CN106607102B - Alumina carrier, preparation method and application thereof - Google Patents
Alumina carrier, preparation method and application thereof Download PDFInfo
- Publication number
- CN106607102B CN106607102B CN201510696619.5A CN201510696619A CN106607102B CN 106607102 B CN106607102 B CN 106607102B CN 201510696619 A CN201510696619 A CN 201510696619A CN 106607102 B CN106607102 B CN 106607102B
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- Prior art keywords
- alumina
- carrier
- catalyst
- divalent metal
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 102
- 229910052751 metal Inorganic materials 0.000 claims abstract description 88
- 239000002184 metal Substances 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001878 scanning electron micrograph Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000012935 Averaging Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 49
- 230000000694 effects Effects 0.000 description 31
- 239000006185 dispersion Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 1
- 229910010250 TiO2—V2O5 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- -1 VIB metals Chemical class 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B01J23/85—Chromium, molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Abstract
The invention relates to an alumina carrier, a preparation method and an application thereof, wherein the carrier contains gamma-alumina and divalent metal elements, the surface of the carrier is provided with a net structure, the net density of the net structure is 0.5-50/square micron, and the net density is determined by a method of calculating the average value of the number of the grids distributed in each square micron area in at least 20 scanning electron micrographs. The invention also provides a preparation method of the alumina carrier, which comprises the steps of dipping the gamma-alumina into a mixture containing urea, water-soluble divalent metal salt and water, and then sequentially carrying out heat treatment, filtration, washing, drying and roasting. The alumina carrier prepared by the method is applied to a hydrogenation catalyst, so that the hydrofining performance of the catalyst is improved, and the service life of the catalyst can be effectively prolonged.
Description
Technical Field
The invention relates to an alumina carrier and a preparation method and application thereof.
Background
The hydrogenation technology is the most important means for producing clean oil products, wherein the high-efficiency hydrogenation catalyst is the core technology of the hydrogenation technology. The group VIB metals W or Mo and the group VIII metals Ni or Co have been the hydrogenation catalyst active components widely used in industry. And gamma-Al2O3Because of larger specific surface area, more concentrated pore distribution, good mechanical strength and thermal stability and low price, the carrier is always the preferred carrier of the industrial hydrogenation catalyst. The industrial preparation technology mainly adopts an impregnation method to introduce active components into a carrier pore channel, and then the hydrogenation catalyst is obtained through aging, drying, roasting and activating. Indeed, during impregnation, aging, drying, firing and even activation, the support surface structure and properties may directly affect the dispersion state and structure morphology of the active components, ultimately affecting the microstructure and intrinsic catalytic activity of the active phase (see Bergwerff et al, catal.today 2008,130:117 and Han et al, j.mater, Chem 2012,22: 25340.). It can be said that the support is one of the most important factors affecting the performance of the catalyst. Therefore, further optimizing the microstructure and properties of the alumina support to deeply exploit its potential as a hydrogenation catalyst support has become one of the important means to upgrade existing industrial hydrogenation catalysts.
At present, gamma-Al is used2O3As a hydrogenation catalyst support, there are mainly the following problems: on the one hand, in the conventional preparation process, aggregation of the active component is easily caused, which results in reduction of the dispersion of the active component and degradation of the support structure parameters, and finally reduction of the number of effective active sites on the catalyst, and on the other hand, a strong "m (metal) -O-Al" chemical bond, i.e., the so-called "support effect", is easily formed, thereby causing the active component of the catalyst to form a spinel structure and lose activity, or causing difficulty in sulfidation of the active component and reducing the activity and the active metal utilization rate of the catalyst (see Bergwerff et Al, catal.
In view of the above problems, researchers have developed a series of modifications of alumina carriers, with the main objective of improving the dispersion state of the active metal and modulating the interaction between the active metal and the carrier. For example, some research works have introduced P, F, B or chelating agent (such as NTA) to modulate the interaction between metal and carrier to form more type II active centers, but the obtained active particles are often too large and have undesirable dispersity, and the physical properties of the carrier are reduced, so that the performance of the hydrogenation catalyst is improved to a very limited extent (see Sun, et al, Catal. Total, 2003,86: 173; Usman, er al, J.Catal.,2004,227:523), and the addition of auxiliary agent P, B or F increases the catalyst surfaceThe surface acidity, which leads to increased coking of the catalyst, shortens the service life of the catalyst (see CN 102836727A). Other research works have been to add organic ligands, such as ethylene glycol, oxalic acid, to support Al2O3The functional modification is carried out, because the strong interaction between precursor ions and a carrier in the impregnation process is weakened, the uniform distribution of active components is promoted, the metal-carrier interaction is coordinated, and the performance of the catalyst is improved to a certain extent (see CN1083475C), but the physicochemical performance of the carrier is often reduced due to the modification of organic groups, and the introduction of organic ligands often causes the acting force between active metals and the carrier to be too weak, which is not beneficial to the long-period stability of the catalyst and influences the service life. There have also been some research efforts to develop composite supports such as TiO2-Al2O3And V2O5-Al2O3The active component is loaded, but the industrial practical application is limited by the poor thermal stability and the higher cost (see Cruz-Perez, et al., Catal. today,2011,172:203 and Wang, et al, J.Catal.,2009,262: 206).
In conclusion, the alumina carriers developed at present are not ideal, and both advantages and disadvantages coexist, so that the benign regulation and control of three aspects of 'active metal dispersion state-interaction of the carrier and active components-surface structure and properties of the carrier' are difficult to realize simultaneously.
Disclosure of Invention
The invention provides an alumina carrier and a preparation method and application thereof, aiming at the defect that the existing alumina carrier preparation technology is difficult to realize benign regulation of three aspects of 'active metal dispersion state-interaction of a carrier and active components-surface structure and property of the carrier', so that the hydrofining performance of a catalyst is poor or the service life of the catalyst is short.
The inventors of the present invention found through research that not only the activity of the catalyst can be improved but also the high activity of the catalyst can be effectively maintained for a long time by modifying gamma-alumina in an aqueous solution containing urea by using a water-soluble divalent metal salt, thereby greatly improving the service life of the catalyst. The reason for this is presumably because the surface of the carrier is formed into a "network" structure (as shown in FIG. 2) that is favorable for efficiently dispersing and anchoring the active component by introducing a water-soluble divalent metal salt into an aqueous solution containing urea, wherein the water-soluble divalent metal salt can be used as the active component and the surface structure of the gamma-alumina is modified. And the subsequent introduction of the metal hydrogenation active component, the surface of the catalyst still maintains the 'net' structure (as shown in figure 3). The 'net-shaped' structure is beneficial to loading, dispersing and anchoring of the active metal component, effectively weakens strong interaction between the active component and the carrier, and increases the specific surface area of the carrier.
Thus, the present invention provides a novel alumina carrier and a method for preparing the same, the carrier containing gamma-alumina and a divalent metal element, the surface of the carrier having a network structure, the network density of the network structure being 0.5 to 50 cells per square micrometer, and the network density being determined by averaging the number of cells distributed per square micrometer area in at least 20 scanning electron micrographs.
The invention also provides a preparation method of the alumina carrier, which comprises the steps of dipping the gamma-alumina into a mixture containing urea, water-soluble divalent metal salt and water, and then sequentially carrying out heat treatment, filtration, washing, drying and roasting.
The invention also provides the application of the alumina carrier prepared by the preparation method provided by the invention as a carrier of a supported catalyst.
The alumina carrier prepared by the preparation method realizes benign regulation of three aspects of 'active metal dispersion state-interaction of the carrier and active components-surface structure and property of the carrier'. The alumina carrier is applied to the catalyst with hydrogenation, so that the hydrofining performance of the catalyst is obviously improved, the service life of the catalyst is effectively prolonged, and the alumina carrier has a good industrial application prospect.
For example, as can be seen from the results in table 1, the carrier prepared by the method provided by the present invention has a large specific surface area and a network structure; table 2 shows that the catalyst prepared using the support provided by the present invention has better dispersion of the active components, for example: the catalyst S-1 and the catalyst D-2 have equivalent active component content, the Mo/Al atomic ratio in the S-1 is 0.112, and the Mo/Al atomic ratio in the catalyst D-2 is 0.07; CoMo/γ -Al prepared in example 7 of FIG. 42O3Hydrogen Temperature Programmed Reduction (TPR) curve (see curve 1) of catalyst and CoMo/gamma-Al prepared in comparative example 22O3The comparison result of the hydrogen Temperature Programmed Reduction (TPR) curve (see curve 2) of the catalyst shows that the method provided by the invention obviously weakens the interaction force between the carrier and the active component.
As can be seen from the data of example 7 and comparative example 2 in Table 3, the catalyst (S-1) prepared using the support provided by the present invention had a relative hydrodesulfurization activity of 167% and a relative hydrodenitrogenation activity of 146% when reacted for 4 hours, while the catalyst (D-2) of comparative example 2 had a relative hydrodesulfurization activity of 112% and a relative hydrodenitrogenation activity of 115% when reacted for 4 hours. The catalyst (S-1) prepared using the support provided by the present invention had a relative hydrodesulfurization activity of 162% and a relative hydrodenitrogenation activity of 142% when reacted for 1000 hours, whereas the catalyst (D-2) of comparative example 2 had a relative hydrodesulfurization activity of 84% and a relative hydrodenitrogenation activity of 87% when reacted for 1000 hours. The relative hydrodesulfurization activity and the relative hydrodenitrogenation activity of the S-1 catalyst were significantly higher than those of the D-2 catalyst in either 4 hours or 1000 hours of the reaction, and the tendency of the relative hydrodesulfurization activity and the relative hydrodenitrogenation activity of the catalyst S-1 catalyst to decrease was significantly smaller than that of the catalyst D-2 catalyst by the extension of the reaction time, and the comparative results of the other examples and comparative examples showed the same tendency.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows unmodified γ -Al from example 12O3SEM image of the support surface;
FIG. 2 is an SEM image of the surface of a Co-modified alumina support of example 1;
FIG. 3 is a diagram of CoMo/γ -Al in example 72O3SEM images of the catalyst surface;
FIG. 4 is a CoMo/γ -Al alloy prepared in example 72O3Hydrogen Temperature Programmed Reduction (TPR) curve (see curve 1) of catalyst and CoMo/gamma-Al prepared in comparative example 22O3Hydrogen Temperature Programmed Reduction (TPR) profile for the catalyst (see profile 2).
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides an alumina carrier, which contains gamma-alumina and divalent metal elements, wherein the surface of the carrier is provided with a reticular structure, the lattice density of the reticular structure is 0.5-50 per square micron, and the lattice density is determined by a method of calculating the average value of the number of the lattices distributed in each square micron area in at least 20 scanning electron micrographs.
According to the invention, the mesh density of the mesh structure is preferably 5 to 20 pieces per square micrometer.
In the present invention, the number of the scanning electron micrographs to be taken is not particularly limited, and the grid density is preferably measured by averaging the number of grids distributed in an area of square micrometers in 30 to 50 scanning electron micrographs.
According to the present invention, the divalent metal element may be any of various metal elements having positive divalent property, and specifically may be one or more selected from the group consisting of a group VIII metal element, a group iia metal element, a group ib metal element, and a group iib metal element.
In the present invention, the group VIII metal element may be one or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum elements. The group IIA metal element may be one or more of calcium, magnesium, strontium and barium. The group IB metal element may be one or more of copper, silver and gold elements. The group IIB metal element can be one or more of zinc and cadmium.
Preferably, the divalent metal element is selected from one or more of cobalt, nickel, iron, calcium, magnesium, copper and zinc elements.
According to the invention, preferably, the molar ratio of gamma-alumina to divalent metal element is between 3 and 20:1, preferably between 4 and 10: 1.
the invention also provides a preparation method of the alumina carrier, which comprises the steps of dipping the gamma-alumina into a mixture containing urea, water-soluble divalent metal salt and water, and then sequentially carrying out heat treatment, filtration, washing, drying and roasting.
According to the present invention, the concentration of the water-soluble divalent metal salt in the mixture is preferably 0.01mol/L to 1mol/L, and more preferably 0.1mol/L to 0.5 mol/L.
According to the present invention, preferably, the water-soluble divalent metal salt is selected from one or more of nitrate, sulfate and chloride salts of divalent metals.
The divalent metal may be selected from one or more of group VIII metals, group iia metals, group ib metals and group iib metals.
In the present invention, the group VIII metal element may be one or more of iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum elements.
The group IIA metal element may be one or more of calcium, magnesium, strontium and barium.
The group IB metal element may be copper and/or gold.
The group IIB metal element may be zinc and/or cadmium.
Preferably, the divalent metal element is selected from one or more of cobalt, nickel, iron, calcium, magnesium, copper and zinc elements.
According to the invention, the molar ratio of urea to water-soluble divalent metal salt in the mixture is preferably 2-10: 1.
According to the present invention, preferably, the heat treatment conditions include a heat treatment temperature of 60 to 140 ℃, more preferably 70 to 90 ℃, and a heat treatment time of 2 to 60 hours, more preferably 12 to 24 hours.
The drying conditions in the present invention are not particularly limited, and may be various drying conditions commonly used in the art, for example, the drying conditions include a drying temperature of 100-.
The conditions of the calcination in the present invention are not particularly limited, and may be various calcination conditions commonly used in the art, for example, the calcination conditions include calcination temperature of 400-600 deg.C, preferably 450-550 deg.C, calcination time of 2-10 hours, preferably 2-6 hours.
According to the invention, preferably, the mass ratio of water to gamma-alumina in the mixture is not less than 1, preferably from 1 to 25.
According to the invention, preferably, the molar ratio of the gamma-alumina to the water-soluble divalent metal salt is 3 to 20:1, preferably 4 to 10: 1.
according to the invention, preferably, the gamma-alumina carrier is gamma-Al2O3And gamma-Al modified by one or more of phosphorus, silicon, fluorine, zirconium, titanium and boron2O3One or more of a carrier. Modified gamma-Al as described above2O3The carrier can be obtained commercially or modified by conventional methods.
According to the invention, the shape of the gamma-alumina carrier can be spherical, strip-shaped, cloverleaf-shaped, cylindrical particles or amorphous powder.
The preferred gamma-alumina carrier of the present invention is a cylindrical particle with a diameter of 1mm to 5 mm.
The method provided by the invention, wherein the gamma-alumina carrier can have the specific surface area and the pore volume of a conventional alumina carrier, preferably the specific surface area of the gamma-alumina is 150-350 square meters/gram, more preferably 200-300 square meters/gram, preferably the pore volume of the gamma-alumina is 0.4-1.2 ml/gram, more preferably 0.5-0.9 ml/gram.
The invention also provides an alumina carrier prepared by the preparation method.
The alumina carrier prepared by the method realizes benign regulation of three aspects of 'active metal dispersion state-interaction of the carrier and active components-surface structure and property of the carrier', so the invention also provides the application of the alumina carrier prepared by the method as a carrier of a catalyst with hydrogenation catalysis.
When the alumina support according to the invention is used as a catalyst support having a hydrogenation catalytic action, the active component having a hydrogenation catalytic action may be supported on the alumina support according to the invention by various methods commonly used in the art (e.g.: impregnation), such as: the catalyst having hydrogenation catalysis can be obtained by impregnating the alumina carrier of the present invention with an aqueous solution containing the active component, and then drying and optionally calcining the alumina carrier loaded with the active component.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
In the following examples and comparative examples, the content of the metal component in the catalyst was measured by X-ray fluorescence spectroscopic analysis method RIPP 132-90 (petrochemical analysis method (RIPP test method), Yangrodin, Kan English, Wu Wenhui ed, science publishers, first 9 months of 1990, p 371,379). The grid density of the catalyst and carrier surface is determined by calculating the average value of the number of grids distributed in each square micron area in 50 scanning electron micrographs obtained by an S250MK3 type scanning electron microscope under the working condition of 20kV, the sample current of 100mA and the working distance of 24 mm. Main agent Mo (or W) in catalyst) The degree of dispersion of (A) is determined by X-ray photoelectron spectroscopy (XPS), wherein the degree of dispersion is represented by the surface metal atom ratio (Mo (W)/Al) given by the XPS analysis result. Information on the specific surface area and pore structure of the alumina support was carried out by means of a physical adsorption apparatus of the ASAP2002 type (Micromeritics, USA) under N2And (4) performing adsorption-desorption characterization to obtain. The hydrogen temperature programmed reduction curve of the catalyst is determined by AutoChemII2920 at 10% H2Flow rate of 50cm under Ar atmosphere3The/min is measured at 50 ℃ at 10 ℃/min up to 1000 ℃.
Examples 1 to 10 are intended to illustrate the alumina carrier and the method for its preparation according to the invention.
Example 1
50.0g of gamma-Al having a diameter of 3mm was added2O3The particles (surface SEM picture shown in FIG. 1, specific surface area, pore volume and average pore diameter shown in Table 1) were immersed in 250.0mL of a mixed aqueous solution containing 0.2mol/L of cobalt nitrate and 1.0mol/L of urea, heat-treated at 80 ℃ for 24 hours, filtered, washed and then dried at 120 ℃ for 4 hours, and calcined at 500 ℃ in a 100mL/min air stream for 4 hours to obtain Co-modified alumina carrier Z-1, the SEM picture of Z-1 being shown in FIG. 2. As can be seen from fig. 2, the Co-modified alumina support surface has a number of network structures, and the network density is listed in table 1. The specific surface area, pore volume and average pore diameter of Z-1 are shown in Table 1.
Example 2
15.0g of gamma-Al having a diameter of 3mm was added2O3The particles are immersed in 50.0mL of mixed aqueous solution containing 0.1mol/L nickel nitrate and 0.4mol/L urea, heat treated at 70 ℃ for 18 hours, filtered, washed and then dried at 130 ℃ for 2 hours, and calcined in 100mL/min air flow at 550 ℃ for 2 hours to obtain the Ni modified alumina carrier Z-2. The lattice density, specific surface area, pore volume and average pore diameter of Z-2 are shown in Table 1.
Example 3
50.0g of gamma-Al having a diameter of 1mm was added2O3Soaking the granules in 250.0mL of mixed aqueous solution containing 0.5mol/L magnesium nitrate and 1.0mol/L urea, performing heat treatment at 90 deg.C for 12 hr, filtering, washing, drying at 100 deg.C for 6 hr, and calcining at 450 deg.C in 100mL/min air flow for 6 hr to obtain Mg-modified aluminaThe lattice density, specific surface area, pore volume and average pore diameter of the bodies Z-3, Z-3 are shown in Table 1.
Example 4
10.0g of gamma-Al having a diameter of 1.5mm was added2O3The particles were immersed in 50.0mL of a mixed aqueous solution containing 0.1mol/L ferrous chloride and 1.2mol/L urea, heat-treated at 70 ℃ for 24 hours, filtered, washed and then dried at 110 ℃ for 12 hours, and calcined at 450 ℃ in a 100mL/min air stream for 4 hours to obtain Fe-modified alumina carrier Z-4, the lattice density, specific surface area, pore volume and average pore size of Z-4 being shown in Table 1.
Example 5
15.0g of gamma-Al having a diameter of 1.5mm was added2O3The pellets were immersed in 50.0mL of a mixed aqueous solution containing 0.2mol/L of copper chloride and 1.2mol/L of urea, heat-treated at 65 ℃ for 24 hours, filtered, washed and then dried at 110 ℃ for 12 hours, and calcined at 450 ℃ for 4 hours in a 100mL/min air stream to obtain a Cu-modified alumina carrier Z-5, the lattice density, specific surface area, pore volume and average pore diameter of Z-5 being shown in Table 1.
Example 6
10.0g of gamma-Al having a diameter of 1.5mm was added2O3The pellets were immersed in 50.0mL of a mixed aqueous solution containing 0.1mol/L zinc nitrate, 0.1mol/L nickel nitrate and 1.2mol/L urea, heat-treated at 80 ℃ for 24 hours, filtered, washed and then dried at 120 ℃ for 12 hours, and calcined at 500 ℃ in a 100mL/min air stream for 4 hours to obtain Zn-and Ni-modified alumina carrier Z-6, the lattice density, specific surface area, pore volume and average pore diameter of Z-6 being shown in Table 1.
Comparative example 1
An alumina carrier was prepared by following the procedure of example 1 except that urea was not contained in the mixed aqueous solution to obtain an alumina carrier D-1. The lattice density, specific surface area, pore volume and average pore diameter of D-1 are shown in Table 1.
Examples 7 to 12 are intended to illustrate the use of the alumina support of the invention as a support for catalysts having a hydrogenation catalytic action.
Example 7
Preparing 35mL of aqueous solution containing 22.2g of ammonium paramolybdate and 11.3g of cobalt nitrate, immersing 50g Z-1 in the aqueous solution for 3 hours, drying the solution at 120 ℃ for 4 hours, and calcining the solution at 450 ℃ in 100mL/min air flow for 4 hours to obtain the catalyst S-1. The SEM image is shown in FIG. 3, the mesh density, specific surface area, pore volume and average pore diameter are shown in Table 1, the temperature-programmed reduction curve of hydrogen is shown in FIG. 4, curve 1, and the metal content and dispersion of catalyst S-1 are shown in Table 2. As can be seen by comparing fig. 3 with fig. 2, the "network" structure of both is substantially the same, indicating that the catalyst still maintains the "network" structure of the support after loading the active metal component.
Comparative example 2
A catalyst was prepared by the method of example 7, except that D-1 was used as the carrier, to obtain catalyst D-2. The lattice density, specific surface area, pore volume and average pore diameter are shown in Table 1, and the metal content and dispersion are shown in Table 2.
Comparative example 3
A catalyst was prepared by the method of example 7, except that the carrier used was γ -Al having a diameter of 3mm as described in example 12O3And granulating to obtain the catalyst D-3. The mesh density, specific surface area, pore volume and average pore diameter are shown in Table 1, the hydrogen temperature programmed reduction curve is shown in FIG. 4, curve 2, and the metal content and dispersion of catalyst S-1 are shown in Table 2.
Example 8
35mL of an aqueous solution containing 22.2g of ammonium paramolybdate and 11.3g of nickel nitrate was prepared, 50g Z-2 was immersed therein for 3 hours, dried at 120 ℃ for 4 hours, and calcined at 450 ℃ in an air stream of 100mL/min for 4 hours to obtain catalyst S-2. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
Comparative example 4
A catalyst was prepared by the method of example 8, except that the carrier used was γ -Al having a diameter of 3mm as described in example 22O3And granulating to obtain the catalyst D-4. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
Example 9
Preparing 35mL of aqueous solution containing 22.2g of ammonium paramolybdate, immersing 50g Z-3 in the aqueous solution for 3 hours, drying the aqueous solution at 120 ℃ for 4 hours, roasting the aqueous solution at 450 ℃ for 4 hours in 100mL/min of air flow to obtain W/Z-3, immersing the W/Z-3 in 35mL of aqueous solution containing 11.3g of cobalt nitrate for 3 hours, drying the aqueous solution at 120 ℃ for 4 hours, and roasting the aqueous solution at 450 ℃ for 4 hours in 100mL/min of air flow to obtain the catalyst S-3. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
Comparative example 5
A catalyst was prepared by the method of example 9, except that the carrier used was γ -Al having a diameter of 1mm as described in example 32O3And granulating to obtain the catalyst D-5. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
Comparative example 6
22.2g of ammonium paramolybdate and 11.3g of cobalt nitrate were added to 35mL of distilled water containing 1.0mL of phosphoric acid (85 wt.%), respectively, and heated to 80 to 90 ℃ with stirring to be dissolved, to obtain a solution a. 50g of gamma-Al having a diameter of 3mm2O3The particles were immersed in solution A for 3 hours, dried at 120 ℃ for 4 hours, and calcined at 450 ℃ in an air stream of 100mL/min for 4 hours to obtain catalyst D-6. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
Comparative example 7
Prepared according to the method described in patent CN 1083475C. Dissolving 22.2g of ammonium paramolybdate, 12g of tartaric acid and 2g of boric acid in 35mL of deionized water, heating to 70 ℃ under stirring for dissolving, adding 1.21mL of phosphoric acid and 11.3g of nickel nitrate after dissolving to obtain a steeping liquor, and then adding 50g of gamma-Al with the diameter of 3mm2O3The particles were immersed in the solution for 3 hours, filtered, washed and then dried at 120 ℃ for 4 hours, and calcined at 450 ℃ in an air stream of 100mL/min for 4 hours to obtain catalyst D-7. The specific surface area and pore structure results of the catalysts are listed in table 1. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
Example 10
A catalyst was prepared by following the procedure of example 7, except that Z-4 was used as the carrier, to obtain catalyst S-4. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
Example 11
A catalyst was prepared by the method of example 7, except that Z-5 was used as the carrier, to obtain catalyst S-5. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
Example 12
A catalyst was prepared by the method of example 7, except that Z-6 was used as the carrier, to obtain catalyst S-6. The lattice density, specific surface area, pore volume and average pore diameter thereof are shown in Table 1, and the metal content and dispersion thereof are shown in Table 2.
TABLE 1
TABLE 2
Test example 1
In the present test example, the desulfurization activity and the denitrification activity of the hydrogenation catalyst using the alumina as a carrier prepared by the method of the present invention and the hydrogenation catalyst provided by the comparative example were evaluated by the following methods, and the evaluation results are shown in table 3 below.
The desulfurization and denitrification activities of the catalyst were evaluated on a hydrogenation microreaction device using an n-heptane solution containing 0.45 mass% of 4, 6-dimethyldibenzothiophene (4,6-DMDBT) and an n-heptane solution containing 1.0 mass% of quinoline, respectively, as raw materials. Before reaction, the catalyst needs to be presulfurized, 0.5g of catalyst is filled, and the presulfurization conditions are as follows: 4.0MPa, 300 ℃, 4h, the hydrogen-oil volume ratio of 300:1, and the oil feeding speed of the vulcanized oil is 8 mL/h. The reaction conditions are as follows: the hydrogen-oil volume ratio is 400 at 360 ℃ under 4.0MPa, and the oil inlet speed of the reaction oil is 20 mL/h. Sampling every 4h after the reaction is stable for 3h, determining the contents of sulfur and nitrogen in the raw materials of hydrodesulfurization and hydrodenitrogenation reactions and the obtained products by gas chromatography, determining for three times in each sample, and taking the average value. In addition, sampling is carried out every 4h after 1000h of reaction, the sulfur and nitrogen contents in the raw materials of hydrodesulfurization and hydrodenitrogenation reactions and the obtained products are measured by gas chromatography for three times, and the average value is taken. Hydrodesulfurization and denitrification reactions were treated as first-order reactions, the hydrodesulfurization and denitrification activities of the catalyst were expressed by hydrodesulfurization and denitrification activities, respectively, with respect to a reference agent D (comparative example 3), and the relative hydrodesulfurization and relative hydrodedenitrification activities of the catalyst were calculated according to the following formulas (1) and (2), respectively:
formula (1)
Formula (2)
Wherein k (S), k (N) respectively represent the hydrodesulfurization and hydrodenitrogenation activities of the catalyst, and k (D)S)、k(DN) Respectively, the hydrodesulfurization and hydrodenitrogenation activities of reference agent D (comparative example 3).
In the formula, SSpThe sulfur content in the reaction product of the catalyst is mass percent; sSfThe sulfur content in the reaction raw material using the catalyst is mass percent; sDpThe sulfur content in the reaction product using the reference agent D is mass percent; sDfThe sulfur content in the reaction raw material using a reference agent D is mass percent; n is a radical ofSpIs the nitrogen content in the reaction product of the catalyst by mass percent; n is a radical ofSfThe nitrogen content in the reaction raw material using the catalyst is mass percent; n is a radical ofDpThe nitrogen content in the reaction product using the reference agent D is the mass percentage; n is a radical ofDfThe nitrogen content in the reaction raw material using the reference agent D is calculated by mass percent; the results of the hydrofinishing evaluations of the catalysts prepared in the respective examples and comparative examples are shown in table 3.
TABLE 3
Note: "-" indicates no detection.
As is clear from Table 1, with gamma-Al which has not been modified2O3Compared with the gamma-Al modified by the technology of the invention2O3Under the condition that the pore structure (pore volume and average pore diameter) of the carrier is not obviously influenced, the specific surface area is not reduced, but obviously improved, which is opposite to the effect of the common conventional modification technology. When adopting saturated dipping technique to unmodified gamma-Al2O3The gamma-Al modified by the technology of the invention2O3Conventional modified gamma-Al2O3(e.g., organic complexing agent, boron, phosphorus, see comparative examples 6 and 7.) incorporation of the same active metal can be seen for the modified γ -Al modified by the inventive technique2O3The specific surface area of the supported catalyst is significantly higher than that of the other two supported catalysts, indirectly indicating that the technology of the present invention can achieve a better dispersion state of the active components.
The data in Table 2 fully demonstrate that, with the same active metal composition, the present technology can achieve a higher Mo (W)/Al atomic ratio at the support surface and thus a higher accessibility of the active sites.
The results in Table 3 demonstrate that the gamma-Al modified by the present technology, despite the similar composition of the two types of catalysts, is comparable to hydrogenation catalysts prepared by conventional methods2O3The catalyst used as the carrier has obviously better hydrodesulfurization and hydrodenitrogenation activity. Comparing the data of the relative hydrodesulfurization activity and the relative hydrodenitrogenation activity between 4 hours and 1000 hours in table 3, it can be seen that the catalyst activity provided by the present invention decreases very little and is significantly smaller than the comparative example for a long time reaction, and therefore, the catalyst prepared by the method provided by the present invention significantly prolongs the service life of the catalyst. The above results fully indicate that the preparation method provided by the invention has other existing methodsThe method has incomparable superiority.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (15)
1. An alumina carrier, characterized in that the carrier contains gamma-alumina and a divalent metal element, the surface of the carrier has a network structure, the network density of the network structure is 0.5-50 per square micron, and the network density is determined by averaging the number of the network distributed in each square micron area in at least 20 scanning electron micrographs;
the preparation method of the alumina carrier comprises the steps of dipping gamma-alumina into a mixture containing urea, water-soluble divalent metal salt and water, and then sequentially carrying out heat treatment, filtration, washing, drying and roasting; wherein the temperature of the heat treatment is 60-90 ℃;
the molar ratio of the gamma-alumina to the divalent metal element is 3-20: 1;
the diameter of the gamma-alumina carrier is 1mm to 5 mm.
2. The carrier of claim 1, wherein the mesh structure has a mesh density of 5-20 per square micron.
3. The carrier according to claim 1 or 2, wherein the grid density is determined by averaging the number of grids distributed per square micrometer area in 30-50 scanning electron micrographs.
4. The carrier according to claim 1 or 2, wherein the divalent metal element is selected from one or more of a group VIII metal element, a group iia metal element, a group ib metal element, and a group iib metal element.
5. The carrier according to claim 1 or 2, wherein the divalent metal element is selected from one or more of the elements cobalt, nickel, iron, calcium, magnesium, copper and zinc.
6. The carrier according to claim 1, wherein the molar ratio of the γ -alumina to a divalent metal element is 4-10: 1.
7. a preparation method of an alumina carrier is characterized in that the preparation method comprises the steps of dipping gamma-alumina into a mixture containing urea, water-soluble divalent metal salt and water, and then sequentially carrying out heat treatment, filtration, washing, drying and roasting;
wherein the temperature of the heat treatment is 60-90 ℃;
the mol ratio of the gamma-alumina to the water-soluble divalent metal salt is 3-20: 1;
the diameter of the gamma-alumina carrier is 1mm to 5 mm;
the surface of the alumina carrier has a net structure, the net density of the net structure is 0.5-50/square micron, and the net density is determined by calculating the average value of the number of the net distributed in each square micron area in at least 20 scanning electron micrographs.
8. The method according to claim 7, wherein the molar ratio of urea to water-soluble divalent metal salt is 2-10: 1.
9. the method according to claim 7 or 8, wherein the mixture has a concentration of a water-soluble divalent metal salt selected from one or more of nitrate, sulfate and chloride salts of a divalent metal selected from one or more of group VIII metals, group IIA metals, group IB metals and group IIB metals in the range of 0.01mol/L to 1 mol/L.
10. The method of claim 9, wherein the divalent metal is selected from one or more of cobalt, nickel, iron, calcium, magnesium, copper, and zinc.
11. The production method according to claim 7 or 8, wherein the time of the heat treatment is 2 to 60 hours; the drying conditions comprise that the drying temperature is 100-250 ℃, and the drying time is 1-12 hours; the roasting conditions comprise that the roasting temperature is 400-600 ℃, and the roasting time is 2-10 hours.
12. The production method according to claim 11, wherein the time of the heat treatment is 12 to 24 hours; the drying conditions comprise that the drying temperature is 100-130 ℃, and the drying time is 2-6 hours; the roasting conditions comprise that the roasting temperature is 450-550 ℃, and the roasting time is 2-6 hours.
13. The production method according to claim 7, wherein the molar ratio of the γ -alumina to the water-soluble divalent metal salt is 4 to 10: 1.
14. an alumina carrier obtained by the preparation method of any one of claims 7 to 13.
15. Use of an alumina support as claimed in any one of claims 1 to 6 and 14 as a support for a catalyst having hydrogenation catalysis.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20020016134A (en) * | 2000-08-24 | 2002-03-04 | 이구택 | Method of preparing gammma-alumina catalyst for high temperature desulfurization |
| CN101368012A (en) * | 2008-09-24 | 2009-02-18 | 上海大学 | Aluminum oxide/iron oxide composite abrasive grain and method of producing the same |
| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20020016134A (en) * | 2000-08-24 | 2002-03-04 | 이구택 | Method of preparing gammma-alumina catalyst for high temperature desulfurization |
| CN101368012A (en) * | 2008-09-24 | 2009-02-18 | 上海大学 | Aluminum oxide/iron oxide composite abrasive grain and method of producing the same |
| CN102441393A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst by taking modified alumina as carrier and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| Enhanced metal dispersion and hydrodechlorination properties of a Ni/Al2O3 catalyst derived from layered double hydroxides;Jun-Ting Feng et al.;《Journal of Catalysis》;20090730;第266卷;第351–358页 * |
| In situ controllable assembly of layered-double-hydroxide-based nickel nanocatalysts for carbon dioxide reforming of methane;Zhenxin Xu et al.;《Catal. Sci. Technol.》;20141128;第5卷;第1588–1597页 * |
| 沉积—沉淀法制备Ni/γ－Al2O3催化剂及TPR行为研究;李军;《科技情报开发与经济》;20101231;第20卷(第15期);第159-161页 * |
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