~ 3:1 ~ 100 ratios in molar ratio with the soluble compound of carrier metal oxide precursor, under 20 ~ 80 ℃, be mixed with the aqueous solution that total ion concentration is 0.05 ~ 0.5 mol, add 0.01 ~ 1 times of template agent and make solution A to active component element molal quantity;
The described soluble compound that contains the reactive metal oxides precursor be in palladium bichloride, ruthenic chloride, radium chloride, platinum chloride, nickel nitrate, cobalt nitrate or the ferric nitrate one or more;
The described soluble compound that contains the auxiliary agent metal oxides precursor be in magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate, calcium chloride, calcium nitrate or the lanthanum nitrate one or more;
The described soluble compound that contains the carrier metal oxide precursor be in zirconium nitrate, zirconyl nitrate or the zirconium oxychloride one or more;
Described template agent be in DTAB, softex kw, polyethylene glycol or the polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer (P123) one or more;
(2) preparation precipitant solution B
Described precipitant solution be sodium hydrate aqueous solution, the potassium hydroxide aqueous solution of 0.05 ~ 0.5 mol, the aqueous sodium carbonate of 0.05 ~ 0.5 mol, the mass fraction of 0.05 ~ 0.5 mol be 5% ~ 25% ammonia spirit or mass fraction be in 5% ~ 25% the urea liquid one or more;
(3) under 20 ~ 80 ℃ of temperature, stir, be added dropwise to solution A and solution B in the reaction vessel jointly, the pH value of control gained mixture is 8 ~ 13, promptly gets the light green color precipitation, and placement was placed aging 2 ~ 12 hours after wearing out and spending deionised water, suction filtration after 2 ~ 12 hours;
(4) reflux digestion 12 ~ 72 hours after step (3) products therefrom adds the reflux medium of 0.2 ~ 6 times of volume;
Described reflux medium be deionized water, absolute ethyl alcohol, mass fraction be 5% ~ 25% ammonia spirit or concentration be 0.01 ~ 0.2 mol sodium hydrate aqueous solution in one or more;
(5) step (4) products therefrom is spent deionised water, dry under 60 ~ 120 ℃ behind the suction filtration, promptly made methane of the present invention-CO 2 reforming reaction catalyst in 3 ~ 7 hours in 200 ~ 700 ℃ of following roastings.
Methane among the present invention-CO 2 reforming reaction catalyst is based on the high activity of reactive metal to methane-CO 2 reforming reaction, can efficiently methane and carbon dioxide be converted into synthesis gas under the high-temperature pressure condition.The meso-hole structure that catalyst has makes catalyst possess excellent catalytic activity and stability in high-temperature reaction process to the limit threshold effect and the metal-oxide strong interaction of metal nanoparticle.But because thereby reactive metal easy-sintering formation at high temperature carbon distribution causes catalysqt deactivation, for strengthening the stability of catalyst, improve the service efficiency of material, carrier and auxiliary agent metal oxides that reactive metal and heat endurance is high combine, formation has the nano composite oxide of meso-hole structure, obtains this effective catalyst at methane-CO 2 reforming reaction.Carrier metal oxide, auxiliary agent metal oxides and reactive metal oxides are chimeric mutually in the catalyst of the present invention's preparation, pile up to have formed spongiform meso-hole structure, and the aperture is at 4 ~ 20nm.
The catalyst application conditions that reaches of the present invention is: reaction temperature is 500 ~ 1000 ℃, and reaction pressure is a normal pressure, and reaction velocity is 6000 ~ 120000ml h
-1g
-1, CH in the reaction feed gas
4: CO
2Mol ratio is 0.3 ~ 3.Catalyst needs before use at H
2Volume fraction is 5% ~ 90% H
2/ N
2In the gaseous mixture, reduced 0.5 ~ 24 hour down in 400 ~ 800 ℃.
Compared with prior art, catalyst disclosed by the invention has following advantage:
(1) has good heat endurance;
(2) has high catalytic activity;
(3) the anti-carbon performance is good, can use continuously more than 100 hours and does not have deactivation phenomenom.
Description of drawings
Fig. 1 is the nitrogen adsorption loop line of the methane-CO 2 reforming reaction catalyst of the present invention's preparation.
The specific embodiment
Further specify the present invention by the following examples.But embodiments of the present invention are not limited to following embodiment.
5 gram P123 are dissolved in 250 ml deionized water, add each 0.01 mole of nickel nitrate and lanthanum nitrate, zirconyl nitrate is configured to solution A for 0.05 mole; Other disposes the potassium hydroxide aqueous solution of 0.1 mol, is designated as solution B.Under 40 ℃ of stirred in water bath, solution A and solution B are slowly splashed in the large beaker, the formation green precipitate that stirs, the gained precipitation continues stirring spends deionised water, suction filtration after 5 hours after the gained filter cake to be placed aging 5 hours.Add 300 milliliters of reflux digestions of 0.1 mol sodium hydroxide solution suction filtration after 48 hours, 110 ℃ dry 24 hours down, 400 ℃ of following roastings 4 hours both required 0.2NiO-0.1La
2O
3-ZrO
2Catalyst.This catalyst is used for methane-CO 2 reforming reaction: take by weighing catalyst sample 0.2 gram, at first at H
2Volume fraction is 20% H
2/ N
2In the gaseous mixture in 500 ℃ of following reductase 12s hour, then at N
2Protection under close N after being warming up to 700 ℃
2, feed CH with the flow velocity of 100 ml/min
4: CO
2Mol ratio is that the gaseous mixture of 1:1 begins reaction.Reaction result sees attached list one and table two.
Embodiment 2
5 gram P123 are dissolved in 250 ml deionized water, add each 0.01 mole in nickel nitrate and calcium nitrate, zirconium nitrate is configured to solution A for 0.05 mole; Other disposes the sodium hydrate aqueous solution of 0.1 mol, is designated as solution B.Under 40 ℃ of stirred in water bath, solution A and solution B are slowly splashed in the large beaker, the formation green precipitate that stirs, the gained precipitation continues stirring spends deionised water, suction filtration after 2 hours after the gained filter cake to be placed aging 12 hours.Add 300 milliliters of reflux digestions of deionized water suction filtration after 48 hours, 110 ℃ dry 24 hours down, 600 ℃ of following roastings 5 hours both required 0.2NiO-0.2CaO-ZrO
2Catalyst.This catalyst is used for methane-CO 2 reforming reaction: take by weighing catalyst sample 0.1 gram, at first at H
2Volume fraction is 30% H
2/ N
2Reduced 1 hour down in 600 ℃ in the gaseous mixture, then at N
2Protection under close N after being warming up to 800 ℃
2, feed CH with the flow velocity of 60 ml/min
4: CO
2Mol ratio is that the gaseous mixture of 1:1 begins reaction.Reaction result sees attached list one and table two.
5 gram P123 are dissolved in 250 ml deionized water, add each 0.01 mole of cobalt nitrate and magnesium nitrate, zirconium nitrate is configured to solution A for 0.05 mole; The configuration quality mark is 20% ammonia spirit in addition, is designated as solution B.Under 40 ℃ of stirred in water bath, solution A and solution B are slowly splashed in the large beaker, the formation green precipitate that stirs, the gained precipitation continues stirring spends deionised water, suction filtration after 12 hours after the gained filter cake to be placed aging 12 hours.Add mass fraction and be 300 milliliters of reflux digestions of ammonia spirit of 20% suction filtration after 12 hours, 110 ℃ dry 24 hours down, 500 ℃ of following roastings 7 hours both required 0.2CoO-0.2MgO-ZrO
2Catalyst.This catalyst is used for methane-CO 2 reforming reaction: take by weighing catalyst sample 0.1 gram, at first at H
2Volume fraction is 10% H
2/ N
2Reduced 1 hour down in 600 ℃ in the gaseous mixture, feed N
2Purge after 10 minutes, with the flow velocity feeding CH of 50 ml/min
4: CO
2Mol ratio is that the gaseous mixture of 1:1 begins reaction.Reaction result sees attached list one and table two.
The product of embodiment 1,2,3 is adopted the somatotype dimension of the methane-CO 2 reforming reaction catalyst surface of nitrogen adsorption method research institute preparation, and nitrogen adsorption loop line as shown in Figure 1 illustrates that the prepared catalyst of the present invention has meso-hole structure.
Claims (5)
1. methane-CO 2 reforming reaction catalyst, it is characterized in that: described catalyst is to be matrix with the carrier metal oxide, auxiliary agent metal oxides and reactive metal oxides are the formed nano composite oxide with meso-hole structure of decentralized photo;
Described carrier metal oxide is a zirconia;
Described auxiliary agent metal oxides be in magnesia, calcium oxide, the lanthana one or more;
Described reactive metal oxides be in palladium oxide, ruthenium-oxide, rhodium oxide, platinum oxide, nickel oxide, cobalt oxide, the di-iron trioxide one or more.
2. methane according to claim 1-CO 2 reforming reaction catalyst is characterized in that: the mol ratio of described reactive metal oxides, described auxiliary agent metal oxides and described carrier metal oxide is 1:0.05 ~ 3:1 ~ 100.
3. methane according to claim 1-CO 2 reforming reaction catalyst is characterized in that: the aperture of described nano composite oxide meso-hole structure is 4 ~ 20nm.
4. the described methane of the arbitrary claim of claim 1 to 3-CO 2 reforming reaction Preparation of catalysts method is characterized in that may further comprise the steps:
(1) will contain the soluble compound of described reactive metal oxides precursor, the soluble compound of auxiliary agent metal oxides precursor mixes for 1:0.05 ~ 3:1 ~ 100 ratios in molar ratio with the soluble compound of carrier metal oxide precursor, preparation becomes the aqueous solution that total ion concentration is 0.05 ~ 0.5 mol under 20 ~ 80 ℃, adds 0.01 ~ 1 times of template agent to active component element molal quantity to make solution A;
(2) preparation precipitant solution B
Described precipitant solution be sodium hydrate aqueous solution, the potassium hydroxide aqueous solution of 0.05 ~ 0.5 mol, the aqueous sodium carbonate of 0.05 ~ 0.5 mol, the mass fraction of 0.05 ~ 0.5 mol be 5% ~ 25% ammonia spirit or mass fraction be in 5% ~ 25% the urea liquid one or more;
(3) under 20 ~ 80 ℃ of temperature, stir, be added dropwise to described solution A and described precipitant solution B in the reaction vessel jointly, the pH value of controlling the gained mixture is 8 ~ 13, gets the light green color precipitation, and placement was worn out 2 ~ 12 hours after placement was worn out and spent deionised water, suction filtration after 2 ~ 12 hours;
(4) in step (3) products therefrom, added behind the reflux medium of 0.2 ~ 6 times of volume reflux digestion 12 ~ 72 hours;
Described reflux medium be in the sodium hydrate aqueous solution that deionized water, absolute ethyl alcohol, mass fraction are 5% ~ 25% ammonia spirit, molar concentration is 0.01 ~ 0.2 mol one or more;
(5) step (4) products therefrom is spent deionised water, dry under 60 ~ 120 ℃ behind the suction filtration, promptly got methane-CO 2 reforming reaction catalyst in 3 ~ 7 hours in 200 ~ 700 ℃ of following roastings.
5. methane according to claim 4-CO 2 reforming reaction Preparation of catalysts method is characterized in that:
The described soluble compound that contains the reactive metal oxides precursor be in palladium bichloride, ruthenic chloride, radium chloride, platinum chloride, nickel nitrate, cobalt nitrate, the ferric nitrate one or more;
The described soluble compound that contains the auxiliary agent metal oxides precursor be in magnesium nitrate, magnesium acetate, magnesium chloride, magnesium sulfate, calcium chloride, calcium nitrate, the lanthanum nitrate one or more;
The described soluble compound that contains the carrier metal oxide precursor be in zirconium nitrate, zirconyl nitrate, the zirconium oxychloride one or more;
Described template agent be in DTAB, softex kw, polyethylene glycol, the polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer one or more.
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