CN109364930A - One kind being used for selective hydrogenation catalyst for pyrolysis gasoline and preparation method - Google Patents
One kind being used for selective hydrogenation catalyst for pyrolysis gasoline and preparation method Download PDFInfo
- Publication number
- CN109364930A CN109364930A CN201811183092.6A CN201811183092A CN109364930A CN 109364930 A CN109364930 A CN 109364930A CN 201811183092 A CN201811183092 A CN 201811183092A CN 109364930 A CN109364930 A CN 109364930A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- selective hydrogenation
- pyrolysis gasoline
- hydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 34
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 31
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 47
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 21
- 229920000620 organic polymer Polymers 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 229920002125 Sokalan® Polymers 0.000 claims description 11
- 239000004584 polyacrylic acid Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 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 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052785 arsenic Inorganic materials 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 abstract description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000395 magnesium oxide Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000001802 infusion Methods 0.000 abstract 1
- 150000001993 dienes Chemical class 0.000 description 25
- 239000003921 oil Substances 0.000 description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 14
- 229910052794 bromium Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- -1 ethylene, propylene Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002941 palladium compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to one kind to be used for selective hydrogenation catalyst for pyrolysis gasoline and preparation method, catalyst includes silicaalumina carrier and the metal active component palladium that is carried on carrier, total weight of the content of palladium based on the catalyst is 0.15-0.45wt%, it include silica, nickel doped lanthanum ferrite and magnesia in silicaalumina carrier, carrier is mesoporous to account for the 3~75% of total hole, and macropore accounts for the 1.5~60% of total hole.Catalyst is prepared using infusion process, and catalyst anticol mass-energy power is good, and anti-arsenic, sulfur resistive, water resistant ability are strong.
Description
Technical field
The catalyst and preparation method thereof that the present invention relates to a kind of for one-stage selective hydrogenation of gasoline splitting.
Background technique
Drippolene is the important by-product of steam cracking industrial production ethylene, propylene, including C5-C10 fraction.Drippolene
It forms very complicated, mainly there is benzene,toluene,xylene, monoolefine, diolefin, linear paraffin, cycloalkane and nitrogen, sulphur, oxygen, chlorine
With the organic compound of heavy metal etc., a component more than totally 200, wherein benzene,toluene,xylene (being referred to as BTX) about 50-90%, no
Saturated hydrocarbons 25-30%.It is the characteristics of according to a large amount of aromatic hydrocarbons are contained in drippolene, widely used, it both can be used as the tune of gasoline
And component, high-octane gasoline is produced, separation production aromatic hydrocarbons etc. can also be passed through.
Since drippolene complicated composition, thermal stability are poor, in general, first removing alkadienes and benzene through one-stage selective hydrogenation
Ethylene after Secondary hydrodesulfurization, is mainly used for Aromatics Extractive Project.Industrial catalyst for selective hydrogenation of cracked gasoline is mainly at present
Pd system or Ni series catalysts, midbarrel (C6~C8Hydrocarbon compound fraction) plus hydrogen or full fraction (C5Hydrocarbon~do is 204 DEG C
Hydrocarbon compound fraction) hydrogenation technique.Due to the difference of each ethylene unit cracking stock and cracking condition, each device drippolene is former
Material composition difference is larger, and especially (it is anti-that polymerization occurs for the unsaturation component such as alkadienes and styrene for the diene of drippolene, colloid
The high molecular polymer that should be generated) and As, content of beary metal there are larger differences；Some device raw pyrolysis gasoline dienes, glue
Matter is high, and the toxic contents such as colloid and As, heavy metal are higher in some device raw pyrolysis gasoline raw materials, and individual device slightly cracks vapour
The toxic contents such as oily diene, colloid and As, heavy metal are high.
Alkadienes and alkynes in drippolene are easy polymerization collagen at high temperature, are deposited on catalyst surface, Yi Zao
At catalyst inactivation, it is necessary to frequently activation and regeneration.Pyrolysis gasoline hydrogenation catalyst mainly has Pd/Al2O3And Ni/Al2O3
Two kinds of catalyst.The advantages that Pd series catalysts have initial temperature low, and hydrogenation activity is big, and adaptation air speed is high, long service life,
The catalyst mode for having industrial application includes Pd-Cr/Al2O3, Pd/Al2O3。
Usual pyrolysis gasoline hydrogenation catalyst is using the metal salt of active component or the solution dipping of organo-metallic compound
The carrier, it is then by processes such as dry, roastings that active component is oxide carried to carrier surface, logical hydrogen is needed before use
Pyrolysis gasoline hydrogenation reaction could be used for after gas reduction.Common carrying alumina body aperture is too small, when colloid, arsenic contain in raw material
When amount, sulfur content are exceeded, the easy coking and blocking in hole on catalyst influences catalyst activity and stabilized hydrogenation.
CN201310379189.5 discloses a kind of pyrolysis gasoline selective hydrogenation catalyst, including carrier and is carried on carrier
On metal active constituent, the active component is in the microemulsion without cosurfactant containing high molecular polymer water phase
It is prepared in law system；The carrier is selected from aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve, kaolinite
At least one of soil, cordierite；The active component is main active component and helps active component, wherein main active component is
Palladium, content are 0.01wt%~1.0wt% of carrier gross weight, and the high molecular polymer is water-soluble high molecular polymerization
Object.The activity of the catalyst in the reaction is higher, and selectivity is more preferable, and appearance glue ability is more preferable, and preparation process is easy, catalyst
Particle shape can be controlled well.CN201110089806.9 is related to a kind of for drippolene or its fraction selective hydrogenation
Palladium-silver/alumina-silica titanium catalyst, the catalyst include the aluminium oxide-titanium oxide compound as carrier, and load
In active component Pd and Ag on the carrier, wherein the content of Pd is based on the total catalyst weight as 0.15-0.5 weight
% is measured, it is 0.8-4.5 weight % that the content of Ag, which is based on the total catalyst weight,.Compared with similar catalyst, present invention catalysis
Agent can be used for drippolene or its fraction plus hydrogen, low temperature hydrogenation selectivity is high, and anti-As impurity ability is strong, and charging capacity is big, and
It is activity stabilized.CN200610029962.5 is related to a kind of method for full-cut fraction pyrolysis gasoline selective hydrogenation, mainly solves
It exists in the prior art and is difficult to the full-cut fraction pyrolysis gasoline high to colloid and free water content and carries out the technology of selective hydrogenation ask
Topic.The present invention is by using with C5The drippolene and hydrogen of the hydrocarbon compound fraction of hydrocarbon~do for 204 DEG C are raw material, anti-
Answering temperature is 30~80 DEG C, and reaction pressure is 2.0~3.0MPa, and green oil air speed is 2.5~5.0 hours- 1, hydrogen/oil volume ratio
Under conditions of 60~120: 1, raw material is contacted with catalyst, is reacted, and diolefin and alkylene aromatic hydrocarbons group in raw material are made
Point it is converted to monoolefine and alkylaromatic hydrocarbon, wherein catalyst includes alumina support, activity component metal palladium or its oxide, extremely
Element or its oxide, at least one IVA or VA in the periodic table of elements of few a kind of IA in the periodic table of elements or IIA
Element or its oxide, carrier specific surface area be 40~160 meters2/ gram, total pore volume is 0.3~1.2 ml/g, and carrier has
There is the technical solution of compound pore size distribution, preferably solve the problems, such as this, can be used for the work of full-cut fraction pyrolysis gasoline selective hydrogenation
In industry production.The preparation method of catalyst of the present invention is identical as common lamella catalyst dipping technique: first with it is a kind of can be with dipping
Liquid that liquid dissolves each other presoaks carrier, then with salt solution impregnation containing palladium, and the carrier after dipping is washed, dry, in air
300~600 DEG C roast up to oxidative catalyst finished product.Finished catalyst only need to lead in the reactor hydrogen reducing and can make
With.The catalyst that the present invention uses has a composite pore structural, it is biggish can several apertures, and rich in abundant mesoporous.The present invention
Catalyst be used for full-cut fraction pyrolysis gasoline selective hydrogenation when have good low temperature active, selectivity and stability, and
And there is good anti-interference, resistance to high colloid and high-content free water performance.In 40 DEG C of inlet temperature, reaction pressure
2.7Mpa, hydrogen/oil volume are than 80: 1, and green oil air speed 3.8 hours-1Under the conditions of, be 150 milligrams/100 grams oil to gum level,
Free water content is the full fraction (C of 1000ppm5The hydrocarbon compound fraction of hydrocarbon~do for 204 DEG C) drippolene selected
Hydrogenation reaction, outlet diene average value are 0.0 gram of iodine/100 gram oil, and diolefin hydrogenation rate is 100%, achieve preferable technology
Effect.The preparation method of the invention carrier include aluminium oxide and modifying agent, peptizing agent, water are mixed in the desired amount, extruded moulding
Afterwards, first 1~24 hour dry at 50~120 DEG C, it is then roasted 1~10 hour at 800~1150 DEG C, obtains carrying alumina
Body.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance
Energy.Since the impurity such as As, S, O, N and gum level are higher in drippolene, catalyst is set to be easy inactivation, it is therefore desirable to crack vapour
Oily catalyst has anticol matter, water resistant ability good, the strong characteristic of anti-arsenic, sulfur resistive ability.
Summary of the invention
The problem to be solved in the present invention is to provide one kind to be used for one-stage selective hydrogenation of gasoline splitting catalyst, the catalyst
Activity in the reaction is higher, and selectivity is more preferable, and anticol matter, anti-arsenic, sulfur resistive ability are strong.The carrier of catalyst is a kind of oxidation
Silicon-alumina support, includes nickel doped lanthanum ferrite in carrier, and catalyst is particularly suitable for drippolene C6-C8Fraction selectively adds
Hydrogen.
The present invention provides a kind of one-stage selective hydrogenation of gasoline splitting catalyst, which includes silica-alumina
Carrier and the metal active component palladium being carried on carrier, the content of palladium are 0.15- based on the total weight of the catalyst
0.45wt% includes the silica of 0.1~12wt%, the nickel ferrite-doping of 0.1~10wt% in silicaalumina carrier
Lanthanum, the magnesium of 0.05~7.8wt%, carrier is mesoporous to account for the 3~75% of total hole, and macropore accounts for the 1.5~60% of total hole.It is micro- in carrier
Hole, mesoporous, macropore uneven distribution.
The above-mentioned preferred 0.20-0.35wt% of Palladium Content in Catalyst.Preferably, mesoporous to account for the 3~65% of total hole, macropore accounts for
The 3~45% of total hole.
The silicaalumina carrier the preparation method is as follows: boehmite and sesbania powder are added to kneader
In be uniformly mixed, inorganic acid solution and organic polymer is added, mediates uniformly, then adds nickel doped lanthanum ferrite, mixing is equal
It is even to obtain alumina precursor, it is spare；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtains
Silicon source-boehmite-organic polymer mixture, the organic polymer of unit content is more quasi- than silicon source-in alumina precursor
The high 2 times or more of content of organic polymer in boehmite-organic polymer mixture (brief note silicon-aluminium-organic admixture),
Then by silicon source -- boehmite-organic polymer mixture is mixed with alumina precursor, adds magnesium source, through extrusion,
Molding, dry, roasting, obtain silicaalumina carrier.The silicon source is silica gel, sodium metasilicate or silicon powder.Silicon-aluminium-is organic
Aluminium oxide accounts for 1~35wt% of aluminium oxide in carrier in object mixture.
The preparation process of above-mentioned silicaalumina carrier, the organic polymer are polyvinyl alcohol, polyacrylic acid, gather
One or more of sodium acrylate, polyethylene glycol, polyacrylate.
Preferably, in above-mentioned silicaalumina carrier nickel doped lanthanum ferrite be 0.1~12wt%, more preferable 0.2~
8wt%, nickel accounts for 0.1~8wt% of cadmium ferrite in nickel doped lanthanum ferrite.
The preparation method of the nickel doped lanthanum ferrite: citric acid is dissolved in stirring and dissolving in deionized water, then by nitric acid
Lanthanum and ferric nitrate are added in citric acid, and Sodium Polyacrylate, polyacrylate or polyacrylic acid, polyacrylic acid is added in stirring and dissolving
The additional amount of sodium, polyacrylate or polyacrylic acid is the 0.1~10wt%, preferably 0.1~8.0wt% of nickel doped lanthanum ferrite.
Nickel compound containing is added, stirs, obtains finished product through drying, roasting, grinding.The nickel compound containing includes nickel nitrate, acetic acid
Nickel etc..
The preparation method of catalyst by active component palladium dipping, can spray to oxidation using the methods of dipping, spraying
On silicon-alumina support, then catalyst is dried, roasts and obtains the catalyst.Such as it can be according to the following steps
It prepares catalyst: preparing palladium-containing solution oxide impregnation silicon-alumina support, dry 3~9 hours through 110~160 DEG C, 400~
650 DEG C roast 4~9 hours, finally obtain catalyst prod.
In the preparation method of catalyst of the present invention, palladium compound used can be any one disclosed in prior art
Suitable for the palladium compound of palladium catalyst processed, such as palladium chloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, four nitre
Base palladium acid sodium, acylate such as oxalic acid palladium of palladium etc..To prepare solvent used in palladium compound solution do not have it is any specifically limited,
As long as it can dissolve used palladium compound.Preferred solvent be for example water, dilute hydrochloric acid, dust technology, dilute sulfuric acid or
Their mixed liquor.
Nickel doped lanthanum ferrite is added in silicaalumina carrier, effectively improves anti-arsenic, sulfur resistive, water repelling property, improves alkynes
Hydrocarbon or diolefin hydrogenation selectivity.In the preparation process of silicaalumina carrier, unit content is organic in alumina precursor
Polymer 2 times or more higher than the content of organic polymer in silicon-aluminium-organic admixture, is not simply reaming, but is carried
Body micropore, mesoporous, macropore uneven distribution are different from simple reaming, can not only improve the pore structure of carrier, keep carrier micro-
Hole, mesoporous, macropore uneven distribution improve catalyst anticol mass-energy power, improve the stability and service life of catalyst, favorably
In device long-term operation；And carrier surface is promoted to produce more active sites load centres, it improves palladium catalyst and adds hydrogen
Activity.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir
30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite.300g boehmite powder and 25.0g sesbania powder are added
Enter into kneader, nitric acid is added, adds 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, nickel doping is then added
Cadmium ferrite is uniformly mixed, obtains alumina precursor.5g Sodium Polyacrylate is dissolved in nitric acid, adds 38g silicon powder and 50g
Boehmite powder, stirs evenly, and obtaining silicon powder-boehmite-Sodium Polyacrylate mixture, (brief note silicon-aluminium-is organic
Object mixture).Silicon-aluminium-the organic admixture for taking 1/8 adds above-mentioned alumina precursor and 4.2g magnesium nitrate, mediates equal
It is even, it is clover shape by kneading-extruded moulding.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain nickeliferous doping
The carrier 1 of the silica-alumina of cadmium ferrite.The mesoporous of carrier accounts for the 55.4% of total hole, and macropore accounts for the 28.6% of total hole.
3, catalyst is prepared
Palladium solution impregnating carrier 1 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain catalyst 1.It urges
1 palladium content of agent is 0.29wt%.
Embodiment 2
260g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite
Preparation with embodiment 1, in silicaalumina carrier include 4.4wt% silica, the nickel doped lanthanum ferrite of 5.7wt%,
The magnesium of 1.2wt%, carrier is mesoporous to account for the 63.8% of total hole, and macropore accounts for the 25.9% of total hole.Unit content in alumina precursor
Sodium Polyacrylate it is 3 times higher than the content of Sodium Polyacrylate in silicon source-organic polymer mixture.The preparation method of catalyst 2
With embodiment 1, palladium amount is 0.35wt%.
Embodiment 3
220g polyacrylic acid is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite, silicaalumina carrier
Preparation includes the silica of 8.4wt% with embodiment 1, in silicaalumina carrier, the nickel doped lanthanum ferrite of 2.6wt%,
The magnesium of 2.1wt%, carrier is mesoporous to account for the 54.9% of total hole, and macropore accounts for the 33.1% of total hole.Unit content in alumina precursor
Polyacrylic acid it is 3.3 times higher than the content of polyacrylic acid in silicon source-organic polymer mixture.The preparation method of catalyst 3 is same
Embodiment 1, palladium amount are 0.21wt%.
Embodiment 4
280g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite
Preparation with embodiment 1, in silicaalumina carrier include 8.4wt% silica, the nickel doped lanthanum ferrite of 2.6wt%,
The magnesium of 2.8wt%, carrier is mesoporous to account for the 50.1% of total hole, and macropore accounts for the 39.7% of total hole.Unit content in alumina precursor
Polyacrylate it is 3.3 times higher than the content of polyacrylate in silicon source-organic polymer mixture.The preparation side of catalyst 3
For method with embodiment 1, palladium amount is 0.26wt%.
Comparative example 1
1, cadmium ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, stir 30min, drying, roasting, grinding obtain nickel doping iron
Sour lanthanum.
2, silicaalumina carrier is prepared
5g Sodium Polyacrylate is dissolved in nitric acid, is added 38g silicon powder and 50g boehmite powder, is stirred evenly, obtain
To silicon powder-boehmite-Sodium Polyacrylate mixture (brief note silicon-aluminium-organic admixture), take 1/8 amount spare,
It is spare that citric acid is added in 4.5g cadmium ferrite.300g boehmite powder and 25.0g sesbania powder are added in kneader, added
Enter nitric acid, add 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is mixed to add above-mentioned silicon powder-Sodium Polyacrylate
Object is closed, mediates uniformly, cadmium ferrite and 4.2g magnesium nitrate is then added, be uniformly mixed, is cloverleaf pattern by kneading-extruded moulding
Shape.7 hours dry at 130 DEG C, 620 DEG C roast 7 hours, obtain the carrier 1-1 of the silica-alumina of Fe-laden acid lanthanum.
3, comparative catalyst 1 is prepared
Palladium solution impregnating carrier 1-1 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain catalyst 1.
1 palladium content of comparative catalyst is 0.29wt%.
Comparative example 2
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds
Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir
30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite, 350g boehmite powder and 25.0g sesbania powder are added
Enter into kneader, nitric acid is added, adds 40.7g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is micro- to add 4.8g silicon
Powder is mediated uniformly, nickel doped lanthanum ferrite and 4.2g magnesium nitrate is then added, is uniformly mixed, and is three leaves by kneading-extruded moulding
Careless shape.7 hours dry at 130 DEG C, 620 DEG C roast 7 hours, obtain the load of the silica-alumina of nickeliferous doped lanthanum ferrite
Body 1-2.
3, comparative catalyst 2 is prepared
Palladium solution impregnating carrier 1-2 is configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain comparison catalysis
Agent 2.2 palladium content of comparative catalyst is 0.29wt%.
Catalyst 1-4 and comparative catalyst 1 and 2 are respectively charged into 100ml insulation bed reaction device, at 130 DEG C of temperature,
It is restored 7 hours under the conditions of the volume ratio 220:1 of hydrogen and catalyst, cools to 40 DEG C of laggard feedstock oils, drippolene C6-C8It evaporates
Point, diene content is 19.51g iodine/100g oil, bromine valency is 26.76g bromine/100g oil, gum level is 41mg/100ml oil, trip
From water content be 1123ppm, sulfur content is 156ppm and arsenic content is 151ppb；Reaction process condition are as follows: 45 DEG C of inlet temperature,
Hydrogen to oil volume ratio 300: 1, reaction pressure 3.5MPa, green oil air speed 3.5h-1；Operating 1 hydrogenated products of 220h catalyst are averaged
Diene is 0.38 gram of iodine/100 gram oil, and bromine valency is 15.68 grams of bromine/100 gram, diolefin hydrogenation rate 98.7%.2 hydrogenated products of catalyst
Average diene be 0.33 gram of iodine/100 gram oil, bromine valency be 14.56 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.8%；Catalyst 3
The average diene of hydrogenated products is 0.42 gram of iodine/100 gram oil, and bromine valency is 16.54 grams of bromine/100 gram, diolefin hydrogenation rate 98.2%.
The average diene of 4 hydrogenated products of catalyst is 0.40 gram of iodine/100 gram oil, and bromine valency is 15.29 grams of bromine/100 gram oil, diolefin hydrogenation
Rate 98.3%.Catalyst activity is higher, and selectivity is more preferable, and anticol matter, water resistant ability are more preferable, and anti-arsenic, sulfur resistive ability are strong.
After catalyst 1-2 operates 500h, the average diene of 1 hydrogenated products of catalyst is 0.40 gram of iodine/100 gram oil, bromine valency
For 20.25 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.5%；The average diene of 2 hydrogenated products of catalyst is 0.45 gram of iodine/100
Gram oil, bromine valency are 20.48 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.7%.Contain nickel doped lanthanum ferrite in catalyst carrier, has
Polymerization reaction occurs conducive to the unsaturated component of inhibition alkadienes and styrene etc.；Catalyst is insensitive to impurity such as water, colloids, urges
Agent anticol matter, water resistant ability are good, and anti-arsenic, sulfur resistive ability are strong, stable in catalytic performance.Catalyst carrier micropore, mesoporous, macropore are not
It is uniformly distributed, palladium catalyst activity is good, and stability is good, long service life, is conducive to device long-term operation.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (10)
1. one kind is used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that catalyst includes silicaalumina carrier
With the metal active component palladium being carried on carrier, the content of palladium is 0.15-0.45wt%, oxygen based on the total weight of the catalyst
In SiClx-alumina support include 0.1~12wt% silica, the nickel doped lanthanum ferrite of 0.1~10wt%, 0.05~
The magnesium of 7.8wt%, carrier is mesoporous to account for the 3~75% of total hole, and macropore accounts for the 1.5~60% of total hole, micropore in carrier, mesoporous, big
Hole uneven distribution.
2. according to claim 1 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that the palladium catalyst
Content be 0.20-0.35wt%.
3. according to claim 1 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that the carrier is mesoporous
The 3~65% of total hole are accounted for, macropore accounts for the 3~45% of total hole.
4. according to claim 1 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that the silica-
Being uniformly mixed the preparation method is as follows: boehmite and sesbania powder are added in kneader for alumina support, is added inorganic
Acid solution and organic polymer are mediated uniformly, then add nickel doped lanthanum ferrite, are uniformly mixed and obtain alumina precursor,
It is spare；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtaining silicon source-boehmite-has
Machine polymeric blends, the organic polymer of unit content is than silicon source-boehmite-organic polymer in alumina precursor
The high 2 times or more of the content of organic polymer in mixture, then by silicon source -- boehmite-organic polymer mixture and oxygen
Change the mixing of aluminium presoma, adds magnesium source, through extrusion, molding, drying, roasting, obtain silicaalumina carrier.
5. according to claim 4 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that the silicon source is silicon
Glue, sodium metasilicate or silicon powder, in silicon source-boehmite-organic polymer mixture aluminium oxide account for aluminium oxide in carrier 1~
35wt%.
6. according to claim 4 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that the organic polymer
Object is one or more of polyvinyl alcohol, polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
7. according to claim 4 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that the silica-
Nickel doped lanthanum ferrite is 0.1~12wt% in alumina support.
8. described in any item according to claim 1~7 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that institute
It states the preparation method of nickel doped lanthanum ferrite: citric acid being dissolved in stirring and dissolving in deionized water, then by lanthanum nitrate and ferric nitrate
It is added in citric acid, stirring and dissolving, Sodium Polyacrylate, polyacrylate or polyacrylic acid, Sodium Polyacrylate, polyacrylic acid is added
The additional amount of ester or polyacrylic acid be nickel doped lanthanum ferrite 0.1~10wt%, add nickel compound containing, stir, through drying,
Roasting, grinding obtain finished product.
9. described in any item according to claim 1~7 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that institute
The preparation method for stating catalyst includes the following steps: to impregnate active component palladium, spray on silicaalumina carrier, so
Catalyst is dried afterwards, roasts and obtains the catalyst.
10. according to claim 9 be used for selective hydrogenation catalyst for pyrolysis gasoline, which is characterized in that the catalyst
Preparation process it is as follows: prepare palladium-containing solution oxide impregnation silicon-alumina support, through 110~160 DEG C dry 3~9 hours, 400
~650 DEG C roast 4~9 hours, finally obtain catalyst prod.
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| CN1830560A (en) * | 2005-03-11 | 2006-09-13 | 石油大学(北京) | Macropore hydrogenation catalyst and its preparation method |
| CN101121899A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
| CN101260320A (en) * | 2008-04-17 | 2008-09-10 | 中国石油天然气集团公司 | Selectivity hydrodeolefin catalyst used for continuously reforming gasoline and preparation method thereof |
| FR2993795A1 (en) * | 2012-07-25 | 2014-01-31 | IFP Energies Nouvelles | Preparing supported catalyst based on metal particles, comprises providing aqueous solution of metal precursor, heating porous support, contacting aqueous solution with porous support by dry impregnation, and drying the product |
| CN103418378A (en) * | 2013-08-01 | 2013-12-04 | 济南开发区星火科学技术研究院 | Catalytic agent for cracking C-4 fraction selective hydrogenating palladium base |
| CN107159279A (en) * | 2017-06-02 | 2017-09-15 | 钦州学院 | A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof |
| CN107754818A (en) * | 2017-11-24 | 2018-03-06 | 福州大学 | A kind of hydrocracking catalyst for suspension bed and preparation method |
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