WO2022145740A1 - 내황성이 향상된 수소화 반응용 촉매 및 이의 제조방법 - Google Patents
내황성이 향상된 수소화 반응용 촉매 및 이의 제조방법 Download PDFInfo
- Publication number
- WO2022145740A1 WO2022145740A1 PCT/KR2021/017696 KR2021017696W WO2022145740A1 WO 2022145740 A1 WO2022145740 A1 WO 2022145740A1 KR 2021017696 W KR2021017696 W KR 2021017696W WO 2022145740 A1 WO2022145740 A1 WO 2022145740A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- petroleum resin
- solution
- hydrogenation reaction
- hydrogenation
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 81
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011593 sulfur Substances 0.000 title claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000003208 petroleum Substances 0.000 claims abstract description 89
- 239000011347 resin Substances 0.000 claims abstract description 86
- 229920005989 resin Polymers 0.000 claims abstract description 86
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 23
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 37
- 229910052759 nickel Inorganic materials 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 13
- 150000001336 alkenes Chemical group 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 241001550224 Apha Species 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000002161 passivation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 239000012695 Ce precursor Substances 0.000 claims description 3
- 239000012691 Cu precursor Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 17
- 231100000572 poisoning Toxicity 0.000 abstract description 9
- 230000000607 poisoning effect Effects 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 32
- 239000000203 mixture Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- -1 ethylene, propylene, butylene Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000002352 steam pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J23/72—Copper
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- B01J23/74—Iron group metals
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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
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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
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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
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
Definitions
- the present invention relates to a catalyst for hydrogenation reaction having improved sulfur resistance and a method for preparing the same.
- a catalyst for hydrogenation reaction having improved sulfur resistance
- a method for preparing the same it is possible to extend the life of the catalyst and improve the activity by improving the sulfur resistance, which is poison-resistant, including cerium and copper, and it is intended to be applied to the hydrogenation reaction of petroleum resins.
- Naphtha cracking is an important process for the production of basic intermediates such as lower olefins (i.e., ethylene, propylene, butylene and butadiene) and aromatics (i.e., benzene, toluene and xylene) used extensively in the petrochemical and chemical industries. to be.
- Thermal cracking or steam pyrolysis is the main type of process for forming these materials, typically in the presence of steam and in the absence of oxygen.
- the feedstock may include, in addition to naphtha, petroleum gas and distillates such as kerosene and gas oil.
- C4 fraction including ethylene, propylene, butane and butadiene
- cracked gasoline including benzene, toluene and xylene
- DCPD dicyclopentadiene
- C5 fraction C8 fraction
- decomposed kerosene C9 or higher oil
- decomposed heavy oil ethylene bottom oil
- hydrogen gas can be produced, and petroleum resin can be prepared by polymerization from oil.
- the C5 fraction is a petroleum fraction obtained through pretreatment, distillation, and polymerization of petroleum, a by-product, and a combination thereof.
- the number of carbon atoms such as cyclopentadiene, isoprene, and piperylene It means five unsaturated hydrocarbons
- C8 fraction is a petroleum fraction obtained through pre-treatment, distillation, and polymerization of petroleum, a by-product, and a combination thereof with 8 carbon atoms such as styrene and octene. It means an unsaturated hydrocarbon
- the C9 fraction is a petroleum fraction obtained through pretreatment, distillation, and polymerization of petroleum, a by-product, and a combination thereof.
- An unsaturated hydrocarbon having 9 carbon atoms, such as vinyltoluene and indene means
- the polymerized petroleum resin includes, in part, a double bond of an aromatic moiety (hereinafter referred to as an 'aromatic double bond') and a double bond of an aliphatic moiety (hereinafter referred to as an 'olefin double bond'), and an olefin double bond If the content is high, the quality of petroleum resin may deteriorate, such as yellow color and odor.
- the hydrogenation reaction of petroleum resin is generally performed by contacting hydrogen and a reaction target to be hydrogenated with a noble metal catalyst such as palladium (Pd) or platinum (Pt) or a nickel (Ni)-based transition metal catalyst.
- a noble metal catalyst such as palladium (Pd) or platinum (Pt) or a nickel (Ni)-based transition metal catalyst.
- the raw material for polymerization of petroleum resin contains various organosulfur components, and the sulfur content in petroleum resin varies according to the composition and composition of the raw material for polymerization.
- a petroleum resin polymerized with C5-based raw materials such as dicyclopentadiene (DCPD) as a main component
- DCPD dicyclopentadiene
- C9-based materials such as decomposed kerosene
- 300 ppmw or more of a sulfur component may be included. Accordingly, a catalyst having low sulfur resistance may quickly lose activity during the hydrogenation reaction, thereby causing a problem in that the hydrogenated petroleum resin productivity is lowered.
- Patent Document 1 Japanese Patent Laid-Open No. 11-57482 (2012.10.12)
- Patent Document 2 Non-Patent Document 2 ACS Omega, 4 (2019) P4770
- An object of the present invention is to solve all of the above problems.
- Another object of the present invention is to provide a catalyst having a small crystal size, uniform particle size distribution, and high dispersion while containing nickel in a high content to provide excellent activity in the hydrogenation reaction.
- the characteristic configuration of the present invention is as follows.
- a catalyst for hydrogenation reaction comprising 40 to 80 parts by weight of nickel, 0.01 to 5 parts by weight of copper, and 0.05 to 5 parts by weight of cerium as a catalytically active component, and 10 to 30 parts by weight of silica as a carrier provided
- a method for hydrogenating a petroleum resin in which the petroleum resin is brought into contact with hydrogen in the presence of the catalyst for the hydrogenation reaction.
- a hydrogenated petroleum resin through the hydrogenation method of the petroleum resin.
- the present invention it is possible to improve the activity and lifespan of the catalyst by improving the resistance to sulfur poisoning due to the sulfur remaining in the petroleum resin in the hydrogenation reaction of the petroleum resin.
- the present invention it is possible to provide a catalyst having a small crystal size, uniform particle size distribution, and high dispersion while containing nickel in a high content for hydrogenation of petroleum resin.
- porous silica powder having a surface area of 300 m 2 /g and an average particle size of 7 ⁇ m
- nickel nitrate 60 g/L nickel
- copper nitrate 0.8 g/L copper
- cerium nitrate 1.5 g/L cerium nitrate
- the pH of the slurry was 8, which was washed with about 2 L of distilled water, filtered, and then dried at 105° C. for at least 8 hours using a drying oven. This was subdivided, and then reduced to a temperature of 400° C. in a hydrogen atmosphere to activate it.
- the activated catalyst was passivated using a nitrogen mixed gas containing 1 vol% oxygen to prepare a hydrogenation catalyst. Specific composition ratios of nickel, copper and cerium are shown in Table 1.
- Example 1 It proceeded in the same manner as in Example 1 except that the specific composition ratios of nickel, copper, and cerium were changed. Specific composition ratios of nickel, copper and cerium are shown in Table 1.
- Example 1 It proceeded in the same manner as in Example 1 except that the specific composition ratios of nickel, copper, and cerium were changed. Specific composition ratios of nickel, copper and cerium are shown in Table 1.
- Example 2 The same procedure as in Example 1 was performed except that porous silica powder having a surface area of 250 m 2 /g and an average particle size of 20 ⁇ m was used. Specific composition ratios of nickel, copper and cerium are shown in Table 1.
- porous silica powder having a surface area of 300 m 2 /g and an average particle size of 7 ⁇ m and 1,875 mL of a solution of nickel nitrate (60 g/L nickel) dissolved in distilled water was placed in a precipitation vessel, and the temperature was raised to 80° C. with stirring. . After reaching 80°C, 1,500 mL of sodium carbonate (175 g/L) solution was injected using a burette within 1 hour. After the precipitation was completed, the pH of the slurry was 8, which was washed with about 2 L of distilled water, filtered, and then dried at 105° C. for at least 8 hours using a drying oven.
- Example 2 It proceeded in the same manner as in Example 1 except that cerium nitrate (1.5 g/L cerium) was not included. Specific composition ratios of nickel and copper are shown in Table 1.
- nickel (Ni), copper (Cu), and cerium (Ce) may exist in the form of an oxide, and the remainder except for constituents in each Example and Comparative Example includes oxygen (O).
- the crystal size of nickel was measured using X-ray diffraction (XRD) analysis and Scherrer equation, and the specific surface area of the catalyst was measured according to the BET method.
- BJH Barrett-Joyner-Halenda
- the average particle size (d 50 ) was measured using a laser diffraction method.
- the hydrogenation target reactant was a petroleum resin (manufactured by Hanwha Solutions, Inc.) containing C9 raw material containing 60 ppmw of sulfur, and was used as a reactant by dissolving it in Exxsol D40, a solvent at a concentration of 30% by weight. Reaction temperature and pressure were respectively 250 °C, H 2 85 bar was applied.
- the hydrogenation conversion rate was measured from the amount of change in the olefin and aromatic content in the resin measured through 1H-NMR before and after the hydrogenation reaction. Specifically, it is as follows.
- Hydrogen conversion rate (%) (1-(sum of hydrogen included in aromatic and olefin groups in petroleum resin after hydrogenation/sum of hydrogen included in aromatic and olefin groups in petroleum resin before hydrogenation)) ⁇ 100
- the amount of hydrogen contained in the aromatic group in the petroleum resin is in the aromatic region, specifically 6.0 to 9.0 ppm compared to the internal standard (0 ppm) of tetra-methyl silane (TMS) in 1H-NMR analysis. It was measured by the number of protons obtained from the area ratio of the hydrogen peaks bound to the aromatic hydrocarbons,
- the amount of hydrogen contained in the olefin group in the petroleum resin was measured as the number of protons obtained from the area ratio of the hydrogen peaks appearing in the olefin region, specifically, in the 4.0 to 6.0 ppm region compared to the internal standard standard (TMS, 0 ppm).
- APHA value was measured by applying ASTM D1209 method after hydrogenation.
- a metal precursor salt solution and a pH adjusting agent react in a carrier dispersion to form a precipitate during catalyst preparation, and these are adsorbed and solidified on the support surface.
- This can provide catalyst uniformity that cannot be compared with metal catalysts prepared by a co-precipitation method or an impregnation method with a conventional catalyst preparation method.
- a catalyst for hydrogenation reaction comprising 40 to 80 parts by weight of nickel, 0.01 to 5 parts by weight of copper, and 0.05 to 5 parts by weight of cerium as a catalytically active component, and 10 to 30 parts by weight of silica as a carrier is provided
- the catalyst for the hydrogenation reaction may be prepared by mixing nickel or nickel oxide in a solvent as a nickel source (precursor), and includes metal salts such as nitrate, acetate, sulfate, chloride, and most preferably a nickel nitrate precursor containing nitrate.
- Copper and copper oxide as a copper source can be prepared by mixing in a solvent.
- a state bound to metal salts such as nitrate, acetate, sulfate, chloride, or combinations thereof may be provided.
- cerium and cerium oxide can be prepared by mixing cerium and cerium oxide together in a solvent as a cerium source (precursor).
- a state bound to a metal salt such as nitrate, acetate, sulfate, chloride, or combinations thereof may be provided.
- the sources may be used in powder form and mixed in a solvent, and the solid carrier may be suspended in the solvent, and the nickel compound and the accelerator may be deposited on the solid carrier to form a precipitate. After that, the catalyst can be finally obtained by washing, filtration, drying, calcining and reduction.
- catalysts containing nickel have the advantage of high activity in hydrogenation reaction compared to catalysts containing other metals.
- the nickel precursor is supported on the carrier by the DP method, the larger the nickel content, the larger the crystal size and the lower the dispersibility, thereby lowering the catalyst activity.
- the present invention can provide a catalyst having a small crystal size, an even particle size distribution, and a high dispersion degree despite the high nickel content by adding copper.
- the present invention can extend the life of the catalyst by improving the resistance to sulfur poisoning by the sulfur remaining in the petroleum resin in the hydrogenation reaction of the petroleum resin, including cerium.
- the crystal size of nickel is 3 to 8 nm.
- the catalyst according to the present invention can maintain high dispersibility while controlling the crystal size of nickel to 3 to 8 nm.
- the catalyst according to the present invention as a result of hydrogenation of a petroleum resin containing sulfur, resistance to sulfur poisoning by addition of cerium and copper increases, so that the activity and lifespan of the catalyst can be improved. This can be confirmed from the results of Examples to be described later.
- the specific surface area, total pore volume, and average pore size of the catalyst may be measured using nitrogen adsorption/desorption analysis.
- the specific surface area is measured by the Brunauer, Emmett, Teller (BET) method, and refers to an analysis method that measures the specific surface area of a powder by measuring the amount of nitrogen gas adsorbed on the catalyst surface.
- BET Brunauer, Emmett, Teller
- the average pore size can be measured using the Barrett-Joyner-Halenda (BJH) adsorption average size.
- the specific surface area of the catalyst provided in the present invention is 150 to 300 m 2 /g, the total pore volume is 0.2 m 3 /g to 0.4 m 3 /g, and the average pore size of the catalyst is provided in the range of 5 to 10 nm. Accordingly, it is possible to provide the effect of increasing the dispersion of nickel and improving the activity of the catalyst in the hydrogenation reaction.
- d 50 is provided as 3 to 100 ⁇ m. Accordingly, it is possible to provide excellent dispersibility and filterability by having a uniform particle size distribution.
- the average particle size (d 50 ) refers to the particle size at 50% of the cumulative distribution of the particle volume according to the particle size during particle size distribution analysis, and can be measured using a laser diffraction method. . Specifically, after dispersing the target catalyst powder in distilled water as a dispersion medium, it is introduced into a laser diffraction particle size measuring device (model name: Malvern Mastersizer 2000) to measure the particle size by measuring the diffraction pattern difference according to the particle size when the particles pass through the laser beam. distribution can be calculated.
- a laser diffraction particle size measuring device model name: Malvern Mastersizer 2000
- the catalyst according to the present invention may be in the form of powder, particles or granules, preferably in the form of a powder.
- a method for preparing a catalyst for a hydrogenation reaction according to the present invention is provided below.
- the same content as the catalyst for the hydrogenation reaction described above may be applied, and the description within the overlapping range will be omitted.
- a method for preparing a hydrogenation catalyst according to an embodiment of the present invention comprises: preparing a first solution by dissolving a nickel precursor in a solvent so that the weight concentration (g/L) of nickel in the solution is 25 to 100; A second solution is prepared by adding a copper precursor and a cerium precursor to the first solution so that the weight concentration (g/L) of copper in the solution is 0.01 to 5 and the weight concentration (g/L) of cerium in the solution is 0.05 to 5 step; preparing a third solution by dispersing the silica carrier in the second solution so that the weight concentration (g/L) of silica in the solution is 5 to 30; Putting the third solution in a precipitation vessel, stirring, and raising the temperature to 50 to 120 °C; preparing a catalyst after precipitation-depositing the precursors on a silica carrier by adding a pH adjuster to the elevated temperature third solution; drying the catalyst after washing and filtering; and reducing and activating the dried catalyst.
- the precursors used in the preparation of the first to third solutions may be provided by nickel, copper, or cerium itself, and are bound to metal salts such as oxides, nitrates, acetates, sulfates, chlorides, or combinations thereof. state may be provided.
- the precipitation of the catalyst precursor may be made in an environment of pH 7 or higher by addition of a base or by electrochemical means, and preferably at a pH of 7 to 9.
- a basic compound may be added as a regulator for pH adjustment, and the basic additive may include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate or a hydrate thereof, but is not limited thereto, and preferably sodium carbonate or a hydrate thereof. may include
- the catalyst in the case of drying that proceeds after washing and filtering the catalyst, it may be dried at a temperature of 100° C. to 200° C. for 5 to 24 hours.
- the reduction is performed at a temperature of 200° C. to 500° C. in a hydrogen atmosphere.
- the method for preparing a catalyst for hydrogenation reaction according to the present invention may further include the step of passivating the activated catalyst.
- the passivation step can be provided in two ways. That is, it may be provided as a step of passivating with a gas or by immersing an organic solvent or petroleum resin in a solution contained in the organic solvent.
- passivation with a gas it may be carried out in a nitrogen mixed gas containing 0.1 to 20% by volume of oxygen.
- Exxsol D40 may be used, and an organic solvent capable of blocking air may be used without limitation.
- a solution containing petroleum resin in an organic solvent can be used.
- the reactant of the hydrogenation reaction may be provided with a petroleum resin (petroleum resin).
- a petroleum resin petroleum resin
- a petroleum resin containing a C5 fraction or a petroleum resin containing a C9 fraction may be provided.
- it may be a petroleum resin consisting of DCPD oil by-products and combinations thereof.
- the petroleum resin may include an olefin group and an aromatic group.
- the unsaturated bonds remaining in the resin due to the unsaturated bonds remaining in the resin (unsaturated bonds of olefins and aromatics), it has a yellow color, smells, and is easily oxidized in air. Therefore, in order to improve the quality of petroleum resin, when the hydrogenation reaction is carried out using the catalyst for hydrogenation according to the present invention under high temperature and high pressure conditions, unsaturated bonds are removed, colorless, odorless, and transparent water with improved thermal stability- White petroleum resin can be provided.
- the petroleum resin may contain 1 to 300 ppmw of a sulfur component.
- a sulfur component such as dicyclopentadiene (DCPD)
- it may contain 30 ppmw or less
- 300 ppmw or less may include
- the hydrogenation reaction of petroleum resin is carried out using the catalyst for hydrogenation reaction having excellent sulfur poisoning resistance according to the present invention, it provides excellent activity and lifespan of the catalyst even under conditions of high sulfur content, providing a satisfactory level of high quality of hydrogenated petroleum resin can be obtained.
- the temperature may be 100 ° C to 400 ° C, preferably 200 ° C to 300 ° C
- the hydrogen pressure may be 1 bar to 200 bar, preferably 50 bar to 100 bar
- the hydrogenation reaction time may vary depending on the temperature, the amount of catalyst and the degree of hydrogenation.
- the hydrogenation reaction may be carried out in various reactors, preferably in a continuous stirring reactor (CSTR) or a loop reactor.
- CSTR continuous stirring reactor
- the petroleum resin according to the present invention is characterized in that it has an APHA value of 30 or less after the hydrogenation reaction is completed in contact with hydrogen.
- APHA color is called Hazen scale or Cobalt (Pt/Co) scale
- the color of hydrogenated petroleum resin is analyzed by APHA value with the color standard analysis method (ASTM D1209) named from the American Public Health Association.
- ASTM D1209 the color standard analysis method
- the color of the petroleum resin is 30 or less, it becomes a water-white resin with almost no color and odor of the petroleum resin, and at this time, the olefin content (NMR % area) measured by 1H-NMR becomes less than 0.1 wt%.
- the present invention it is possible to improve the activity and lifespan of the catalyst by improving the resistance to sulfur poisoning due to the sulfur remaining in the petroleum resin in the hydrogenation reaction of the petroleum resin.
- the present invention it is possible to provide a catalyst having a small crystal size, uniform particle size distribution, and high dispersion while containing nickel in a high content for hydrogenation of petroleum resin.
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Abstract
Description
Claims (17)
- 촉매활성성분으로 니켈 40 내지 80 중량부, 구리 0.01 내지 5 중량부 및 세륨 0.05 내지 5 중량부를 포함하고,담체로 실리카 10 내지 30 중량부를 포함하는 수소화 반응용 촉매.
- 제 1항에 있어서,상기 니켈, 구리 및 세륨은 금속 또는 산화물 상태인 수소화 반응용 촉매.
- 제 1항에 있어서,상기 니켈의 결정 크기는 3 내지 8 nm 인 수소화 반응용 촉매.
- 제1항에 있어서,상기 촉매는 BET 비표면적이 150 내지 300 m2/g인 수소화 반응용 촉매.
- 제 1항에 있어서,상기 촉매는 전체기공부피가 0.2 m3/g 내지 0.4 m3/g인 수소화 반응용 촉매.
- 제1항에 있어서,상기 촉매는 평균기공크기가 5 내지 10 nm인 수소화 반응용 촉매.
- 제 1항에 있어서,상기 촉매의 평균입자크기(d50)는 3 내지 100 ㎛인 수소화 반응용 촉매.
- 용액 내 니켈의 중량농도(g/L)가 25 내지 100이 되도록 니켈 전구체를 용매에 용해하여 제1용액을 제조하는 단계;용액 내 구리의 중량농도(g/L) 0.01 내지 5 및 용액 내 세륨의 중량농도(g/L) 0.05 내지 5가 되도록 제1용액에 구리 전구체와 세륨 전구체를 첨가하여 제2용액을 제조하는 단계;용액 내 실리카의 중량농도(g/L)가 5 내지 30이 되도록 제2용액에 실리카 담체를 넣고 분산시켜 제3용액을 제조하는 단계;제3용액을 침전 용기에 넣고 교반하며, 50 내지 120 ℃로 승온하는 단계;승온된 제3용액에 pH 조절제를 첨가하여 상기 전구체들을 실리카 담체에 침전-침적시킨 후 촉매를 제조하는 단계;상기 촉매를 세척 및 여과한 후 건조하는 단계;건조된 촉매를 환원하여 활성화하는 단계;를 포함하는 수소화 반응용 촉매의 제조방법.
- 제8항에 있어서,활성화된 촉매를 부동화하는 단계;를 더 포함하는 것인 수소화 반응용 촉매의 제조방법.
- 제9항에 있어서,상기 부동화는 0.1 내지 20 부피%의 산소가 포함된 질소 혼합가스로 부동화하는 것인 수소화 반응용 촉매의 제조방법.
- 제9항에 있어서,상기 부동화는 활성화된 촉매를 유기용매 혹은 석유수지가 유기용매에 포함된 용액에 침적하여 부동화하는 것인 수소화 반응용 촉매 제조방법.
- 제1항에 따른 수소화 반응용 촉매의 존재 하에서 석유수지를 수소와 접촉시키는 석유수지의 수소화 방법.
- 제12항에 있어서,상기 석유수지는 C5계, C8계 및 C9계 석유 분획 및 부산물 및 이들의 조합물에서 선택된 적어도 어느 하나를 포함하는 원료로부터 중합된 것인 석유수지의 수소화 방법.
- 제12항에 있어서,상기 석유수지는 올레핀 그룹, 방향족 그룹 및 이들의 조합들로 이루어진 군으로부터 선택되는 물질을 포함하는 것인 석유수지의 수소화 방법.
- 제12항에 있어서,상기 석유수지는 황 성분을 1 내지 300 ppmw 포함하는 것인 석유수지의 수소화 방법.
- 제12항에 있어서,상기 수소화 방법 이후 석유수지의 APHA 값은 30 이하인 석유수지의 수소화 방법.
- 제12항에 따른 수소화 방법을 통해 수소화된 석유수지.
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CN117003943B (zh) * | 2023-10-07 | 2023-12-01 | 潍坊工程职业学院 | 一种加氢石油树脂的制备方法 |
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