CN103394354B - A kind of load Synthetic holography Fe-series catalyst on carbon ball and preparation method thereof - Google Patents
A kind of load Synthetic holography Fe-series catalyst on carbon ball and preparation method thereof Download PDFInfo
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- CN103394354B CN103394354B CN201310368342.4A CN201310368342A CN103394354B CN 103394354 B CN103394354 B CN 103394354B CN 201310368342 A CN201310368342 A CN 201310368342A CN 103394354 B CN103394354 B CN 103394354B
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- exchange resin
- carbon ball
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- 239000003054 catalyst Substances 0.000 title claims abstract description 184
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 109
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000001093 holography Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 34
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 43
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 43
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- -1 iron ion Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003957 anion exchange resin Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001721 carbon Chemical class 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- UEUDBBQFZIMOQJ-UHFFFAOYSA-K ferric ammonium oxalate Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UEUDBBQFZIMOQJ-UHFFFAOYSA-K 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011324 bead Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000007598 dipping method Methods 0.000 abstract description 15
- 239000008187 granular material Substances 0.000 abstract description 13
- 238000001556 precipitation Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011805 ball Substances 0.000 description 96
- 238000000034 method Methods 0.000 description 32
- 239000011347 resin Substances 0.000 description 27
- 229920005989 resin Polymers 0.000 description 27
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 16
- 239000004005 microsphere Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000004480 active ingredient Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000009938 salting Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 2
- 241000143432 Daldinia concentrica Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FRYDSOYOHWGSMD-UHFFFAOYSA-N [C].O Chemical compound [C].O FRYDSOYOHWGSMD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
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- 239000010985 leather Substances 0.000 description 2
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- 238000000465 moulding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005120 petroleum cracking Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- GTUVXOOHBUUGBH-UHFFFAOYSA-N furan;methanol Chemical compound OC.C=1C=COC=1 GTUVXOOHBUUGBH-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a kind of load Synthetic holography Fe-series catalyst on carbon ball and preparation method thereof, described carbon ball carrier is the ion exchange resin beads of carbonization, the active principle of described catalyst and/or auxiliary agent or their precursor before described ion exchange resin carbonization through ion-exchange, absorption, precipitation and/or dipping by load equably in the surface and/or duct of ion exchange resin beads.The preparation method of described catalyst is simple to operate, be convenient to control, and the catalyst granules ball-type degree obtained is good, and mechanical strength is high, shows higher catalytic activity and excellent selectivity of light olefin in Synthetic holography reaction.
Description
Technical field
The present invention relates to the Synthetic holography Fe-series catalyst of a kind of load on carbon ball, particularly, relate to the catalyst on carbon ball that a kind of load is ion exchange resin at precursor.
Background technology
In the preparation method of loaded catalyst, spray drying process and infusion process are two kinds of the most frequently used preparation methods.Although but loaded catalyst particle good sphericity prepared by spray drying process, preparation method is complicated, although loaded catalyst preparation process prepared by infusion process is relatively simple, the particle sphericity of catalyst is bad.Find the method for preparing catalyst that a kind of preparation process is simple, particle good sphericity, granule strength are large to be one of task of field of catalyst preparation researcher all the time.
Through studying for many years, Many researchers finds: the catalytic performance quality of loaded catalyst not only depends on the composition of catalyst itself, the kind of the active principle of such as catalyst, auxiliary agent and carrier and content, different preparation method also depends on method for preparing catalyst, because may cause the mixing dispersing mode between the different active principle of catalyst different with uniformity.So, usually there will be the situation that catalyst catalytic performance difference that composition identical catalyst finally obtains when adopting different preparation methods to prepare is huge.
Usually, it is believed that: the active principle of catalyst and/or auxiliary agent disperse or mix more even, the catalytic activity of catalyst is better, the active principle of catalyst and/or auxiliary agent distribute more even in the carrier, the performance of catalyst is also better, and so just determining and ensureing that active principle and/or auxiliary agent are uniformly dispersed and ensure that active principle and/or auxiliary agent are evenly distributed in the carrier is the key producing high-performance supported type catalyst.
Further, for loaded catalyst, the compatibility of catalyst active principle and/or auxiliary agent and carrier and the cooperative effect between them are also the key factors obtaining high-performance supported type catalyst.
In recent years, the research using carbon ball as the catalyst of carrier is increasing, and such as, CN10269875A discloses a kind of nanometer iron oxide/carbon sphere compound catalyst, preparation method and application.Wherein, load is at carbon ball on the surface equably for ferric oxide nanometer particle.Its preparation method be utilize Fenton to react, strong oxidizing property when namely utilizing hydrogen peroxide and ferrous ion to coexist modifies carbon ball surface, thus nano level iron oxide particles is distributed equably or load at carbon ball on the surface, thus obtain nanometer iron oxide/carbon sphere compound catalyst.Disclosed in this patent document, method solves the problems such as nano level iron oxide catalyst particles serious agglomeration, and the catalyst obtained can be used as efficient burning catalyst, the agent of light degradation catalytic organism and petroleum cracking catalyst.
The carbon ball carrier common intensity that above-mentioned catalyst uses is lower, by nanometer ferro oxide or its presoma by Fenton reaction load carbon ball on the surface time, need the described carbon ball of long-time stirring, like this, just likely carbon ball carrier is caused damage, thus it is damaged to a certain extent to make it occur, this likely has influence on the sphericity of final catalyst granules.
CN102125844A discloses a kind of method and the application thereof of preparing iron charcoal sphere material, this iron charcoal sphere material is obtained containing the aqueous solution of sugar with molysite by single step reaction under hydrothermal conditions, wherein, iron oxide nanoparticle is evenly dispersed in the carbon ball of micron-scale, this iron charcoal sphere material can be used as the catalyst of Fischer-Tropsch synthesis, and it has higher C than existing not modified iron catalyst
5the advantage such as+hydrocarbon-selective and stability.
The preparation method of the iron charcoal sphere material recorded in the document is actually and is just incorporated in the raw material preparing carbon ball presoma by iron component in carbon ball precursor power process, thus, the presoma of iron oxide nanoparticle is uniform-distribution with in the carbon ball presoma formed, by carbonization or roasting, form iron oxide nanoparticle and be evenly dispersed in unique texture in the carbon ball of micron-scale, but such preparation method be difficult to ensure to make most of ferriferous oxide distribution of particles the surface of carbon ball and or duct in.
Above-mentioned disclosed carbon ball material or carbon ball carrier material ubiquity the shortcoming of the not high and preparation process complexity of mechanical strength.How to overcome above-mentioned shortcoming and find that a kind of process is simple, end product good sphericity, mechanical strength large and be very urgent to the preparation method that specific reaction or product have better catalytic activity and an optionally carbon sphere catalyst.
The present invention is intended to solve above-mentioned technical barrier and makes every effort to find a kind of with the better preparation method of the carbon ball catalyst that is carrier, thus, make the catalyst obtained show higher catalytic activity and selectivity of product, better catalyst granules sphericity and larger catalyst granules intensity.
Summary of the invention
According to a first aspect of the invention, the Synthetic holography Fe-series catalyst of a kind of load on carbon ball is provided, it is characterized in that: this carbon ball carrier is the ion exchange resin of carbonization, the active principle of described catalyst and/or auxiliary agent or their precursor before described ion exchange resin carbonization through ion-exchange, absorption, precipitation and/or dipping by load equably in the surface and/or duct of ion exchange resin.
Usually, described ion exchange resin is highly basic or weak basic anion exchange resin microballoon or strong acid or Weak-acid cation exchange resin microballoon, such as, described ion exchange resin is macroporous type highly basic or weak basic anion exchange resin microballoon or macroporous type strong acid or Weak-acid cation exchange resin microballoon further.
As the exemplary and nonrestrictive example of above-mentioned catalyst, but the oxide of the active principle iron content of above-mentioned catalyst and/or carbide; The precursor of the active principle of described catalyst can thermal decomposition be the water-soluble salt solution of the oxide of iron; But the oxide of the auxiliary agent copper of described catalyst, potassium, cobalt, nickel and/or manganese, the precursor of the auxiliary agent of described catalyst can thermal decomposition be the water-soluble salt solution of the oxide of copper, potassium, cobalt, nickel and/or manganese.Particularly, the precursor of the active principle of above-mentioned catalyst is the anion state metal complex or the cationic slaine of iron that contain iron ion further.
Equally, as the exemplary and nonrestrictive example of above-mentioned catalyst, but the catalyst of above-mentioned catalyst synthesis gas one step producing light olefins catalyst, fischer-tropsch synthetic catalyst, methanation catalyst prepared by synthetic gas or simultaneously co-producing light olefins, light oil and methane.
According to a second aspect of the present invention, the preparation method of the Synthetic holography Fe-series catalyst of a kind of load on carbon ball is provided, comprises the following steps:
(1) described ion exchange resin beads is put into the active principle of described catalyst and/or the aqueous solution of auxiliary agent or their precursor, carry out sufficient Agitation and mixing, carry out sufficient ion-exchange, absorption, precipitation and/or dipping to make the active principle of catalyst and/or auxiliary agent or their precursor and described ion exchange resin.Thus by load equably in the surface and/or duct of described ion exchange resin;
(2) clean the described ion exchange resin beads after above-mentioned steps (1), to remove unnecessary catalyst active principle and/or auxiliary agent or their precursor, then, carry out drying, to remove moisture;
(3) under an inert atmosphere, described ion exchange resin beads after roasting above-mentioned steps (2), to make described ion exchange resin beads carbonization become carbon ball, simultaneously, the active principle of described catalyst and/or the precursor of auxiliary agent are thermal decomposited active principle into described catalyst and/or auxiliary agent, thus, obtain active principle and/or auxiliary agent by the catalyst of load in carbon ball surface and/or duct equably.
Preferably, in step (1), the Agitation and mixing time can be 8-24 hour; In step (2), baking temperature can be 80-150 DEG C, and drying time can be 2-24 hour; In step (3), sintering temperature can be 300-650 DEG C, roasting time can 2-8 hour.
In above-mentioned preparation method, preferably, the particle diameter of described ion exchange resin beads is 0.2-1.0 millimeter, the precursor of the active principle of described catalyst can carry out the Organic Iron salting liquid of ion-exchange, the such as potassium ferricyanide, ammonium ferric oxalate, ferric ammonium sulfate and/or ferric citrate etc. with described ion exchange resin beads; Or ironic citrate, iron chloride, ferric nitrate, ferric sulfate, ferrous sulfate, ferric oxalate, ferric acetate, iron pentacarbonyl.
Accompanying drawing explanation
Fig. 1 is the scanning electron photo of catalyst prepared by preparation method of the present invention;
Detailed description of the invention
The present invention is further explained in detail by the description below with reference to accompanying drawing, but below describe only for enabling general technical staff of the technical field of the invention clearly understand principle of the present invention and marrow, and do not mean that any type of restriction is carried out to the present invention.
Material with carbon element has wide application in a lot of fields, carbon ball is as a kind of special shape of material with carbon element, the spherical structure special because of it and good surface modificability, be used as the carrier material of electrode material, energy storage hydrogen storage material, sorbing material, lubricant material and some high performance catalysts gradually.Simultaneously, carbon ball itself also possesses certain catalytic activity, and under certain conditions, the effect of catalyst promoter can be played, when carbon ball is used as catalyst carrier, in some cases, it can play multiple action, particularly, when its carrier as the oxide catalyst of oxide catalyst, such as iron, itself and oxide catalyst active principle show extraordinary compatibility and synergy, are the desirable carrier materials of oxide catalyst.
Usually, carbon ball can be prepared by organic carbon hydrate, such as, prepare carbon ball by glucose as carbon source through Hydrothermal Synthesis; Or prepare hollow carbon balls by organic carbon sources such as sulfonated polystyrene microballoon, furancarbinol and phenolic resins.An example of most typical carbon ball preparation method is as follows:
1) polystyrene microsphere template of uniform diameter is prepared; 2) polystyrene moulding being added sulfonation in the concentrated sulfuric acid, by controlling sulfonation time, obtaining the polystyrene moulding that sulfonation degree is different; 3) phenolic resins and sulfonated polystyrene micro ball template is utilized to prepare polystyrene/phenolic resin composite balls; 4) by composite balls carbonization, carbon ball is obtained.
Carbon ball prepared by said method can be used as electrode material, energy storage hydrogen storage material, sorbing material and lubricant, also can be used as catalyst carrier.
Generally speaking, carbon ball preparation method can comprise chemical vapour deposition technique, solvent-thermal method and template etc., and these methods cut both ways, but the most frequently used be template, mostly carbon source is organic carbon hydrate.Usually, carbon ball can be divided into nanoscale, submicron order, micron order and grade carbon ball, nanoscale and submicron order carbon ball because size is little, easily reunite, so less stable, usually, the carbon ball as catalyst carrier is micron order and grade carbon ball.
The carbon ball of various sizes not only can be used to build various multi-functional dopant material, and itself also can be used for catalysis, medicine carrying, nano-device etc.But these application but depend on size and the dispersiveness of carbon ball to a great extent.Therefore, prepare good dispersion, the high-quality carbon ball of moderate dimensions just seems particularly important.At present, generally acknowledge that preparing carbon ball most effectual way is phenolic resins polymerization in the world.The method preparation easily, Heat stability is good, easily change into carbon ball.But raw material-phenol that the method uses and formaldehyde have high carcinogenic.Therefore, the carbon ball of low toxicity Material synthesis heat endurance and favorable dispersibility is adopted to have very large meaning to its practical application.
Some patent documents also disclose the preparation method of some carbonaceous materials, particularly carbon ball, such as, CN1480397A discloses a kind of preparation method of high-strength resin-based spheric active carbon, it take spherical resin as raw material, through swelling, degree of depth sulfonation, gradient concentration acid elution, again through high temperature cabonization and steam activation, obtain spherical activated carbon.
CN102247819A discloses a kind of preparation method of magnetic carbonized resin microspheres, it comprises and being mixed with anion exchange resin by potassium ferricyanide solution, ion-exchange is carried out to make them, afterwards, again the resin of drying is carried out carbonization, obtain load and to be magnetic the carbon ball of particle, this magnetic carbon sphere is used as sorbent material, effectively can reduce the COD value of leather waste water, and sulphur, the chromium content in leather waste water can be reduced.
CN102643513A discloses a kind of preparation method of m-aminophenyl resinox ball and the preparation method of carbon ball.Wherein, m-aminophenol and formaldehyde is made to carry out polymerisation under ammoniacal liquor and/or ethylene glycol catalytic action, micella is formed in course of reaction, m-aminophenol and formaldehyde carry out polymerisation in micella, form m-aminophenyl resinox ball, the m-aminophenyl resinox ball obtained has higher monodispersity and dimensional controllability, after this m-aminophenyl resinox ball roasting, can obtain corresponding carbon ball, carbon ball also has higher monodispersity.This carbon ball can be used as the decorative material of electrode after loaded metal platinum, for the reduction of oxygen and the catalytic oxidation of methyl alcohol.
For the micron being used as catalyst carrier and/or grade carbon ball, except sphericity, particle diameter and the dispersiveness of carbon ball itself, distribution situation on carbon ball carrier of the active ingredient of catalyst and auxiliary agent and dispersing uniformity also most important to final catalyst performance.
Therefore, find and a kind ofly make the active ingredient of catalyst and/or auxiliary agent high degree of dispersion and be evenly distributed on as the method in the carbon ball surface of catalyst carrier and duct to be prepare the key of the high-quality catalyst of load on carbon ball.
Clearly, the method by simply flooding or precipitate by the active ingredient of catalyst and/or auxiliary agent high degree of dispersion and cannot be evenly distributed in carbon ball surface and duct.
As mentioned above, organic resin, such as phenolic resins can be used as organic carbon source the carbon source material preparing carbon ball, if the active ingredient of above-mentioned catalyst and/or auxiliary agent can be dispersed in presoma, the i.e. carbon source material of carbon ball by certain technological means, after the carbonization of carbon ball presoma, they just can realize high degree of dispersion with in the surface being evenly distributed on carbon ball and duct.
According to this thinking, the present inventor is through repeatedly studying and testing, find that ion exchange resin can be used as presoma, the i.e. carbon source material of above-mentioned carbon ball, and preferably, the active ingredient of above-mentioned catalyst and/or the presoma of auxiliary agent can carry out the water-soluble salt solution of ion-exchange, absorption, precipitation and/or dipping with above-mentioned ion exchange resin.More preferably, simultaneously the active ingredient of above-mentioned catalyst and/or the presoma of auxiliary agent can carry out the water-soluble salt solution of ion-exchange, absorption, precipitation and dipping with above-mentioned ion exchange resin.
Usually, ion exchange resin methodology of organic synthesis is made.Conventional raw material is styrene or acrylic acid (ester), the skeleton with three dimensions dimensional network structure is generated by polymerisation, on skeleton, import the dissimilar chemical active radical being generally acidity or basic group again, thus make it possess the characteristic of ion-exchange.
Water insoluble and the common solvent of ion exchange resin.Great majority make graininess, also have some to make threadiness or powdery.The size of resin particle is generally within the scope of 0.3-1.2 millimeter, and major part is between 0.4 ~ 0.6.They have higher mechanical strength, and chemical property is also very stable, has longer service life under normal circumstances.
Containing one or more chemical active radicals in ion exchange resin, namely it be exchange functional group, dissociation can go out some cation, such as H in aqueous
+or Na
+or anion, such as OH
-or Cl
-, meanwhile, other cations originally had in adsorbent solution or anion.Namely the ion in resin and the ion in solution realize intercoursing.
In ion exchange resin, chemical active radical kind determines its main character and classification.First, it is divided into resin cation and the large class of resin anion (R.A.) two, and they can carry out ion-exchange with the cation in solution and anion respectively.Resin cation is divided into again highly acid and faintly acid two class, and resin anion (R.A.) is divided into again strong basicity and alkalescent two class.
Ion exchange resin is divided into phenylethylene resin series and acrylic resin according to the kind of its matrix, and can be divided into gel-type ion-exchange resin and macroreticular ion exchange resin according to the physical arrangement of resin.
Macroreticular ion exchange resin adds pore-foaming agent when polymerisation, and form the skeleton of mandruka columnar structure, there are a large amount of permanent micropore and/or duct in inside, then import cation exchange groups and make.It also has minute aperture and large mesh, and when it is wetting, aperture reaches 100 ~ 500 nanometers, and its size and number can control in the preparation.The surface area in duct can increase above 1000m
2/ g.This is not only ion-exchange and provides good contact conditions, shorten the distance of ion diffuse, also add many chain link activated centres, Molecular Adsorption effect can be produced by intermolecular Van der Waals force, various nonionic material can be adsorbed as active carbon, expand its function.
The hole of macroreticular ion exchange resin inside is many, and surface area is large, and activated centre is many, and ion diffuse speed is fast, and ion-exchange speed is also fast, usually, and its about fast than gel-type ion-exchange resin about ten times.During use, effect is fast, efficiency is high, and the required processing time shortens.Macroreticular ion exchange resin also has multiple advantage: swelling resistance, not easily broken, and resistance to oxidation is wear-resistant, heat-resisting and resistance to variations in temperature.
Therefore, in the present invention, most preferably, the presoma as the carbon ball of catalyst carrier is various types of macroreticular ion exchange resins.Such resin properties and structure make its not only can with the active ingredient of catalyst, auxiliary agent and/or their precursor solution realize sufficient ion exchange process, also can adsorb easily, precipitation and/or dipping process, thus, the active ingredient of catalyst and/or the load capacity of auxiliary agent is not only made significantly to increase, and, just can realize the active ingredient of catalyst in the short period of time, auxiliary agent and/or their presoma high degree of dispersion are with in the surface being evenly distributed on ion exchange resin and duct, and then ensure can high degree of dispersion and being evenly distributed on as in the carbon ball surface of catalyst carrier and duct at the active ingredient of ion exchange resin carbonization rear catalyst and/or auxiliary agent.
It should be noted that: catalyst of the present invention comprises any loaded catalyst being carrier with carbon ball, especially, the supported oxide catalyst being carrier with carbon ball, particularly, the loading type iron oxide being carrier with carbon ball and/or ferrous-carbide catalyst.
Equally, it should be noted that: catalyst of the present invention is not restricted to oxide catalyst or ferrum-based catalyst, catalyst of the present invention comprises any loaded catalyst being carrier with carbon ball, and wherein, carbon ball carrier is the ion exchange resin beads of carbonization; The active principle of described catalyst and/or auxiliary agent or their precursor before described ion exchange resin beads carbonization becomes carbon ball can through ion-exchange, absorption, precipitation and/or dipping by load equably in the surface and/or duct of ion exchange resin.
Theoretically, in the present invention, special restriction is not done to the relative scale between catalyst active principle and auxiliary agent, also do not do to limit especially to the relative scale between carbon ball carrier and catalyst active principle and/or auxiliary agent, but preferably, part by weight between catalyst promoter and active principle is 0-1, such as 0-0.5; Catalyst active principle and/or the part by weight between auxiliary agent and carbon ball carrier are 0.05-5, such as 0.1-1, particularly, and 0.15-0.7.
Particularly, in the present invention, the selective of catalyst can be changed by the composition and preparation parameter that regulate catalyst, wherein, Synthetic holography ferrum-based catalyst is modal catalyst, when it is used as the catalysts of synthesizing low-carbon alkene, be considered to be conducive to improve selectivity of light olefin with material with carbon element, such as carbon ball as catalyst carrier, but usually not high by the catalyst strength of material with carbon element, the load of such as carbon ball, so, in use easily loss.Therefore, the Synthetic holography Fe-series catalyst intensity improving the load of carbon ball is one of free-revving engine of the present invention.
Usually, the catalyst activity component that the load of carbon ball can be made different by the selection of the selection of amberlite lipid species and/or the precursor kind of catalyst active principle and/or auxiliary agent and/or auxiliary agent.Such as, when the catalyst active principle of load on carbon ball be iron oxide and/or cementite time, the selectivity of light olefin of catalyst is just higher, now, catalyst is suitable as the technique by synthesis gas one step producing light olefins, and when the catalyst active principle of load on carbon ball is mainly iron sulfide, the methane selectively of catalyst is just higher, now, catalyst is suitable as by the technique of preparing methane by synthetic gas.
In the present invention, load can exist with the form of nano particle with the catalyst active principle in duct and/or auxiliary agent on the surface at carbon ball, also can exist with the form of sub-micron and/or micro particles.
Such catalyst is such as the catalyst etc. of efficient burning catalyst, the agent of light degradation catalytic organism, petroleum cracking catalyst, synthesis gas one step producing light olefins catalyst, fischer-tropsch synthetic catalyst, methanation catalyst prepared by synthetic gas or simultaneously co-producing light olefins, light oil and methane.
Below; by exemplary and non-limiting specific embodiment explains the present invention in further detail; to make those of ordinary skill in the art clearly understand essence of the present invention and marrow, but following examples do not form any restriction to scope.
Embodiment
Embodiment 1
1.5 grams of potassium ferricyanides are dissolved in 300 ml deionized water, be configured to ion exchanged soln, described ion exchanged soln is the precursor solution of catalyst active principle containing Fe phase, the macroporous type strong-base anion-exchange resin D201 microballoon formed 30 grams by styrene polymerization (is purchased, average grain diameter is 0.6 millimeter, density is 0.85 grams per milliliter, and specific area is 550m
2/ g) put into above-mentioned ion exchanged soln, after ultrasonic wave process, stir 24 hours continuously, the unnecessary salting liquid of resin microsphere Adsorption on Surface is washed again off by deionized water, afterwards, resin microsphere is put into 90 DEG C of drying boxes and dry 8 hours, obtain yellow bead.Dried resin microsphere sample (yellow bead) is put into quartz boat (roaster), at N
2at atmosphere and 500 DEG C, roasting 4 hours, obtains black ball type catalyst.The mean intensity recording this catalyst granules is 440N/mm.The physical characteristic of this catalyst and chemical composition are respectively as shown in Table 1 and Table 2.
Fig. 1 is the scanning electron photo of the loaded catalyst of the present invention of preparation in embodiment 1, can obviously find out from Fig. 1: the sphericity of supported catalyst particle of the present invention is very good, it is uniformly dispersed with catalyst active principle containing Fe phase, does not have agglomeration containing Fe phase on carbon ball carrier surface.
Comparative example 1
(be purchased, average grain diameter is 0.6 millimeter to the macroporous type strong-base anion-exchange resin D201 microballoon formed 30 grams by styrene polymerization, and density is 0.85 grams per milliliter, and specific area is 550m
2/ g) put into 90 DEG C of drying boxes oven dry 12 hours.Dried resin microsphere sample is put into quartz boat (roaster), at N
2roasting 4 hours at atmosphere and 500 DEG C, obtain hollow carbon balls, this carbon ball intensity is extremely low, and hand touches namely broken, cannot carry out the load of catalyst active principle and/or auxiliary agent.
Embodiment 2
3.8 grams of ammonium ferric oxalates are dissolved in 300 ml deionized water, be configured to ion exchanged soln, described ion exchanged soln is the precursor solution of catalyst active principle containing Fe phase, the macroporous type strong-base anion-exchange resin D201 microballoon formed 10 grams by styrene polymerization (is purchased, average grain diameter is 0.5 millimeter, density is 0.75 grams per milliliter, and specific area is 450m
2/ g) put into above-mentioned ion exchanged soln, after ultrasonic wave process, stir 12 hours continuously, the unnecessary salting liquid of resin microsphere Adsorption on Surface is washed again off by deionized water, afterwards, resin microsphere is put into 120 DEG C of drying bakers dry 10 hours, obtain comprehensive look bead.Dried resin microsphere sample (brown bead) is put into quartz boat (roaster), at N
2at atmosphere and 700 DEG C, roasting 4 hours, obtains black ball type catalyst.The mean intensity recording this catalyst granules is 285N/mm.The physical characteristic of this catalyst and chemical composition are respectively as shown in Table 1 and Table 2.
Embodiment 3
1.1 grams of ferric citrates are dissolved in 800 ml deionized water, be configured to ion exchanged soln, described ion exchanged soln is the precursor solution of catalyst active principle containing Fe phase, the macroporous type strong-base anion-exchange resin D201 microballoon formed 20 grams by styrene polymerization (is purchased, average grain diameter is 0.6 millimeter, density is 0.85 grams per milliliter, and specific area is 550m
2/ g) put into above-mentioned ion exchanged soln, after ultrasonic wave process, stir 24 hours continuously, the unnecessary salting liquid of resin microsphere Adsorption on Surface is washed again off by deionized water, afterwards, resin microsphere is put into 120 DEG C of drying boxes and dry 12 hours, obtain pale red comprehensive look bead.Dried resin microsphere sample (pale red comprehensive look bead) is put into quartz boat (roaster), at N
2at atmosphere and 500 DEG C, roasting 4 hours, obtains black ball type catalyst.The mean intensity recording this catalyst granules is 363N/mm.The physical characteristic of this catalyst and chemical composition are as shown in Table 1 and Table 2.
Embodiment 4
3.0 grams of iron chloride are dissolved in 300 ml deionized water, be configured to ion exchanged soln, described ion exchanged soln is the precursor solution of catalyst active principle containing Fe phase, macroporous type storng-acid cation exchange resin 732 microballoon formed 20 grams by styrene polymerization (is purchased, average grain diameter is 0.8 millimeter, density is 0.8 grams per milliliter, and specific area is 450m
2/ g) put into above-mentioned ion exchanged soln, after ultrasonic wave process, stir 12 hours continuously, the unnecessary salting liquid of resin microsphere Adsorption on Surface is washed again off by deionized water, afterwards, resin microsphere is put into 60 DEG C of drying boxes and dry 12 hours, obtain light red transparent beads.Dried resin microsphere sample (light red transparent beads) is put into quartz boat (roaster), at N
2at atmosphere and 700 DEG C, roasting 4 hours, obtains black ball type catalyst.The mean intensity recording this catalyst granules is 212N/mm.The physical characteristic of this catalyst and chemical composition are as shown in Table 1 and Table 2.
Comparative example 2
6.54 grams of ferric citrates are dissolved in 10 ml deionized water, be configured to dipping solution, described dipping solution is the precursor solution of catalyst active principle containing Fe phase, 5 grams (are purchased with porous carbon ball carrier prepared by phenolic resins polymerization, average grain diameter is 0.4 millimeter, density is 1.35 grams per milliliters, and specific area is 500m
2/ g) put into above-mentioned dipping solution, after ultrasonic wave process, leave standstill 12 hours, then the carbon ball carrier after dipping is put into 120 DEG C of drying bakers dry 16 hours.To flood and dried carbon ball carrier in still air and roasting 4 hours at 500 DEG C, obtain black ball type catalyst.The mean intensity recording this catalyst granules is 187N/mm.The physical characteristic of this catalyst and chemical composition are as shown in Table 1 and Table 2.
Comparative example 3
Be dissolved in 10 ml deionized water by 6.5 grams of ferric citrates, be configured to dipping solution, described dipping solution is the precursor solution of catalyst active principle containing Fe phase, by 5 grams of spheric active carbon carriers (be purchased, average grain diameter is 0.5 millimeter, density 0.55 grams per milliliter, specific area is 1500m
2/ g) put into above-mentioned dipping solution, after ultrasonic wave process, leave standstill 12 hours, then the absorbent charcoal carrier after dipping is put into 120 DEG C of drying boxes oven dry 14 hours.To flood with dried absorbent charcoal carrier at N
2at atmosphere and 350 DEG C, roasting 4 hours, obtains black ball type catalyst.The mean intensity recording this catalyst granules is 195N/mm.The physical characteristic of this catalyst and chemical composition are as shown in Table 1 and Table 2.
Table 1
Table 2
Test case
Test case 1
The catalyst prepared in embodiment 1-3 and comparative example 2-3 is carried out catalytic performance test in laboratory scale fixed bed reactors, and experiment condition is: air speed 6000ml/g/h, reaction temperature 340 DEG C, reaction pressure 2Mpa.
The raw material of synthetic gas H used
2/ CO volume ratio is 2.0, when reactor brings into operation, H
2be preheated to 250 DEG C with CO entering before in reactor, catalyst carries out reduction activation with hydrogen before use, and acquired results represents in the following Table 3.
Table 3
Data as can be seen from table 3: relative to existing catalyst (comparative example 1 and 2), hydrocarbon content, C in the gas-phase product using catalyst of the present invention (embodiment 1 and 3) to be formed
2-C
4olefin(e) centent, C
5+ hydrocarbon content obviously increases, simultaneously, ethylenic alkoxy rate in the mean intensity of catalyst granules and gas-phase product also significantly improves, this illustrates: physics and the catalytic performance, especially catalyst granules ball-type degree and mechanical strength of catalyst of the present invention (embodiment 1 and 3) obviously improve, it shows higher catalytic activity and excellent selectivity of light olefin in Synthetic holography reaction, and this catalyst being prepared by existing method is unattainable.The data of table 2 also illustrate: Fe-series catalyst (embodiment 1 and 3) prepared by the inventive method is particularly suitable for being used in the technique of synthesis gas one step producing light olefins.
Test case 2
The catalyst of preparation in embodiment 4 is carried out catalytic performance test in laboratory scale fixed bed reactors, and experiment condition is: air speed 6000ml/g/h, reaction temperature 340 DEG C, reaction pressure 1Mpa.
The raw material of synthetic gas H used
2/ CO volume ratio is 2.0, when reactor brings into operation, H
2be preheated to 250 DEG C with CO entering before in reactor, catalyst carries out reduction activation with hydrogen before use, and acquired results represents in the following Table 4.
Table 4
Data as can be seen from table 4: in the gas-phase product using catalyst of the present invention (embodiment 4) to be formed, the content of methane is the highest, this illustrates: this catalyst has good catalytic activity to methanation reaction and has methane production higher selective, and it is suitable for use in the technique of preparing methane by synthetic gas.
The term that this description is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary, those of ordinary skill in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (5)
1. the application of the Fe-series catalyst of load on carbon ball carrier in Synthetic holography reaction, is characterized in that:
This carbon ball carrier is the styrene ion exchange resin of carbonization, the active principle of described catalyst and/or the precursor of auxiliary agent before described ion exchange resin carbonization through ion-exchange by load equably in the surface and/or duct of ion exchange resin,
Wherein, described styrene ion exchange resin is highly basic or weak basic anion exchange resin microballoon or strong-acid cation-exchange resin microballoon; The precursor of described catalyst active principle is the anion state metal complex or the cationic slaine of iron that contain iron ion; The precursor of the auxiliary agent of described catalyst thermal decomposition to be the water soluble salt of the oxide of copper, potassium, cobalt, nickel and/or manganese.
2. application according to claim 1, wherein, the precursor of the active principle of described catalyst is the potassium ferricyanide, ammonium ferric oxalate, ferric ammonium sulfate and/or ferric citrate; Or ironic citrate, iron chloride, ferric nitrate, ferric sulfate, ferrous sulfate, ferric oxalate, ferric acetate and/or iron pentacarbonyl.
3. application according to claim 1, wherein, the active principle of described catalyst is oxide and/or the carbide of iron content; The auxiliary agent of described catalyst is the oxide of copper, potassium, cobalt, nickel and/or manganese.
4. application according to claim 1, wherein, described styrene ion exchange resin is macroreticular ion exchange resin microballoon further.
5. according to one of any described application of claim 1-4, wherein, the Fe-series catalyst of described load on carbon ball carrier is used as the catalyst of synthesis gas one step producing light olefins catalyst, fischer-tropsch synthetic catalyst, methanation catalyst prepared by synthetic gas or simultaneously co-producing light olefins, light oil and methane.
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| CN112108181A (en) * | 2019-06-21 | 2020-12-22 | 中国科学院大连化学物理研究所 | Catalyst for preparing low-carbon olefin by directly converting synthesis gas and preparation method thereof |
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| CN115475637B (en) * | 2021-06-16 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by Fischer-Tropsch synthesis, and preparation method and application thereof |
| CN114452977B (en) * | 2021-12-31 | 2024-03-26 | 南京师范大学 | Dual-functional material capable of circularly integrating and simultaneously adsorbing and catalyzing to remove VOCs under low temperature condition, and preparation method and application thereof |
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