CN114749193B - Hydrogenation catalyst for producing low-sulfur ship combustion and preparation method thereof - Google Patents
Hydrogenation catalyst for producing low-sulfur ship combustion and preparation method thereof Download PDFInfo
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- CN114749193B CN114749193B CN202210024856.7A CN202210024856A CN114749193B CN 114749193 B CN114749193 B CN 114749193B CN 202210024856 A CN202210024856 A CN 202210024856A CN 114749193 B CN114749193 B CN 114749193B
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- producing
- hydrogenation catalyst
- water
- acid
- low sulfur
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- 239000003054 catalyst Substances 0.000 title claims abstract description 150
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 110
- 239000011593 sulfur Substances 0.000 title claims abstract description 110
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 238000009841 combustion method Methods 0.000 title description 2
- 238000002485 combustion reaction Methods 0.000 claims abstract description 86
- 229910052751 metal Inorganic materials 0.000 claims abstract description 86
- 239000002184 metal Substances 0.000 claims abstract description 86
- 239000002002 slurry Substances 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 72
- 229910052782 aluminium Inorganic materials 0.000 claims description 70
- 238000004519 manufacturing process Methods 0.000 claims description 55
- 239000002253 acid Substances 0.000 claims description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 34
- 229910052710 silicon Inorganic materials 0.000 claims description 34
- 239000010703 silicon Substances 0.000 claims description 34
- 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
- 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 25
- 230000002378 acidificating effect Effects 0.000 claims description 25
- 229910052708 sodium Inorganic materials 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 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
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 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
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 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
- 239000007787 solid Substances 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 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
- 150000007522 mineralic acids Chemical class 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
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 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
- 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
- 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
- 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
- 239000000295 fuel oil Substances 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
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims 1
- 235000011162 ammonium carbonates Nutrition 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 8
- 230000023556 desulfurization Effects 0.000 abstract description 8
- -1 VIB metals Chemical class 0.000 abstract description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 56
- 239000002905 metal composite material Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 20
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- 239000008367 deionised water Substances 0.000 description 13
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- 230000000694 effects Effects 0.000 description 10
- 238000010438 heat treatment Methods 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000020477 pH reduction Effects 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
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- 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
- 230000001105 regulatory effect Effects 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
- 238000011156 evaluation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 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
- 239000012670 alkaline solution Substances 0.000 description 2
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- 239000000084 colloidal system Substances 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 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 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
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- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004411 aluminium Substances 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
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 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 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 238000012921 fluorescence analysis Methods 0.000 description 1
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- 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
- 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 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 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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- 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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- 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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- 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
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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 boat combustion 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 at least one of IVB metal, VIB metal and VIII metal; the second metal is at least one selected from the group consisting of group VIB metals and group VIII metals. Preparing a first solution, preparing 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 carrier 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 the low-sulfur ship combustion process for producing heavy inferior 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 in particular relates to a catalytic material for producing low-sulfur ship combustion and a preparation method thereof.
Background
With the continuous aggravation of global environmental problems, environmental regulations are continuously put out at home and abroad to limit the sulfur content of marine fuel oil (hereinafter referred to as ship combustion). The international maritime organization requires that the upper limit of the ship sulfur content be reduced to 0.5wt% on 1 month 1 year 2020. After the sulfur policy in IMO2020, it is expected that the low sulfur heavy ship will burn in about 45% of the total consumption in the short term and about 40% in the long term, i.e. the low sulfur heavy ship will have a gap of about 9500 ten thousand tons/year.
At present, high-sulfur heavy ship combustion is mainly produced by adopting a blending method, blending components mainly come from non-ideal byproducts such as high-sulfur residual oil which is difficult to process in a refinery, catalytic slurry oil, low-quality secondary processing distillate oil and the like, and the key points of blending are that the viscosity, stability and the content of metal aluminum and silicon (catalyst powder in the catalytic slurry oil) meet the quality requirements. However, it is difficult to directly produce a residual low sulfur ship fuel having less than 0.5wt% sulfur by fully utilizing the current blending components and the low sulfur residual oil must be added for blending. Residue type marine combustion with sulfur content lower than 0.5% in China mainly depends on import. And if a large amount of high-price low-sulfur straight-run residual oil is adopted for blending to produce heavy ship combustion, the production cost of the heavy ship combustion is greatly increased. The boiling bed residuum hydrogenation technology is characterized by that it can treat poor quality high-sulfur residuum raw material, can implement higher desulfurization rate, in particular, in recent years the boiling bed residuum hydrogenation technology can be developed quickly in China, and according to statistics, 3 sets of boiling bed residuum hydrogenation equipment which are built and established in China are combined with existent boiling bed residuum hydrogenation equipment, the aimed development of residuum hydrogenation catalyst with high desulfurization property is an effective means for economically producing low-sulfur ship combustion.
CN200910086744.9 discloses a grading combination of hydrogenation catalysts. The reactor is respectively filled with hydrodemetallization and hydrodesulphurization catalysts from top to bottom; the material flow is from top to bottom, the catalyst activity is gradually increased along the material flow direction, the pore diameter is gradually reduced, the granularity is gradually reduced, and the porosity is gradually reduced; the concentration gradient of the active metal component and the acid 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 demetallization, carbon residue removal, desulfurization activity and stability. The HDS catalyst may be Al 2 O 3 The HDS catalyst with different metal gradients is prepared by taking the catalyst as a carrier, spraying water vapor, soaking solutions with different active metal components and acid auxiliary agent concentrations in multiple steps, and drying and roasting.
CN201511001449.0 discloses a residual oil hydrodesulfurization catalyst and a preparation method thereof, wherein alumina is used as a carrier, and Mo or W and Co or Ni are used as active components; the pore volume of the catalyst is 0.4-1.8 ml/g, and the specific surface area is 100-280 m 2 And/g. The preparation method comprises the following steps: the residual oil hydrodesulfurization catalyst containing Mo or W and Co or Ni is obtained by taking alumina as a carrier and taking Mo or W and Ni or Co as active components, adopting a step-by-step impregnation method, contacting a salt solution of Mo or W with the alumina carrier, drying and roasting, then introducing Ni or Co, and drying and roasting.
CN03133545.4 discloses a heavy and residual oil hydrodesulfurization catalyst and a preparation method thereof. The catalyst is gamma-Al 2 O 3 Is a carrier and takes VIB group and VIII group metals as living bodiesAnd the sex component takes Ti and the like as active auxiliary agents. The catalyst is prepared by adding an alkaline solution containing Mo and/or W into aluminum hydroxide dry rubber powder which is introduced with Ti through ultrasonic wave, fully kneading until the aluminum hydroxide powder is fully wetted by the alkaline solution, adding an acidic solution containing Co and/or Ni, kneading until the materials become a plastic body, extruding strips, forming, drying and roasting. The catalyst auxiliary Ti prepared by the method has more uniform distribution, obviously improves the pore volume and specific surface area of the catalyst, and has excellent service performance. Titanium dioxide in the titanium-containing alumina dry gel is 1-20 w%, the pore volume is 0.7-1.1 mL/g, and the specific surface is 360-450 m 2 Dispersity I of titanium on alumina Ti /I Al Is 0.3 or more.
At present, the desulfurization catalyst in the prior art is mainly developed from two aspects, namely, the improvement of a catalytic material and the preparation of a catalytic material with large pore volume and strong acidity; on the other hand, the metal dispersion is optimized, and the utilization rate of 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 boat combustion and a preparation method thereof. The catalyst preparation is based on the preparation of a silicon-aluminum-metal composite material. The silicon-aluminum-metal composite material has the characteristics of mesoporous-macroporous multilevel pore canal structure, large pore volume, high B acid content, low impurity content and the like. Meanwhile, after the carrier is immersed 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 being applied to the heavy inferior residuum to produce the low-sulfur ship combustion process.
The first aspect of the invention provides a hydrogenation catalyst for producing low sulfur marine combustion, the 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 at least one selected from IVB metal, VIB metal and VIII metal, and preferably is VIB metal; the second metal is at least one selected from the group consisting of group VIB metals and group VIII metals.
Further, in the production of the low-sulfur marine hydrogenation catalyst, the specific surface area of the catalyst is 160-250 m 2 Preferably 160 to 230 m 2 The pore volume per gram 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.
Further, in the hydrogenation catalyst for producing low-sulfur boat combustion, the content of the VIB group metal calculated by oxide is 6-15%, preferably 8-15% based on the weight of the catalyst; the group VIII metal is 2-10%, preferably 2-6% by oxide, and the group IVB metal is 0.1-4.0%, preferably 0.5-4.0% by oxide.
The second aspect of the invention provides a preparation method of a hydrogenation catalyst for producing low-sulfur marine combustion, 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, the forming agent and the adhesive obtained in the step (3), and then forming, drying and roasting to obtain a carrier;
(5) And mixing the carrier with the 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-mentioned method for producing a low-sulfur marine 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, silica sol, preferably water glass).
Further, in the above-described method for producing a hydrogenation catalyst for use in low-sulfur marine combustion, 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 30wt% (preferably 15 to 30 wt%) based on the total weight of the aqueous solution, with a modulus of typically 2.5 to 3.2.
Further, in the above-mentioned method for producing a low sulfur marine hydrogenation catalyst, 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).
Further, in the above-described production method of a hydrogenation catalyst for use in low-sulfur marine combustion, 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-mentioned preparation method of the hydrogenation catalyst for producing low sulfur marine combustion, the weight ratio of the silicon source (calculated as SiO 2) to the acidic aluminum source (calculated as Al2O 3) is 1:1-9:1 (preferably 1:1-7:1).
Further, in the above-mentioned preparation method of the hydrogenation catalyst for low sulfur boat combustion, in order to achieve more excellent technical effects of the present invention, in particular, 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 added to obtain the mixed solution a).
Further, in the above-described method for producing a low-sulfur marine hydrogenation catalyst, the acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid, hydrochloric acid, preferably sulfuric acid).
Further, in the above-described method for producing a hydrogenation catalyst for use in low-sulfur marine combustion, the acid is used in the form of an aqueous solution. The concentration of the acid is 2-6wt% (preferably 2-5 wt%wt) based on the total weight of the aqueous solution.
Further, in the above-mentioned method for producing a low-sulfur marine hydrogenation catalyst, the acid is added in such an amount that the pH value of the mixed liquor A is 2 to 4 (preferably 3 to 4).
Further, in the above-mentioned method for preparing a hydrogenation catalyst for producing low sulfur marine combustion, in step (1), in general, the aluminum content of the mixed solution A is 5-20g Al2O3/L in terms of Al2O3, and the silicon content is 5-40g SiO2/L in terms of SiO 2.
Further, in the above-mentioned method for producing a low sulfur marine combustion hydrogenation catalyst, 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, particularly an alkali metal metaaluminate, more preferably one or more selected from sodium metaaluminate and potassium metaaluminate, and preferably sodium metaaluminate).
Further, in the above-mentioned method for producing a low-sulfur marine hydrogenation catalyst, the alkaline aluminum source is used in the form of an aqueous solution. The alkaline aluminium source (calculated as Al2O 3) has a concentration of 130-350g/L (preferably 150-250 g/L) and a caustic ratio of generally 1.15-1.35, preferably 1.15-1.30, based on the total weight of the aqueous solution.
Further, in the above-mentioned production method of the hydrogenation catalyst for low sulfur marine combustion, 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 alkaline aluminum source and water.
Further, in the above-mentioned production method of the hydrogenation catalyst for low sulfur marine combustion, the amount of the alkaline aluminum source is 20 to 40vol% (preferably 25 to 40 vol%) based on the total volume of the mixed liquid A, the alkaline aluminum source and water.
Further, in the above-mentioned production method of a hydrogenation catalyst for low sulfur marine combustion, the amount of water to be used is 10 to 20vol% (preferably 13 to 20 vol%) based on the total volume of the mixed liquid A, the alkaline aluminum source and water.
Further, in the above preparation method of the hydrogenation catalyst for low sulfur boat combustion, the mixed solution a and the alkaline aluminum source are added to water sequentially or simultaneously (preferably, the mixed solution a and the alkaline aluminum source are added to water in a parallel flow mode).
Further, in the above preparation method of the hydrogenation catalyst for producing low sulfur boat combustion, the flow rate of the mixed solution A is 15-50mL/min (preferably 20-40 mL/min).
Further, in the above-mentioned production method of a hydrogenation catalyst for low sulfur marine combustion, 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, more preferably 8.5 to 10.5).
Further, in the above-mentioned preparation method of the hydrogenation catalyst for low sulfur boat combustion, in order to achieve more excellent technical effects of the present invention, in particular, in order to obtain a carrier precursor with a larger pore volume, in 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 added to obtain the slurry B).
Further, in the above-mentioned method for producing a low sulfur marine combustion hydrogenation catalyst, the water-soluble carbonate is selected from one or more carbonates of alkali metal and ammonium (preferably, from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, preferably, sodium carbonate).
Further, in the above-described method for producing a low-sulfur marine hydrogenation catalyst, the water-soluble carbonate is used in the form of a solid.
Further, in the above-mentioned method for producing a low-sulfur marine hydrogenation catalyst, the water-soluble carbonate is added in such an amount that the pH of the slurry B is 10.5 to 12 (preferably 11 to 12).
Further, in the above-mentioned production method of a hydrogenation catalyst for boat combustion with low sulfur, in the step (3), the carrier precursor is separated from the reaction system of the hydrothermal treatment, washed to be neutral, and then dried. The washing may be carried out by a washing method conventional in the art, preferably deionized water, and more preferably at 50 to 90 ℃. In addition, the separation can adopt any means in the field for realizing the separation of liquid-solid two-phase materials, such as filtration, centrifugal separation and the like, and particularly, the separation can be carried out in a filtration separation mode, so that a solid-phase material and a liquid-phase material are obtained after the separation, and the solid-phase material is washed and dried to obtain the carrier precursor.
Further, in the above method for preparing a hydrogenation catalyst for producing low sulfur marine combustion, the drying conditions include: the drying temperature is 100-150deg.C, and the drying time is 6-10 hr.
Further, in the above-mentioned method for producing a low sulfur marine hydrogenation catalyst, in the step (1), the temperature is 25 to 50 ℃ (preferably 25 to 40 ℃) and the pressure is normal pressure.
Further, in the above-mentioned method for producing a low sulfur marine hydrogenation catalyst, in the step (2), the temperature is 50 to 90 ℃ (preferably 50 to 80 ℃), and the pressure is normal pressure.
Further, in the above-mentioned method for producing a low sulfur marine combustion hydrogenation catalyst, in the step (3), the temperature is 180 to 300 ℃ (preferably 180 to 280 ℃, more preferably 180 to 250 ℃), and the pressure is 0.1 to 0.5MPa (preferably 0.1 to 0.3 MPa).
Further, in the above-mentioned preparation method of the hydrogenation catalyst for producing low sulfur marine combustion, in order to achieve more excellent technical effects of the present invention, in the step (3), the hydrothermal treatment time is 0.5-20h (preferably 2-16 h).
Furthermore, in the preparation method of the hydrogenation catalyst for producing the low-sulfur boat combustion, one or more auxiliary agents such as P2O5, B2O3 or TiO2 can be added according to actual needs. For this purpose, these precursors may be added in the form of water-soluble inorganic salts during the reaction of step (1). Examples of the inorganic salt include borates, sulfates, nitrates, and the like. In addition, the addition amount of the auxiliary agents can be arbitrarily adjusted according to the requirements of the subsequent catalysts and the like. In general, these auxiliaries are generally present in amounts of from 1 to 8% by weight, preferably from 2 to 6% by weight, based on the oxides, relative to 100% by weight of the total weight of the support precursor.
Further, in the above method for preparing a hydrogenation catalyst for producing low sulfur marine combustion, the first metal in the step (1) is at least one selected from the group consisting of a group IVB metal, a group VIB metal and a group VIII metal, and further the first metal salt is a soluble metal salt, such as any one of sulfate and nitrate. The first metal can be one or more of Ni, co, fe, zr, and further, the first metal salt can be one or more of nickel nitrate, cobalt nitrate, nickel sulfate, cobalt sulfate, ferric nitrate, ferric sulfate, zirconium nitrate and zirconium sulfate.
Further, in the above method for preparing a hydrogenation catalyst for low sulfur marine combustion, in the step (4), the molding agent is one or more of cellulose and starch, preferably cellulose, more preferably methylcellulose.
Further, in the above method for preparing a hydrogenation catalyst for producing low sulfur marine combustion, in the step (4), the binder is an organic acid, and specifically may be one or more of acetic acid, citric acid, etc., and preferably is citric acid.
In the preparation method of the hydrogenation catalyst for producing the low-sulfur marine combustion, 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.
Furthermore, in the above method for preparing the hydrogenation catalyst for low sulfur boat combustion, the molding in the step (4) may be a molding method commonly used in the existing catalyst preparation, and the specific molding shape may be selected according to actual needs, for example, may be spherical, bar-shaped, clover-shaped, and the like.
In the preparation method of the hydrogenation catalyst for producing the low-sulfur marine combustion, 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 producing low sulfur marine combustion, the calcination in step (5) is performed under a mixed atmosphere of water vapor and an 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 ℃, preferably 400-550 ℃; roasting for 3-8 hours.
The third aspect of the invention provides an application of the catalyst or the catalyst obtained by adopting the preparation method in low-sulfur ship combustion production by hydrogenation of inferior residual oil.
Further, in the above application, the reaction conditions are: 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 -1 The volume ratio of the hydrogen oil is 400-800.
Compared with the prior art, the hydrogenation catalyst for producing low-sulfur boat combustion and the preparation method thereof have the following advantages:
1. in the preparation method of the hydrogenation catalyst for producing low-sulfur boat combustion, a first metal component is firstly introduced in the preparation of the carrier, 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 immersed, the second metal is dispersed more uniformly due to the 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-stage pore channel structure can be formed, the acid center is exposed, and meanwhile, 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 combustion, in the carrier preparation, firstly, a method of firstly acidic aluminum source and then metal hydrochloride is adopted for a silicon source, so that cations (sodium ions and the like) in silicic acid polymers enveloped in rings or cages in the silicon source are dissociated, acidified silica gel groups are adsorbed on aluminum hydroxide colloid, so that the sodium ions are effectively separated from the silica gel groups, and meanwhile, 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 subsequent difficulty of washing and removing sodium is greatly reduced, and the washing water consumption is 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 macropore capacity and mesoporous-macropore multistage pore channels, and meanwhile, the composite addition of silicon and metal improves the characteristics of high B acid content, low sodium content and the like. The catalyst prepared by the method has good hydrogenation performance, particularly good desulfurization performance, and is suitable for the natural hydrogenation process for producing low-sulfur residues with heavy inferior quality.
3. In the preparation method of the hydrogenation catalyst for producing the low-sulfur boat combustion, the acidified silica gel group is adsorbed on the aluminum hydroxide colloid, so that crystal nucleus is provided for subsequent reaction, the grain size of the prepared carrier precursor is promoted to be increased, and the carrier precursor with large pore volume and large pore diameter is formed.
4. According to the preparation method of the hydrogenation catalyst for producing the low-sulfur ship combustion, the pH value of the slurry is regulated, the slurry system is changed from the initial fluidity state to the gel-like thixotropic state in the high-temperature treatment process, the slurry system is changed into the fluidity state after a period of treatment, and the silicon-aluminum material and water form a changeable silicon-aluminum-oxygen network structure in the gel-like thixotropic state, so that the preparation of the carrier precursor with large pore volume is facilitated.
Detailed Description
The following detailed description of the invention is provided in connection with specific examples, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the claims.
In the context of the present specification, the pore volume and specific surface area of the silica-alumina material are analyzed using a low temperature nitrogen adsorption method.
In the context of the present specification, the pore volume, specific surface area and pore size distribution are measured using a low temperature nitrogen adsorption method. Total acid, B acid and L acid were measured by pyridine IR adsorption. Sodium oxide and silica were measured using fluorescence analysis. The active metal content is measured spectrophotometrically. The wear index was measured using an air jet method.
All percentages, parts, ratios, etc. referred to in this specification are by weight and pressure is gauge unless explicitly indicated.
Any two or more embodiments of the invention may be combined in any desired manner within the context of this specification, and the resulting solution is part of the original disclosure of this specification, while still falling within the scope of the invention.
Example 1
(1) Preparation of silicon-aluminum-metal composite material
The concentration of the mixture is 40gAl 2 O 3 Aluminum sulfate solution/L and 60g SiO concentration 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use, and preparing a first metal salt solution with the concentration of 50gNiO/L for later use. Preparation of caustic ratio 1.20, concentration 150 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
1.5L of 60g SiO concentration was measured 2 adding/L silica sol solution into a container, slowly adding 1L of 40g Al under stirring 2 O 3 Aluminum sulfate solution/L, which has been colloidal in aluminum hydroxide, but the solution is still in liquid form. Then, a first metal salt solution with a concentration of 50g NiO/L was added to adjust the pH to 3 and the amount of the solution was 0.1L, thereby completing the acidification treatment and obtaining a mixed solution A.
1000mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, after the deionized water is heated to 60 ℃, the mixed solution A is added into the reactor at 20mL/min, meanwhile, the prepared sodium metaaluminate solution is added in parallel flow, the pH value of the reaction is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction was completed, the amount of sodium metaaluminate was 500mL, and 48g of ammonium carbonate was added to the reactor with stirring to adjust the pH to 10.5. The slurry is put into a reactor, and the treatment temperature is 220 ℃ and the treatment pressure is 0.3MPa under the condition of stirring, and the treatment is carried out for 2 hours. Washing the treated slurry with hot water at 90 ℃ until the slurry is neutral, drying at 120 ℃ for 6 hours to obtain a sample PO-1 of the dried silicon-aluminum-metal composite material, and roasting at 600 ℃ for 5 hours to obtain the silicon-aluminum-metal composite material P-1, wherein the properties are shown in Table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of 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, forming a ball, and roasting the ball-formed sample at 650 ℃ for 3 hours to obtain a carrier Z1 with the granularity 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, heating and stirring are carried out until the solution is completely dissolved, and distilled water is used for fixing the volume of the solution to 1000mL, so that solution L1 is obtained. The carrier Z1 is saturated and impregnated with a solution L1 solution, dried for 2 hours at 110 ℃, and the volume ratio of air to water vapor is 3:1, roasting for 5 hours at 480 ℃ to obtain a catalyst C1, wherein the specific properties are shown in Table 2.
Example 2
Other conditions were the same as in example 1, except that: changing silica sol into water glass solution, changing the dosage of first metal salt into 0.05L, adjusting the acidification pH to 4.0, controlling the flow rate of the mixed solution A to 30mL/min, heating deionized water in a reactor to 70 ℃ to obtain a silica-alumina-metal composite material dried sample PO-2, and roasting at 600 ℃ for 5 hours to obtain the silica-alumina-metal composite material P-2, wherein the properties are shown in Table 1.
Taking 500g of 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, forming into a ball, and roasting the ball-formed sample at 600 ℃ for 4 hours to obtain a carrier Z2 with the granularity of 0.3-0.8 mm.
The carrier Z2 is saturated and impregnated with a solution L1, dried for 2 hours at 110 ℃, and the volume ratio of air to water vapor is 4:1, roasting for 4 hours at a roasting temperature of 580 ℃ to obtain a catalyst C2, wherein the specific properties are shown in Table 2.
Example 3
Other conditions were the same as in example 1, except that: changing silica sol into 40gSiO 2 and/L, regulating the acidification pH to 3.5, regulating the flow rate of the mixed solution A to 15mL/min, adding 61g of ammonium carbonate into the reactor under stirring to regulate the pH value to 11.0, regulating the treatment temperature to 250 ℃, regulating the treatment pressure to 0.4MPa, obtaining a silicon-aluminum-metal composite material dried sample PO-3, and roasting at 600 ℃ for 5 hours to obtain the silicon-aluminum-metal composite material P-3, wherein the properties are shown in Table 1.
Taking 500g of 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, forming a ball, and roasting the ball-formed sample at 700 ℃ for 4 hours to obtain a carrier Z3 with the granularity of 0.3-0.8 mm.
The carrier Z3 is saturated and impregnated with a solution L1, dried for 2 hours at 110 ℃, and the volume ratio of air to water vapor is 1:1, roasting for 3 hours at a 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 concentration of the preparation is 30gAl 2 O 3 Aluminum sulfate solution/L and 60g SiO concentration 2 Silica sol solution with the modulus of 2.8 and the concentration of 30gZrO is prepared for standby 2 and/L the first metal salt solution for standby. Preparation of caustic ratio 1.25, concentration 130 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
1.5L of 60g SiO concentration was measured 2 adding/L silica sol solution into a container, slowly adding 1L of 30gAl under stirring 2 O 3 Aluminum sulfate solution/L, which has been colloidal in aluminum hydroxide, but the solution is still in liquid form. Then adding 30g ZrO 2 and/L the first metal salt solution is adjusted to pH 3.5, the dosage is 0.05L, and the acidification treatment is completed, so as to obtain a mixed solution A.
800mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, after the deionized water is heated to 70 ℃, the mixed solution A is added into the reactor at the speed of 25mL/min, meanwhile, the prepared sodium metaaluminate solution is added in parallel flow, the pH value of the reaction is controlled to be 8.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction was completed, the amount of sodium metaaluminate was 560mL, and 76g of ammonium carbonate was added to the reactor with stirring to adjust the pH to 10.5. The slurry is put into a reactor, and the treatment temperature is 240 ℃ and the treatment pressure is 0.3MPa under the condition of stirring, and the treatment is carried out for 4 hours. Washing the treated slurry with hot water at 90 ℃ until the slurry is neutral, drying at 120 ℃ for 6 hours to obtain a sample PO-4 of the dried silicon-aluminum-metal composite material, and roasting at 600 ℃ for 5 hours to obtain the silicon-aluminum-metal composite material P-4, wherein the properties are shown in Table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of 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, forming a ball, and roasting the ball-formed sample at 550 ℃ for 3 hours to obtain a carrier Z4 with the granularity 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, heating and stirring are carried out until the solution is completely dissolved, and distilled water is used for fixing the volume of the solution to 1000mL, so that solution L2 is obtained. The carrier Z4 is saturated and impregnated with a solution L2 solution, dried at 110 ℃ for 2 hours, and the volume ratio of air to water vapor is 4:1, roasting for 4 hours at the roasting temperature of 450 ℃ to obtain a catalyst C4, wherein the specific properties are shown in Table 2.
Example 5
Other conditions were the same as in example 4, except that: changing silica sol into water glass, adjusting acidification pH to 3.0, adjusting the adding amount of bottom water of a reactor to 1000mL, heating deionized water to 70 ℃, adjusting the treatment temperature to 260 ℃, adjusting the treatment pressure to 0.5MPa, obtaining a silica-alumina material dried sample PO-5, and roasting at 600 ℃ for 5 hours to obtain a silica-alumina material P-5, wherein the properties are shown in Table 1.
Taking 500g of 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, forming a ball, and roasting the ball-formed sample at 700 ℃ for 4 hours to obtain a carrier Z5 with the granularity of 0.3-0.8 mm.
The carrier Z5 is saturated and impregnated with a solution L2 solution, dried at 110 ℃ for 2 hours, and the volume ratio of air to water vapor is 2:1, roasting for 5 hours at 420 ℃ to obtain a catalyst C5, wherein the specific properties are shown in Table 3.
Comparative example 1
(1) Preparation of silicon-aluminum-metal composite material
The concentration of the mixture is 40gAl 2 O 3 Aluminum sulfate solution/L and 60g SiO concentration 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use. Preparation of caustic ratio 1.20, concentration 150 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
1000mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, aluminum sulfate is added into the reactor at 20mL/min and 30mL/min of silica sol after the deionized water is heated to 60 ℃, meanwhile, the prepared sodium metaaluminate solution is added in parallel, the pH value of the reaction is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction was completed, the amount of sodium metaaluminate was 500mL, and 48g of ammonium carbonate was added to the reactor with stirring to adjust the pH to 10.5. The slurry is put into a reactor, and the treatment temperature is 220 ℃ and the treatment pressure is 0.3MPa under the condition of stirring, and the treatment is carried out for 2 hours. Washing the treated slurry with hot water at 90 ℃ until the slurry is neutral, drying at 120 ℃ for 6 hours to obtain a sample PFO-1 of the dried silicon-aluminum-metal composite material, and roasting at 600 ℃ for 5 hours to obtain the silicon-aluminum-metal composite material PF-1, wherein the properties of the sample PFO-1 are shown in the table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of 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, forming a ball, and roasting the ball-formed sample at 650 ℃ for 3 hours to obtain a carrier ZF1 with the granularity of 0.3-0.8 mm.
The carrier ZF1 is saturated and impregnated with a solution L1 solution, dried at 110 ℃ for 2 hours, and the volume ratio of air to water vapor is 3:1, roasting for 5 hours at 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 concentration of the mixture is 40gAl 2 O 3 Aluminum sulfate solution/L and 60g SiO concentration 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use, and preparing a first metal salt solution with the concentration of 50gNiO/L for later use. Preparation of caustic ratio 1.20, concentration 150 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
1L of 40gAl was metered in 2 O 3 adding/L aluminum sulfate solution into a container, slowly adding 1.5L of 60g SiO under stirring 2 Silica sol solution of/L, the process generates a large amount of aluminium hydroxide gel, flowThe mobility is poor. Then, a first metal salt solution with a concentration of 50g NiO/L was added to adjust the pH to 3 and the amount of the solution was 0.1L, thereby completing the acidification treatment and obtaining a mixed solution A.
1000mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, after the deionized water is heated to 60 ℃, the mixed solution A is added into the reactor at 20mL/min, meanwhile, the prepared sodium metaaluminate solution is added in parallel flow, the pH value of the reaction is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction was completed, the amount of sodium metaaluminate was 500mL, and 48g of ammonium carbonate was added to the reactor with stirring to adjust the pH to 10.5. The slurry is put into a reactor, and the treatment temperature is 220 ℃ and the treatment pressure is 0.3MPa under the condition of stirring, and the treatment is carried out for 2 hours. Washing the treated slurry with hot water at 90 ℃ until the slurry is neutral, drying at 120 ℃ for 6 hours to obtain a sample PFO-2 of the silicon-aluminum-metal composite material after drying, and roasting at 600 ℃ for 5 hours to obtain the silicon-aluminum-metal composite material PF-2, wherein the properties of the sample PFO-2 are shown in Table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of 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, forming a ball, and roasting the ball-formed sample at 650 ℃ for 3 hours to obtain a carrier ZF2 with the granularity of 0.3-0.8 mm.
The carrier ZF2 is saturated and impregnated with a solution L1, dried for 2 hours at 110 ℃, and the volume ratio of air to water vapor is 3:1, roasting for 5 hours at 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 concentration of the mixture is 40gAl 2 O 3 Aluminum sulfate solution/L and 60g SiO concentration 2 And (3) preparing a silica sol solution with the modulus of 2.8 for later use, and preparing a first metal salt solution with the concentration of 50gNiO/L for later use. Preparation of caustic ratio 1.20, concentration 150 gAl 2 O 3 And (3) preparing a sodium metaaluminate solution for later use.
1.5L of 60g SiO concentration was measured 2 adding/L of silica sol solution toSlowly adding 1L of 40g Al under stirring into a container 2 O 3 Aluminum sulfate solution/L, which has been colloidal in aluminum hydroxide, but the solution is still in liquid form. Then, a first metal salt solution with a concentration of 50g NiO/L was added to adjust the pH to 3 and the amount of the solution was 0.1L, thereby completing the acidification treatment and obtaining a mixed solution A.
1000mL of deionized water is added into a 5000mL reactor as bottom water, stirring and heating are started, after the deionized water is heated to 60 ℃, the mixed solution A is added into the reactor at 20mL/min, meanwhile, the prepared sodium metaaluminate solution is added in parallel flow, the pH value of the reaction is controlled to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and the temperature and the pH value of slurry in the reactor are kept constant. After the reaction is finished, the dosage of sodium metaaluminate is 500mL. Washing the reacted slurry with hot water at 90 ℃ until the slurry is neutral, drying the slurry at 120 ℃ for 6 hours to obtain a sample PFO-3 of the silicon-aluminum-metal composite material after drying, and roasting the sample PFO-3 at 600 ℃ for 5 hours to obtain the silicon-aluminum-metal composite material PF-3, wherein the properties of the sample PF-3 are shown in a table 1.
(2) Hydrogenation catalyst preparation
Taking 500g of 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, forming a ball, and roasting the ball-formed sample at 650 ℃ for 3 hours to obtain a carrier ZF3 with the granularity of 0.3-0.8 mm.
The carrier ZF3 is saturated and impregnated with a solution L1, dried at 110 ℃ for 2 hours, and the volume ratio of air to water vapor is 3:1, roasting for 5 hours at 480 ℃ to obtain the catalyst CF3, wherein the specific properties are shown in Table 2.
Table 1 properties of the composite material
TABLE 2 Properties of the catalysts
The activity of the catalyst was evaluated on a continuous tank reactor (CSTR) apparatus using high sulfur vacuum residuum, and the properties and evaluation conditions are shown in table 3. The production oil was sampled and analyzed for 1000 hours of operation, and the results of other evaluations after comparing the activity with that of comparative example 3 are shown in Table 4, with the activity of comparative example 3 being 100.
TABLE 3 Properties of high Sulfur vacuum residuum and evaluation conditions
Table 4 results of catalyst evaluation
From the data in each table, it can be seen that: 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 the comparative example, the catalyst for the low-sulfur ship combustion hydrogenation prepared by the silicon-aluminum-metal composite material has the advantages that the impurity removal rate is increased, particularly the desulfurization activity is obviously improved, meanwhile, asphaltene is effectively converted, and a high-quality raw material is provided for generating low-sulfur ship combustion from unconverted oil.
Claims (37)
1. A hydrogenation catalyst for producing low sulfur marine combustion, 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 at least one of IVB metal, VIB metal and VIII metal, and the second metal is at least one of VIB metal and VIII metal; the specific surface area of the catalyst is 160-250 m 2 The pore volume per gram is 0.4-0.7 mL/g, the total acid value of the catalyst is 0.3-0.6 mol/g, and the ratio of B acid to L acid is 0.3-1.0;
the preparation method of the hydrogenation catalyst for producing the low-sulfur ship combustion 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, the forming agent and the adhesive obtained in the step (3), and then forming, drying and roasting to obtain a carrier;
(5) And mixing the carrier with the second metal salt solution, and further drying and roasting to obtain the catalyst.
2. The hydrogenation catalyst for producing low sulfur marine combustion according to claim 1, wherein the specific surface area of the catalyst is 160 to 230 m 2 The pore volume per gram is 0.45-0.65 mL/g, the total acid value of the catalyst is 0.35-0.6 mol/g, and the ratio of B acid to L acid is 0.3-0.8.
3. The hydrogenation catalyst for producing low sulfur boat combustion according to claim 1, wherein the content of the group VIB metal is 6 to 15% by oxide and/or the content of the group VIII metal is 2 to 10% by oxide and/or the content of the group IVB metal is 0.1 to 4.0% by oxide based on the weight of the catalyst.
4. A hydrogenation catalyst for producing low sulfur marine combustion according to claim 1 or 3, wherein the group VIB metal is 8 to 15% by oxide and/or the group VIII metal is 2 to 6% by oxide and/or the group IVB metal is 0.5 to 4.0% by oxide based on the weight of the catalyst.
5. The method for preparing the hydrogenation catalyst for producing low sulfur marine combustion according to claim 1, 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, the forming agent and the binder obtained in the step (3), and then forming, drying and roasting to obtain a carrier;
(5) And mixing the carrier with the second metal salt solution, and further drying and roasting to obtain the catalyst.
6. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the silicon source in step (1) is a water-soluble or water-dispersible basic silicon-containing compound, and/or the silicon source is used in the form of an aqueous solution, and the silicon source is used as SiO based on the total weight of the aqueous solution 2 At a concentration of 5 to 30wt%, and/or the acidic aluminum source is a water-soluble acidic aluminum-containing compound, and/or the acidic aluminum source is used in the form of an aqueous solution, and the acidic aluminum source is used as Al based on the total weight of the aqueous solution 2 O 3 At a concentration of 30-100g/L, and/or the silicon source is in the form of SiO 2 Counting the acid aluminum source and the acid aluminum source by Al 2 O 3 The weight ratio of the two components is 1:1-9:1.
7. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 6, wherein the silicon source in step (1) is a water-soluble or water-dispersible basic inorganic silicon-containing compound, and/or the silicon source is used in the form of an aqueous solution and the silicon source is represented by SiO based on the total weight of the aqueous solution 2 At a concentration of 15 to 30wt%, and/or the acidic aluminum source is a water-soluble acidic inorganic aluminum-containing compound, and/or the acidic aluminum source is used in the form of an aqueous solution, and the acidic aluminum source is used as Al based on the total weight of the aqueous solution 2 O 3 At a concentration of 30-80g/L, and/or the silicon source is SiO 2 Counting the acid aluminum source and the acid aluminum source by Al 2 O 3 The weight ratio of the two components is 1:1-7:1.
8. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 6, wherein in the step (1), the silicon source is one or more of a water-soluble silicate and a silica sol, and/or the acidic aluminum source is a water-soluble inorganic strong acid aluminum salt selected from one or more of aluminum sulfate, aluminum nitrate and aluminum chloride.
9. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 6, wherein the silicon source in step (1) is water glass and/or the acidic aluminum source is aluminum sulfate.
10. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein an acid is further added in step (1), and/or the acid is a water-soluble acid, and/or the acid is used in the form of an aqueous solution, and the concentration of the acid is 2 to 6% by weight based on the total weight of the aqueous solution, and/or the acid is added in such an amount that the pH of the mixed liquor a is 2 to 4.
11. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 10, wherein in step (1), the acidic aluminum source is added to the silicon source and then an acid is added to obtain the mixed liquor a, and/or the acid is a water-soluble inorganic acid selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, and/or the acid is used in the form of an aqueous solution and the concentration of the acid is 2 to 5wt% based on the total weight of the aqueous solution, and/or the acid is added in such an amount that the pH of the mixed liquor a is 3 to 4.
12. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 11, wherein the inorganic acid is sulfuric acid.
13. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein said basic aluminum source in step (2) is water-soluble basic aluminum-containingThe compound, and/or the alkaline aluminum source is used in the form of an aqueous solution, and the alkaline aluminum source is used as Al based on the total weight of the aqueous solution 2 O 3 130-350g/L, a caustic ratio of 1.15-1.35, and/or a quantity of the mixed liquor a of 40-70 vol.%, based on the total volume of the mixed liquor a, the alkaline aluminum source and water, and/or a quantity of the alkaline aluminum source of 20-40 vol.%, based on the total volume of the mixed liquor a, the alkaline aluminum source and water, and/or a quantity of the water of 10-20 vol.%, based on the total volume of the mixed liquor a, the alkaline aluminum source and water, and/or a quantity of the mixed liquor a and the alkaline aluminum source are added to water sequentially or simultaneously, and/or a flow rate of the mixed liquor a is 15-50mL/min, and/or a flow rate of the alkaline aluminum source is controlled such that a pH value of the slurry B is maintained at 7.5-10.5.
14. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 13, wherein said basic aluminum source in step (2) is a water-soluble basic inorganic aluminum-containing compound, and/or said basic aluminum source is used in the form of an aqueous solution, and said basic aluminum source is used in the form of Al based on the total weight of said aqueous solution 2 O 3 The concentration is 150-250g/L, the caustic ratio is 1.15-1.30, and/or the amount of the mixed liquor A is 40-65vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the amount of the alkaline aluminum source is 25-40vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the amount of the water is 13-20vol% based on the total volume of the mixed liquor A, the alkaline aluminum source and the water, and/or the mixed liquor A and the alkaline aluminum source are added to the water in a parallel flow mode, and/or the adding flow rate of the mixed liquor A is 20-40mL/min, and/or the adding flow rate of the alkaline aluminum source is controlled, so that the pH value of the slurry B is maintained at 8.0-10.5.
15. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 13, wherein the alkaline aluminum source in step (2) is an alkali metal meta-aluminate selected from one or more of sodium meta-aluminate and potassium meta-aluminate, and/or the flow rate of addition of the alkaline aluminum source is controlled so that the pH of the slurry B is maintained at 8.5 to 10.5.
16. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein a water-soluble carbonate is further added in step (2), and/or the water-soluble carbonate is selected from one or more of alkali metal and ammonium carbonates, and/or the water-soluble carbonate is used in a solid form, and/or the water-soluble carbonate is added in such an amount that the pH of the slurry B is 10.5 to 12.
17. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 16, wherein in step (2), said mixed liquor a and said alkaline aluminum source are added to water, followed by adding a water-soluble carbonate to obtain said slurry B, and/or said water-soluble carbonate is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, and/or said water-soluble carbonate is used in a solid form, and/or said water-soluble carbonate is added in such an amount that the pH of said slurry B is 11 to 12.
18. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 17, wherein the water-soluble carbonate is sodium carbonate.
19. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the carrier precursor is separated from the reaction system of the hydrothermal treatment in step (3), washed to be neutral, and then dried, and/or the drying conditions include: the drying temperature is 100-150deg.C, and the drying time is 6-10 hr.
20. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the temperature is 25 to 50 ℃ and the pressure is normal pressure in step (1), and/or the temperature is 50 to 90 ℃ and the pressure is normal pressure in step (2), and/or the temperature is 180 to 300 ℃ and the pressure is 0.1 to 0.5MPa in step (3), and/or the time of the hydrothermal treatment is 0.5 to 20 hours in step (3).
21. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 20, wherein the temperature is 25 to 40 ℃ and the pressure is normal pressure in step (1), and/or the temperature is 50 to 80 ℃ and the pressure is normal pressure in step (2), and/or the temperature is 180 to 280 ℃ and the pressure is 0.1 to 0.3MPa in step (3), and/or the time of the hydrothermal treatment is 2 to 16 hours in step (3).
22. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 21, wherein the temperature in step (3) is 180 to 250 ℃.
23. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein an auxiliary agent is added, the auxiliary agent being selected from one or more of phosphorus, boron and titanium, and/or the auxiliary agent is contained in an amount of 1 to 8% by weight in terms of oxide relative to 100% by weight of the total weight of the carrier precursor.
24. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 23, wherein the additive is contained in an amount of 2 to 6wt% in terms of oxide, based on 100wt% of the total weight of the carrier precursor.
25. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the first metal salt is a soluble metal salt, and the soluble metal salt is any one of sulfate and nitrate; the first metal is one or more of Ni, co, fe, zr.
26. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 25, wherein the first metal salt is one or more of nickel nitrate, cobalt nitrate, nickel sulfate, cobalt sulfate, iron nitrate, iron sulfate, zirconium nitrate, zirconium sulfate.
27. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the molding agent in the step (4) is one or more of cellulose and starch.
28. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 27, wherein said molding agent in step (4) is a cellulose.
29. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 28, wherein said shaping agent in step (4) is methyl cellulose.
30. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the binder in step (4) is an organic acid, and the organic acid is one or more of acetic acid and citric acid.
31. The method for producing a low sulfur marine combustion hydrogenation catalyst of claim 30 wherein the organic acid is citric acid.
32. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the drying temperature in the step (4) is 100 to 150 ℃ and the calcination temperature is 500 to 950 ℃.
33. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5 or 32, wherein the calcination temperature in step (4) is 550 to 900 ℃.
34. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the drying temperature in step (5) is 100 to 150 ℃.
35. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 5, wherein the calcination in step (5) is performed under a mixed atmosphere of water vapor and an oxygen-containing gas in a volume ratio of 5: 1-1:1, wherein the oxygen-containing gas is any one of oxygen and air; the roasting temperature is 400-650 ℃.
36. The method for producing a low sulfur marine combustion hydrogenation catalyst according to claim 35, wherein the calcination temperature in step (5) is 400 to 550 ℃.
37. Use of the hydrogenation catalyst for producing low-sulfur marine fuels according to any one of claims 1 to 4 or obtained by the preparation method according to any one of claims 5 to 36 in the hydrogenation of inferior residuum to produce low-sulfur marine fuels.
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| US6872685B2 (en) * | 2002-11-08 | 2005-03-29 | Chevron U.S.A. Inc. | Method for preparing a highly homogeneous amorphous silica-alumina composition |
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| US4226743A (en) * | 1979-03-12 | 1980-10-07 | W. R. Grace & Co. | Silica-alumina hydrogel catalyst |
| 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 |
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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. |