CN114749193A - Hydrogenation catalyst for producing low-sulfur marine fuel and preparation method thereof - Google Patents
Hydrogenation catalyst for producing low-sulfur marine fuel and preparation method thereof Download PDFInfo
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- CN114749193A CN114749193A CN202210024856.7A CN202210024856A CN114749193A CN 114749193 A CN114749193 A CN 114749193A CN 202210024856 A CN202210024856 A CN 202210024856A CN 114749193 A CN114749193 A CN 114749193A
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- Prior art keywords
- water
- aluminum
- metal
- acid
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 87
- 239000011593 sulfur Substances 0.000 title claims abstract description 87
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 239000000295 fuel oil Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 84
- 239000002184 metal Substances 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000000446 fuel Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- -1 VIB group metals Chemical class 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 50
- 229910052782 aluminium Inorganic materials 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 27
- 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 claims description 26
- 229910052708 sodium Inorganic materials 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 13
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 150000005323 carbonate salts Chemical class 0.000 claims 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 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 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 25
- 238000006477 desulfuration reaction Methods 0.000 abstract description 8
- 230000023556 desulfurization Effects 0.000 abstract description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- 239000002905 metal composite material Substances 0.000 description 38
- 238000003756 stirring Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000008213 purified water Substances 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 230000020477 pH reduction Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003518 caustics Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 229940024545 aluminum hydroxide Drugs 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 5
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 5
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 5
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010747 number 6 fuel oil Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- 229940100445 wheat starch Drugs 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940024546 aluminum hydroxide gel Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
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- 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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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/082—Decomposition and pyrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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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
- 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
Abstract
The invention discloses a hydrogenation catalyst for producing low-sulfur marine fuel and a preparation method thereof, wherein the catalyst comprises a silicon-aluminum material, and a first metal and a second metal which are loaded on the silicon-aluminum material; wherein the first metal is selected from at least one of IVB group metals, VIB group metals and VIII group metals; the second metal is selected from at least one of VIB group metals and VIII group metals. Preparing a first solution, then preparing to obtain slurry B, processing to obtain a carrier precursor, and further forming, drying and roasting to obtain a carrier; and then introducing a second metal onto the support to obtain the catalyst. The catalyst provided by the invention has the advantages of high utilization rate of active metal, good wear resistance, high hydrogenation performance, particularly good desulfurization performance and cracking performance, and the like, and is suitable for being applied to a process for producing low-sulfur ship fuel from heavy and poor residual oil.
Description
Technical Field
The invention belongs to the field of petrochemical industry, relates to a catalytic material and a preparation method thereof, and particularly relates to a catalytic material for producing low-sulfur ship fuel and a preparation method thereof.
Background
With the increasing global environmental problem, environmental regulations have been developed at home and abroad to limit the sulfur content of bunker fuel oil (hereinafter referred to as bunker fuel). The international maritime organization requires that the upper limit of the burning sulfur content of the ship is reduced to 0.5wt% in 1/2020. After implementation of the sulfur policy in the year 2020 of IMO, the low-sulfur heavy fuel ship is expected to account for about 45% of the total consumption in a short period and about 40% in a long period, namely the low-sulfur heavy fuel ship has a gap of about 9500 ten thousand tons/year.
At present, the high-sulfur heavy ship fuel is mainly produced by a blending method, blending components mainly come from high-sulfur residual oil which is difficult to treat in a refinery, and non-ideal byproducts such as catalytic slurry oil and low-quality secondary processing distillate oil, and the key points of blending are that the viscosity, the stability and the content of metallic aluminum and silicon (catalyst powder in the catalytic slurry oil) meet the quality requirement. However, direct production of a residuum-type low sulfur ship fuel having a sulfur content of less than 0.5 wt.% using the present blending components is difficult and requires blending with the addition of a low sulfur residuum. The domestic residue type ship fuel with the sulfur content of less than 0.5 percent mainly depends on import. And if a large amount of high-price low-sulfur straight-run residual oil is blended to produce the heavy ship fuel, the production cost of the heavy ship fuel can be greatly increased. The boiling bed residual oil hydrogenation technology has the characteristics that inferior high-sulfur residual oil raw materials can be treated, higher desulfurization rate is realized, especially, the boiling bed residual oil hydrogenation technology is developed very rapidly in China in recent years, 3 sets of boiling bed residual oil hydrogenation devices built in China and under construction are counted, and a residual oil hydrogenation catalyst with high desulfurization performance is developed in a targeted manner by combining the current boiling bed residual oil hydrogenation device, so that an effective means for economically producing low-sulfur ship fuel is provided.
CN200910086744.9 discloses a graded combination of hydrogenation catalysts. The reactor is respectively filled with hydrodemetallization and hydrodesulfurization catalysts from top to bottom; the raw material flow is from top to bottom, the catalyst activity is gradually increased, the pore diameter is gradually reduced, the particle size is gradually reduced, and the porosity is gradually reduced along the material flow direction; the concentration gradient of the active metal component and the acidic auxiliary agent of the hydrodesulfurization catalyst is reduced; the catalyst is used for hydrogenation catalysis of heavy distillate oil and residual oil, and has better demetalization, carbon residue removal, desulfurization activity and stability. The HDS catalyst may be Al2O3And (3) as a carrier, spraying water vapor, soaking solutions with different active metal components and acidic auxiliary agent concentrations in multiple steps, and drying and roasting to prepare the HDS catalyst with different metal gradients.
CN201511001449.0 discloses a residual oil hydrodesulfurization catalyst and its preparationThe method takes alumina as a carrier and Mo or W and Co or Ni as active components; the catalyst has a pore volume of 0.4-1.8 ml/g and a specific surface area of 100-280 m2(ii) in terms of/g. The preparation method comprises the following steps: the method comprises the steps of taking alumina as a carrier, taking Mo or W and Ni or Co as active components, contacting a salt solution of the Mo or W with the alumina carrier by a step-by-step impregnation method, introducing the Ni or Co after drying and roasting, and finally obtaining the residual oil hydrodesulfurization catalyst containing the Mo or W and the Co or Ni after drying and roasting.
CN03133545.4 discloses a heavy oil and residual oil hydrodesulfurization catalyst and a preparation method thereof. The catalyst is prepared from gamma-Al2O3As carrier, VIB group and VIII group metals as active components, and Ti and the like as active auxiliary agents. The catalyst is prepared through the complete mixing and kneading process including adding Mo and/or W containing alkali solution into dry aluminum hydroxide powder, mixing and kneading until the aluminum hydroxide powder is wetted completely, adding Co and/or Ni containing acid solution, mixing and kneading until the material becomes plastic, extruding to form, drying and roasting. The catalyst promoter prepared by the method of the invention has more uniform distribution of Ti, obviously improved pore volume and specific surface area, and excellent service performance. 1-20 w% of titanium dioxide in the titanium-containing alumina dry glue, the pore volume of 0.7-1.1 mL/g, and the specific surface of 360-450 m2G, dispersity of titanium on alumina ITi/IAlIs 0.3 or more.
At present, in the prior art, a desulfurization catalyst is mainly developed from two aspects, namely, the improvement of a catalytic material to prepare the catalytic material with large pore volume and strong acidity; on the other hand, the dispersion of the metal is optimized, and the utilization rate of the active metal is improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a hydrogenation catalyst for producing low-sulfur marine fuel and a preparation method thereof. The preparation of the catalyst is based on the preparation of a silicon-aluminum-metal composite material. The silicon-aluminum-metal composite material has the characteristics of a mesoporous-macroporous multistage pore channel structure, large pore volume, high B acid content, low impurity content and the like. Meanwhile, after the carrier is impregnated with metal, a roasting mode of water vapor is adopted, so that metal aggregation is reduced, and the utilization rate of active metal is improved. The prepared catalyst has the advantages of high utilization rate of active metal, good wear resistance, high hydrogenation performance, particularly good desulfurization performance and cracking performance, and the like, and is suitable for the process for producing low-sulfur ship fuel by using heavy and poor residual oil.
The invention provides in a first aspect a hydrogenation catalyst for producing low sulfur marine fuel, said catalyst comprising a silica-alumina material, and a first metal and a second metal supported on the silica-alumina material; wherein the first metal is selected from at least one of group IVB metal, group VIB metal and group VIII metal, preferably the group VIB metal; the second metal is selected from at least one of VIB group metals and VIII group metals.
Furthermore, in the hydrogenation catalyst for producing low-sulfur marine fuel, the specific surface area of the catalyst is 160-250 m2A ratio of 160 to 230 m/g is preferred2The pore volume is 0.4-0.7 mL/g, preferably 0.45-0.65 mL/g, the total acid value of the catalyst is 0.3-0.6 mol/g, preferably 0.35-0.6 mol/g, and the ratio of B acid to L acid is 0.3-1.0, preferably 0.3-0.8.
Furthermore, in the hydrogenation catalyst for producing low-sulfur marine fuel, the content of the VIB group metal in terms of oxides is 6-15%, preferably 8-15% based on the weight of the catalyst; the content of the VIII group metal is 2-10%, preferably 2-6% calculated by oxide, and the content of the IVB group metal is 0.1-4.0%, preferably 0.5-4.0% calculated by oxide.
In a second aspect, the invention provides a preparation method for producing a low-sulfur hydrogenation catalyst for ship fuel, which comprises the following steps:
(1) Adding an acidic aluminum source into a silicon source, and then mixing with a first metal salt solution to obtain a mixed solution A;
(2) contacting the mixed solution A with an alkaline aluminum source in the presence of water to obtain slurry B;
(3) carrying out hydrothermal treatment on the slurry B to obtain a carrier precursor;
(4) uniformly mixing the carrier precursor obtained in the step (3), a forming agent and an adhesive, forming, drying and roasting to obtain a carrier;
(5) and mixing the carrier with a second metal salt solution, and further drying and roasting to obtain the catalyst.
According to the present invention, in step (1), an acidic aluminum source is added to the silicon source, instead of adding the silicon source to the acidic aluminum source, which would otherwise result in the formation of a large amount of precipitate.
Further, in the above preparation method for producing a low-sulfur marine fuel hydrogenation catalyst, in the step (1), the silicon source is a water-soluble or water-dispersible basic silicon-containing compound (preferably a water-soluble or water-dispersible basic inorganic silicon-containing compound, more preferably one or more selected from water-soluble silicate, water glass and silica sol, and preferably water glass).
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the silicon source is used in the form of an aqueous solution. The silicon source (calculated as SiO 2) is present in a concentration of 5 to 30 wt.% (preferably 15 to 30 wt.%), based on the total weight of the aqueous solution, and its modulus is typically 2.5 to 3.2.
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the acidic aluminum source is a water-soluble acidic aluminum-containing compound (preferably a water-soluble acidic inorganic aluminum-containing compound, especially a water-soluble inorganic strong acid aluminum salt, more preferably one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, and preferably aluminum sulfate).
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the acidic aluminum source is used in the form of an aqueous solution, and the concentration of the acidic aluminum source (calculated as Al2O 3) is 30 to 100g/L (preferably 30 to 80 g/L) based on the total weight of the aqueous solution.
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the weight ratio of the silicon source (calculated as SiO 2) to the acidic aluminum source (calculated as Al2O 3) is 1:1 to 9:1 (preferably 1:1 to 7: 1).
Further, in the above-mentioned preparation method of the hydrogenation catalyst for low-sulfur ship fuel production, in order to achieve the technical effects of the present invention more excellently, particularly in order to obtain a carrier precursor having a larger pore volume and a lower impurity content, in step (1), an acid is further added (preferably, the acidic aluminum source is added to the silicon source, and then the acid is further added to obtain the mixed solution a).
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid and hydrochloric acid, and preferably sulfuric acid).
Further, in the above-described method for preparing a hydrogenation catalyst for low-sulfur marine fuel, the acid is used in the form of an aqueous solution. The acid concentration is 2 to 6wt% (preferably 2 to 5 wt%) based on the total weight of the aqueous solution.
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the acid is added in an amount such that the pH of the mixed solution a is 2 to 4 (preferably 3 to 4).
Further, in the above preparation method of the hydrogenation catalyst for low-sulfur marine fuel, in the step (1), generally, the aluminum content of the mixed liquor A is 5-20gAl2O3/L calculated as Al2O3, and the silicon content is 5-40gSiO2/L calculated as SiO 2.
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, in the step (2), the alkaline aluminum source is a water-soluble alkaline aluminum-containing compound (preferably a water-soluble alkaline inorganic aluminum-containing compound, especially an alkali metal metaaluminate, more preferably one or more selected from sodium metaaluminate and potassium metaaluminate, and preferably sodium metaaluminate).
Further, in the above method for preparing a hydrogenation catalyst for producing low-sulfur marine fuel, the alkali aluminum source is used in the form of an aqueous solution. The concentration of the alkaline aluminum source (calculated as Al2O 3) is 130-350g/L (preferably 150-250 g/L) based on the total weight of the aqueous solution, and the caustic ratio is generally 1.15-1.35, preferably 1.15-1.30.
Further, in the above method for preparing a hydrogenation catalyst for producing low sulfur marine fuel, the amount of the mixed solution a is 40 to 70vol% (preferably 40 to 65 vol%) based on the total volume of the mixed solution a, the alkali aluminum source and water.
Further, in the above method for preparing a hydrogenation catalyst for producing low sulfur marine fuel, the amount of the alkali aluminum source is 20 to 40vol% (preferably 25 to 40 vol%) based on the total volume of the mixed solution a, the alkali aluminum source and water.
Further, in the above method for preparing a hydrogenation catalyst for producing low sulfur marine fuel, the amount of water is 10 to 20vol% (preferably 13 to 20 vol%) based on the total volume of the mixed solution a, the alkali aluminum source and water.
Further, in the above method for preparing a hydrogenation catalyst for producing low sulfur ship fuel, the mixed solution a and the alkali aluminum source are added to water sequentially or simultaneously (preferably, the mixed solution a and the alkali aluminum source are added to water in a concurrent manner).
Further, in the preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the adding flow rate of the mixed liquid A is 15-50mL/min (preferably 20-40 mL/min).
Further, in the above-described method for producing a hydrogenation catalyst for low-sulfur ship fuel, the flow rate of the alkaline aluminum source is controlled so that the pH of the slurry B is maintained at 7.5 to 10.5 (preferably 8.0 to 10.5, and more preferably 8.5 to 10.5).
Further, in the above-described method for producing a hydrogenation catalyst for low-sulfur ship fuel, in order to achieve the technical effects of the present invention more excellently, particularly in order to obtain a carrier precursor having a larger pore volume, in the step (2), a water-soluble carbonate is further added (preferably, the mixed solution a and the alkaline aluminum source are added to water, and then the water-soluble carbonate is further added to obtain the slurry B).
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the water-soluble carbonate is selected from one or more carbonates of alkali metals and ammonium (preferably, one or more carbonates of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate, preferably sodium carbonate).
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the water-soluble carbonate is used in the form of a solid.
Further, in the above method for preparing a hydrogenation catalyst for low sulfur marine fuel, the water-soluble carbonate is added in an amount such that the slurry B has a pH of 10.5 to 12 (preferably 11 to 12).
Further, in the above preparation method of the hydrogenation catalyst for producing low sulfur marine fuel, in step (3), the carrier precursor is separated from the reaction system of the hydrothermal treatment, washed to neutrality, and then dried. Here, the washing may be performed by a washing method conventional in the art, preferably by deionized water, and more preferably at 50 ℃ to 90 ℃. In addition, the separation can adopt one of the means which can realize the separation of liquid-solid two-phase materials in the field, such as filtration, centrifugal separation and the like, and concretely, the separation can adopt a filtration separation mode to separate, solid-phase materials and liquid-phase materials are obtained after separation, and the solid-phase materials are washed and dried to obtain the carrier precursor.
Further, in the above preparation method of the hydrogenation catalyst for producing low sulfur marine fuel, the drying conditions include: the drying temperature is 100-150 ℃, and the drying time is 6-10 hours.
Further, in the above preparation method of the hydrogenation catalyst for low-sulfur ship fuel, in the step (1), the temperature is 25 to 50 ℃ (preferably 25 to 40 ℃), and the pressure is normal pressure.
Further, in the above preparation method of the hydrogenation catalyst for low sulfur marine fuel, in the step (2), the temperature is 50 to 90 ℃ (preferably 50 to 80 ℃), and the pressure is normal pressure.
Further, in the above preparation method of the hydrogenation catalyst for producing low sulfur marine fuel, in the step (3), the temperature is 180-.
Further, in the above-mentioned method for preparing a hydrogenation catalyst for low-sulfur marine fuel, in order to achieve the technical effects of the present invention more excellently, in the step (3), the hydrothermal treatment time is 0.5 to 20 hours (preferably 2 to 16 hours).
Furthermore, in the preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, an auxiliary agent, such as one or more of P2O5, B2O3 or TiO2, can be added according to actual needs. For this purpose, these precursors may be added during the reaction of step (1) in the form of water-soluble inorganic salts. Specific examples of the inorganic salt include borate, sulfate, and nitrate. The addition amount of these auxiliaries can be arbitrarily adjusted according to the requirements of the subsequent catalyst and the like. In general, these auxiliaries are generally present in a weight content, calculated as oxide, of from 1 to 8% by weight, preferably from 2 to 6% by weight, relative to 100% by weight of the total weight of the support precursor.
Further, in the preparation method of the hydrogenation catalyst for producing low sulfur marine fuel, in the step (1), the first metal is at least one selected from group IVB metals, group VIB metals and group VIII metals, and further, the first metal salt is any one of soluble metal salts, such as sulfate or nitrate. The first metal may specifically be one or more of Ni, Co, Fe, and Zr, and further, the first metal salt may be one or more of nickel nitrate, cobalt nitrate, nickel sulfate, cobalt sulfate, iron nitrate, iron sulfate, zirconium nitrate, and zirconium sulfate.
Further, in the preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, in the step (4), the forming agent is one or more of cellulose and starch, preferably cellulose, and more preferably methyl cellulose.
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the binder in step (4) is an organic acid, specifically, one or more of acetic acid, citric acid and the like, and preferably citric acid.
Further, in the preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the drying temperature in the step (4) is 100-150 ℃, and the drying time is 4-10 hours. The roasting temperature is 500-950 ℃, preferably 550-900 ℃, and the roasting time is 2-6 h.
Further, in the above preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the forming in the step (4) may adopt a forming mode commonly used in the existing catalyst preparation, and the specific forming shape may be selected according to actual needs, such as a spherical shape, a strip shape, a clover shape, etc.
Further, in the preparation method of the hydrogenation catalyst for producing low-sulfur marine fuel, the drying temperature in the step (5) is 100-150 ℃, and the drying time is 4-10 hours.
Further, in the above preparation method of the hydrogenation catalyst for low-sulfur marine fuel, in the step (5), the calcination is performed in a mixed atmosphere of water vapor and oxygen-containing gas, and the volume ratio of the oxygen-containing gas to the water vapor is 5: 1-1: 1, wherein the oxygen-containing gas is any one of oxygen and air. The roasting temperature is 400-650 ℃, and preferably 400-550 ℃; the roasting time is 3-8 h.
The third aspect of the invention provides an application of the catalyst or the catalyst obtained by the preparation method in the hydrogenation production of low-sulfur ship fuel from inferior residual oil.
Further, in the above application, the reaction conditions are as follows: the reaction pressure is 10-18 MPaG, the reaction temperature is 380-430 ℃, and the liquid hourly space velocity is 0.1-0.6 h -1The volume ratio of hydrogen to oil is 400-800.
Compared with the prior art, the hydrogenation catalyst for producing low-sulfur marine fuel and the preparation method thereof provided by the invention have the following advantages:
1. in the preparation method of the hydrogenation catalyst for producing the low-sulfur marine fuel, the first metal component is introduced in the preparation of the carrier at first, and occupies neutral and alkaline surface hydroxyl groups in the silicon-aluminum material, so that the acidity of the carrier is modulated. Then when the second metal solution is soaked, the second metal is dispersed more uniformly due to the space occupying effect of the first metal on the carrier, and the non-framework aluminum and the non-framework silicon are removed under the roasting condition of mixing water vapor and oxygen, so that a multi-level pore structure can be formed, an acid center is exposed, the acidity of the catalyst is enhanced, and the hydrogenation performance of the catalyst is improved.
2. In the preparation method of the hydrogenation catalyst for producing the low-sulfur ship fuel, provided by the invention, in the preparation of the carrier, firstly, the silicon source is acidified by using the acidic aluminum source and then using the metal salt, so that cations (sodium ions and the like) in silicic acid polymers enveloped in rings or cages in the silicon source are dissociated, the acidified silica gel groups are adsorbed on aluminum hydroxide colloid, the sodium ions are effectively separated from the silica gel groups, and meanwhile, the added metal is multivalent, has high charge energy and plays a role of isolating the dissociated sodium ions with the acidic aluminum source, so that the subsequent removal of the sodium ions is easier, the difficulty in removing the sodium by subsequent washing is greatly reduced, and the water consumption for washing can be reduced. More importantly, sodium ions are effectively removed, metal ions are supplemented, the hydroxyl distribution of the silicon-aluminum-metal composite material is changed, the carrier has higher acidity and has large pore volume and mesoporous-macroporous multilevel pore channels, and the characteristics of high B acid content, low sodium content and the like are improved by the composite addition of silicon and metal. The catalyst prepared by the method has good hydrogenation performance, particularly desulfurization performance, and is suitable for hydrogenation process for producing low-sulfur marine oil from heavy and poor-quality residual oil.
3. In the preparation method of the hydrogenation catalyst for producing the low-sulfur marine fuel, the acidified silica gel group is adsorbed on the aluminum hydroxide colloid, so that a crystal nucleus is provided for subsequent reaction, the crystal grain of the prepared carrier precursor is promoted to be enlarged, and the carrier precursor with large pore volume and large pore diameter is favorably formed.
4. According to the preparation method of the low-sulfur marine fuel hydrogenation catalyst, the pH value of the slurry is adjusted, the slurry system form is changed into a gel-like thixotropic form from a flowing state at the beginning in the high-temperature treatment process, the slurry system form is changed into the flowing state after being treated for a period of time, a silicon-aluminum material and water form a changeable silicon-aluminum-oxygen network structure in the process of being changed into the gel-like thixotropic form, and the preparation method is favorable for preparing a carrier precursor with large pore volume.
Detailed Description
The following detailed description of the embodiments of the present invention is provided in conjunction with specific examples, but it should be noted that the scope of the present invention is not limited by these specific examples, but is defined by the claims.
In the context of the present specification, the pore volume and specific surface area of the sialon material were analyzed using low temperature nitrogen adsorption.
In the context of the present specification, the pore volume, specific surface area and pore size distribution are measured using low temperature nitrogen adsorption. Total acid, B acid and L acid were measured by pyridine infrared adsorption. Sodium oxide and silica were measured using fluorescence analysis. The active metal content was measured spectrophotometrically. The wear index was measured using an air jet method.
All percentages, parts, ratios, etc. referred to within this specification are by weight and pressures are gauge pressures unless explicitly indicated.
In the context of this specification, any two or more embodiments of the invention may be combined in any combination, and the resulting solution is part of the original disclosure of this specification, and is within the scope of the invention.
Example 1
(1) Preparation of silicon-aluminum-metal composite material
The preparation concentration is 40gAl2O3Aluminum sulfate solution/L and a concentration of 60gSiO2The sol solution with the modulus of 2.8 is prepared for later use, and the first metal salt solution with the concentration of 50gNiO/L is prepared for later use. The caustic ratio is 1.20, the concentration is 150 gAl2O3and/L of sodium metaaluminate solution for later use.
1.5L of the solution with the concentration of 60gSiO is measured2Adding the/L silica sol solution into a container, and slowly adding 1L of 40gAl under stirring 2O3Aluminum sulfate solution/L, during which aluminum hydroxide colloid is formed, but the solution is still in liquid form. And then adding a first metal salt solution with the concentration of 50gNiO/L to adjust the pH value to 3, wherein the dosage is 0.1L, and completing the acidification treatment to obtain a mixed solution A.
Adding 1000mL of deionized water serving as bottom water into a 5000mL reactor, starting stirring and heating, heating the deionized water to 60 ℃, adding the mixed solution A into the reactor at a rate of 20mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the using amount of sodium metaaluminate is 500mL, and 48g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor and is treated for 2 hours under the condition of stirring at the treatment temperature of 220 ℃ and the treatment pressure of 0.3 MPa. Washing the treated slurry with hot water of 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a dried sample PO-1 of the silicon-aluminum-metal composite material, and roasting at 600 ℃ for 5h to obtain the silicon-aluminum-metal composite material P-1, wherein the properties of the silicon-aluminum-metal composite material P-1 are shown in Table 1.
(2) Preparation of hydrogenation catalyst
And taking 500g of the prepared PO-1 silicon-aluminum-metal composite material dry sample, adding 3.9g of hydroxypropyl methyl cellulose, 10.54g of citric acid and 470g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 650 ℃ for 3 hours to obtain a carrier Z1 with the particle size of 0.3-0.8 mm.
50.29g of phosphoric acid is weighed, 800mL of distilled water is added, 177.57g of molybdenum oxide and 75.12g of basic nickel carbonate are sequentially added, the solution is heated and stirred until the molybdenum oxide and the basic nickel carbonate are completely dissolved, and the solution is made to be 1000mL by using distilled water, so that a solution L1 is obtained. The support Z1 was saturated with the solution L1, dried at 110 ℃ for 2h, dried at a volume ratio of air to water vapor of 3: 1, roasting for 5 hours at the roasting temperature of 480 ℃ to obtain the catalyst C1, wherein the specific properties are shown in Table 2.
Example 2
The other conditions were the same as in example 1 except that: changing the silica sol into a water glass solution, changing the dosage of the first metal salt into 0.05L, adjusting the acidification pH to 4.0, adjusting the flow rate of the mixed solution A to 30mL/min, heating deionized water in a reactor to 70 ℃ to obtain a silicon-aluminum-metal composite material dry sample PO-2, and roasting at 600 ℃ for 5 hours to obtain the silicon-aluminum-metal composite material P-2, wherein the properties of the silicon-aluminum-metal composite material P-2 are shown in Table 1.
And taking 500g of the prepared PO-2 silicon-aluminum-metal composite material dry sample, adding 7.0g of wheat starch, 12.8g of acetic acid (85 wt%) and 450g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 600 ℃ for 4 hours to obtain a carrier Z2 with the particle size of 0.3-0.8 mm.
The support Z2 was saturated with the solution L1, dried at 110 ℃ for 2h, dried at a volume ratio of air to water vapor of 4: 1, roasting for 4 hours at the roasting temperature of 580 ℃, and obtaining the catalyst C2, wherein the specific properties are shown in Table 2.
Example 3
Other conditions were the same as in example 1 except that: the silica sol is changed into 40gSiO2Adjusting acidification pH to 3.5, adjusting the flow rate of the mixed solution A to 15mL/min, adding 61g of ammonium carbonate into the reactor under the stirring condition to adjust the pH value to 11.0, adjusting the treatment temperature to 250 ℃ and the treatment pressure to 0.4MPa to obtain a silicon-aluminum-metal composite material dry sample PO-3, and roasting at 600 ℃ for 5 hours to obtain a silicon-aluminum-metal composite material P-3, wherein the properties of the material are shown in Table 1.
And taking 500g of the prepared PO-3 silicon-aluminum-metal composite material dry sample, adding 10.0g of wheat starch, 8.8g of tartaric acid and 480g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 700 ℃ for 4 hours to obtain the carrier Z3 with the particle size of 0.3-0.8 mm.
The support Z3 was saturated with the solution L1, dried at 110 ℃ for 2h and dried at a volume ratio of air to water vapor of 1: 1, roasting for 3 hours at the roasting temperature of 500 ℃ to obtain a catalyst C3, wherein the specific properties are shown in Table 3.
Example 4
(1) Preparation of silicon-aluminum-metal composite material
The preparation concentration is 30gAl2O3Aluminum sulfate solution/L and a concentration of 60gSiO2The silica sol solution with the modulus of 2.8 and the concentration of 30g ZrO is prepared for standby2The first metal salt solution is ready for use. The caustic ratio was 1.25, the concentration was 130 gAl 2O3and/L of sodium metaaluminate solution for later use.
1.5L of 60gSiO in concentration is measured2Adding the/L silica sol solution into a container, and slowly adding 1L of 30gAl under the condition of stirring2O3Aluminum sulfate solution/L, during which aluminum hydroxide colloid is formed, but the solution is still in liquid form. Then, 30g of ZrO was added2Adjusting the pH value to 3.5 by using 0.05L of the first metal salt solution, and completing acidification treatment to obtain mixed solution A.
Adding 800mL of deionized water serving as bottom water into a 5000mL reactor, starting stirring and heating, heating the deionized water to 70 ℃, adding the mixed solution A into the reactor at a rate of 25mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 8.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the dosage of sodium metaaluminate is 560mL, and 76g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor and treated for 4 hours under the condition of stirring at the treatment temperature of 240 ℃ and the treatment pressure of 0.3 MPa. Washing the treated slurry with hot water of 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a dried sample PO-4 of the silicon-aluminum-metal composite material, and roasting at 600 ℃ for 5h to obtain the silicon-aluminum-metal composite material P-4, wherein the properties of the silicon-aluminum-metal composite material P-4 are shown in Table 1.
(2) Preparation of hydrogenation catalyst
And taking 500g of the prepared PO-4 silicon-aluminum-metal composite material dry sample, adding 5.1g of hydroxypropyl methyl cellulose, 8.76g of tartaric acid and 490g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 550 ℃ for 3h to obtain a carrier Z4 with the particle size of 0.3-0.8 mm.
50.47g of phosphoric acid is weighed, 800mL of distilled water is added, 137.06g of molybdenum oxide and 48.76g of basic cobalt carbonate are sequentially added, the solution is heated and stirred until the molybdenum oxide and the basic cobalt carbonate are completely dissolved, and the solution is made to be 1000mL by using distilled water, so that a solution L2 is obtained. The support Z4 was saturated with the solution L2, dried at 110 ℃ for 2h and dried at a volume ratio of air to water vapor of 4: 1, roasting for 4 hours at the roasting temperature of 450 ℃ to obtain the catalyst C4, wherein the specific properties are shown in Table 2.
Example 5
The other conditions were the same as in example 4 except that: changing the silica sol into water glass, adjusting the acidification pH value to 3.0, adjusting the adding amount of reactor bottom water to 1000mL, heating deionized water to 70 ℃, adjusting the treatment temperature to 260 ℃ and the treatment pressure to 0.5MPa to obtain a silicon-aluminum material dry sample PO-5, and roasting at 600 ℃ for 5 hours to obtain a silicon-aluminum material P-5, wherein the properties of the silicon-aluminum material P-5 are shown in Table 1.
And taking 500g of the prepared PO-5 silicon-aluminum-metal composite material dry sample, adding 12.3g of methyl cellulose, 5.5g of citric acid and 460g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 700 ℃ for 4 hours to obtain the carrier Z5 with the particle size of 0.3-0.8 mm.
The support Z5 was saturated with the solution L2, dried at 110 ℃ for 2h, dried at a volume ratio of air to water vapor of 2: 1, roasting for 5 hours at the roasting temperature of 420 ℃ to obtain the catalyst C5, wherein the specific properties are shown in Table 3.
Comparative example 1
(1) Preparation of silicon-aluminum-metal composite material
The preparation concentration is 40gAl2O3Aluminum sulfate solution/L and a concentration of 60gSiO2The silica sol solution with the modulus of 2.8 is ready for use. The caustic ratio is 1.20, the concentration is 150 gAl2O3and/L of sodium metaaluminate solution for later use.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding aluminum sulfate into the reactor at 20mL/min and 30mL/min of silica sol, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature of slurry in the reactor and the pH value constant. After the reaction is finished, the using amount of sodium metaaluminate is 500mL, and 48g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor and treated for 2 hours under the condition of stirring at the treatment temperature of 220 ℃ and the treatment pressure of 0.3 MPa. Washing the treated slurry with hot water at 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a sample PFO-1 after the silicon-aluminum-metal composite material is dried, and roasting at 600 ℃ for 5h to obtain the silicon-aluminum-metal composite material PF-1, wherein the properties of the silicon-aluminum-metal composite material are shown in Table 1.
(2) Preparation of hydrogenation catalyst
Taking 500g of the prepared PFO-1 silicon-aluminum-metal composite material dry sample, adding 3.9g of hydroxypropyl methyl cellulose, 10.54g of citric acid and 470g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 650 ℃ for 3h to obtain a carrier ZF1 with the particle size of 0.3-0.8 mm.
The carrier ZF1 was saturated with solution L1 and dried at 110 ℃ for 2h at an air to water vapor volume ratio of 3: 1, roasting for 5 hours at the roasting temperature of 480 ℃ to obtain the catalyst CF1, wherein the specific properties are shown in Table 2.
Comparative example 2
(1) Preparation of silicon-aluminum-metal composite material
The preparation concentration is 40gAl2O3Aluminum sulfate solution/L and a concentration of 60gSiO2The sol solution with the modulus of 2.8 is prepared for later use, and the first metal salt solution with the concentration of 50gNiO/L is prepared for later use. The caustic ratio is 1.20, the concentration is 150 gAl2O3and/L of sodium metaaluminate solution for later use.
1L of 40gAl is metered in2O3Adding the/L aluminum sulfate solution into a container, and slowly adding 1.5L of 60gSiO under stirring2The process of the preparation of the/L silica sol solution generates a large amount of aluminum hydroxide gel, and the fluidity is poor. And then adding a first metal salt solution with the concentration of 50gNiO/L to adjust the pH value to 3, wherein the dosage is 0.1L, and completing acidification treatment to obtain a mixed solution A.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding the mixed solution A into the reactor at a rate of 20mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the using amount of sodium metaaluminate is 500mL, and 48g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor and is treated for 2 hours under the condition of stirring at the treatment temperature of 220 ℃ and the treatment pressure of 0.3 MPa. Washing the treated slurry with hot water at 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a sample PFO-2 after the silicon-aluminum-metal composite material is dried, and roasting at 600 ℃ for 5h to obtain the silicon-aluminum-metal composite material PF-2, wherein the properties of the silicon-aluminum-metal composite material are shown in Table 1.
(2) Preparation of hydrogenation catalyst
Taking 500g of the prepared PFO-2 silicon-aluminum-metal composite material dry sample, adding 3.9g of hydroxypropyl methyl cellulose, 10.54g of citric acid and 470g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 650 ℃ for 3h to obtain a carrier ZF2 with the particle size of 0.3-0.8 mm.
The carrier ZF2 was saturated with solution L1 and dried at 110 ℃ for 2h at an air to water vapor volume ratio of 3: 1, roasting for 5 hours at the roasting temperature of 480 ℃ to obtain the catalyst CF2, wherein the specific properties are shown in Table 2.
Comparative example 3
(1) Preparation of silicon-aluminum-metal composite material
The preparation concentration is 40gAl2O3Aluminum sulfate solution/L and a concentration of 60gSiO2The sol solution with the modulus of 2.8 is prepared for later use, and the first metal salt solution with the concentration of 50gNiO/L is prepared for later use. The caustic ratio is 1.20, the concentration is 150 gAl2O3and/L of sodium metaaluminate solution for later use.
1.5L of the solution with the concentration of 60gSiO is measured2Adding the/L silica sol solution into a container, and slowly adding 1L of 40gAl under stirring2O3Aluminum sulfate solution/L, during which aluminum hydroxide colloids are formed, but the solution is still in liquid form. And then adding a first metal salt solution with the concentration of 50gNiO/L to adjust the pH value to 3, wherein the dosage is 0.1L, and completing acidification treatment to obtain a mixed solution A.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding the mixed solution A into the reactor at a rate of 20mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the using amount of sodium metaaluminate is 500 mL. Washing the reacted slurry with hot water at 90 ℃ until the liquid is neutral, drying at 120 ℃ for 6h to obtain a sample PFO-3 after the silicon-aluminum-metal composite material is dried, and roasting at 600 ℃ for 5h to obtain the silicon-aluminum-metal composite material PF-3, wherein the properties of the silicon-aluminum-metal composite material are shown in Table 1.
(2) Preparation of hydrogenation catalyst
Taking 500g of the prepared PFO-3 silicon-aluminum-metal composite material dry sample, adding 3.9g of hydroxypropyl methyl cellulose, 10.54g of citric acid and 470g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 650 ℃ for 3h to obtain a carrier ZF3 with the particle size of 0.3-0.8 mm.
The carrier ZF3 was saturated with solution L1 and dried at 110 ℃ for 2h at an air to water vapor volume ratio of 3: 1, roasting for 5 hours at the roasting temperature of 480 ℃ to obtain the catalyst CF3, wherein the specific properties are shown in Table 2.
TABLE 1 Properties of the composite materials
TABLE 2 Properties of the catalysts
The above catalysts were subjected to activity evaluation on a continuous tank reactor (CSTR) unit, and high sulfur vacuum residue was used for the evaluation, and the properties and evaluation conditions thereof are shown in table 3. The oil produced after 1000h running was sampled and analyzed, and the activity of comparative example 3 was taken as 100, and the results of other evaluations compared with the activity of comparative example 3 are shown in Table 4.
TABLE 3 high-sulfur vacuum residue Properties and evaluation conditions
TABLE 4 catalyst evaluation results
As can be seen from the data in the tables: the silicon-aluminum-metal composite material prepared by the method has large pore volume, small proportion of <10nm pores, low sodium oxide content and high B acid content. Compared with the catalyst prepared by a comparative example, the hydrogenation catalyst for producing the low-sulfur ship fuel prepared by the silicon-aluminum-metal composite material increases the impurity removal rate, particularly remarkably improves the desulfurization activity, effectively converts the asphaltene and provides a high-quality raw material for generating the low-sulfur ship fuel by the unconverted oil.
Claims (18)
1. A hydrogenation catalyst for producing low sulfur marine fuel, said catalyst comprising a silica-alumina material, and a first metal and a second metal supported on a silica-alumina material; wherein the first metal is selected from at least one of group IVB metal, group VIB metal and group VIII metal, preferably the group VIB metal; the second metal is selected from at least one of VIB group metals and VIII group metals.
2. The hydrogenation catalyst for producing low-sulfur marine fuel according to claim 1, wherein the specific surface area of the catalyst is 160 to 250m2Preferably 160 to 230 m/g2The pore volume is 0.4-0.7 mL/g, preferably 0.45-0.65 mL/g, the total acid value of the catalyst is 0.3-0.6 mol/g, preferably 0.35-0.6 mol/g, and the ratio of B acid to L acid is 0.3-1.0, preferably 0.3-0.8.
3. The hydrogenation catalyst for producing low-sulfur marine fuel according to claim 1, wherein the group VIB metal is present in an amount of 6 to 15%, preferably 8 to 15%, calculated as oxide, based on the weight of the catalyst; the content of the VIII group metal is 2-10%, preferably 2-6% calculated by oxide, and the content of the IVB group metal is 0.1-4.0%, preferably 0.5-4.0% calculated by oxide.
4. A method of making a hydrogenation catalyst for the production of low sulfur marine fuels, the method comprising:
(1) Adding an acidic aluminum source into a silicon source, and then mixing with a first metal salt solution to obtain a mixed solution A;
(2) contacting the mixed solution A with an alkaline aluminum source in the presence of water to obtain slurry B;
(3) carrying out hydrothermal treatment on the slurry B to obtain a carrier precursor;
(4) uniformly mixing the carrier precursor, the forming agent and the adhesive obtained in the step (3), forming, drying and roasting to obtain a carrier;
(5) and mixing the carrier with a second metal salt solution, and further drying and roasting to obtain the catalyst.
5. The method for preparing a hydrogenation catalyst for producing low-sulfur marine fuel as claimed in claim 4, wherein in step (1), the silicon source is a water-soluble or water-dispersible basic silicon-containing compound (preferably a water-soluble or water-dispersible basic inorganic silicon-containing compound, more preferably one or more selected from water-soluble silicate, water glass, silica sol, preferably water glass), and/or the silicon source is used in the form of an aqueous solution, and the concentration of the silicon source (calculated as SiO 2) is 5-30wt% (preferably 15-30 wt%) based on the total weight of the aqueous solution, and/or the acidic aluminum source is a water-soluble acidic aluminum-containing compound (preferably a water-soluble acidic inorganic aluminum-containing compound, particularly a water-soluble inorganic strong acid aluminum salt, more preferably one or more selected from aluminum sulfate, aluminum nitrate, aluminum chloride, preferably aluminum sulfate), and/or the source of acidic aluminum is used in the form of an aqueous solution and the concentration of the source of acidic aluminum (calculated as Al2O 3) is 30-100g/L (preferably 30-80 g/L) based on the total weight of the aqueous solution, and/or the weight ratio of the source of silicon (calculated as SiO 2) to the source of acidic aluminum (calculated as Al2O 3) is 1:1-9:1 (preferably 1:1-7: 1).
6. The method according to claim 4, wherein in step (1), an acid is further added (preferably, the acidic aluminum source is added to the silicon source and then the acid is added to obtain the mixed solution A), and/or the acid is a water-soluble acid (preferably, a water-soluble inorganic acid, more preferably, one or more selected from sulfuric acid, nitric acid and hydrochloric acid, preferably, sulfuric acid), and/or the acid is used in the form of an aqueous solution, and the concentration of the acid is 2 to 6wt% (preferably, 2 to 5 wt%) based on the total weight of the aqueous solution, and/or the acid is added in an amount such that the pH of the mixed solution A is 2 to 4 (preferably, 3 to 4).
7. The method for preparing a hydrogenation catalyst for producing low-sulfur marine fuel as claimed in claim 4, wherein in step (2), the alkaline aluminum source is a water-soluble alkaline aluminum-containing compound (preferably a water-soluble alkaline inorganic aluminum-containing compound, particularly an alkali metaaluminate, more preferably one or more selected from sodium metaaluminate and potassium metaaluminate, preferably sodium metaaluminate), and/or the alkaline aluminum source is used in the form of an aqueous solution, and the concentration of the alkaline aluminum source (calculated as Al2O 3) is 130-350g/L (preferably 150-250 g/L) and the causticity ratio is 1.15-1.35, preferably 1.15-1.30, based on the total weight of the aqueous solution, and/or the amount of the mixed solution A is 40-70vol% (preferably 40-65 vol%), and/or, the amount of the alkali aluminum source is 20-40vol% (preferably 25-40 vol%), based on the total volume of the mixed liquid a, the alkali aluminum source and water, and/or, the amount of the water is 10-20vol% (preferably 13-20 vol%), based on the total volume of the mixed liquid a, the alkali aluminum source and water, and/or, the mixed liquid a and the alkali aluminum source are added to the water sequentially or simultaneously (preferably, the mixed liquid a and the alkali aluminum source are added to the water in a concurrent manner), and/or, the adding flow rate of the mixed liquid a is 15-50mL/min (preferably 20-40 mL/min), and/or, the adding flow rate of the alkali aluminum source is controlled, so that the pH value of the slurry B is maintained at 7.5-10.5 (preferably, 8.0-10.5, more preferably 8.5 to 10.5).
8. The method according to claim 4, wherein in step (2), a water-soluble carbonate salt is further added (preferably, the mixed solution A and the alkaline aluminum source are added to water, and then the water-soluble carbonate salt is added to obtain the slurry B), and/or the water-soluble carbonate salt is selected from one or more carbonates of alkali metals and ammonium (preferably, one or more carbonates selected from sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium carbonate and ammonium hydrogen carbonate, and preferably sodium carbonate), and/or the water-soluble carbonate salt is used in a solid form, and/or the water-soluble carbonate salt is added in an amount such that the pH value of the slurry B is 10.5 to 12 (preferably, 11 to 12).
9. The method for preparing a hydroprocessing catalyst for the production of low sulfur marine fuel as claimed in claim 4, wherein in step (3) said support precursor is separated (such as by filtration or centrifugation), washed to neutrality and then dried from said hydrothermally treated reaction system, and/or said drying conditions include: the drying temperature is 100-150 ℃, and the drying time is 6-10 hours.
10. The method for preparing a hydrogenation catalyst for producing low sulfur ship fuel as claimed in claim 4, wherein in step (1), the temperature is 25-50 ℃ (preferably 25-40 ℃), the pressure is normal pressure, and/or, in step (2), the temperature is 50-90 ℃ (preferably 50-80 ℃), the pressure is normal pressure, and/or, in step (3), the temperature is 180-.
11. Process for the preparation of a hydroprocessing catalyst for the production of low sulphur marine fuels according to claim 4, wherein an auxiliary agent (preferably one or several selected from the group consisting of phosphorus, boron and titanium) is further added and/or wherein said auxiliary agent is present in an amount of 1 to 8wt% (preferably 2 to 6 wt%) calculated as oxide, relative to 100wt% of the total weight of said support precursor.
12. The method for preparing a hydrogenation catalyst for producing low-sulfur marine fuel according to claim 4, wherein the first metal in the step (1) is at least one selected from group IVB metals, group VIB metals and group VIII metals, and further the first metal salt is any one of soluble metal salts, specifically sulfate or nitrate; further, the first metal is one or more of Ni, Co, Fe, and Zr, and further, the first metal salt is one or more of nickel nitrate, cobalt nitrate, nickel sulfate, cobalt sulfate, ferric nitrate, ferric sulfate, zirconium nitrate, and zirconium sulfate.
13. The method for preparing a hydrogenation catalyst for use in the production of low-sulfur marine fuel according to claim 4, wherein the forming agent in the step (4) is one or more of cellulose and starch, preferably cellulose, and more preferably methyl cellulose.
14. The method for preparing a hydrogenation catalyst for producing low-sulfur marine fuel according to claim 4, wherein the binder in the step (4) is an organic acid, specifically one or more of acetic acid, citric acid and the like, and preferably citric acid.
15. The method for preparing a hydrogenation catalyst for producing low-sulfur marine fuel according to claim 4, wherein the drying temperature in the step (4) is 100 to 150 ℃, and the roasting temperature is 500 to 950 ℃, preferably 550 to 900 ℃.
16. The method for preparing a hydrogenation catalyst for use in the production of low-sulfur marine fuel according to claim 4, wherein the drying temperature in the step (5) is 100 to 150 ℃.
17. The method for preparing a hydrogenation catalyst for low-sulfur marine fuel according to claim 4, wherein the calcination in the step (5) is performed in a mixed atmosphere of steam and oxygen-containing gas, and the volume ratio of the oxygen-containing gas to the steam is 5: 1-1: 1, wherein the oxygen-containing gas is any one of oxygen and air; the roasting temperature is 400-650 ℃, and preferably 400-550 ℃.
18. Use of the catalyst according to any of claims 1 to 3 or obtained by the method according to any of claims 4 to 23 for the hydrogenation of low-sulfur marine fuels from low-quality residues.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001144A (en) * | 1975-12-19 | 1977-01-04 | Kaiser Aluminum & Chemical Corporation | Process for modifying the pore volume distribution of alumina base catalyst supports |
| US4226743A (en) * | 1979-03-12 | 1980-10-07 | W. R. Grace & Co. | Silica-alumina hydrogel catalyst |
| US20040092390A1 (en) * | 2002-11-08 | 2004-05-13 | Timken Hye Kyung C. | Method for preparing a highly homogeneous amorphous silica-alumina composition |
| CN105056928A (en) * | 2015-09-10 | 2015-11-18 | 中国海洋石油总公司 | Preparation method for silicon-aluminium composite oxide with controllable pore structure |
| CN105709789A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Heavy oil hydrocracking catalyst, and preparation method and applications thereof |
| CN108940351A (en) * | 2017-05-26 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of catalysis material |
-
2022
- 2022-01-11 CN CN202210024856.7A patent/CN114749193B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001144A (en) * | 1975-12-19 | 1977-01-04 | Kaiser Aluminum & Chemical Corporation | Process for modifying the pore volume distribution of alumina base catalyst supports |
| US4226743A (en) * | 1979-03-12 | 1980-10-07 | W. R. Grace & Co. | Silica-alumina hydrogel catalyst |
| US20040092390A1 (en) * | 2002-11-08 | 2004-05-13 | Timken Hye Kyung C. | Method for preparing a highly homogeneous amorphous silica-alumina composition |
| CN105709789A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Heavy oil hydrocracking catalyst, and preparation method and applications thereof |
| CN105056928A (en) * | 2015-09-10 | 2015-11-18 | 中国海洋石油总公司 | Preparation method for silicon-aluminium composite oxide with controllable pore structure |
| CN108940351A (en) * | 2017-05-26 | 2018-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of catalysis material |
Non-Patent Citations (1)
| Title |
|---|
| 夏继平;李晓云;李世鹏;: "不同硅源改性拟薄水铝石的制备及表征", 无机盐工业, no. 05 * |
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Effective date of registration: 20231225 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |