CN107597199A - Recirculating fluidized bed hydrocarbon reforming catalyst and its preparation method and application - Google Patents
Recirculating fluidized bed hydrocarbon reforming catalyst and its preparation method and application Download PDFInfo
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- CN107597199A CN107597199A CN201710820742.2A CN201710820742A CN107597199A CN 107597199 A CN107597199 A CN 107597199A CN 201710820742 A CN201710820742 A CN 201710820742A CN 107597199 A CN107597199 A CN 107597199A
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- hexa
- aluminate
- fluidized bed
- nickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- 238000002407 reforming Methods 0.000 title claims abstract description 38
- 230000003134 recirculating effect Effects 0.000 title claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 33
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 32
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 75
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 37
- 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 36
- 239000007789 gas Substances 0.000 claims description 26
- 239000004005 microsphere Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 159000000008 strontium salts Chemical class 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims 1
- 229940078494 nickel acetate Drugs 0.000 claims 1
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 206010068052 Mosaicism Diseases 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 27
- 239000003643 water by type Substances 0.000 description 25
- 238000005470 impregnation Methods 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229910052593 corundum Inorganic materials 0.000 description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- 239000002028 Biomass Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000002309 gasification Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical class O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000004087 circulation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- -1 nickel aluminate Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011269 tar Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011806 microball Substances 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 239000011285 coke tar Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910002340 LaNiO3 Inorganic materials 0.000 description 2
- 239000005084 Strontium aluminate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical class [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical class O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001193 catalytic steam reforming Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- DOARWPHSJVUWFT-UHFFFAOYSA-N lanthanum nickel Chemical compound [Ni].[La] DOARWPHSJVUWFT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical class [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- 229910003303 NiAl2O4 Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical class O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer 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
Abstract
The invention discloses a kind of recirculating fluidized bed hydrocarbon reforming catalyst and its preparation method and application, the catalyst includes hexa-aluminate modified aluminium oxide supports and the active metal nickel being supported on hexa-aluminate modified aluminium oxide supports, hexa-aluminate modified aluminium oxide supports include activated alumina microballoon matrix and hexa-aluminate, and hexa-aluminate is supported in activated alumina microballoon matrix surface and endoporus.Catalyst prepared by the present invention, due to hexa-aluminate modified aluminium oxide supports can mosaicism, active nickel is highly dispersed in hexa-aluminate lattice, improve catalyst to heat endurance and reproducibility, so that catalyst is resistant in recirculating fluidized bed continuous redox requirement, catalytic activity is high, good to heat endurance, can recycle 120h under big space velocities and methane conversion is up to 90~60%；Catalyst reforming activity of the present invention is high, and stability is good, available for recirculating fluidized bed hydrocarbon reforming preparing synthetic gas.
Description
Technical field
The present invention relates to Catalyst Production technology, in particular to a kind of recirculating fluidized bed hydrocarbon reforming catalyst and its preparation side
Method and application.
Background technology
The utilization of biomass resource is that solve fossil energy crisis, slow down CO2 emission and cause global climate to deteriorate
One of important channel.Wherein, using biomass gasification technology produce synthesis gas, and using synthesis gas as raw material by F- T synthesis,
The technologies such as methanol-fueled CLC, synthesis gas gasoline produce liquid fuel；Or using the gas that gasifies be fuel by gas turbine power generation,
It is the extensive important channel for utilizing biomass material, is widely used exploitation.
In existing comparative maturity, good economy performance biomass fluid bed gasification process, generally contain in crude synthesis gas product
There is 10~100g/Nm3Tar and 5~20% lower carbon number hydrocarbons.Tar in crude synthesis gas holds in the cooling procedure of gas
The problems such as easily causing equipment scaling, pipeline blockage, meanwhile, the biomass coke tar of residual can cause in the synthetic catalyst of downstream
Poison.In addition, methane and more than the C2 hydrocarbon compound contained in crude synthesis gas is as inert gas, it is impossible to participates in synthetic reaction life
Into target product, the charcoal efficiency of system is reduced.The tar in crude synthesis gas is removed, and effectively by the hydro carbons in crude synthesis gas
Compound, which is converted into, is effectively synthesized gas, is to improve the important technology approach in gasification of biomass indirect liquefaction technique.Water vapour turns
Change is tar and lower carbon number hydrocarbons is converted into the Main Means for being effectively synthesized gas.
In crude synthesis gas caused by the fluidized gasification technology of generally use, in addition to containing tar, lower carbon number hydrocarbons, also contain
30mg~10g/Nm3Solid impurity, mainly gasification byproducts solid is burnt and the dust for gasification heat carrier.Utilize
Industrial ripe fixed-bed catalytic Steam Reforming carries out detar to crude synthesis gas and hydrocarbon converts, and solid impurity easily causes
Bed blocks, meanwhile, the tarry impurities using polycyclic aromatic hydrocarbon as Main Ingredients and Appearance easily cause catalyst carbon deposit, cause catalyst inactivation
Improved with bed pressure drop, limit the economy of fixed-bed catalytic Steam Reforming purification crude synthesis gas.
For foregoing problems, RenTech companies of the U.S. have carried out a series of researchs, such as：United States Patent (USP) US8591610 is first
The technology that the purification of gasification of biomass crude synthesis gas product is carried out using circulating fluidized bed technique is proposed, it is right that the technology passes through
The problems such as circular regeneration of catalyst solves catalyst inactivation in above-mentioned fixed bed reactors, bed blocks.It is ciculation fluidized
Bed process includes two fluidized-bed reactors, i.e. reforming reactor and regeneration reactor, solid catalyst two reactors it
Between Rapid Circulation, not only act as reform activation effect, can also realize heat transfer, while complete to regenerate and react the need of heat supply
Will, it is the reforming process with application prospect.
Catalyst used in Circulating Fluidized Bed Process not only requires appropriate particle size range, grain density to ensure to urge
Catalyst particles are inner circulation fluidized in reactor, it is necessary to which there are excellent abrasion resistance properties to reduce catalyst attrition.In addition,
In regeneration reactor, active nickel is exposed to oxidizing atmosphere, is oxidized to the oxide of nickel, and then occur admittedly with alumina catalyst support
Phase reaction, generate the compound poor to reforming catalytic activity, such as nickel aluminate.It is therefore desirable to nickel be resistant to it is a certain amount of
Oxygen or suppress nickel oxide and carrier between solid phase reaction；And catalyst after regeneration is transferred in reforming reactor
When, and can is reduced into rapidly the active nickel catalytic reforming reaction of lower valency under reducing atmosphere.In order to achieve the above object,
There must be the interaction of appropriateness between nickel and carrier, if the interaction of nickel and carrier is too weak, can be obtained under high temperature " from
By " nickel, generation migrate, gather, growing up, cause rapid catalyst deactivation；But if the interaction of nickel and carrier is too strong, such as
Nickel aluminate is formed, then is difficult to reduce, catalytic activity is not high.Therefore, catalyst must also have good oxidationreduction energy
Power.
It is to continue to use in fixed bed reactors to sieve mostly although the research in existing literature to Ni-based reforming catalyst is more
The catalyst elected, it is actually rare suitable for the Ni-based reforming catalyst of recirculating fluidized bed, when using it for recirculating fluidized bed
Often have the following disadvantages：1) reforming activity that is difficult to take into account Ni-based reforming catalyst and fluidity；2) in recirculating fluidized bed by
Abrasion is easily produced in catalyst granules and reaction unit, the fluidizing agent and friction between its own so that catalyst grain size
Decline, bring the problems such as running agent, contamination of products and needing frequently supplement catalyst.
The content of the invention
, should present invention aim to provide a kind of recirculating fluidized bed hydrocarbon reforming catalyst and its preparation method and application
Catalyst is the catalyst suitable for the high activity of Circulating Fluidized Bed Process, high stability and high-wearing feature.
The technical solution adopted by the present invention is：A kind of recirculating fluidized bed hydrocarbon reforming catalyst, including hexa-aluminate are modified oxygen
Change alumina supporter and the active metal nickel being supported on the hexa-aluminate modified aluminium oxide supports, the hexa-aluminate is modified oxidized
Alumina supporter includes activated alumina microballoon matrix and hexa-aluminate, is supported in the activated alumina microballoon matrix surface and endoporus
The hexa-aluminate.
Further, the formula of the hexa-aluminate is AMxAl12-xO19-δ(0≤x,δ<5), wherein, A be calcium, strontium, barium and
One kind in lanthanum, M are combination more than one or both of iron, cobalt, nickel, copper and magnesium；The hexa-aluminate weight is catalysis
The 1~50% of agent weight, the active metal nickel weight are calculated as the 1~20% of catalyst weight with oxide, and surplus is described
Activated alumina microballoon matrix.
Further, alumina content ＞ 90% in the activated alumina microballoon matrix, particle diameter are 50~500um, D50
For 80~300um, than surface >=50m2/ g, total pore volume >=0.1cm3/ g, abrasion index ＜ 0.5%/h.
Further, calcium, strontium, barium and the lanthanum for forming the hexa-aluminate are selected from anhydrous nitrate, nitric hydrate salt, chlorination
Salt, sulfate and acetate, formed the hexa-aluminate iron, cobalt, nickel, copper and magnesium be selected from anhydrous chlorate, chloride hydrate salt,
Nitrate, sulfate and acetate, the weight of the hexa-aluminate are the 5~30% of catalyst weight.
Further, the active metal nickel comes from Dehydrated nickel chloride, hydrated nickel chloride, nickel nitrate, nickel sulfate and acetic acid
It is more than one or both of nickel.
A kind of preparation method of above-mentioned recirculating fluidized bed hydrocarbon reforming catalyst, it is characterised in that：Comprise the following steps：
1) calcium salt, strontium salt, barium salt or lanthanum salt are dissolved in water and are made into dipping solution I, or by calcium salt, strontium salt, barium salt or lanthanum salt
Water is dissolved in together with more than one or both of molysite, cobalt salt, nickel salt, mantoquita and magnesium salts and is made into dipping solution I, will be impregnated molten
Liquid I is impregnated on activated alumina microballoon, and modified support precursor is made；
2) modified support precursor made from step 1) is formed into modified aluminium oxide supports after low temperature drying and high-temperature calcination；
3) nickel salt is dissolved in water and is made into dipping solution II, be impregnated on the modified aluminium oxide supports that step 2) obtains；
4) by the mixture that step 3) obtains after low temperature drying and high-temperature calcination, you can obtain the recirculating fluidized bed hydrocarbon
Reforming catalyst.
Further, in the step 1), calcium, strontium, barium or lanthanum dosage with oxide be calculated as catalyst weight 0.1~
20%；Dosage more than one or both of iron, cobalt, nickel, copper, magnesium is calculated as the 0.1~20% of catalyst weight with oxide.
Further, in the step 4), high-temperature calcination uses two-part temperature programming, first with 1~10 DEG C/min liter
Warm speed is warming up to 300~450 DEG C, is incubated 0.5~3h, then be warming up to 600~800 with 0.5~5 DEG C/min heating rate
DEG C, it is incubated 0.5~3h.
Further, the step 2) and 4) in, low temperature drying is carried out in air dry oven, drying temperature be 80~
150 DEG C, drying time is 3~10h.
Further, in the step 2), high-temperature calcination is to be carried out in Muffle furnace under air atmosphere, and calcining heat is
800~1200 DEG C, calcination time is 3~10h.
A kind of above-mentioned application for following recirculating fluidized bed hydrocarbon reforming catalyst, the catalyst are applied to recirculating fluidized bed methane
Water preparing synthetic gas by reforming, its process conditions are：Reaction temperature is 700~900 DEG C, and reaction pressure is 0.1~0.5MPa, and air speed is
10000~1200000h-1, steam/hydrocarbons ratio ＜ 3: 1.
Compared with prior art, the present invention has advantages below：
First, the hexa-aluminate modified aluminas nickel-loaded catalyst for preparing of the present invention, due to hexa-aluminate can mosaicism,
Active nickel is highly dispersed in hexa-aluminate lattice, improve catalyst to heat endurance and reproducibility so that catalyst
The requirement of continuous oxidationreduction in recirculating fluidized bed is resistant to, catalytic activity is high, good to heat endurance, in big air speed (1.1
×106h-1) under the conditions of can recycle 120h and methane conversion is up to 90~60%.
Second, the present invention using the activated alumina microballoon with appropriate particle size scope and high mechanical properties as carrier,
Catalyst has good fluidizing performance and abrasion resistance properties, avoid it is ciculation fluidized during catalyst run agent, contamination of products
The problems such as with regular replenishment catalyst is needed.
Third, the method for preparing catalyst of the present invention is simple, and it is environment-friendly, it is easy to industrialized production, available for methane weight
The catalytic reforming process containing burnt gas such as Cheng Jimei, biomass gasified gas, coke oven tail gas is had suffered, be particularly suitable for use in recirculating fluidized bed
Catalytic reforming process.
Brief description of the drawings
Fig. 1 is fresh catalyst prepared by the embodiment of the present invention 5 and passes through continuous program heating reduction (TPR)-program liter
The X-ray powder diffraction figure of temperature oxidation (TPO) rear catalyst.
Fig. 2 is that the embodiment of the present invention 5 prepares the temperature programmed reduction figure (TPR) of catalyst and through temperature programmed oxidation
(TPO) temperature programmed reduction figure (TPR-2) again after.
The methane conversion that Fig. 3 prepares catalyst for the embodiment of the present invention 5 changes over time curve map.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings, is easy to more clearly understand the present invention, but they
The present invention is not formed and limited.(agents useful for same in following examples, it is chemically pure reagent unless otherwise indicated.)
Embodiment 1
(1) 0.884g lanthanum nitrate hexahydrates are dissolved in 7.8ml deionized waters, are configured to incipient impregnation liquid I, are impregnated into
20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, lanthanum hexaaluminate modified aluminas microballoon is made.
(3) 5.934g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
1, NiO/LaAl11O18/Al2O3, NiO content 6.97wt.%, hexa-aluminate content is 6.68wt.%, and surplus is that aluminum oxide is micro-
Ball.
Embodiment 2
(1) 0.471g calcium nitrate tetrahydrates are dissolved in 7.8ml deionized waters, are configured to incipient impregnation liquid I, are impregnated into
20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, calcium hexaluminate modified aluminas microballoon is made.
(3) 5.870g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
2, NiO/CaAl12O19/Al2O3, NiO content 6.97wt.%, hexa-aluminate content is 6.24wt.%, and surplus is that aluminum oxide is micro-
Ball.
Embodiment 3
(1) 0.429g strontium nitrates are dissolved in 7.8ml deionized waters, are configured to incipient impregnation liquid I, be impregnated into 20g oxidations
Aluminium microballoon.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, six strontium aluminate modified aluminas microballoons are made.
(3) 5.964g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
3, NiO/SrAl12O19/Al2O3, NiO content 6.97wt.%, hexa-aluminate content is 6.68wt.%, and surplus is that aluminum oxide is micro-
Ball.
Embodiment 4
(1) 0.533g barium nitrates are dissolved in 7.8ml deionized waters, are configured to incipient impregnation liquid I, be impregnated into 20g oxidations
Aluminium microballoon.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, barium aluminates modified aluminas microballoon is made.
(3) 5.928g Nickelous nitrate hexahydrates are dissolved in 2ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, be configured to
Incipient impregnation liquid II, it is impregnated into above-mentioned modified aluminas microballoon.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
4, NiO/BaAl12O19/Al2O3, NiO content 6.97wt.%, hexa-aluminate content is 7.14wt.%, and surplus is that aluminum oxide is micro-
Ball.
Embodiment 5
(1) 0.884g lanthanum nitrate hexahydrates and 0.581g Nickelous nitrate hexahydrates are dissolved in 6.8ml deionized waters, are configured to
Volume impregnation liquid I, it is impregnated into 20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, nickel doping lanthanum hexaaluminate modified aluminas microballoon is made.
(3) 5.934g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
5, NiO/LaNiAl11O19-δ/Al2O3, NiO content 7.60wt.%, hexa-aluminate content is 7.41wt.%, and surplus is aluminum oxide
Microballoon.
Embodiment 6
(1) 0.471g calcium nitrate tetrahydrates and 0.580g Nickelous nitrate hexahydrates are dissolved in 7.2ml deionized waters, are configured to
Volume impregnation liquid I, it is impregnated into 20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, nickel doping calcium hexaluminate modified aluminas microballoon is made.
(3) 5.290g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
6, NiO/CaNiAl11O19-δ/Al2O3, NiO content 6.28wt.%, hexa-aluminate content is 6.45wt.%, and surplus is aluminum oxide
Microballoon.
Embodiment 7
(1) 0.429g strontium nitrates and 0.589g Nickelous nitrate hexahydrates are dissolved in 7.2ml deionized waters, are configured to soak in equal volume
Stain liquid I, it is impregnated into 20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, nickel is made and adulterates six strontium aluminate modified aluminas microballoons.
(3) 5.375g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
7, NiO/SrNiAl11O19-δ/Al2O3, NiO content 6.35wt.%, hexa-aluminate content is 6.96wt.%, and surplus is aluminum oxide
Microballoon.
Embodiment 8
(1) 0.533g barium nitrates and 0.593g Nickelous nitrate hexahydrates are dissolved in 7.4ml deionized waters, are configured to soak in equal volume
Stain liquid I, it is impregnated into 20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, nickel doping barium aluminates modified aluminas microballoon is made.
(3) 5.335g Nickelous nitrate hexahydrates are dissolved in 2.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
8, NiO/BaNiAl11O19-δ/Al2O3, NiO content 6.27wt.%, hexa-aluminate content is 7.45wt.%, and surplus is aluminum oxide
Microballoon.
Embodiment 9
(1) 0.890g lanthanum nitrate hexahydrates and 0.598g cabaltous nitrate hexahydrates are dissolved in 7.2ml deionized waters, are configured to
Volume impregnation liquid I, it is impregnated into 20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, cobalt doped lanthanum hexaaluminate modified aluminas microballoon is made.
(3) 5.980g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
9, NiO/LaCoAl11O19-δ/Al2O3, NiO content 6.97wt.%, hexa-aluminate content is 7.45wt.%, and surplus is aluminum oxide
Microballoon.
Embodiment 10
(1) 0.891g lanthanum nitrate hexahydrates and 0.831g Fe(NO3)39H2Os are dissolved in 5.2ml deionized waters, are configured to
Volume impregnation liquid I, it is impregnated into 20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, Fe2O3 doping lanthanum hexaaluminate modified aluminas microballoon is made.
(3) 5.983g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
10, NiO/LaFeAl11O19-δ/Al2O3, NiO content 6.97wt.%, hexa-aluminate content is 7.43wt.%, and surplus is aluminum oxide
Microballoon.
Embodiment 11
(1) 0.891g lanthanum nitrate hexahydrates and 0.497g Gerhardites are dissolved in 6.8ml deionized waters, are configured to
Volume impregnation liquid I, it is impregnated into 20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, Copper-cladding Aluminum Bar lanthanum hexaaluminate modified aluminas microballoon is made.
(3) 5.983g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
11, NiO/LaCuAl11O19-δ/Al2O3, NiO content 6.97wt.%, hexa-aluminate content is 7.50wt.%, and surplus is aluminum oxide
Microballoon.
Embodiment 12
(1) 0.887g lanthanum nitrate hexahydrates and 0.525g magnesium nitrate hexahydrates are dissolved in 6.3ml deionized waters, are configured to
Volume impregnation liquid I, it is impregnated into 20g aluminum oxide micro-spheres.
(2) aluminum oxide micro-sphere is placed in 100 DEG C of dry 5h in baking oven, 1200 DEG C is risen to 5 DEG C/min in Muffle furnace
5h is calcined, mg-doped lanthanum hexaaluminate modified aluminas microballoon is made.
(3) 5.959g Nickelous nitrate hexahydrates are dissolved in 1.5ml deionized waters, are heated to 50~60 DEG C and are completely dissolved, prepared
Into incipient impregnation liquid II, above-mentioned modified aluminas microballoon is impregnated into.
(4) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Support type microspherical catalyst is prepared
12, NiO/LaMgAl11O19-δ/Al2O3, NiO content 7.00wt.%, hexa-aluminate content is 7.13wt.%, and surplus is aluminum oxide
Microballoon.
Comparative example
(1) 20g aluminum oxide micro-spheres are placed in Muffle furnace and 1100 DEG C of calcining 5h is risen to 5 DEG C/min, be made modified oxidized
Aluminium microballoon.
(2) 5.837g Nickelous nitrate hexahydrates are dissolved in 2ml deionized waters, are configured to incipient impregnation liquid, are impregnated into the above
Aluminum oxide micro-sphere.
(3) said mixture is placed in 100 DEG C of dry 5h in baking oven, heats up and calcine then at Muffle furnace internal program, first with 3
DEG C/min rises to 350 DEG C, 1h is stopped, then 650 DEG C are risen to 1.5 DEG C/min, stop 2h.Comparative example catalyst is prepared,
NiO/Al2O3, NiO contents 6.973wt.%.
Catalyst characterization：
The catalyst 5 prepared to embodiment 5 has carried out the sign of structure and performance.X-ray diffraction spectrogram is shown in Fig. 1 (a).
The catalyst contains Alpha-alumina, NiO and lanthanum nickel hexa-aluminate LaNiAl11O19-δCrystalline phase.LaNiAl11O19-δFeature diffraction
Peak appears in 18.8 °, 20.0 °, 32.1 °, 34.0 °, 35.1 °, 39.3 °, 40.8 °, 42.7 °, 58.5 ° and 59.9 °, and most strong three
Individual characteristic peak appears in 32.1 °, 34.0 ° and 35.1 °, belongs to Magnetoplumbate-type hexa-aluminate crystal phase structure, JCPDS card numbers 36-
1316.Perovskite LaAlO is had no in spectrogram3、LaNiO3Deng dephasign, spinelle NiAl is also had no2O4Generation.Prove to utilize this
The method of invention, the hexa-aluminate modified aluminas load with nickel doping can be prepared by being modified gama-alumina using lanthanum, nickel
Body, after nickel oxide active component is supported, Al can be avoided2O3Act on forming inactive spinelle at high temperature with NiO
NiAl2O4Or perovskite LaNiO3Deng.
In order to investigate the stability of the oxidationreduction of the catalyst, line program is entered to the catalyst using chemical adsorption instrument
Heating reduction (TPR)-temperature programmed oxidation (TPO) is tested, the condition of reformation-regeneration in simulation loop fluid bed, and to passing through
Catalyst after TPR-TPO carries out XRD signs, and XRD spectra is shown in Fig. 1 (b).As seen from the figure, after reduction and oxidation regeneration
Catalyst still includes Alpha-alumina, NiO and lanthanum nickel hexa-aluminate LaNiAl11O19-δCrystalline phase, each feature diffraction of hexa-aluminate
Peak position does not change, shows that the crystal phase structure of the catalyst is not destroyed after redox, shows
Hexa-aluminate Magnetoplumbate-type structure has the stability of good redox, meets that catalyst needs exist in recirculating fluidized bed
The requirement constantly circulated in reformation-regeneration reactor.
In order to investigate the reproducibility under catalyst high temperature, the catalyst has been carried out continuous temperature programmed reduction (TPR)-
Temperature programmed oxidation (TPO)-temperature programmed reduction (TPR) test, TPR result is shown in Fig. 2 twice.Contrast is found, although this is urged
The reduction peak of agent can be to high temperature displacement during second of TPR, and the relative amount for being easy to the NiO of reduction declines, but should
The temperature of all reduction peaks of catalyst is respectively less than 800 DEG C, illustrates operating condition (850 DEG C) of the catalyst in reforming reactor
Under can obtain reduction activation, catalyst has good reducing activity.
Catalyst activity is evaluated：
In the coke tar reforming and conversion of methane of crude synthesis gas, coke tar reforming is easier to realize than methane conversion, because
This, by the use of the methane conversion capability of catalyst as evaluation index, screens and is adapted to the detar of recirculating fluidized bed crude synthesis gas, hydro carbons
Reforming catalyst is effective catalyst research and development method.Catalyst with excellent methane steam conversion performance will disclosure satisfy that
The detar of recirculating fluidized bed crude synthesis gas, the technological requirement of the hydrocarbon conversion.
Catalyst prepared by embodiment 1~12 and comparative example is reacted for reforming of methane on Ni-Ce, in reaction temperature
850 DEG C of degree, normal pressure, air speed 1.1 × 106h-1, the reformation performance of catalyst is tested under the conditions of steam/hydrocarbons ratio 2.8: 1.Specific steps are such as
Under：
1) 0.05g catalyst is weighed, 10g alumina supports is added and is uniformly mixed therewith as diluent, it is micro- to be placed in normal pressure
In type fluidized-bed reactor, 5%H is passed through2- Ar complete reducing catalysts at 850 DEG C.
2) CH that flow is 100ml/min and 334ml/min is each led into reactor4And N2, and with 280ml/min's
Water vapour mixes, and reacts 30min after being preheated to 850 DEG C.
3) it is passed through the 4%H that flow is 300ml/min2/ 3%O2/ 93%N2Regeneration gas, 850 DEG C regenerate to catalyst,
Regeneration period is 8min.With 300ml/min N after the completion of regeneration2Purged.
4) by flow it is respectively again 100ml/min and 334ml/min CH4And N2Introduce reactor, and and 280ml/
Min water vapour mixing, reacts 30min after being preheated to 850 DEG C.
5) repeat step 3), 4), altogether carry out 6 circulation tests, simulation catalyst passed through in circulating fluid bed reactor
Go through " reaction-regeneration-reaction-regeneration " process.
The composition of reaction product is determined using U.S. ARI Raman spectrum on-line gas analysis instrument.Methane conversion is according to such as
Lower formula calculates.
XCH4=(FCO,out+FCO2,out)/FCH4,in× 100%
The average value of (30min) methane conversion is as reactivity using within the reforming reaction cycle, under acquired results import
Table 1.
Table 1
The methane conversion of the catalyst prepared it can be seen from the data of table 1 using the inventive method is apparently higher than contrast
Example, it can be seen that the catalytic activity of the catalyst of embodiment 1~12 is higher than comparative example catalyst.
In order to investigate the reaction stability of catalyst, the catalysis weight of continuous 150 circulations (120h) has been carried out to catalyst 5
Whole reaction, (reforming reaction 30min) represents the activity of catalyst with average value in each circulation, and methane average conversion is with the time
Change curve see Fig. 3.As seen from Figure 3, in the 10h after reaction starts, catalyst experienced more obvious inactivation, methane
Conversion ratio is down to 80% from 90%, but within ensuing 110h reaction time, slowly inactivation, first is presented in catalyst
The conversion ratio of alkane is 80~60%, is illustrated in high-speed (1.1 × 106h-1) reaction condition under, catalyst has good work
Property and stability.With reference to TPR and XRD results, it is believed that due to foring hexa-aluminate crystalline phase in the catalyst of design, not only have
High thermal resistance, improve alumina support to heat endurance, and under the conditions of reformation-regeneration cycle of recirculating fluidized bed, bear
Nickel instead of aluminium and step into hexa-aluminate crystalline phase so as to high degree of dispersion in the nickel active component of load, effectively prevent nickel from
By moving and gathering inactivation, while inhibit species such as spinelle of the nickel with alumina catalyst support effect into low activity under hot conditions
Deng so as to improve catalytic activity and stability.
Claims (11)
- A kind of 1. recirculating fluidized bed hydrocarbon reforming catalyst, it is characterised in that：Including hexa-aluminate modified aluminium oxide supports and load Active metal nickel on the hexa-aluminate modified aluminium oxide supports, the hexa-aluminate modified aluminium oxide supports include activity Aluminum oxide micro-sphere matrix and hexa-aluminate, the hexa-aluminate is supported in the activated alumina microballoon matrix surface and endoporus.
- 2. recirculating fluidized bed hydrocarbon reforming catalyst according to claim 1, it is characterised in that：The formula of the hexa-aluminate is AMxAl12-xO19-δ(0≤x,δ<5), wherein, A is one kind in calcium, strontium, barium and lanthanum, and M is one kind in iron, cobalt, nickel, copper and magnesium Or two or more combination；The hexa-aluminate weight is the 1~50% of catalyst weight, and the active metal nickel weight is with oxygen Compound is calculated as the 1~20% of catalyst weight, and surplus is the activated alumina microballoon matrix.
- 3. recirculating fluidized bed hydrocarbon reforming catalyst according to claim 1 or claim 2, it is characterised in that：The activated alumina is micro- Alumina content ＞ 90% in ball matrix, particle diameter are 50~500um, and D50 is 80~300um, than surface >=50m2/ g, total pore volume ≥0.1cm3/ g, abrasion index ＜ 0.5%/h.
- 4. recirculating fluidized bed hydrocarbon reforming catalyst according to claim 2, it is characterised in that：Form the hexa-aluminate Calcium, strontium, barium and lanthanum are selected from anhydrous nitrate, nitric hydrate salt, chlorate, sulfate and acetate, form the hexa-aluminate Iron, cobalt, nickel, copper and magnesium be selected from anhydrous chlorate, chloride hydrate salt, nitrate, sulfate and acetate, the hexa-aluminate Weight be catalyst weight 5~30%.
- 5. recirculating fluidized bed hydrocarbon reforming catalyst according to claim 1 or claim 2, it is characterised in that：The active metal nickel comes From more than one or both of Dehydrated nickel chloride, hydrated nickel chloride, nickel nitrate, nickel sulfate and nickel acetate.
- A kind of 6. preparation method of recirculating fluidized bed hydrocarbon reforming catalyst described in claim 1, it is characterised in that：Including following step Suddenly：1) calcium salt, strontium salt, barium salt or lanthanum salt are dissolved in water and are made into dipping solution I, or by calcium salt, strontium salt, barium salt or lanthanum salt and iron More than one or both of salt, cobalt salt, nickel salt, mantoquita and magnesium salts water is dissolved in together and is made into dipping solution I, by dipping solution I It is impregnated on activated alumina microballoon, modified support precursor is made；2) modified support precursor made from step 1) is formed into modified aluminium oxide supports after low temperature drying and high-temperature calcination；3) nickel salt is dissolved in water and is made into dipping solution II, be impregnated on the modified aluminium oxide supports that step 2) obtains；4) by the mixture that step 3) obtains after low temperature drying and high-temperature calcination, you can obtain the recirculating fluidized bed hydrocarbon reforming Catalyst.
- 7. the preparation method of recirculating fluidized bed hydrocarbon reforming catalyst according to claim 6, it is characterised in that：The step 1) In, calcium, strontium, the dosage of barium or lanthanum are calculated as the 0.1~20% of catalyst weight with oxide；One kind in iron, cobalt, nickel, copper, magnesium Or two or more dosages is calculated as the 0.1~20% of catalyst weight with oxide.
- 8. according to the preparation method of the recirculating fluidized bed hydrocarbon reforming catalyst of claim 6 or 7, it is characterised in that：The step It is rapid 4) in, high-temperature calcination uses two-part temperature programming, is first warming up to 300~450 DEG C with 1~10 DEG C/min heating rate, 0.5~3h is incubated, then 600~800 DEG C are warming up to 0.5~5 DEG C/min heating rate, is incubated 0.5~3h.
- 9. according to the preparation method of the recirculating fluidized bed hydrocarbon reforming catalyst of claim 6 or 7, it is characterised in that：The step It is rapid 2) and 4) in, low temperature drying is carried out in air dry oven, and drying temperature is 80~150 DEG C, and drying time is 3~10h.
- 10. according to the preparation method of the recirculating fluidized bed hydrocarbon reforming catalyst of claim 6 or 7, it is characterised in that：The step It is rapid 2) in, high-temperature calcination is to be carried out in Muffle furnace under air atmosphere, calcining heat be 800~1200 DEG C, calcination time be 3~ 10h。
- 11. the application of recirculating fluidized bed hydrocarbon reforming catalyst is followed described in a kind of claim 1, it is characterised in that：The catalyst Applied to recirculating fluidized bed methane water preparing synthetic gas by reforming, its process conditions is：Reaction temperature is 700~900 DEG C, reaction pressure For 0.1~0.5MPa, air speed is 10000~1200000h-1, steam/hydrocarbons ratio ＜ 3: 1.
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