CN104258864A - Nanocomposite catalyst and preparation method and application thereof - Google Patents
Nanocomposite catalyst and preparation method and application thereof Download PDFInfo
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- CN104258864A CN104258864A CN201410443980.2A CN201410443980A CN104258864A CN 104258864 A CN104258864 A CN 104258864A CN 201410443980 A CN201410443980 A CN 201410443980A CN 104258864 A CN104258864 A CN 104258864A
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- catalyst
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- methane
- alumina carrier
- complex catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002114 nanocomposite Substances 0.000 title abstract 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 85
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 21
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 14
- 238000006057 reforming reaction Methods 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 238000001556 precipitation Methods 0.000 claims description 41
- 239000002131 composite material Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 23
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- 238000000975 co-precipitation Methods 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- 150000008064 anhydrides Chemical class 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 17
- 230000001376 precipitating effect Effects 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 230000029087 digestion Effects 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000000320 mechanical mixture Substances 0.000 claims description 2
- 150000002927 oxygen compounds Chemical class 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- 230000004048 modification Effects 0.000 abstract description 14
- 238000012986 modification Methods 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- 238000002407 reforming Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910003281 Ni-Mg-Al Inorganic materials 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 238000001802 infusion Methods 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 238000010025 steaming Methods 0.000 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 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- 235000012245 magnesium oxide Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a nanocomposite catalyst which is characterized by comprising nano composites with the size of 5-30nm, wherein the nano composites comprise the following components in parts by weight: 1-20% of active metal oxide, 0-20% of an alkaline oxide accelerant, 0-20% of an oxidation-reduction additive and 40-99% of an aluminium oxide carrier. The invention also discloses a preparation method of the catalyst and application of the catalyst to reforming reaction of methane. By optimizing active components, improving interaction between the active components and the carrier and properly performing passivation modification on the catalyst carrier, the activity, stability and the capabilities of resisting sintering and carbon deposition of the catalyst at high temperature under high pressure are improved, the methane conversion rate of the catalyst reaches up to over 90% at the high temperature of 700-1,100 DEG C under high pressure of 1-10bar at the space velocity of 500-250,000cm<3>/(gh), and the catalyst can stably operate for more than 1,000h.
Description
Technical field
The present invention relates to chemical catalyst area, specifically, relate to nano-complex Catalysts and its preparation method, and the application in methane reforming reaction.
Background technology
The main method of industrial preparing synthetic gas is the steam reformation of methane, is suitable for producing synthetic ammonia and hydrogen manufacturing.At present, although the steam reformation of methane realizes industrialization, but still all multi-catalysts and problem of materials is faced.Though the research of other single methane reforming producing synthesis gas reaction achieves very large development, but still is difficult to realize industrialization, subject matter also comes from catalyst and high-temperature material.
In recent years, researcher have developed again the new technology of the preparing synthetic gas such as methane carbon dioxide reformation, partial oxidation and self-heating recapitalization.The CO 2 reformation of methane, and be that the methane self-heating recapitalization of main reactant has far-reaching CO with carbon dioxide
2reduce discharging environmental effect, therefore receive much concern.It is very valuable that a kind of effective reforming methane with carbon dioxide method (dry weight is whole) of exploitation carrys out extensive producing synthesis gas for the non-traditional gas downstream process that carbon dioxide and methane coexist.But compared with reforming with conventional steam, the sintering that methane does carbon distribution in reforming process and active metal more easily causes the inactivation of catalyst.As weight in wet base is whole, dry weight is whole also must in the face of 20-30bar high pressure in commercial Application in the future, and the test of 800-1100 DEG C of high temperature, and the methane under high-temperature and high-pressure conditions is done reforming process and is made carbon distribution and sinter the inactivation that causes more serious, therefore, develop a kind of high temperature, catalyst that high pressure stability inferior is good is significant.
The catalyst of methane reforming producing synthesis gas is primarily of carrier, and active component, auxiliary agent form, and wherein the reactivity worth of character to catalyst such as the crystalline phase composition of carrier, specific surface, pore structure and heat resistance has a significant impact.Such reaction carriers needs to have suitable specific surface and pore structure, to be conducive to reactant molecule in catalyst surface absorption, activation, also be conducive to product molecule desorption and leave catalyst surface simultaneously, prevent the generation of side reaction (carbon deposit reaction), and shift out reaction heat in time, avoid focus produce and make catalysqt deactivation.For this reason, to solve the problem of catalyst must accomplish following some: first want choose reasonable active component and carrier material, while realizing catalyst cheap, simplify synthesis step; Next adds alkaline element or redox auxiliary agent promotes to disappear carbon and anti-caking power; Finally optimize carrier structure, prevented sintering and the carbon distribution of active metal by the strong interaction strengthening catalyst carrier and active metal.Chinese patent CN1234366A discloses a kind of Ni-ZrO
2the preparation method of the dry reforming catalyst of methane, comprises carrier ZrO
2preparation and the supporting of active metal Ni.The standby catalyst nano-particles yardstick of this legal system is comparatively large, and the activity of catalyst is general, and preparation technology is tediously long, overall economics and environmental-protecting performance poor.US Patent No. 2009/0214993 A1 discloses the dry reforming catalyst of a kind of Ni-Co bimetallic methane, but this catalyst surface area is lower, and the activity in monometallic situation and stability are all poor.
Obviously, realize the high activity of the dry reforming catalyst of methane and high anti-carbon performance, make catalyst even running be an arduous challenge especially at elevated pressures.Patent at present also not about the dry reforming catalyst of methane that is high pressure resistant, high temperature is open.
Summary of the invention
One of the technical problem to be solved in the present invention is to provide a kind of nano-complex catalyst, its catalytic activity is high, good stability, anti-caking power by force, not easily carbon distribution, high pressure resistant high temperature.
For solving the problems of the technologies described above, nano-complex catalyst of the present invention, be made up of the nano-complex of yardstick 5 ~ 30nm, comprise following component and corresponding weight portion content: reactive metal oxides 1 ~ 20%, basic anhydride promoter 0 ~ 20%, oxidation-reduction quality auxiliary agent 0 ~ 20% and alumina carrier 40 ~ 99%.
Described reactive metal oxides comprises NiO, Co
3o
4, Fe
2o
3, RuO
2, Rh
2o
3, PtO
2, one or more combination in PdO, described basic anhydride promoter comprises CaO, MgO, K
2o, Na
2o, Li
2one or more combination in O, BaO, described oxidation-reduction quality auxiliary agent comprises CeO
2, La
2o
3, Y
2o
3, HfO
2in one or more combination.
The specific area of described catalyst is 20 ~ 280m
2/ g, pore volume is 0.05 ~ 0.80cm
3/ g, average pore size is 3 ~ 30nm.
Two of the technical problem to be solved in the present invention is to provide the preparation method of above-mentioned nano-complex catalyst.
For solving the problems of the technologies described above, the first preparation method of nano-complex catalyst of the present invention, adopt infusion process, step comprises:
1) take a certain amount of alumina carrier, calculate the amount of the salt precursor body of required basic anhydride promoter and redox auxiliary agent; Measure the water absorption rate of alumina carrier, calculate the amount of required water according to water absorption rate; Be dissolved in water by the salt precursor body of basic anhydride promoter and redox auxiliary agent, mixed by gained solution with alumina carrier, leave standstill aging, dry, roasting, obtains modified alumina carrier;
2) take a certain amount of modified alumina carrier, calculate the amount of the salt precursor body of required reactive metal oxides; Measure the water absorption rate of modified alumina carrier, calculate the amount of required water according to water absorption rate; The salt precursor body of reactive metal oxides is dissolved in water and obtains active component solution; Mixed with modified alumina carrier by active component solution, leave standstill aging, dry, roasting, obtains nano-complex catalyst.
The water absorption rate of alumina carrier can adopt titration measuring.
The second preparation method of nano-complex catalyst of the present invention, adopt coprecipitation, step comprises:
1) weight portion of corresponding precursor needed for the weight portion cubage of reactive metal oxides, basic anhydride promoter, oxidation-reduction quality auxiliary agent and alumina carrier, be that 0.05 ~ 0.5mol/L is for standard with aluminium ion concentration, calculate the weight portion of required water, reactive metal oxides precursor, basic anhydride promoter precursor, oxidation-reduction quality auxiliary agent precursor and alundum (Al2O3) precursor are dissolved in required water and obtain mixing salt solution;
2) compound concentration is that the alkaline solution of 0.5 ~ 4mol/L is as precipitating reagent;
3) under vigorous stirring, mixing salt solution and alkaline precipitating agent are carried out co-precipitation, obtain composite precipitation thing; In coprecipitation process, the pH value controlling precipitation solution is 8 ~ 13;
4) dry, roasting, obtains nano-complex catalyst.
Step 2), described precipitating reagent comprise in NaOH, sodium carbonate, potassium hydroxide, potash, ammoniacal liquor, urea one or more.
Step 3), the pH value of precipitation solution controls 11 ~ 12.5 better.
Step 4), before it is dried, can carry out reflux digestion as required to composite precipitation thing, reflux temperature is 80 ~ 100 DEG C, and return time is 5 ~ 48h.Catalyst granules after backflow is thinner, evenly specific area is larger, is more suitable for less than 900 DEG C temperature and uses; But shortcoming is at a higher temperature, easily sinters, become large.Reflux digestion process can be adopted and be carried out in two ways: one is at composite precipitation thing direct reflux digestion under alkaline mother liquor, then multiple times of filtration washing, is neutral, can obtains aging composite precipitation thing to filtrate pH value; Also first composite precipitation thing can be spent deionized water to neutral, then use deionized water reflux digestion, obtain aging composite precipitation thing.
Dry employing vacuum drying or constant pressure and dry, roasting can be carried out under air or inert atmosphere, and inert atmosphere comprises nitrogen, argon gas and helium.
The third preparation method of nano-complex catalyst of the present invention, adopt physics mixed grind method, step comprises:
1) according to reactive metal oxides, basic anhydride promoter, oxidation-reduction quality auxiliary agent and the weight portion cubage requisite oxygen compound of alumina carrier or the weight portion of corresponding precursor;
2) by step 1) in all material mechanical mixture;
3) standing aging, dry, roasting.
For making mixing more even, in step 2) in can add account for all quality of material summations 0 ~ 50% water.
In the first infusion process above-mentioned and the third physics mixed grind method, as required, can carry out active component to obtained nano-complex catalyst and flood, dipping method is with the step 2 in the first infusion process).
The precursor of reactive metal oxides recited above, basic anhydride promoter, oxidation-reduction quality auxiliary agent precursor can be nitrate or the chlorate of respective metal.Alumina carrier precursor can be the one in aluminum nitrate, aluminium hydroxide, various boehmite, various form aluminium oxide.
Three of the technical problem to be solved in the present invention is to provide the application of above-mentioned nano-complex catalyst in methane reforming reaction.This nano-complex catalyst methane that can be used under catalysis normal pressure or high pressure does reforming reaction (namely for methane CO 2 reforming reaction), methane wets reforming reaction and methane does wet mixing conjunction reforming reaction.
This nano-complex catalyst is before for methane reforming reaction, first by hydrogen/inert gas or carbon monoxide/inert gas at 500 ~ 1000 DEG C of reduction 0.5 ~ 3h, wherein, inert gas is the one in nitrogen, helium or argon gas, and the volume content of inert gas is 0 ~ 95%.The Applicable temperature of this nano-complex catalyst when catalytic methane CO 2 reforming reaction is 700 ~ 1100 DEG C, air speed is 500 ~ 250000cm
3/ (gh), unstripped gas CO
2: CH
4mol ratio is more than or equal to 1.
The present invention, by optimizing active component, enhances the interaction between active component and carrier, and makes active component be dispersed on carrier preferably; Meanwhile, modify by carrying out suitable passivation to catalyst carrier, improve anti-carbon and the caking power of catalyst; In addition, the existence of basic anhydride promoter and oxidation-reduction quality auxiliary agent facilitates the absorption of carbon dioxide and dissociates, and enhances the elimination to carbon species.Compared with existing methane reforming catalyst, nano-complex catalyst of the present invention has following advantage and beneficial effect:
1. catalyst particle size is little, is uniformly dispersed.Carrier A l
2o
3particle size be 5 ~ 30nm, the particle size of reactive metal oxides is 3 ~ 20nm, and the integral particle of catalyst is of a size of 5 ~ 30nm.
2. catalyst surface area, pore volume, aperture is adjustable.
3. preparation method is simple, and can according to field condition, and select any one in dipping, precipitation, mixed grind method, application window is wide.
4. preparation cost is low.Used carrier is industrial common aluminium oxide, and auxiliary agent is also common compounds; Without any need for alcohol wash replacement process in catalyst preparation process, do not need HTHP hydrothermal treatment consists and inert atmosphere protection roasting, also do not need the organic principles such as the template adding any costliness, therefore production cost is lower.
5. the carbon accumulation resisting ability of catalyst is strong, active and good stability.At 850 ~ 900 DEG C of high temperature, 1 ~ 10bar high pressure, 79000 ~ 122000cm
3under/(gh) high-speed, this catalyst to methane conversion all up to more than 90%, and can stable operation 1000h above non-inactivation; At ambient pressure can stable operation 2000h non-inactivation.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of the nano-complex catalyst n i-Ca-Zr-AlO of the embodiment of the present invention 1.
Fig. 2 is the whole activity curve of the nano-complex catalyst n i-Ca-Zr-AlO catalytic methane dry weight of the embodiment of the present invention 1.
Fig. 3 is the nano-complex catalyst 20Ni/10Mg-Al of the embodiment of the present invention 2
2o
3the activity curve that under catalysis high pressure, methane dry weight is whole.
Fig. 4 is the nano-complex catalyst 20Ni/2Zr-Al of the embodiment of the present invention 3
2o
3the activity curve that under catalysis high pressure, methane dry weight is whole.
Fig. 5 is the nano-complex catalyst n i/Ni-Mg-Al of the embodiment of the present invention 4
2o
3composite oxides XRD characterizes spectrogram.
Fig. 6 is the nano-complex catalyst n i/Ni-Mg-Al of the embodiment of the present invention 4
2o
3the activity curve that under catalysis high pressure, methane dry weight is whole.
Fig. 7 is the nano-complex catalyst n i/Ni-Mg-Al of the embodiment of the present invention 4
2o
3tG-DSC curve (air atmosphere) after high pressure dry weight is whole.
Detailed description of the invention
Understand more specifically for having technology contents of the present invention, feature and effect, now by reference to the accompanying drawings, details are as follows:
Embodiment 1 coprecipitation prepares high pressure resistant nano-complex catalyst n i-Ca-Zr-AlO
Prepared the method for high pressure resistant nano-complex catalyst n i-Ca-Zr-AlO by co-precipitation, comprise the following steps:
(1) preparation of mixing salt solution and alkaline precipitating agent:
By reactive metal oxides NiO, basic anhydride accelerant C aO, redox auxiliary agent ZrO in 10g nano-complex catalyst
2, carrier A l
2o
3mass ratio be 0.13,0.06,0.04,0.80 quality calculating required nickel nitrate, calcium nitrate, zirconium nitrate and aluminum nitrate, and with the concentration of aluminum nitrate for 0.1mol/L calculate needed for amount of deionized water.Required nickel nitrate, calcium nitrate, zirconium nitrate and aluminum nitrate are dissolved in deionized water and are made into mixing salt solution.
Compound concentration is that the NaOH aqueous solution of 1mol/L is as alkaline precipitating agent.
(2) co-precipitation of mixing salt solution:
Under vigorous stirring, mixing salt solution and alkaline precipitating agent are carried out co-precipitation and obtain composite precipitation thing.In coprecipitation process, the temperature controlling precipitation solution is 50 DEG C, and pH value is 10.5.
(3) reflux digestion of composite precipitation thing:
First composite precipitation thing is spent deionized water to neutral, then to reflux under the condition of temperature 80 DEG C 24h by deionized water, obtain aging composite precipitation thing.
(4) aging composite precipitation thing drying and roasting:
By above aging composite precipitation thing at 100 DEG C of vacuum drying 24h, obtain the nano combined sediment with high-specific surface area, by nano combined sediment roasting 5h at 600 DEG C, obtain high-dispersion nano complex catalyst, its parameter of pore structure is as shown in table 1:
The parameter of pore structure of table 1 catalyst n i-Ca-Zr-AlO
| Catalyst | Surface area (m 2/g) | Pore volume (cm 3/g) | Average pore size (nm) |
| Ni-Ca-Zr-AlO | 170 | 0.36 | 14.5 |
As shown in Figure 1, the integral particle size of photo display nano-complex catalyst is less than 20nm to the transmission electron microscope photo (TEM) of this nano-complex catalyst n i-Ca-Zr-AlO.
The nano-complex catalyst n i-Ca-Zr-AlO of above-mentioned acquisition is used 50%H at 700 DEG C
2/ N
2in-situ reducing 1h, for CH4 production, at 850 DEG C (furnace temperature), 1bar pressure, air speed 79000cm
3/ (gh), unstripped gas CO
2: CH
4the performance of detecting catalyst under the condition of mol ratio 1.2, as shown in Figure 2, curve shows catalytic activity and the stability that this nano-complex catalyst has superelevation to its result.
Embodiment 2 infusion process prepares high pressure resistant nano-complex catalyst 20Ni/10Mg-Al
2o
3
High pressure resistant nano-complex catalyst 20Ni/10Mg-Al is prepared by infusion process
2o
3method, comprise the following steps:
(1) modification of carrier gama-alumina
Take a certain amount of gama-alumina, Mg (NO required when calculating MgO load capacity is 10%
3)
24H
2o quality, calculates the amount of required water simultaneously according to surveyed gama-alumina water absorption rate.Mg (the NO of gained quality will be calculated
3)
24H
2o is dissolved in required water, is then added in gama-alumina, and limit edged stirs, and makes liquid-solid mixing as far as possible, gained mixing is left standstill 2h, liquid is permeated completely (period can stir several times) in carrier hole.
Sample after dipping is steamed 1 hour at 60 DEG C of backspins, then continues to revolve steaming 1 hour at 80 DEG C, put into 100 DEG C of baking ovens to spend the night revolving the sample after steaming oven dry.Afterwards, by the roasting 5 hours (heating rate is 3 DEG C/min) at 1000 DEG C of dried sample, obtain modified aluminas.
(2) load of nickel nitrate on modification gama-alumina
A certain amount of modification gama-alumina in (1) above taking, Ni (NO required when calculating Ni load capacity is 20%
3)
26H
2o quality, calculates the amount of required water simultaneously according to surveyed water absorption rate.Ni (the NO of gained quality will be calculated
3)
26H
2o is dissolved in required water, is then added in modification gama-alumina, and limit edged stirs, and makes liquid-solid mixing as far as possible, and gained mixing is left standstill 2h, and liquid is permeated completely (period stirs as seen several times) in carrier hole.
Sample after dipping is steamed 1 hour at 60 DEG C of backspins, then continues to revolve steaming 1 hour at 80 DEG C, put into 100 DEG C of baking ovens to spend the night revolving the sample after steaming oven dry.
By the roasting 5 hours at 600 DEG C of dried sample, obtain reforming catalyst 20Ni/10Mg-Al
2o
3.The structural parameters such as its specific surface are as shown in table 2:
Table 2 catalyst 20Ni/10Mg-Al
2o
3structural parameters
The nano-complex catalyst of above-mentioned acquisition is used 50%H at 700 DEG C
2/ N
2in-situ reducing 1h, for methane reforming with carbon dioxide.At 5bar high pressure, 900 DEG C (furnace temperature), air speed 122400cm
3/ (hg), unstripped gas CO
2: CH
4under the condition of mol ratio 2.4, this catalyst is to CH
4conversion ratio reaches 98% and the active 1000h that keeps does not reduce, as shown in Figure 3.
Embodiment 3 infusion process prepares high pressure resistant nano-complex catalyst 20Ni-2Zr-Al
2o
3
High pressure resistant nano-complex catalyst 20Ni-2Zr-Al is prepared by infusion process
2o
3method, comprise the following steps:
(1) modification of carrier gama-alumina
Take a certain amount of 100g gama-alumina, calculate 2g ZrO
2zirconium nitrate quality needed for load capacity, calculates the amount of required water simultaneously according to surveyed gama-alumina water absorption rate.Be dissolved in required water by the zirconium nitrate calculating gained quality, be then added in gama-alumina, limit edged stirs, and makes liquid-solid mixing as far as possible, gained mixing is left standstill 2h, liquid is permeated completely in carrier hole.By dipping after sample in an oven 50 DEG C dry 8 hours, improve temperature to 100 DEG C, continue oven dry of spending the night.Afterwards, by the roasting 5 hours at 1100 DEG C of dried sample, heating rate is 3 DEG C/min, obtains ZrO
2the aluminium oxide of modification.
(2) load of nickel nitrate on modification gama-alumina
A certain amount of modification gama-alumina in (1) above taking, Ni (NO required when calculating Ni load capacity is 20%
3)
26H
2o quality, calculates the amount of required water simultaneously according to surveyed water absorption rate.Ni (the NO of gained quality will be calculated
3)
26H
2o is dissolved in required water, then be added in modification gama-alumina, limit edged stirs, and makes liquid-solid mixing as far as possible, and gained mixing is left standstill 2h, liquid is made to permeate completely in carrier hole, by the sample after dipping 50 degree oven dry in an oven 8 hours, raising temperature, to 100 DEG C, continues oven dry of spending the night, by the roasting 5 hours at 600 DEG C of dried sample, obtain reforming catalyst 20Ni/2Zr-Al
2o
3, the structural parameters such as its specific surface are as shown in table 3:
Table 3 20Ni/2Zr-Al
2o
3the structural parameters of catalyst
The nano-complex catalyst of above-mentioned acquisition is used 50%H at 700 DEG C
2/ N
2in-situ reducing 1h, for methane reforming with carbon dioxide.At 10bar high pressure, 900 DEG C (furnace temperature), air speed 122400cm
3/ (hg), unstripped gas CO
2: CH
4under the condition of mol ratio 2.4, this catalyst is to CH
4conversion ratio reaches 98% and the active 1400h that keeps does not reduce, as shown in Figure 4.
Embodiment 4 physics mixed grind legal system is for high pressure resistant complex catalyst Ni/Ni-Mg-Al
2o
3
High pressure resistant complex catalyst Ni/Ni-Mg-Al is prepared by physics mixed grind
2o
3method, comprise the following steps:
(1) Ni-Mg-Al is prepared by mixed grind
2o
3composite oxides:
By the light MgO of 0.2mol, 0.4mol γ-Al
2o
3by pulverizer, mortar mixed grind, 0.1mol nickel acetate is dissolved in the deionized water of 200ml, is poured in above-mentioned mixed grind material afterwards, continue mixed grind 2h.Display 12h afterwards, 80 DEG C of oven dry.After 400 DEG C of pre-burning 2h at 1000 DEG C of temperature air atmosphere roasting 4h, obtain catalyst n i/MgAlO composite oxides.
(2) Ni-Mg-Al obtained in (1) above 50g is got
2o
3composite oxides, are separately dissolved in the deionized water of 20ml by 0.01mol nickel acetate, are poured into above-mentioned Ni-Mg-Al afterwards
2o
3in composite oxides, continue mixed grind 2h.Display 12h afterwards, 80 DEG C of oven dry.600 DEG C of air atmosphere roasting 4h, obtain catalyst n i/Ni-Mg-Al
2o
3composite oxides.
100 mesh sieves pulverized by catalyst, then compressing tablet, and grinding screen becomes 40 order ~ 60 orders for subsequent use.Carry out XRD sign to the powder after roasting, spectrogram is shown in Fig. 5.In catalyst raw material, γ-Al
2o
3for the key component of catalyst, but γ is-Al
2o
3aobvious acid, easy carbon distribution, after adding alkaline MgO, effectively can suppress carbon distribution.NiO, in catalyst preparation process, is disperseed well, so XRD characterizes the thing phase composition that spectrogram does not respond, catalyst is finally by Spinel and periclase two phase compositions mutually, this is conducive to the alkalescence improving catalyst, prevents carbon distribution, contributes to the dispersion of catalyst activity component simultaneously.
By the nano-complex catalyst n i/Ni-Mg-Al of above-mentioned acquisition
2o
350%H is used at 700 DEG C
2/ N
2in-situ reducing 1h, for methane reforming with carbon dioxide.At 5bar high pressure, 900 DEG C (furnace temperature), air speed 122400cm
3/ (hg), unstripped gas CO
2: CH
4under the condition of mol ratio 2.4, this catalyst is to CH
4conversion ratio reaches 98%, and the active 1700h that keeps does not reduce, and response curve is shown in Fig. 6.
Ni/Ni-Mg-Al
2o
3after catalyst high pressure dry weight is whole, carry out TG test, to measure the carbon deposition quantity of generation, the TG-DSC curve (air atmosphere) of this catalyst is shown in Fig. 7, and the carbon deposition quantity that can be calculated catalyst through TG curve is 0.007g/g catalyst.Carbon deposition rate also only has 9.53 × 10
-5gC/hg catalyst, this catalyst has good anti-carbon performance as seen.
Embodiment 5 coprecipitation prepares high-dispersion nano complex catalyst Ni-Ca-Ce-AlO
The step being prepared high-dispersion nano complex catalyst Ni-Ca-Ce-Al by coprecipitation method is comprised:
(1) preparation of mixing salt solution and alkaline precipitating agent:
By reactive metal oxides NiO, basic anhydride accelerant C aO, oxidation-reduction quality auxiliary agent Ce in 10g nano-complex catalyst
2o
3with carrier A l
2o
3mass ratio be 0.20,0.20,0.10,0.40 quality calculating required nickel nitrate, calcium nitrate, cerous nitrate and aluminum nitrate, and with the concentration of aluminum nitrate for 0.1mol/L calculate needed for amount of deionized water.Mixing salt solution is made into by required nickel nitrate, calcium nitrate, cerous nitrate and aluminum nitrate deionized water.
Compound concentration is that the NaOH aqueous solution of 4mol/L is as alkaline precipitating agent.
(2) co-precipitation of mixing salt solution:
Under vigorous stirring, mixing salt solution and alkaline precipitating agent are carried out co-precipitation and obtain composite precipitation thing.In coprecipitation process, the temperature controlling precipitation solution is 80 DEG C, and pH value is 12.
(3) reflux digestion of composite precipitation thing:
Composite precipitation thing is spent deionized water to neutral, then to reflux under the condition of temperature 100 DEG C 24h by deionized water, obtain aging composite precipitation thing.
(4) drying of aging composite precipitation thing and roasting:
By aging composite precipitation thing at 120 DEG C of constant pressure and dry 24h, obtain the nano combined sediment with high-specific surface area, by nano combined sediment roasting 5h at 600 DEG C, obtain high-dispersion nano complex catalyst.
The nano-complex catalyst n i-Ca-Ce-AlO of above-mentioned acquisition is used 20%H at 700 DEG C
2/ N
2in-situ reducing 1h, for methane reforming with carbon dioxide.At 850 DEG C (furnace temperature), 1bar pressure, air speed 75000cm
3/ (gh), unstripped gas CO
2: CH
4under the condition of mol ratio 1.2, this catalyst is to CH
4conversion ratio reaches 91%, and the active 1200h that keeps does not reduce.
Embodiment 6 infusion process prepares high pressure resistant nano-complex catalyst 15Ni/5Ca-5Ce-Al
2o
3
High pressure resistant nano-complex catalyst 15Ni/5Ca-5Ce-Al is prepared by infusion process
2o
3method, comprise the following steps:
(1) modification of carrier gama-alumina
Take a certain amount of gama-alumina, calculate CaO, Ce
2o
3ca (NO required when load capacity is 5%
3)
24H
2o and Ce (NO
3)
36H
2o quality, calculates the amount of required water simultaneously according to surveyed gama-alumina water absorption rate.Ca (the NO of gained quality will be calculated
3)
24H
2o and Ce (NO
3)
36H
2o is dissolved in required water, is then added in gama-alumina, and limit edged stirs, and makes liquid-solid mixing as far as possible, gained mixing is left standstill 2h, liquid is permeated completely (period can stir several times) in carrier hole.
Sample after dipping is steamed 1 hour at 60 DEG C of backspins, then continues to revolve steaming 1 hour at 80 DEG C, put into 100 DEG C of baking ovens to spend the night revolving the sample after steaming oven dry.Afterwards, by the roasting 5 hours (heating rate is 3 DEG C/min) at 1000 DEG C of dried sample, obtain modified aluminas.
(2) load of nickel nitrate on modification gama-alumina
A certain amount of modification gama-alumina in (1) above taking, Ni (NO required when calculating Ni load capacity is 15%
3)
26H
2o quality, calculates the amount of required water simultaneously according to surveyed water absorption rate.Ni (the NO of gained quality will be calculated
3)
26H
2o is dissolved in required water, is then added in modification gama-alumina, and limit edged stirs, and makes liquid-solid mixing as far as possible, and gained mixing is left standstill 2h, and liquid is permeated completely (period stirs as seen several times) in carrier hole.
Sample after dipping is steamed 1 hour at 60 DEG C of backspins, then continues to revolve steaming 1 hour at 80 DEG C, put into 100 DEG C of baking ovens to spend the night revolving the sample after steaming oven dry.
By the roasting 5 hours at 600 DEG C of dried sample, obtain reforming catalyst 15Ni/5Ca-5Ce-Al
2o
3.
By the nano-complex catalyst 15Ni/5Ca-5Ce-Al of above-mentioned acquisition
2o
350%H is used at 700 DEG C
2/ N
2in-situ reducing 1h, for methane reforming with carbon dioxide.At 5bar high pressure, 900 DEG C (furnace temperature), air speed 122400cm
3/ (hg), unstripped gas CO
2: H
2o:CH
4under the condition of mol ratio 1.4:1:1, this catalyst is to CH
4conversion ratio reaches 98%, and the active 300h that keeps does not reduce.
Embodiment 7 high-dispersion nano complex catalyst Pt-Ca-Al
2o
3preparation
The high-dispersion nano complex catalyst Pt-Ca-Al of the present embodiment
2o
3preparation method, comprise the following steps:
(1) preparation of mixing salt solution and alkaline precipitating agent:
By reactive metal oxides PtO in 10g nano-complex catalyst
2, CaO and carrier A l
2o
3mass ratio be 0.01,0.03,0.99 weight calculating required platinum chloride, calcium nitrate and aluminum nitrate.With the amount of deionized water of the concentration of aluminum nitrate needed for 0.1mol/L calculating.Required platinum chloride, calcium nitrate and aluminum nitrate are dissolved in deionized water and are made into mixing salt solution.
Compound concentration is that the NaOH aqueous solution of 2mol/L is as alkaline precipitating agent.
(2) co-precipitation of mixing salt solution:
Under vigorous stirring, mixing salt solution and alkaline precipitating agent are carried out co-precipitation and obtain composite precipitation thing.In coprecipitation process, the temperature controlling precipitation solution is 30 DEG C, and pH value is 11.
(3) reflux digestion of composite precipitation thing:
Composite precipitation thing is spent deionized water to neutral, then to reflux under the condition of temperature 100 DEG C 24h by deionized water, aging composite precipitation thing can be obtained.
(4) aging composite precipitation thing drying and roasting:
Aging composite precipitation thing can be obtained the nano combined sediment with high-specific surface area at 120 DEG C of constant pressure and dry 24h, by nano combined sediment roasting 5h at 600 DEG C, obtain high-dispersion nano complex catalyst.
The nano-complex catalyst of above-mentioned acquisition is used 20%H at 800 DEG C
2/ N
2in-situ reducing 1h, for methane reforming with carbon dioxide.At 900 DEG C (furnace temperature), 1bar pressure, air speed 75000cm
3/ (gh), unstripped gas CO
2: CH
4under the condition of mol ratio 1.2, this catalyst is to CH
4conversion ratio reaches 85%, and the active 300h that keeps does not reduce.
Embodiment 8 high-dispersion nano complex catalyst Ni-Pt-Ca-Al
2o
3preparation
The high-dispersion nano complex catalyst Ni-Pt-Ca-Al of the present embodiment
2o
3preparation method, comprise the following steps:
(1) preparation of mixing salt solution and alkaline precipitating agent:
By reactive metal oxides PtO in 10g nano-complex catalyst
2, NiO and CaO and carrier A l
2o
3mass ratio be 0.01,0.03,0.09,0.90 calculate required platinum chloride, calcium nitrate, aluminum nitrate weight.Amount of deionized water with aluminum nitrate concentration needed for 0.2mol/L calculating.Being dissolved in deionized water of required platinum chloride, nickel nitrate, calcium nitrate and aluminum nitrate is made into mixing salt solution.
Compound concentration is that the NaOH aqueous solution of 2mol/L is as alkaline precipitating agent.
(2) co-precipitation of mixing salt solution:
Under vigorous stirring, mixing salt solution and alkaline precipitating agent are carried out co-precipitation and obtain composite precipitation thing.In coprecipitation process, the temperature controlling precipitation solution is 50 DEG C, and pH value is 12.5.
(3) reflux digestion of composite precipitation thing:
Composite precipitation thing is spent deionized water to neutral, then to reflux under the condition of temperature 100 DEG C 24h by deionized water, obtain aging composite precipitation thing.
(4) aging composite precipitation thing drying and roasting:
By aging composite precipitation thing at 120 DEG C of constant pressure and dry 24h, obtain the nano combined sediment with high-specific surface area.By nano combined sediment roasting 5h at 600 DEG C, obtain high-dispersion nano complex catalyst.
The nano-complex catalyst of above-mentioned acquisition is used 20%H at 700 DEG C
2/ N
2in-situ reducing 1h, for methane reforming with carbon dioxide.At 850 DEG C (furnace temperature), 1bar pressure, air speed 75000cm
3/ (gh), unstripped gas CO
2: CH
4under the condition of mol ratio 1.2, this catalyst is to CH
4conversion ratio reaches 95%, and the active 600h that keeps does not reduce.
Claims (13)
1. nano-complex catalyst, it is characterized in that, be made up of the nano-complex of yardstick 5 ~ 30nm, comprise following component and corresponding weight portion content: reactive metal oxides 1 ~ 20%, basic anhydride promoter 0 ~ 20%, oxidation-reduction quality auxiliary agent 0 ~ 20% and alumina carrier 40 ~ 99%.
2. catalyst as claimed in claim 1, it is characterized in that, described reactive metal oxides comprises NiO, Co
3o
4, Fe
2o
3, RuO
2, Rh
2o
3, PtO
2, one or more combination in PdO, described basic anhydride promoter comprises CaO, MgO, K
2o, Na
2o, Li
2one or more combination in O, BaO, described oxidation-reduction quality auxiliary agent comprises CeO
2, La
2o
3, Y
2o
3, HfO
2in one or more combination.
3. catalyst as claimed in claim 1, it is characterized in that, specific area is 20 ~ 280m
2/ g, pore volume is 0.05 ~ 0.80cm
3/ g, average pore size is 3 ~ 30nm.
4. the preparation method of catalyst described in any one of claims 1 to 3, it is characterized in that, step comprises:
1) take a certain amount of alumina carrier, calculate the amount of the salt precursor body of required basic anhydride promoter and redox auxiliary agent; Measure the water absorption rate of alumina carrier, calculate the amount of required water according to water absorption rate; Be dissolved in water by the salt precursor body of basic anhydride promoter and redox auxiliary agent, mixed by gained solution with alumina carrier, leave standstill aging, dry, roasting, obtains modified alumina carrier;
2) take a certain amount of modified alumina carrier, calculate the amount of the salt precursor body of required reactive metal oxides; Measure the water absorption rate of modified alumina carrier, calculate the amount of required water according to water absorption rate; The salt precursor body of reactive metal oxides is dissolved in water and obtains active component solution; Mixed with modified alumina carrier by active component solution, leave standstill aging, dry, roasting, obtains nano-complex catalyst.
5. the preparation method of catalyst described in any one of claims 1 to 3, it is characterized in that, step comprises:
1) weight portion of corresponding precursor needed for the weight portion cubage of reactive metal oxides, basic anhydride promoter, oxidation-reduction quality auxiliary agent and alumina carrier, be that 0.05 ~ 0.5mol/L is for standard with aluminium ion concentration, calculate the weight portion of required water, reactive metal oxides precursor, basic anhydride promoter precursor, oxidation-reduction quality auxiliary agent precursor and alundum (Al2O3) precursor are dissolved in required water and obtain mixing salt solution;
2) compound concentration is that the alkaline solution of 0.5 ~ 4mol/L is as precipitating reagent;
3) under vigorous stirring, mixing salt solution and alkaline precipitating agent are carried out co-precipitation, obtain composite precipitation thing; In coprecipitation process, the pH value controlling precipitation solution is 8 ~ 13;
4) dry, roasting, obtains nano-complex catalyst.
6. method as claimed in claim 5, is characterized in that, step 3), the pH value controlling precipitation solution is 11 ~ 12.5.
7. method as claimed in claim 5, is characterized in that, step 4), before it is dried, carry out reflux digestion to composite precipitation thing, reflux temperature is 80 ~ 100 DEG C, and return time is 5 ~ 48h.
8. method as claimed in claim 5, is characterized in that, step 4), baking temperature is 60 ~ 160 DEG C, and drying time is 6 ~ 48h, and sintering temperature is 400 ~ 900 DEG C, and roasting time is 1 ~ 10h.
9. the preparation method of catalyst described in any one of claims 1 to 3, it is characterized in that, step comprises:
1) according to reactive metal oxides, basic anhydride promoter, oxidation-reduction quality auxiliary agent and the weight portion cubage requisite oxygen compound of alumina carrier or the weight portion of corresponding precursor;
2) by step 1) in all material mechanical mixture;
3) standing aging, dry, roasting.
10. method as claimed in claim 9, is characterized in that, step 2), add account for all quality of material summations 0 ~ 50% water.
Described in 11. any one of claims 1 to 3, the application of nano-complex catalyst, is characterized in that, does reforming reaction, methane wets reforming reaction and methane does wet mixing conjunction reforming reaction for the methane under catalysis normal pressure ~ 30bar pressure.
12. application according to claim 11, it is characterized in that, this nano-complex catalyst is before for catalytic methane reforming reaction, first by the mist of hydrogen and inert gas, or the mist of carbon monoxide and inert gas, reduction 0.5 ~ 3h at 500 ~ 1000 DEG C, wherein, inert gas is the one in nitrogen, helium or argon gas, and the volume content of inert gas is 0 ~ 95%.
13. application according to claim 12, is characterized in that, the Applicable temperature that this nano-complex catalyst methane does reforming reaction is 700 ~ 1100 DEG C, air speed is 500 ~ 250000cm
3/ (gh), unstripped gas CO
2: CH
4mol ratio is more than or equal to 1.
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| CN117046478A (en) * | 2023-08-25 | 2023-11-14 | 中国海洋石油集团有限公司 | Alkaline metal oxide-containing methane carbon dioxide dry reforming reaction catalyst and preparation method and application thereof |
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