WO2023125044A1 - Method and system for producing solvent oil from raffinate oil - Google Patents
Method and system for producing solvent oil from raffinate oil Download PDFInfo
- Publication number
- WO2023125044A1 WO2023125044A1 PCT/CN2022/139297 CN2022139297W WO2023125044A1 WO 2023125044 A1 WO2023125044 A1 WO 2023125044A1 CN 2022139297 W CN2022139297 W CN 2022139297W WO 2023125044 A1 WO2023125044 A1 WO 2023125044A1
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- WIPO (PCT)
- Prior art keywords
- tower
- metal component
- active metal
- catalyst
- rectification
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000002904 solvent Substances 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 114
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 101
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 35
- 230000023556 desulfurization Effects 0.000 claims abstract description 35
- 230000018044 dehydration Effects 0.000 claims abstract description 17
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 110
- 239000002184 metal Substances 0.000 claims description 103
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 99
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 79
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 44
- 239000002808 molecular sieve Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 38
- 239000002243 precursor Substances 0.000 claims description 37
- 238000010606 normalization Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 26
- 238000002407 reforming Methods 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 18
- 208000005156 Dehydration Diseases 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003463 adsorbent Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 238000003795 desorption Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 70
- 235000019198 oils Nutrition 0.000 description 67
- 239000000243 solution Substances 0.000 description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 36
- 239000001257 hydrogen Substances 0.000 description 35
- 229910052739 hydrogen Inorganic materials 0.000 description 35
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 30
- 239000002994 raw material Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000004604 Blowing Agent Substances 0.000 description 13
- 238000005194 fractionation Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 9
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008157 edible vegetable oil Substances 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 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 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- -1 n-hexane alkane Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229940035674 anesthetics Drugs 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003193 general anesthetic agent Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical group [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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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
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- B01J23/78—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 alkali- or alkaline earth metals
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- 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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- B01J35/615—100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/633—Pore volume less than 0.5 ml/g
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- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/16—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring
- C07C13/18—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a six-membered ring with a cyclohexane ring
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- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2772—Catalytic processes with metal oxides
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- 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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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
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- C07C2601/14—The ring being saturated
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- 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
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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/18—Solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention relates to the technical field of reformed raffinate treatment, in particular to a method and system for producing solvent oil from reformed raffinate.
- Reformed raffinate is a by-product in the production of aromatics. Due to the low content of impurities such as sulfur, nitrogen and heavy metals, it is a good petrochemical raw material. According to different boiling points, different high value-added components can be distilled, which is suitable for the production of high-quality Solvent oil and high value-added hexane oil and isohexane oil, etc.
- Reformed raffinate contains a small amount of unsaturated components such as olefins and aromatics, which seriously affects the properties of raffinate as high value-added solvent oil.
- n-hexane is mainly used as solvent for the polymerization of olefins such as propylene, edible vegetable oil extractant, rubber and paint solvent, and pigment thinner, etc., with clear restrictions on unsaturated hydrocarbons such as benzene
- 6# solvent oil is used for the production of edible oils and fats During the production process, there will be some residues in the edible oil, and the carcinogenic aromatic hydrocarbons in the solvent oil will also remain in the edible oil, which will cause harm to the human body.
- the content of the aromatic hydrocarbons in the 6# solvent oil must be strictly controlled; Alkanes blowing agents are mainly used as solvents, making artificial ice, anesthetics, etc., and the bromine index is clearly required to be ⁇ 100mgBr/100g. Therefore, in order to rationally utilize reformed raffinate and endow it with higher economic value, it is necessary to carry out hydrodealkenization and dearomatization to remove unsaturated hydrocarbons.
- representative hydrodeolefination and dearomatization catalysts are mainly divided into two categories: noble metals and non-noble metals, and Ni, Pt, and Pd three metal catalysts are widely used.
- Pd hydrogenation performance K Pd is 1/7 of metal Ni
- Pt activity K Pt is 2.5 times that of Ni
- the price of palladium and platinum is hundreds of times higher than nickel, and it is toxic to sulfur, arsenic and other materials in raw materials Material requirements are high
- the process of reforming raffinate to produce high value-added products varies according to the nature of raw materials and product requirements, mainly including hydrogenation followed by fractionation, and fractionation followed by hydrogenation.
- the technological process of first hydrogenation and then fractionation is basically used to ensure that the benzene content of the product meets the standard requirements; Small, but higher requirements for hydrogen purity. Due to the existence of component azeotropy in the fractionation process, the requirements for the number of trays and columns are different.
- nickel-based hydrodeenification and debenzene catalysts have poor thermal stability at high temperatures, NiO particles are easy to agglomerate and sinter, and there are problems such as poor dispersion and utilization, and impurities such as sulfur, nitrogen, and heavy metals in the raw materials are easy to cause catalyst degradation. Poisoning will affect the service life of the catalyst and lead to increased operating costs, requiring pretreatment of raw materials. Therefore, the existing process often has problems such as low utilization rate of reformed raffinate, single processed product, low product yield, short operating cycle of hydrogenation catalyst, and insensitivity to temperature rise. It is necessary to comprehensively consider the nature of raw materials, product types, Catalyst stability, sulfur resistance, fractionation precision and other factors to achieve efficient utilization of reformed raffinate.
- C5 and below components without hydrogenation saturation treatment will easily lead to unqualified benzene and bromine index and cannot meet the requirements of pentane blowing agent, and are not suitable for raw materials with high benzene content; in logistics II It is a C6 mixture, which has the problem of low isomerization conversion rate; hydrogenation and isomerization products have not undergone gas-liquid separation, resulting in high light hydrocarbon components in isohexane in the subsequent fractionation process; raw materials entering the hydrogenation reactor have not undergone Desulfurization treatment can easily lead to poisoning and deactivation of the hydrogenation catalyst.
- the object of the present invention is to provide a method and system for producing solvent oil by reforming raffinate oil.
- the method is suitable for the separation and utilization of the reformed raffinate with high benzene and olefin content, and can use the reformed raffinate to produce various solvent oils, effectively increasing the added value of the reformed raffinate.
- the present invention provides a hydrogenation catalyst comprising a carrier, a first active metal component loaded on the carrier and a second active metal component, wherein the metal of the first active metal component Elements include nickel, based on the total weight of the catalyst as 100%, the weight content of the first active metal component in the catalyst is 40-70%, and the carrier (calculated as oxide) in the catalyst The weight content is 20-59%, and the balance is the second active metal component.
- the nickel content in the hydrogenation catalyst provided by the invention is higher, and the dispersion of Ni metal is higher, which can reach more than 10% , has more hydrogenation active centers, so the hydrogenation catalyst has a better and more thorough removal effect on benzene and olefins.
- the weight of the first active metal component in the catalyst is generally controlled to be 40-70%, such as 40%, 45%, 50%, 55%, 60%, 65%, 70% % or a range consisting of any two of them.
- the weight content of the carrier in the catalyst is 20-59%, such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 59% % or a range consisting of any two of them.
- the specific surface area of the hydrogenation catalyst is generally 200-500m 2 /g, such as 200m 2 /g, 250m 2 /g, 300m 2 /g, 350m 2 /g, 400m 2 / g g, 450m 2 /g, 500m 2 /g or any combination thereof.
- the pore volume of the hydrogenation catalyst is generally 0.3-0.6 cm 3 /g, such as 0.3 cm 3 /g, 0.35 cm 3 /g, 0.4 cm 3 / g, 0.45 cm 3 /g g, 0.5cm 3 /g, 0.55cm 3 /g, 0.6cm 3 /g or any combination thereof.
- the support is generally an oxide, for example, it may include one of alumina, silicon oxide, titanium oxide, and cerium oxide, and may also include at least one of silicon oxide, titanium oxide, and cerium oxide.
- the first active metal component and the second active metal component in the above catalyst usually exist in the form of metal oxides.
- the metal elements of the second active metal component may include one or a combination of two or more of copper, lanthanum, magnesium, and the like.
- the nickel content, nickel dispersion and hydrogenation active center content in the catalyst can be increased.
- the present invention further provides the preparation method of above-mentioned hydrogenation catalyst, and this preparation method comprises:
- the second mixed system is subjected to aging treatment, and the aged product is roasted to obtain the hydrogenation catalyst.
- the carrier precursor is transformed into a carrier of the hydrogenation catalyst after being dried and calcined.
- the carrier precursor may include pseudo-boehmite, and then the pseudo-boehmite is converted into alumina after being dried and calcined.
- the nickel content, nickel dispersion and hydrogenation in the catalyst can be improved. active center content.
- the precipitating agent can not only be used to adjust the pH value, but also precipitate metal elements in the precursor of the first active metal component and metal elements in the precursor of the second active metal component.
- the precipitant may include an alkaline precipitant, preferably a soluble carbonate, for example potassium carbonate and/or sodium carbonate.
- the amount of the precipitating agent can be determined according to the amount required for adjusting the pH value and precipitating the metal elements in the precursor of the first active metal component and the metal element in the precursor of the second active metal component.
- the precursor of the first active metal component can be a compound of the metal element in the first active metal component, for example, a metal salt comprising the metal element in the first active metal component, preferably comprising the first active metal component
- the soluble metal salt of the metal element for example, includes the nitrate of the metal element in the first active metal component, such as nickel nitrate and the like.
- the precursor of the second active metal component can be a compound of the metal element in the second active metal component, for example, a metal salt comprising the metal element in the second active metal component, preferably comprising the second active metal component
- the soluble metal salt of the metal element for example, includes the nitrate of the metal element in the second active metal component, such as magnesium nitrate and the like.
- the amount of the carrier precursor, the first active metal component precursor, and the second active metal component precursor corresponds to the amount of the carrier, the first active metal component, and the second active metal component in the above-mentioned hydrogenation catalyst.
- the weight content of metal components corresponds to the amount of the carrier, the first active metal component, and the second active metal component in the above-mentioned hydrogenation catalyst.
- the first active metal component precursor and the second active metal component precursor can be added to the first mixing system as a mixed solution of the two;
- the solution form is added to the first mixed reaction system.
- the nickel content in the catalyst can be effectively controlled , nickel dispersion and hydrogenation active center content.
- the drop rate of the mixed solution of the first active metal component precursor and the second active metal component precursor is generally controlled to be 20-100ml/min, and the drop rate of the precipitant solution is The general control is 10-300ml/min.
- the alkaline pH value is 8-11, such as 8, 9, 10, 11 or any combination thereof.
- the precipitation reaction temperature is 40-90°C, such as 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or any combination thereof.
- the aging treatment temperature may be the same as or different from the precipitation reaction temperature.
- the temperature of the aging treatment is generally 40-90°C, such as 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or any combination thereof.
- the aging treatment time is generally controlled within 1-5 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or any combination thereof.
- the temperature of the calcination can generally be controlled at 300-600°C, such as 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C or any combination thereof. .
- the calcination time is generally 1-5h, such as 1h, 2h, 3h, 4h, 5h or any combination thereof.
- the preparation method generally further includes the operations of filtering, washing and drying in sequence after aging treatment and before roasting.
- the washing generally stops when the filtrate reaches neutrality.
- the obtained filter cake is subjected to subsequent drying and roasting.
- the drying temperature may be in the range of 100-130°C, such as 100°C, 110°C, 120°C, 130°C or any combination thereof.
- the drying time is generally 1-5 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or any combination thereof.
- the preparation method of above-mentioned hydrogenation catalyst can comprise:
- the present invention also provides a method for reforming raffinate to produce solvent oil, the method comprising:
- the sulfur content in terms of volume percentage, in reformed raffinate without desulfurization and dehydration, the sulfur content is below 20 mg/kg, the benzene content is 3-5v%, and the olefin content is 1 -3v%, the total content of n-hexane and isohexane is greater than 50v%.
- the above method further includes: S1, performing desulfurization and dehydration treatment on the reformed raffinate, and the product S ⁇ 1mg/kg.
- the space velocity in the desulfurization and dehydration process is 1-10h -1 ;
- the adsorbent used in the desulfurization and dehydration process in S1 includes a molecular sieve adsorbent, such as one or more combinations of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and 13A molecular sieve;
- the molecular sieve adsorbent used in S1 generally has a specific surface area of 400-700 m 2 /g.
- the pore volume of the molecular sieve adsorbent is generally 0.05-0.30 cm 3 /g.
- the hydrogenation catalyst in S2, can effectively remove benzene and olefins in the reformed residual oil.
- the benzene content is ⁇ 0.01%
- the bromine index is ⁇ 50mgBr/100g.
- the conditions of the hydrodebenzene and deolefination reactions can generally be controlled as follows: temperature 90-200°C, reaction pressure 1.0-3.0MPa, hydrogen-to-oil volume ratio 100-300: 1. Volumetric space velocity 1.0-3.0h -1 ;
- the pressure of the rectification is generally 0-0.2 MPa.
- the rectification process of S4 can be completed in the rectification tower, then the tower top temperature of the rectification tower can be 30-50 °C, the tower bottom temperature can be 90-110 °C, the pressure in the tower 0-0.2MPa.
- the pressure of the rectification is generally 0-0.1 MPa.
- the rectification process of S5 can be completed in the rectification tower, the tower top temperature of the rectification tower is 55-75 °C, the bottom temperature is 70-90 °C, and the pressure in the tower is 0 -0.1 MPa.
- the pressure of the rectification is 0-0.1 MPa.
- the rectification process of S6 can be completed in the rectification tower, the tower top temperature of the rectification tower is 50-70 DEG C, the tower bottom temperature is 60-80 DEG C, and the pressure in the tower is 0-80 DEG C. 0.1 MPa.
- the isohexane obtained in S6 can be directly exported as 6# solvent oil. According to actual needs, the isohexane obtained in S6 can also be converted into normal hexane by normalization reaction, and the purity of the normal hexane product is ⁇ 80%.
- the method further includes: S7, converting the isohexane obtained in S6 into normal hexane through a normalization reaction.
- the conditions of the normalization reaction are: reaction temperature 200-400°C, reaction pressure 1.0-3.0MPa, hydrogen-oil volume ratio 100-300:1, volume space velocity 1.0 -3.0h -1 .
- the catalyst for the normalization reaction may be a molecular sieve catalyst.
- the molecular sieve catalyst may include a third active metal component, a non-molecular sieve support and a molecular sieve support.
- the molecular sieve carrier includes one or a combination of two or more of MOR, MCM-41, ZSM-22 and SAPO-11.
- the metal elements of the third active metal component may include elements in Group VIB and/or Group VIII.
- the third active metal component is generally present in the form of a metal oxide.
- the non-molecular sieve support comprises alumina.
- the weight of the molecular sieve carrier accounts for 10-80% of the total weight of the catalyst, and the third active metal component (calculated as oxide) The weight accounts for 0.01-5% (such as 0.1-0.5%) of the total weight of the catalyst, and the rest is non-molecular sieve carrier.
- the purity of isohexane, the raw material for the normalization reaction is above 90%, preferably above 95%.
- the method for producing solvent oil from the reformed raffinate may specifically include:
- the present invention also provides a system for producing solvent oil by reforming raffinate oil, which can realize the method for producing solvent oil by reforming raffinate oil.
- the system for producing solvent oil from the reforming raffinate includes a desorption and desulfurization reactor, a hydrogenation reactor, a first gas-liquid separator, a first rectification tower, and a second desulfurization reactor connected in sequence.
- the second rectification tower and the third rectification tower are connected in sequence.
- connection relationship of each device in the above system can be: the inlet of the desorption and desulfurization reactor is used to receive the reformed raffinate, and the inlet is generally located at the top of the tower;
- the outlet of the desorption and desulfurization reactor at the bottom of the tower is connected with the inlet of the hydrogenation reactor (at the top of the tower);
- the outlet of the hydrogenation reactor at the bottom of the tower is connected with the inlet (located at the side line) of the first gas-liquid separator;
- the outlet at the bottom of the first gas-liquid separator is connected with the inlet (at the side line) of the first rectifying tower;
- the outlet of the first rectification tower located at the measuring line is connected with the inlet of the second rectification tower;
- the outlet of the second rectifying tower located at the top of the tower is connected with the inlet of the third rectifying tower;
- the outlet of the third rectifying column at the top of the column is used to output isohexane.
- the outlet of the first gas-liquid separator at the top of the tower is used to output hydrogen
- the outlet of the first rectification tower at the top of the tower is used to output C5 components
- the first rectification tower is located at
- the outlet at the bottom of the tower is used to output components above C7
- the outlet of the first rectification column at the measuring line is used to output C6 components
- the outlet at the top of the second rectification column is used to output n-hexane and isohexane
- the mixture of alkanes the outlet of the second rectification tower at the bottom of the tower is used to export cyclohexane
- the outlet of the third rectification tower at the bottom of the tower is used to output normal hexane
- the third rectification tower is located at the bottom of the tower
- the top outlet is used to output isohexane.
- the system for producing solvent oil from the reforming raffinate also includes a normalization reactor and a second gas-liquid separator, and the inlet of the normalization reactor is connected to the third
- the rectifying tower is connected at the outlet at the top of the tower, and the outlet of the normalization reactor is connected with the inlet (at the side line) of the second gas-liquid separator, and the outlet at the top of the second gas-liquid separator is used for Hydrogen is output, and the outlet of the second gas-liquid separator at the bottom of the tower is used to output n-hexane.
- the above-mentioned system may further include a hydrogen pipeline, which is used to supplement hydrogen to the hydrogenation reactor and/or the normalization reactor.
- the hydrogen pipeline can be provided with a circulating hydrogen compressor, and the inlet of the compressor can be connected with the gas outlet of the first gas-liquid separator and/or the second gas-liquid separator, that is, the compressor can be separated by the first gas-liquid device, the second gas-liquid separator gas supply.
- the method provided by the present invention pretreats the raw material by filling the adsorption reactor with a molecular sieve adsorbent, and performs desulfurization, dehydration and impurity removal to solve the subsequent hydrodebenzene catalyst caused by sulfolane in the reforming raffinate raw material in the prior art.
- the problem of poisoning can effectively protect the service life of high-nickel hydrogenation catalysts in subsequent hydrodeolefins and debenzene units, prolong the operation period of the unit, reduce the increase in operating costs caused by frequent replacement of catalysts, and the separated components above C7 meet 120 # Solvent oil sulfur content requirements; at the same time, it avoids the cumbersome start-up process of the device due to the need for pre-sulfurization of the hydrodesulfurization catalyst in the prior art, and the difficult replacement of residual sulfide oil affects the start-up period of the device.
- the method provided by the present invention can set up rectification units step by step from the perspective of molecular oil refining, and use isohexane normalization reaction to improve the purity and yield of n-hexane to produce n-hexane and pentane Foaming agent and 120# solvent oil to realize efficient utilization of reforming raffinate. Effectively solve the problems of low utilization rate of reforming raffinate, single processed product, and low product yield.
- the nickel-based hydrogenation catalyst provided by the present invention can realize the high dispersion of high-content nickel active components on the carrier alumina, and carry out hydrodeolefination and debenzene reactions on the reformed raffinate, ensuring the hydrogenation unit operating cycle.
- Fig. 1 is a process flow diagram and a schematic diagram of system connection for producing solvent oil from reformed raffinate according to the present invention.
- Adsorption desulfurization reactor 1 hydrogenation reactor 2, first gas-liquid separator 3, first rectification tower 4, second rectification tower 5, third rectification tower 6, normalization reactor 7, second rectification tower Gas-liquid separator 8, circulating hydrogen compressor 9.
- the metal dispersion of the hydrogenation catalyst is carried out in a static chemisorption instrument, with H 2 is the adsorption gas, and the specific measurement method is as follows:
- the sample was degassed at 130°C, then H2 reduction was performed at 400°C, the first saturated adsorption was performed after cooling down to 35°C, and the second saturated adsorption was performed after vacuuming.
- the difference between the two saturation adsorptions is the volume of hydrogen gas chemisorbed.
- V H2 is the volume of chemisorbed hydrogen in L
- W is the total mass of the catalyst in g
- P is the percentage of Ni
- M Ni is the molecular mass of Ni.
- Present embodiment provides a kind of hydrogenation catalyst, and its preparation method comprises:
- Step 1 Mix and stir 11.50g of pseudo-boehmite powder (containing 70wt% Al 2 O 3 ) and 40ml of deionized water to obtain the first slurry;
- Step 2 Add the first slurry to the reaction kettle, turn on the stirring speed of 200rmp, heat to the reaction temperature of 60°C, add 1.3ml of the third solution to the reaction kettle, adjust the pH of the first slurry to 10, and form the first mixing system ;
- Step 3 Stir and age the second mixed system at 60°C for 2 hours. After aging, filter the filter cake and wash it until neutral. Dry the filter cake in an oven at 120°C for 4 hours. After grinding, pass through a muffle at 500°C Furnace roasting for 5h to obtain nickel hydrogenation catalyst.
- the mass content of nickel oxide is 60%, and the mass content of magnesium oxide is 5%.
- the test of the catalyst in this example shows that the dispersion degree of Ni metal is 15.08%, the specific surface area is 251 m 2 /g, and the pore volume of the hydrogenation catalyst is 0.41 cm 3 /g.
- Present embodiment provides a kind of hydrogenation catalyst, and its preparation method comprises:
- Step 1 Mix and stir 16.10g of pseudo-boehmite powder (containing 70wt% Al 2 O 3 ), 2.30g of silicon oxide and 55ml of deionized water to obtain the first slurry;
- ammonium bicarbonate 15.81g was dissolved in deionized water, and the volume was adjusted to 200ml to prepare a 1mol/L ammonium bicarbonate solution. Measure 191.1ml of 1mol/L ammonium bicarbonate solution as the third solution.
- Step 2 Add the first slurry to the reaction kettle, turn on the stirring speed of 200rmp, heat to the reaction temperature of 80°C, add 1.2ml of the third solution to the reaction kettle, adjust the pH of the first slurry to 8, and form the first mixed system;
- Step 3 Stir and age the second mixed system at 80°C for 3 hours. After aging, filter the filter cake and wash it until neutral. Dry the filter cake in an oven at 120°C for 4 hours. After grinding, pass through a 500°C muffle Furnace roasting for 5h to obtain nickel hydrogenation catalyst.
- the mass content of nickel oxide is 40%, and the mass content of lanthanum oxide is 1%.
- the test of the catalyst in this example shows that the dispersion degree of Ni metal is 16.18%, the specific surface area is 246 m 2 /g, and the pore volume of the hydrogenation catalyst is 0.40 cm 3 /g.
- Present embodiment provides a kind of hydrogenation catalyst, and its preparation method comprises:
- Step 1 Mix and stir 11.50g of pseudo-boehmite powder (containing 70wt% Al 2 O 3 ) and 40ml of deionized water to obtain the first slurry;
- Dissolve 207.32g of anhydrous potassium carbonate in deionized water set the volume to 1000ml, and prepare a 1.5mol/L potassium carbonate solution. Measure 621.4ml of the 1.5mol/L potassium carbonate solution as the third solution.
- Step 2 Add the first slurry to the reaction kettle, turn on the stirring speed of 100rmp, heat to the reaction temperature of 60°C, add 1.3ml of the third solution to the reaction kettle, adjust the pH of the first slurry to 10, and form the first mixing system ;
- Step 3 Stir and age the second mixed system at 60°C for 2 hours. After aging, filter the filter cake and wash it until neutral. Dry the filter cake in an oven at 120°C for 4 hours. After grinding, pass through a muffle at 500°C Furnace calcination for 5h, and reduction in high-purity H2 at 400°C for 10h to obtain a nickel hydrogenation catalyst.
- the mass content of nickel oxide is 60%, and the mass content of copper oxide is 5%.
- the test of the catalyst in this example shows that the Ni metal dispersion is 14.74%, the specific surface area is 248 m 2 /g, and the pore volume of the hydrogenation catalyst is 0.42 cm 3 /g.
- the method for reforming raffinate to produce solvent oil in embodiment 2a to embodiment 2e is carried out in the system as shown in Figure 1, and this system comprises desorption desulfurization reactor 1, hydrogenation reactor 2, the first gas Liquid separator 3, first rectification tower 4, second rectification tower 5, third rectification tower 6, normalization reactor 7, second gas-liquid separator 8, circulating hydrogen compressor 9.
- the top of the desorption desulfurization reactor 1 is provided with an inlet, and the bottom of the tower is provided with an outlet;
- the top of the hydrogenation reactor 2 is provided with an inlet, and the bottom of the tower is provided with an outlet;
- There is an inlet, and an outlet is respectively provided at the bottom and the top of the tower;
- the measuring line of the first rectifying tower 4 is provided with an inlet, and the tower top and the tower bottom are respectively provided with an outlet;
- the measuring line of the second rectifying tower 5 is provided with an inlet, and the measuring line of the tower
- the top and the bottom of the tower are respectively provided with an outlet;
- the measuring line of the third rectification tower 6 is provided with an inlet, and the tower top and the tower bottom are respectively provided with an outlet;
- the tower top of the normalization reactor 7 is provided with an inlet, and the tower bottom is provided with an outlet ;
- the measuring line of the second gas-liquid separator 8 is provided with an inlet, and the top and the bottom of the
- connection relationship between each device is: the outlet of the desorption and desulfurization reactor 1 at the bottom of the tower is connected with the inlet of the hydrogenation reactor 2 (at the top of the tower); the hydrogenation reactor 2 is at the bottom of the tower
- the outlet of the first gas-liquid separator 3 is connected to the inlet; the outlet at the bottom of the first gas-liquid separator 3 is connected to the inlet of the first rectification tower 4; the first rectification tower 4 is located at the The outlet of the line is connected with the inlet of the second rectifying tower 5; the outlet of the second rectifying tower 5 at the top of the tower is connected with the inlet of the third rectifying tower 6; the third rectifying tower 6 is positioned at the top of the tower Outlet is connected with the inlet of normalization reactor 7; The outlet of the gas-liquid separator 3 at the top of the tower is respectively connected to the inlet of the circulating hydrogen compressor 9; the outlet of the circulating hydrogen compressor 9 is connected to the inlet of the hydrogenation reactor 2 and the inlet of the normal
- the separated liquid product is discharged from the bottom of the gas-liquid separator, and the separated hydrogen-rich gas is discharged from the top of the gas-liquid separator.
- the hydrogen-rich gas can be It is mixed with fresh hydrogen and used as circulating hydrogen after being boosted by a circulating hydrogen compressor;
- the C6 component coming out of the side line of the first rectification tower enters the second rectification tower for fractionation, the top of the tower is a mixture of n-hexane and isohexane, and the bottom of the tower is cyclohexane;
- Table 1 shows the raw material composition of the reformed raffinate in the following examples 2a to 2e, comparative example 1 and comparative example 2.
- This embodiment provides a method for reforming raffinate oil to produce solvent oil, including:
- the reformed raffinate enters the adsorption reactor for desulfurization and dehydration, and the catalyst used is an industrial 5A molecular sieve adsorbent;
- Adsorption desulfurization reaction conditions normal temperature, normal pressure, space velocity of 3h -1 , product S ⁇ 1mg/kg;
- the product of the hydrogenation reactor enters the separator for gas-liquid separation, the liquid product is discharged from the bottom of the tower, and the hydrogen-rich gas is discharged from the top.
- the hydrogen-rich gas can be mixed with the new hydrogen of the reforming unit, and is used as a cycle after being boosted by the circulating hydrogen compressor. Hydrogen use;
- reaction conditions of fixed bed hydrogenation reactor reaction temperature 120°C, reaction pressure 1.0MPa, hydrogen-to-oil volume ratio 100:1, volume space velocity 3.0h -1 , the measured benzene removal rate is 100%;
- the liquid product at the bottom of the separator enters the first rectification tower, the top of the tower is the C5 component, the measuring line discharges the C6 component, and the bottom of the tower is the C7 and above components;
- the operating conditions of the first rectification tower the pressure inside the tower is 0.1MPa, the temperature at the top of the tower is 35°C, and the temperature at the bottom of the tower is 95°C. , the C6 component is discharged from the side line; the bromine index is measured by a bromine index analyzer according to the principle of microcoulomb titration, the bromine index of the C5 component is 5.1mgBr/100g, and the bromine index of the C7 and above components is 9.8mgBr/100g;
- the C6 component coming out of the side line enters the second rectification tower for fractionation, the top of the tower is a mixture of n-hexane and isohexane, and the bottom of the tower is cyclohexane;
- the isohexane product at the top of the tower enters the normalization reactor for reaction, and the obtained product enters the separator for gas-liquid separation, and the bottom product of the separator is high-concentration n-hexane, which is then mixed with the n-hexane product at the bottom of the third rectification tower, Further increase the yield of n-hexane.
- reaction conditions of the normalization reactor are: reaction temperature 380°C, reaction pressure 2.0MPa, hydrogen oil volume ratio 200:1, volume space velocity 1.5h -1 , conversion rate 91%, selectivity >99wt%;
- the catalyst used in the normalization reaction is a molecular sieve catalyst
- the molecular sieve catalyst is composed of a molecular sieve carrier, a non-molecular sieve carrier and a third active metal component, wherein the molecular sieve carrier is a mercerized molecular sieve MOR, and the weight content in the catalyst is 80% ;
- the third active metal component is palladium oxide, which accounts for 0.35% by weight in the catalyst; the balance is alumina as a non-molecular sieve catalyst.
- the purity of n-hexane is 83wt%, and the yield is 54%; the purity of cyclohexane is >97wt%; the C5 component meets the standard requirements of pentane blowing agent; the C7 and above components meet the 120# solvent oil standard requirements .
- This embodiment provides a method for reforming raffinate oil to produce solvent oil, including:
- Example 2a the raw materials used, process flow, adsorption desulfurization reaction, hydrogenation reaction and normalization reaction conditions are exactly the same as those in Example 2a, the difference is that the operating conditions of the three rectification towers are changed.
- the operating conditions of the first rectification tower the pressure inside the tower is 0.1MPa, the temperature at the top of the tower is 40°C, the temperature at the bottom of the tower is 102°C, the C5 component at the top of the tower is pentane foaming agent, the bromine index is 5.8mgBr/100g, and the bottom C7 and above The component is 120# solvent oil, the bromine index is 8.3mgBr/100g;
- the product obtained in this embodiment the purity of n-hexane is 88wt%, and the yield is 53%; the purity of cyclohexane is >99wt%; the C5 component meets the standard requirements of pentane blowing agent; the C7 and above components meet the 120# solvent oil standard requirements .
- This embodiment provides a method for reforming raffinate oil to produce solvent oil, comprising:
- Example 2b the raw materials used, process flow, adsorption desulfurization reaction, hydrogenation reaction and normalization reaction conditions are exactly the same as those in Example 2b, the difference is that the operating conditions of the three rectification towers are changed.
- the operating conditions of the first rectification tower the pressure inside the tower is 0.1MPa, the temperature at the top of the tower is 50°C, and the temperature at the bottom of the tower is 110°C.
- the component is 120# solvent oil, the bromine index is 8.9mgBr/100g;
- the purity of n-hexane is 85wt%, and the yield is 51%; the purity of cyclohexane is >98wt%; the C5 component meets the standard requirements of pentane blowing agent; the C7 and above components meet the 120# solvent oil standard requirements .
- the raw materials used, the process flow, the operation conditions of the rectification tower, the conditions of the adsorption desulfurization reaction and the normalization reaction are exactly the same as those of Example 2b, and the difference is the fixed bed hydrogenation reaction conditions.
- reaction conditions of fixed bed hydrogenation reactor reaction temperature 180°C, reaction pressure 1.0MPa, hydrogen oil volume ratio 100:1, volume space velocity 3.0h -1 , benzene removal rate 100%;
- the product of the first rectification tower is 1.2mgBr/100g, which meets the requirements of pentane blowing agent; the bromine index of C7 and above components at the bottom of the tower is 3.5mgBr/100g, which meets the requirements of 120# solvent oil;
- the obtained product the purity of n-hexane is 88wt%, and the yield is 53%; the purity of cyclohexane is >99wt%; the C5 component meets the standard requirement of pentane blowing agent; the C7 and above components meet the standard requirement of 120# solvent oil.
- the raw materials used, the process flow, the operating conditions of the rectification tower, the conditions of the adsorption desulfurization reaction and the fixed bed hydrogenation reaction are exactly the same as those of Example 2b, and the difference is the normalization reaction conditions.
- reaction conditions of the normalization reactor are: reaction temperature 300°C, reaction pressure 2.0MPa, hydrogen oil volume ratio 200:1, volume space velocity 1.5h -1 , conversion rate 73%, selectivity >99wt%;
- the obtained product the purity of n-hexane is 82wt%, and the yield is 52%; the purity of cyclohexane is >99wt%; the C5 component meets the standard requirement of pentane blowing agent; the C7 and above components meet the standard requirement of 120# solvent oil.
- This comparative example provides a kind of method of reforming raffinate production solvent oil:
- the raw materials used, the process flow, the operation conditions of the rectification tower, the conditions of the adsorption desulfurization reaction and the normalization reaction are exactly the same as those of Example 2b, and the difference is the fixed bed hydrogenation reaction conditions.
- reaction conditions of fixed bed hydrogenation reactor reaction temperature 80°C, reaction pressure 1.0MPa, hydrogen oil volume ratio 100:1, volume space velocity 3.0h -1 , benzene removal rate 83%;
- the product of the first rectification tower the bromine index of C5 component at the top of the tower is 121.2mgBr/100g, which does not meet the requirements of pentane blowing agent; the bromine index of C7 and above components at the bottom of the tower is 133.7mgBr/100g, which does not meet the requirements of 120# solvent oil Require;
- This comparative example provides a kind of method for reforming raffinate to produce solvent oil, and used raw material is identical with embodiment 2b, and this method comprises:
- the raw material of reformed raffinate is first debenzene and deolefinization in a hydrogenation reactor, and the catalyst used is a conventional hydrogenation deolefination catalyst;
- reaction conditions of the hydrogenation reactor are: reaction temperature 120°C, reaction pressure 1.0MPa, hydrogen oil volume ratio 100:1, volume space velocity 3.0h -1 , benzene removal rate 82%;
- the preparation method is as follows: Weigh 82.9 g of aluminum nitrate nonahydrate, make it into a constant volume of 240 ml, and prepare a 1 mol/L aluminum nitrate solution. Measure 190ml of 1mol/L nickel nitrate solution, 30ml of 1mol/L magnesium nitrate solution and 170ml of 1mol/L aluminum nitrate solution and mix them evenly to form a mixed metal solution for use. Measure 1.5mol/L potassium carbonate as 1000ml of precipitant solution and set it aside. Add 40ml of clean water into the reaction kettle, turn on the stirring speed of 250rmp, and heat to the reaction temperature of 50°C.
- the mixed metal solution and the precipitant solution were added in parallel at 35ml/min and 71ml/min respectively, and the pH value was kept constant at 9.
- the solution was added dropwise, it was stirred and aged at 50° C. for 2 h.
- the resulting material was filtered and washed until the filtrate was neutral.
- the filter cake was dried in an oven at 120°C for 4 hours, and after grinding, it was roasted in a muffle furnace at 500°C for 5 hours and ground to obtain the catalyst
- the hydrogenation reaction product enters the separator for gas-liquid separation, the liquid product is discharged from the bottom, and the hydrogen-rich gas discharged from the top is mixed with the new hydrogen of the reforming unit, and is used as circulating hydrogen after being boosted by the circulating hydrogen compressor;
- the liquid product at the bottom of the separator enters the first rectification tower for fractionation, the C5 component is discharged from the top of the tower, the C6 component is discharged from the side line, and the C7 and above components are discharged from the bottom of the tower;
- the operating conditions of the first rectification tower the pressure inside the tower is 0.1MPa, the temperature at the top of the tower is 40°C, the temperature at the bottom of the tower is 102°C, the C5 component at the top of the tower is a pentane blowing agent, and the bromine index is 131.1mgBr/100g, which does not meet the requirements of pentane blowing agent.
- Foaming agent requirements, the bromine index of C7 and above components at the bottom of the tower is 138.9mgBr/100g, which does not meet the requirements of 120# solvent oil;
- the C6 component enters the second rectification tower for fractionation, the top of the tower is a mixture of n-hexane and isohexane, and the bottom of the tower is cyclohexane;
- n-hexane and isohexane enters the third rectification tower for fractionation, the top of the tower is isohexane, and the bottom of the tower is n-hexane;
- This comparative example obtains the product: the purity of normal hexane is 88wt%, and the yield is 31%; The purity of isohexane is 91wt% (can be used as 6# solvent oil), and the purity of cyclohexane>99wt%.
- Table 2 shows the evaluation results of the products of Example 2a-Example 2e and Comparative Example 1 to Comparative Example 2.
- Comparative Example 2 adopts the process of hydrogenation first and then cutting, and treats the reformed raffinate with a conventional hydrogenation catalyst. Due to the slightly poor hydrogenation performance of the catalyst, the removal rate of olefins and benzene is low, and the C5 component cannot be recovered due to the presence of olefins.
- Example 2a to -Example 2e adopt the technological process of the present invention to treat the reformed raffinate, and realize the efficient utilization of the reformed raffinate by adding an adsorption desulfurization unit and a normalization reaction unit.
- embodiment 2a to embodiment 2c can realize the regulation and control of the purity and yield of n-hexane by adjusting the operating temperature of the rectifying tower top and bottom;
- embodiment 2b and embodiment 2d can be achieved by changing the operating temperature of the hydrogenation catalyst To achieve different degrees of removal of benzene and olefins.
- the operating temperature of the hydrogenation catalyst in Comparative Example 1 did not reach 90°C-200°C, and the removal of benzene and olefins was not complete;
- Example 2b, Example 2e By changing the normalization reaction conditions, different degrees of normalization of isohexane can be achieved to generate n-hexane, and the purity of n-hexane can be adjusted.
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Abstract
Provided are a method and a system for producing a solvent oil from a raffinate oil. The method comprises a hydrogenation reaction of the raffinate oil with a hydrogenation catalyst for removing aromatic hydrocarbons and olefins after desulfurization and dehydration, and a number of rectifications, so as to acquire the solvent oil. Also provided is a system for implementing the method. The method is suitable for the separation and utilization of raffinate oil with high aromatic hydrocarbon and olefin content, and can improve the added value of the raffinate oil.
Description
本发明涉及重整抽余油处理技术领域,尤其涉及一种重整抽余油生产溶剂油的方法及系统。The invention relates to the technical field of reformed raffinate treatment, in particular to a method and system for producing solvent oil from reformed raffinate.
重整抽余油是芳烃生产中的副产物,由于硫、氮和重金属等杂质含量很低,是良好的石油化工原料,根据沸点不同可分馏出不同的高附加值组分,适合生产优质的溶剂油和高附加值的己烷油和异己烷油等。Reformed raffinate is a by-product in the production of aromatics. Due to the low content of impurities such as sulfur, nitrogen and heavy metals, it is a good petrochemical raw material. According to different boiling points, different high value-added components can be distilled, which is suitable for the production of high-quality Solvent oil and high value-added hexane oil and isohexane oil, etc.
重整抽余油中含有少量的烯烃和芳烃等不饱和组分,严重影响抽余油作为高附加值溶剂油的性质。如:正己烷主要用于丙烯等烯烃聚合时的溶剂、食用植物油提取剂、橡胶和涂料溶剂以及颜料稀释剂等,对苯等不饱和烃具有明确限制;6#溶剂油是用作生产食用油脂的有机溶剂,生产过程中会在食用油脂中有部分残留,而溶剂油中的致癌物芳烃也会残留于食用油脂中,对人体产生危害,必须严格控制6#溶剂油中的芳烃含量;戊烷发泡剂主要用作溶剂、制造人造冰、麻醉剂等,明确要求溴指数≤100mgBr/100g。因此,要合理利用重整抽余油并赋予其更高的经济价值,必须进行加氢脱烯烃、脱芳烃处理脱除其中的不饱和烃。目前,代表性加氢脱烯烃、脱芳烃催化剂主要分为贵金属、非贵金属两大类,Ni、Pt、Pd三种金属催化剂应用较多。Pd加氢性能K
Pd为金属Ni的1/7,Pt活性K
Pt为Ni的2.5倍,但钯和铂的价格却比镍高至几百倍,且对原料中的硫、砷和其他有毒物质要求较高,
Reformed raffinate contains a small amount of unsaturated components such as olefins and aromatics, which seriously affects the properties of raffinate as high value-added solvent oil. For example: n-hexane is mainly used as solvent for the polymerization of olefins such as propylene, edible vegetable oil extractant, rubber and paint solvent, and pigment thinner, etc., with clear restrictions on unsaturated hydrocarbons such as benzene; 6# solvent oil is used for the production of edible oils and fats During the production process, there will be some residues in the edible oil, and the carcinogenic aromatic hydrocarbons in the solvent oil will also remain in the edible oil, which will cause harm to the human body. The content of the aromatic hydrocarbons in the 6# solvent oil must be strictly controlled; Alkanes blowing agents are mainly used as solvents, making artificial ice, anesthetics, etc., and the bromine index is clearly required to be ≤100mgBr/100g. Therefore, in order to rationally utilize reformed raffinate and endow it with higher economic value, it is necessary to carry out hydrodealkenization and dearomatization to remove unsaturated hydrocarbons. At present, representative hydrodeolefination and dearomatization catalysts are mainly divided into two categories: noble metals and non-noble metals, and Ni, Pt, and Pd three metal catalysts are widely used. Pd hydrogenation performance K Pd is 1/7 of metal Ni, Pt activity K Pt is 2.5 times that of Ni, but the price of palladium and platinum is hundreds of times higher than nickel, and it is toxic to sulfur, arsenic and other materials in raw materials Material requirements are high,
目前,重整抽余油生产高附加值产品,根据原料性质及产品需求不同采用的工艺流程也不尽相同,主要包括先加氢再分馏、先分馏再加氢两种。苯和烯烃含量偏高时基本采用先加氢再分馏的工艺流程,以保证产品苯含量符合标准要求;苯和烯烃含量偏低时基本采用先分馏再加氢的工艺流程,加氢操作负荷较小,但对氢气纯度要求较高。分馏过程中由于存在组分共沸现象对塔板数及塔的个数要求不同。同时,镍系加氢脱烯脱苯催化剂在高温下热稳性较差,NiO粒子易团聚和烧结,存在分散度差利用率等问题,并且由于原料中硫、氮和重金属等杂质易导致催化剂中毒,影响催化剂使用寿命,导致操作成本增加,需要对原料进行预处理。因此,现有工艺流程常存在重整抽余油利用率低、加工产品单一、产品收率偏低及加氢催化剂运行周期短、提温不敏感等问题,需要综合考虑原料性质、产品种类、催化剂稳定性及抗硫性、分馏精度等多方面因素以实现重整抽余油的高效利用。At present, the process of reforming raffinate to produce high value-added products varies according to the nature of raw materials and product requirements, mainly including hydrogenation followed by fractionation, and fractionation followed by hydrogenation. When the content of benzene and olefins is high, the technological process of first hydrogenation and then fractionation is basically used to ensure that the benzene content of the product meets the standard requirements; Small, but higher requirements for hydrogen purity. Due to the existence of component azeotropy in the fractionation process, the requirements for the number of trays and columns are different. At the same time, nickel-based hydrodeenification and debenzene catalysts have poor thermal stability at high temperatures, NiO particles are easy to agglomerate and sinter, and there are problems such as poor dispersion and utilization, and impurities such as sulfur, nitrogen, and heavy metals in the raw materials are easy to cause catalyst degradation. Poisoning will affect the service life of the catalyst and lead to increased operating costs, requiring pretreatment of raw materials. Therefore, the existing process often has problems such as low utilization rate of reformed raffinate, single processed product, low product yield, short operating cycle of hydrogenation catalyst, and insensitivity to temperature rise. It is necessary to comprehensively consider the nature of raw materials, product types, Catalyst stability, sulfur resistance, fractionation precision and other factors to achieve efficient utilization of reformed raffinate.
对于采用先分馏后加氢的工艺,C5及以下组分未经加氢饱和处理易导致苯及溴指数不合格无法满足戊烷发泡剂要求,不适合苯含量偏高的原料;物流II中为C6混合物,存在异构化转化率低的问题;加氢、异构化产品未经过气液分离导致后续分馏过程中异己烷中轻烃组分偏高;进入加氢反应器的原料未经过脱硫处理,易导致加氢催化剂中毒失活。For the process of hydrogenation after fractional distillation, C5 and below components without hydrogenation saturation treatment will easily lead to unqualified benzene and bromine index and cannot meet the requirements of pentane blowing agent, and are not suitable for raw materials with high benzene content; in logistics II It is a C6 mixture, which has the problem of low isomerization conversion rate; hydrogenation and isomerization products have not undergone gas-liquid separation, resulting in high light hydrocarbon components in isohexane in the subsequent fractionation process; raw materials entering the hydrogenation reactor have not undergone Desulfurization treatment can easily lead to poisoning and deactivation of the hydrogenation catalyst.
对于采用先加氢后分离的工艺,在进行精馏处理时,环丁砜、水和杂质从塔底排出,易造成部分重馏分流失影响120#溶剂油收率,同时未对精馏塔顶C6产物进行精馏分离易导致正己烷收率偏低、无法生产价格优于6#溶剂油的高纯度正己烷,未实现抽余油的高效利用。For the process of separation after hydrogenation, during rectification treatment, sulfolane, water and impurities are discharged from the bottom of the tower, which will easily cause the loss of some heavy fractions and affect the yield of 120# solvent oil. At the same time, the C6 product at the top of the rectification tower is not treated Carrying out rectification and separation will easily lead to a low yield of n-hexane, and it is impossible to produce high-purity n-hexane whose price is better than 6# solvent oil, and the efficient utilization of raffinate oil has not been realized.
同时,有文献或宣传报道重整抽余油生产溶剂油过程采用两段加氢工艺流程进行加氢脱苯,第一段采用加氢脱硫催化剂脱除环丁砜以保护后续催化剂,第二段采用高镍加氢催化剂脱除苯,但由于加氢脱硫催化剂需要先预硫化,而第二段催化剂需要先预还原,两者无法同时操作,开工过程繁琐,且第一段的残留硫化油势必也会对第二段催化剂造成影响,因此需要大量原料油进行冲洗,影响装置开工周期。At the same time, there are literature or publicity reports that the process of reforming raffinate to produce solvent oil uses a two-stage hydrogenation process for hydrodebenzene hydrogenation. The first stage uses a hydrodesulfurization catalyst to remove sulfolane to protect the subsequent catalyst. Nickel hydrogenation catalyst removes benzene, but since the hydrodesulfurization catalyst needs to be presulfided first, and the second stage catalyst needs to be prereduced first, the two cannot be operated at the same time, the start-up process is cumbersome, and the residual sulfurized oil in the first stage will inevitably It affects the catalyst in the second stage, so a large amount of raw material oil is required for flushing, which affects the start-up period of the unit.
发明内容Contents of the invention
为了解决上述问题,本发明的目的在于提供一种重整抽余油生产溶剂油的方法及系统。该方法适用于苯和烯烃含量偏高的重整抽余油的分离和利用,可以利用重整抽余油生产多种溶剂油,有效提升重整抽余油附加值。In order to solve the above problems, the object of the present invention is to provide a method and system for producing solvent oil by reforming raffinate oil. The method is suitable for the separation and utilization of the reformed raffinate with high benzene and olefin content, and can use the reformed raffinate to produce various solvent oils, effectively increasing the added value of the reformed raffinate.
为了达到上述目的,本发明提供了一种加氢催化剂,该催化剂包括载体、负载于载体的第一活性金属组分和第二活性金属组分,其中,所述第一活性金属组分的金属元素包括镍,以催化剂总重量为100%计,所述第一活性金属组分在所述催化剂中的重量含量为40-70%,所述载体(以氧化物计)在所述催化剂中的重量含量为20-59%,余量为第二活性金属组分。In order to achieve the above object, the present invention provides a hydrogenation catalyst comprising a carrier, a first active metal component loaded on the carrier and a second active metal component, wherein the metal of the first active metal component Elements include nickel, based on the total weight of the catalyst as 100%, the weight content of the first active metal component in the catalyst is 40-70%, and the carrier (calculated as oxide) in the catalyst The weight content is 20-59%, and the balance is the second active metal component.
在本发明的具体实施方案中,相比于现有的镍系催化剂和加氢催化剂,本发明提供的加氢催化剂中镍含量更高,并且Ni金属的分散度更高、可以达到10%以上,具有更多的加氢活性中心,因此该加氢催化剂对苯、烯烃的脱除效果更好、脱除更彻底。In a specific embodiment of the present invention, compared with existing nickel-based catalysts and hydrogenation catalysts, the nickel content in the hydrogenation catalyst provided by the invention is higher, and the dispersion of Ni metal is higher, which can reach more than 10% , has more hydrogenation active centers, so the hydrogenation catalyst has a better and more thorough removal effect on benzene and olefins.
在上述加氢催化剂中,所述第一活性金属组分在所述催化剂中的重量一般控制为40-70%,例如40%、45%、50%、55%、60%、65%、70%或其中的任意两者组成的范围。In the above-mentioned hydrogenation catalyst, the weight of the first active metal component in the catalyst is generally controlled to be 40-70%, such as 40%, 45%, 50%, 55%, 60%, 65%, 70% % or a range consisting of any two of them.
在上述加氢催化剂中,所述载体在所述催化剂中的重量含量为20-59%,例如20%、25%、30%、35%、40%、45%、50%、55%、59%或其中的任意两者组成的范围。In the above hydrogenation catalyst, the weight content of the carrier in the catalyst is 20-59%, such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 59% % or a range consisting of any two of them.
在本发明的具体实施方案中,所述加氢催化剂的比表面积一般为200-500m
2/g,例如200m
2/g、250m
2/g、300m
2/g、350m
2/g、400m
2/g、450m
2/g、500m
2/g或其中的任意两者组成的范围。
In a specific embodiment of the present invention, the specific surface area of the hydrogenation catalyst is generally 200-500m 2 /g, such as 200m 2 /g, 250m 2 /g, 300m 2 /g, 350m 2 /g, 400m 2 / g g, 450m 2 /g, 500m 2 /g or any combination thereof.
在本发明的具体实施方案中,所述加氢催化剂的孔容一般为0.3-0.6cm
3/g,例如0.3cm
3/g、0.35cm
3/g、0.4cm
3/g、0.45cm
3/g、0.5cm
3/g、0.55cm
3/g、0.6cm
3/g或其中的任意两者组成的范围。
In a specific embodiment of the present invention, the pore volume of the hydrogenation catalyst is generally 0.3-0.6 cm 3 /g, such as 0.3 cm 3 /g, 0.35 cm 3 /g, 0.4 cm 3 / g, 0.45 cm 3 /g g, 0.5cm 3 /g, 0.55cm 3 /g, 0.6cm 3 /g or any combination thereof.
在本发明的具体实施方案中,所述载体一般为氧化物,例如可以包括氧化铝、氧化硅、氧化钛、氧化铈中的一种,也可以包括氧化硅、氧化钛、氧化铈中的至少一种与氧化铝的混合物。即,所述载体可以包括氧化铝、氧化硅、氧化钛、氧化铈中的一种或两种以上的组合,且氧化铝的含量不为0。In a specific embodiment of the present invention, the support is generally an oxide, for example, it may include one of alumina, silicon oxide, titanium oxide, and cerium oxide, and may also include at least one of silicon oxide, titanium oxide, and cerium oxide. A mixture with aluminum oxide. That is, the carrier may include one or a combination of two or more of alumina, silica, titania, and ceria, and the content of alumina is not zero.
在本发明的具体实施方案中,上述催化剂中的第一活性金属组分、第二活性金属组分通常是以金属氧化物形式存在。In a specific embodiment of the present invention, the first active metal component and the second active metal component in the above catalyst usually exist in the form of metal oxides.
在本发明的具体实施方案中,所述第二活性金属组分的金属元素可以包括铜、镧、镁等中的一种或两种以上的组合。在本发明的具体实施方案中,通过在催化剂制备过程中控制金属活性组分的共沉淀过程和沉淀pH值,可以提高催化剂中镍含量、镍分散度和加氢活性中心含量。In a specific embodiment of the present invention, the metal elements of the second active metal component may include one or a combination of two or more of copper, lanthanum, magnesium, and the like. In a specific embodiment of the present invention, by controlling the co-precipitation process of the metal active components and the precipitation pH value during the catalyst preparation process, the nickel content, nickel dispersion and hydrogenation active center content in the catalyst can be increased.
本发明进一步提供了上述加氢催化剂的制备方法,该制备方法包括:The present invention further provides the preparation method of above-mentioned hydrogenation catalyst, and this preparation method comprises:
使载体前驱体的浆液的温度达到沉淀反应温度,并调节使载体前驱体的浆液的pH值达到碱性pH值(pH值的调节可以通过加入沉淀剂实现),得到第一混合体系;Make the temperature of the slurry of the carrier precursor reach the precipitation reaction temperature, and adjust the pH value of the slurry of the carrier precursor to reach an alkaline pH value (the adjustment of the pH value can be realized by adding a precipitating agent), to obtain the first mixed system;
向所述第一混合体系同时加入第一活性金属组分前驱体、第二活性金属组分前驱体、沉淀剂,保持体系pH为碱性pH值,得到第二混合体系;Adding the first active metal component precursor, the second active metal component precursor, and the precipitant to the first mixed system at the same time, keeping the pH of the system at an alkaline pH value, to obtain a second mixed system;
将第二混合体系进行老化处理,将老化产物焙烧,得到所述加氢催化剂。The second mixed system is subjected to aging treatment, and the aged product is roasted to obtain the hydrogenation catalyst.
在上述制备方法中,所述载体前驱体在经过上述干燥、焙烧后转化为加氢催化剂的载体。在具体实施方案中,所述载体前驱体可以包括拟薄水铝石,则拟薄水铝石经干燥、焙烧后转化为氧化铝。In the above preparation method, the carrier precursor is transformed into a carrier of the hydrogenation catalyst after being dried and calcined. In a specific embodiment, the carrier precursor may include pseudo-boehmite, and then the pseudo-boehmite is converted into alumina after being dried and calcined.
在上述制备方法中,通过调整第一活性金属组分的前驱体种类、第二活性金属组分的前驱体种类以及沉淀剂前驱体的种类,可以提高催化剂中镍含量、镍分散度和加氢活性中心含量。In the above preparation method, by adjusting the precursor type of the first active metal component, the precursor type of the second active metal component and the type of precipitant precursor, the nickel content, nickel dispersion and hydrogenation in the catalyst can be improved. active center content.
在上述制备方法中,所述沉淀剂不仅可以用于调节pH值,还可沉淀第一活性金属组分前驱体中的金属元素和第二活性金属组分前驱体中的金属元素。具体地,所述沉淀 剂可以包括碱性沉淀剂,优选包括可溶性碳酸盐,例如包括碳酸钾和/或碳酸钠。In the above preparation method, the precipitating agent can not only be used to adjust the pH value, but also precipitate metal elements in the precursor of the first active metal component and metal elements in the precursor of the second active metal component. Specifically, the precipitant may include an alkaline precipitant, preferably a soluble carbonate, for example potassium carbonate and/or sodium carbonate.
在上述制备方法中,所述沉淀剂的用量可以根据调节pH值以及沉淀第一活性金属组分前驱体中的金属元素和第二活性金属组分前驱体中的金属元素所需用量确定。In the above preparation method, the amount of the precipitating agent can be determined according to the amount required for adjusting the pH value and precipitating the metal elements in the precursor of the first active metal component and the metal element in the precursor of the second active metal component.
在上述制备方法中,第一活性金属组分前驱体可以是第一活性金属组分中金属元素的化合物,例如包括第一活性金属组分中金属元素的金属盐,优选包括第一活性金属组分中金属元素的可溶性金属盐,例如包括第一活性金属组分中金属元素的硝酸盐,如硝酸镍等。In the above preparation method, the precursor of the first active metal component can be a compound of the metal element in the first active metal component, for example, a metal salt comprising the metal element in the first active metal component, preferably comprising the first active metal component The soluble metal salt of the metal element, for example, includes the nitrate of the metal element in the first active metal component, such as nickel nitrate and the like.
在上述制备方法中,第二活性金属组分前驱体可以是第二活性金属组分中金属元素的化合物,例如包括第二活性金属组分中金属元素的金属盐,优选包括第二活性金属组分中金属元素的可溶性金属盐,例如包括第二活性金属组分中金属元素的硝酸盐,如硝酸镁等。In the above preparation method, the precursor of the second active metal component can be a compound of the metal element in the second active metal component, for example, a metal salt comprising the metal element in the second active metal component, preferably comprising the second active metal component The soluble metal salt of the metal element, for example, includes the nitrate of the metal element in the second active metal component, such as magnesium nitrate and the like.
在上述制备方法中,所述载体前驱体、第一活性金属组分前驱体、第二活性金属组分前驱体的用量对应于上述加氢催化剂中载体、第一活性金属组分、第二活性金属组分的重量含量。In the above preparation method, the amount of the carrier precursor, the first active metal component precursor, and the second active metal component precursor corresponds to the amount of the carrier, the first active metal component, and the second active metal component in the above-mentioned hydrogenation catalyst. The weight content of metal components.
在发明的具体实施方案中,所述第一活性金属组分前驱体、第二活性金属组分前驱体可以以二者的混合溶液加入至第一混合体系中;所述沉淀剂也一般是以溶液形式加入第一混合反应体系中。通过将第一活性金属组分前驱体和第二活性金属组分前驱体的混合溶液以及沉淀剂溶液的并流加入方式、以及控制两种混合溶液的滴加速率,可以有效控制催化剂中镍含量、镍分散度和加氢活性中心含量。在具体实施方案中,所述第一活性金属组分前驱体和第二活性金属组分前驱体的混合溶液的滴加速率一般控制为20-100ml/min,所述沉淀剂溶液的滴加速率一般控制为10-300ml/min。In a specific embodiment of the invention, the first active metal component precursor and the second active metal component precursor can be added to the first mixing system as a mixed solution of the two; The solution form is added to the first mixed reaction system. By adding the mixed solution of the first active metal component precursor and the second active metal component precursor and the precipitant solution in parallel, and controlling the drop rate of the two mixed solutions, the nickel content in the catalyst can be effectively controlled , nickel dispersion and hydrogenation active center content. In a specific embodiment, the drop rate of the mixed solution of the first active metal component precursor and the second active metal component precursor is generally controlled to be 20-100ml/min, and the drop rate of the precipitant solution is The general control is 10-300ml/min.
在上述制备方法中,所述碱性pH值为8-11,例如8、9、10、11或其中的任意两者组成的范围。In the above preparation method, the alkaline pH value is 8-11, such as 8, 9, 10, 11 or any combination thereof.
在上述制备方法中,所述沉淀反应温度为40-90℃,例如40℃、50℃、60℃、70℃、80℃、90℃或其中的任意两者组成的范围。In the above preparation method, the precipitation reaction temperature is 40-90°C, such as 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or any combination thereof.
在上述制备方法中,所述老化处理的温度与所述沉淀反应温度可以相同或不同。所述老化处理的温度一般为40-90℃,例如40℃、50℃、60℃、70℃、80℃、90℃或其中的任意两者组成的范围。In the above preparation method, the aging treatment temperature may be the same as or different from the precipitation reaction temperature. The temperature of the aging treatment is generally 40-90°C, such as 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or any combination thereof.
在上述制备方法中,所述老化处理的时间一般控制为1-5h,例如1h、2h、3h、4h、5h或其中的任意两者组成的范围。In the above preparation method, the aging treatment time is generally controlled within 1-5 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or any combination thereof.
在上述制备方法中,所述焙烧的温度一般可以控制为300-600℃,例如300℃、350℃、400℃、450℃、500℃、550℃、600℃或其中的任意两者组成的范围。In the above preparation method, the temperature of the calcination can generally be controlled at 300-600°C, such as 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C or any combination thereof. .
在上述制备方法中,所述焙烧的时间一般为1-5h,例如1h、2h、3h、4h、5h或其中的任意两者组成的范围。In the above preparation method, the calcination time is generally 1-5h, such as 1h, 2h, 3h, 4h, 5h or any combination thereof.
在本发明的具体实施方案中,所述制备方法一般还包括在老化处理后、焙烧之前依次进行过滤、洗涤、干燥的操作。In a specific embodiment of the present invention, the preparation method generally further includes the operations of filtering, washing and drying in sequence after aging treatment and before roasting.
在上述制备方法中,所述洗涤一般在滤液达到中性时停止。将获得滤饼进行后续的干燥和焙烧。In the above preparation method, the washing generally stops when the filtrate reaches neutrality. The obtained filter cake is subjected to subsequent drying and roasting.
在上述制备方法中,所述干燥的温度可以为100-130℃,例如100℃、110℃、120℃、130℃或其中的任意两者组成的范围。In the above preparation method, the drying temperature may be in the range of 100-130°C, such as 100°C, 110°C, 120°C, 130°C or any combination thereof.
在上述制备方法中,所述干燥的时间一般为1-5h,例如1h、2h、3h、4h、5h或其中的任意两者组成的范围。In the above preparation method, the drying time is generally 1-5 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours or any combination thereof.
根据本发明的具体实施方案,上述加氢催化剂的制备方法可以包括:According to specific embodiments of the present invention, the preparation method of above-mentioned hydrogenation catalyst can comprise:
将载体前驱体与水形成的浆液边搅拌边升温至沉淀反应温度40-90℃,向该浆液中加入沉淀剂水溶液,使体系的pH值为8-11,得到第一混合体系;保持搅拌,向第一混合体系中同时加入第一活性金属组分前驱体和第二活性金属组分前驱体的混合水溶液(该混合水溶液可以是第一活性金属组分前驱体的水溶液和第二活性金属组分前驱体的水溶液混合形成的)以及沉淀剂的水溶液,保持体系pH值为8-11,得到第二混合体系;将第二混合体系在40-90℃进行老化处理1-5h,过滤、洗涤至滤液为中性,将滤饼干燥、300-600℃焙烧1-5h,得到所述加氢催化剂。Stirring the slurry formed by the carrier precursor and water to a precipitation reaction temperature of 40-90°C, adding a precipitating agent aqueous solution to the slurry to make the pH of the system 8-11 to obtain the first mixed system; keep stirring, Add the mixed aqueous solution of the first active metal component precursor and the second active metal component precursor simultaneously in the first mixed system (this mixed aqueous solution can be the aqueous solution of the first active metal component precursor and the second active metal component The aqueous solution of the precursor) and the aqueous solution of the precipitating agent are kept, and the pH value of the system is kept at 8-11 to obtain the second mixed system; the second mixed system is subjected to aging treatment at 40-90°C for 1-5h, filtered and washed Until the filtrate is neutral, the filter cake is dried and calcined at 300-600° C. for 1-5 hours to obtain the hydrogenation catalyst.
本发明还提供了一种重整抽余油生产溶剂油的方法,该方法包括:The present invention also provides a method for reforming raffinate to produce solvent oil, the method comprising:
S2、利用加氢催化剂,催化经过脱硫脱水的重整抽余油进行加氢脱苯、脱烯烃反应,得到反应产物;其中,所述加氢催化剂包括上述加氢催化剂;S2. Using a hydrogenation catalyst to catalyze the desulfurization and dehydration of the reformed raffinate to undergo hydrodebenzene and deolefination reactions to obtain a reaction product; wherein the hydrogenation catalyst includes the above-mentioned hydrogenation catalyst;
S3、对S2得到的反应产物进行气液分离;S3, performing gas-liquid separation on the reaction product obtained in S2;
S4、将分离得到的液体进行精馏,分别馏出C5组分、C6组分和C7以上组分;S4, performing rectification on the separated liquid, respectively distilling out C5 components, C6 components and C7 or more components;
S5、对所述C6组分进行精馏,分别馏出环己烷以及正己烷和异己烷的混合物;S5, performing rectification on the C6 component, and distilling off the mixture of cyclohexane and n-hexane and isohexane respectively;
S6、对所述正己烷和异己烷的混合物进行精馏,分别馏出异己烷和正己烷,完成溶剂油的生产。S6. Perform rectification on the mixture of n-hexane and isohexane to distill off isohexane and n-hexane respectively to complete the production of solvent oil.
在本发明的具体实施方案中,以体积百分含量计,在未经脱硫、脱水的重整抽余油中,硫含量为20mg/kg以下,苯含量为3-5v%,烯烃含量为1-3v%,正己烷与异己烷的 总含量大于50v%。In a specific embodiment of the present invention, in terms of volume percentage, in reformed raffinate without desulfurization and dehydration, the sulfur content is below 20 mg/kg, the benzene content is 3-5v%, and the olefin content is 1 -3v%, the total content of n-hexane and isohexane is greater than 50v%.
在本发明的具体实施方案中,上述方法还包括:S1、对重整抽余油进行脱硫、脱水处理,产品S≤1mg/kg。In a specific embodiment of the present invention, the above method further includes: S1, performing desulfurization and dehydration treatment on the reformed raffinate, and the product S≤1mg/kg.
在本发明的具体实施方案中,在S1中,所述脱硫、脱水过程中的空速为1-10h
-1;
In a specific embodiment of the present invention, in S1, the space velocity in the desulfurization and dehydration process is 1-10h -1 ;
在本发明的具体实施方案中,S1中脱硫脱水的过程采用的吸附剂包括分子筛吸附剂,例如3A分子筛、4A分子筛、5A分子筛和13A分子筛中的一种或两种以上的组合;In a specific embodiment of the present invention, the adsorbent used in the desulfurization and dehydration process in S1 includes a molecular sieve adsorbent, such as one or more combinations of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and 13A molecular sieve;
在本发明的具体实施方案中,S1所用的分子筛吸附剂的比表面积一般为400-700m
2/g。分子筛吸附剂的孔容一般为0.05-0.30cm
3/g。
In a specific embodiment of the present invention, the molecular sieve adsorbent used in S1 generally has a specific surface area of 400-700 m 2 /g. The pore volume of the molecular sieve adsorbent is generally 0.05-0.30 cm 3 /g.
在本发明的具体实施方案中,S2中,加氢催化剂可以有效去除重整余油中的苯和烯烃。根据本发明的具体实施方案,在S2得到的反应产物中,苯含量≤0.01%,溴指数≤50mgBr/100g。In a specific embodiment of the present invention, in S2, the hydrogenation catalyst can effectively remove benzene and olefins in the reformed residual oil. According to a specific embodiment of the present invention, in the reaction product obtained in S2, the benzene content is ≤0.01%, and the bromine index is ≤50mgBr/100g.
在本发明的具体实施方案中,S2中,所述加氢脱苯、脱烯烃反应的条件一般可以控制为:温度90-200℃、反应压力1.0-3.0MPa、氢油体积比100-300:1、体积空速1.0-3.0h
-1;
In a specific embodiment of the present invention, in S2, the conditions of the hydrodebenzene and deolefination reactions can generally be controlled as follows: temperature 90-200°C, reaction pressure 1.0-3.0MPa, hydrogen-to-oil volume ratio 100-300: 1. Volumetric space velocity 1.0-3.0h -1 ;
在本发明的具体实施方案中,S4中,所述精馏的压力一般为0-0.2MPa。In a specific embodiment of the present invention, in S4, the pressure of the rectification is generally 0-0.2 MPa.
在本发明的具体实施方案中,S4的精馏过程可以在精馏塔内完成,则精馏塔的塔顶温度可以为30-50℃、塔底温度可以为90-110℃、塔内压力为0-0.2MPa。In a specific embodiment of the present invention, the rectification process of S4 can be completed in the rectification tower, then the tower top temperature of the rectification tower can be 30-50 ℃, the tower bottom temperature can be 90-110 ℃, the pressure in the tower 0-0.2MPa.
在本发明的具体实施方案中,S5中,所述精馏的压力一般为0-0.1MPa。In a specific embodiment of the present invention, in S5, the pressure of the rectification is generally 0-0.1 MPa.
在本发明的具体实施方案中,S5的精馏过程可以在精馏塔内完成,精馏塔的塔顶温度为55-75℃、塔底温度为70-90℃、塔内的压力为0-0.1MPa。In a specific embodiment of the present invention, the rectification process of S5 can be completed in the rectification tower, the tower top temperature of the rectification tower is 55-75 ℃, the bottom temperature is 70-90 ℃, and the pressure in the tower is 0 -0.1 MPa.
在本发明的具体实施方案中,S6中,所述精馏的压力为0-0.1MPa。In a specific embodiment of the present invention, in S6, the pressure of the rectification is 0-0.1 MPa.
在本发明的具体实施方案中,S6的精馏过程可以在精馏塔内完成,精馏塔的塔顶温度为50-70℃、塔底温度为60-80℃、塔内压力为0-0.1MPa。In a specific embodiment of the present invention, the rectification process of S6 can be completed in the rectification tower, the tower top temperature of the rectification tower is 50-70 DEG C, the tower bottom temperature is 60-80 DEG C, and the pressure in the tower is 0-80 DEG C. 0.1 MPa.
在本发明的具体实施方案中,S6得到的异己烷可直接作为6#溶剂油输出,根据实际需要,S6得到的异己烷也可通过正构化反应转化为正己烷,该正己烷产品纯度≥80%。In a specific embodiment of the present invention, the isohexane obtained in S6 can be directly exported as 6# solvent oil. According to actual needs, the isohexane obtained in S6 can also be converted into normal hexane by normalization reaction, and the purity of the normal hexane product is ≥ 80%.
在本发明的具体实施方案中,该方法还包括:S7、将S6得到的异己烷通过正构化反应转化为正己烷。In a specific embodiment of the present invention, the method further includes: S7, converting the isohexane obtained in S6 into normal hexane through a normalization reaction.
在本发明的具体实施方案中,S7中,所述正构化反应的条件为:反应温度200-400℃、反应压力1.0-3.0MPa、氢油体积比100-300:1、体积空速1.0-3.0h
-1。
In a specific embodiment of the present invention, in S7, the conditions of the normalization reaction are: reaction temperature 200-400°C, reaction pressure 1.0-3.0MPa, hydrogen-oil volume ratio 100-300:1, volume space velocity 1.0 -3.0h -1 .
在本发明的具体实施方案中,S7中,正构化反应的催化剂可以是分子筛催化剂。具体地,该分子筛催化剂可以包括第三活性金属组分、非分子筛载体和分子筛载体。In a specific embodiment of the present invention, in S7, the catalyst for the normalization reaction may be a molecular sieve catalyst. Specifically, the molecular sieve catalyst may include a third active metal component, a non-molecular sieve support and a molecular sieve support.
在上述分子筛催化剂中,所述分子筛载体包括MOR、MCM-41、ZSM-22、SAPO-11的一种或两种以上的组合。In the above molecular sieve catalyst, the molecular sieve carrier includes one or a combination of two or more of MOR, MCM-41, ZSM-22 and SAPO-11.
在上述分子筛催化剂中,所述第三活性金属组分的金属元素可以包括第VIB和/或第VIII族中的元素。在具体实施方案中,第三活性金属组分通常以金属氧化物形式存在。In the above molecular sieve catalyst, the metal elements of the third active metal component may include elements in Group VIB and/or Group VIII. In particular embodiments, the third active metal component is generally present in the form of a metal oxide.
在上述分子筛催化剂中,所述非分子筛载体包括氧化铝。In the above molecular sieve catalyst, the non-molecular sieve support comprises alumina.
在上述分子筛催化剂中,以所述分子筛催化剂的总重量为100%计,所述分子筛载体的重量占催化剂总重的10-80%、所述第三活性金属组分(以氧化物计)的重量占催化剂总重的0.01-5%(例如0.1-0.5%),余量为非分子筛载体。In the above-mentioned molecular sieve catalyst, based on the total weight of the molecular sieve catalyst as 100%, the weight of the molecular sieve carrier accounts for 10-80% of the total weight of the catalyst, and the third active metal component (calculated as oxide) The weight accounts for 0.01-5% (such as 0.1-0.5%) of the total weight of the catalyst, and the rest is non-molecular sieve carrier.
在本发明的具体实施方案中,S7中,正构化反应的原料异己烷的纯度在90%以上,优选为95%以上。In a specific embodiment of the present invention, in S7, the purity of isohexane, the raw material for the normalization reaction, is above 90%, preferably above 95%.
在本发明的具体实施方案中,所述重整抽余油生产溶剂油的方法具体可以包括:In a specific embodiment of the present invention, the method for producing solvent oil from the reformed raffinate may specifically include:
S1、利用分子筛吸附剂对重整抽余油进行脱硫、脱水;S1. Using molecular sieve adsorbent to desulfurize and dehydrate the reformed raffinate;
S2、利用加氢催化剂,催化经过脱硫脱水的重整抽余油进行加氢脱苯、脱烯烃反应,得到反应产物;其中,所述加氢催化剂包括上述加氢催化剂;S2. Using a hydrogenation catalyst to catalyze the desulfurization and dehydration of the reformed raffinate to undergo hydrodebenzene and deolefination reactions to obtain a reaction product; wherein the hydrogenation catalyst includes the above-mentioned hydrogenation catalyst;
S3、对S2得到的反应产物进行气液分离,输出富氢气体和液体;S3, performing gas-liquid separation on the reaction product obtained in S2, and outputting hydrogen-rich gas and liquid;
S4、将分离得到的液体进行精馏,分别馏出C5组分(可作为戊烷发泡剂)、C6组分和C7以上组分(可作为120#溶剂油);S4, carry out rectification with the separated liquid, distill out C5 component (can be used as pentane blowing agent), C6 component and C7 above component (can be used as 120# solvent oil) respectively;
S5、对所述C6组分进行精馏,分别馏出环己烷以及正己烷和异己烷的混合物;S5, performing rectification on the C6 component, and distilling off the mixture of cyclohexane and n-hexane and isohexane respectively;
S6、对所述正己烷和异己烷的混合物进行精馏,分别馏出异己烷和正己烷;S6. Rectifying the mixture of n-hexane and isohexane to distill out isohexane and n-hexane respectively;
S7、将S6得到的异己烷通过正构化反应转化为正己烷,完成溶剂油的生产。S7, converting the isohexane obtained in S6 into normal hexane through a normalization reaction to complete the production of solvent oil.
本发明还提供了一种重整抽余油生产溶剂油的系统,该系统能够实现上述重整抽余油生产溶剂油的方法。The present invention also provides a system for producing solvent oil by reforming raffinate oil, which can realize the method for producing solvent oil by reforming raffinate oil.
在本发明的具体实施方案中,所述重整抽余油生产溶剂油的系统包括依次连接的脱附脱硫反应器、加氢反应器、第一气液分离器、第一精馏塔、第二精馏塔、第三精馏塔。In a specific embodiment of the present invention, the system for producing solvent oil from the reforming raffinate includes a desorption and desulfurization reactor, a hydrogenation reactor, a first gas-liquid separator, a first rectification tower, and a second desulfurization reactor connected in sequence. The second rectification tower and the third rectification tower.
上述系统中各装置的连接关系可以是:所述脱附脱硫反应器的入口用于接收重整抽余油、该入口一般位于塔顶;The connection relationship of each device in the above system can be: the inlet of the desorption and desulfurization reactor is used to receive the reformed raffinate, and the inlet is generally located at the top of the tower;
所述脱附脱硫反应器位于塔底的出口与加氢反应器的入口(位于塔顶)连接;The outlet of the desorption and desulfurization reactor at the bottom of the tower is connected with the inlet of the hydrogenation reactor (at the top of the tower);
所述加氢反应器位于塔底的出口与第一气液分离器的入口(位于侧线)连接;The outlet of the hydrogenation reactor at the bottom of the tower is connected with the inlet (located at the side line) of the first gas-liquid separator;
所述第一气液分离器的位于塔底的出口与第一精馏塔的入口(位于侧线)连接;The outlet at the bottom of the first gas-liquid separator is connected with the inlet (at the side line) of the first rectifying tower;
所述第一精馏塔位于测线的出口与第二精馏塔的入口连接;The outlet of the first rectification tower located at the measuring line is connected with the inlet of the second rectification tower;
所述第二精馏塔位于塔顶的出口与第三精馏塔的入口连接;The outlet of the second rectifying tower located at the top of the tower is connected with the inlet of the third rectifying tower;
所述第三精馏塔位于塔顶的出口用于输出异己烷。The outlet of the third rectifying column at the top of the column is used to output isohexane.
在上述系统中,所述第一气液分离器位于塔顶的出口用于输出氢气,所述第一精馏塔位于塔顶的出口用于输出C5组分,所述第一精馏塔位于塔底的出口用于输出C7以上组分,所述第一精馏塔位于测线的出口用于输出C6组分,所述第二精馏塔位于塔顶的出口用于输出正己烷和异己烷的混合物,所述第二精馏塔位于塔底的出口用于输出环己烷,所述第三精馏塔位于塔底的出口用于输出正己烷,所述第三精馏塔位于塔顶的出口用于输出异己烷。In the above system, the outlet of the first gas-liquid separator at the top of the tower is used to output hydrogen, the outlet of the first rectification tower at the top of the tower is used to output C5 components, and the first rectification tower is located at The outlet at the bottom of the tower is used to output components above C7, the outlet of the first rectification column at the measuring line is used to output C6 components, and the outlet at the top of the second rectification column is used to output n-hexane and isohexane The mixture of alkanes, the outlet of the second rectification tower at the bottom of the tower is used to export cyclohexane, the outlet of the third rectification tower at the bottom of the tower is used to output normal hexane, and the third rectification tower is located at the bottom of the tower The top outlet is used to output isohexane.
在本发明的具体实施方案中,所述重整抽余油生产溶剂油的系统还包括正构化反应器和第二气液分离器,所述正构化反应器的入口与所述第三精馏塔位于塔顶的出口连接,所述正构化反应器的出口与所述第二气液分离器的入口(位于侧线)连接,第二气液分离器的位于塔顶的出口用于输出氢气,第二气液分离器位于塔底的出口用于输出正己烷。In a specific embodiment of the present invention, the system for producing solvent oil from the reforming raffinate also includes a normalization reactor and a second gas-liquid separator, and the inlet of the normalization reactor is connected to the third The rectifying tower is connected at the outlet at the top of the tower, and the outlet of the normalization reactor is connected with the inlet (at the side line) of the second gas-liquid separator, and the outlet at the top of the second gas-liquid separator is used for Hydrogen is output, and the outlet of the second gas-liquid separator at the bottom of the tower is used to output n-hexane.
在本发明的具体实施方案中,上述系统还可以包括氢气管线,该氢气管线用于向加氢反应器和/或正构化反应器补充氢气。该氢气管线可以设有循环氢压缩机,该压缩机的入口可以与第一气液分离器和/或第二气液分离器的气体出口连接,即,该压缩机可以由第一气液分离器、第二气液分离器供气。In a specific embodiment of the present invention, the above-mentioned system may further include a hydrogen pipeline, which is used to supplement hydrogen to the hydrogenation reactor and/or the normalization reactor. The hydrogen pipeline can be provided with a circulating hydrogen compressor, and the inlet of the compressor can be connected with the gas outlet of the first gas-liquid separator and/or the second gas-liquid separator, that is, the compressor can be separated by the first gas-liquid device, the second gas-liquid separator gas supply.
本发明的有益效果在于:The beneficial effects of the present invention are:
1、本发明提供的方法通过在吸附反应器内装填分子筛吸附剂对原料预处理,进行脱硫、脱水及脱杂质以解决现有技术中重整抽余油原料中环丁砜造成后续加氢脱苯催化剂中毒的问题,有效保护后续加氢脱烯烃、脱苯单元高镍加氢催化剂使用寿命,延长装置运行周期,减少由于频繁更换催化剂带来的运行成本增加,并且分离出的C7以上组分满足120#溶剂油硫含量要求;同时避免了现有技术中由于加氢脱硫催化剂需要预硫化造成装置开工过程繁琐,且残留硫化油难置换影响装置开工周期的问题。1. The method provided by the present invention pretreats the raw material by filling the adsorption reactor with a molecular sieve adsorbent, and performs desulfurization, dehydration and impurity removal to solve the subsequent hydrodebenzene catalyst caused by sulfolane in the reforming raffinate raw material in the prior art. The problem of poisoning can effectively protect the service life of high-nickel hydrogenation catalysts in subsequent hydrodeolefins and debenzene units, prolong the operation period of the unit, reduce the increase in operating costs caused by frequent replacement of catalysts, and the separated components above C7 meet 120 # Solvent oil sulfur content requirements; at the same time, it avoids the cumbersome start-up process of the device due to the need for pre-sulfurization of the hydrodesulfurization catalyst in the prior art, and the difficult replacement of residual sulfide oil affects the start-up period of the device.
2、本发明提供的方法可以根据原料组成、沸点不同,从分子炼油角度出发逐级设置精馏单元,并利用异己烷正构化反应,提高正己烷纯度及收率,生产正己烷、戊烷发泡剂和120#溶剂油,实现重整抽余油高效利用。有效解决重整抽余油利用率低、加工产品单一、产品收率偏低等问题。2. According to the composition and boiling point of the raw materials, the method provided by the present invention can set up rectification units step by step from the perspective of molecular oil refining, and use isohexane normalization reaction to improve the purity and yield of n-hexane to produce n-hexane and pentane Foaming agent and 120# solvent oil to realize efficient utilization of reforming raffinate. Effectively solve the problems of low utilization rate of reforming raffinate, single processed product, and low product yield.
3、本发明提供的镍基加氢催化剂能够实现高含量的镍活性组分在载体氧化铝上的高度分散,对重整抽余油进行加氢脱烯烃、脱苯反应,保障了加氢装置的运行周期。3. The nickel-based hydrogenation catalyst provided by the present invention can realize the high dispersion of high-content nickel active components on the carrier alumina, and carry out hydrodeolefination and debenzene reactions on the reformed raffinate, ensuring the hydrogenation unit operating cycle.
图1为本发明的重整抽余油生产溶剂油的工艺流程图及系统连接示意图。Fig. 1 is a process flow diagram and a schematic diagram of system connection for producing solvent oil from reformed raffinate according to the present invention.
主要组件符号说明:Description of main component symbols:
吸附脱硫反应器1、加氢反应器2、第一气液分离器3、第一精馏塔4、第二精馏塔5、第三精馏塔6、正构化反应器7、第二气液分离器8、循环氢压缩机9。 Adsorption desulfurization reactor 1, hydrogenation reactor 2, first gas-liquid separator 3, first rectification tower 4, second rectification tower 5, third rectification tower 6, normalization reactor 7, second rectification tower Gas-liquid separator 8, circulating hydrogen compressor 9.
为了对本发明的技术特征、目的和有益效果有更加清楚的理解,现对本发明的技术方案进行以下详细说明,但不能理解为对本发明的可实施范围的限定。In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.
以下的实施例和对比例中,加氢催化剂的金属分散度在静态化学吸附仪进行,以H
2为吸附气体,具体测定方法如下:
In the following examples and comparative examples, the metal dispersion of the hydrogenation catalyst is carried out in a static chemisorption instrument, with H 2 is the adsorption gas, and the specific measurement method is as follows:
将样品在130℃脱气,然后400℃进行H
2还原,降温至35℃后进行第一次饱和吸附,抽真空后进行第二次饱和吸附。两次饱和吸附之差为化学吸附的氢气体积。
The sample was degassed at 130°C, then H2 reduction was performed at 400°C, the first saturated adsorption was performed after cooling down to 35°C, and the second saturated adsorption was performed after vacuuming. The difference between the two saturation adsorptions is the volume of hydrogen gas chemisorbed.
金属分散度计算公式:Metal dispersion calculation formula:
公式中V
H2是化学吸附的氢气体积、单位是L,W为催化剂的总质量、单位是g,P是Ni的百分含量,M
Ni是Ni的分子质量。
In the formula, V H2 is the volume of chemisorbed hydrogen in L, W is the total mass of the catalyst in g, P is the percentage of Ni, and M Ni is the molecular mass of Ni.
实施例1aExample 1a
本实施例提供了一种加氢催化剂,其制备方法包括:Present embodiment provides a kind of hydrogenation catalyst, and its preparation method comprises:
步骤1、将11.50g拟薄水铝石粉体(含70wt%的Al
2O
3)与40ml去离子水混合搅拌均匀得到第一浆液;
Step 1. Mix and stir 11.50g of pseudo-boehmite powder (containing 70wt% Al 2 O 3 ) and 40ml of deionized water to obtain the first slurry;
将58.16g六水硝酸镍溶于去离子水中,定容至200ml,配制成1mol/L的硝酸镍溶液;将12.82g六水硝酸镁溶于去离子水中,定容至50ml,配制成1mol/L的硝酸镁溶液。量取1mol/L硝酸镍溶液184.7ml与1mol/L硝酸镁溶液28.5ml混合均匀得到第二溶液;Dissolve 58.16g of nickel nitrate hexahydrate in deionized water, set the volume to 200ml, and prepare a 1mol/L nickel nitrate solution; L of magnesium nitrate solution. Measure 184.7ml of 1mol/L nickel nitrate solution and 28.5ml of 1mol/L magnesium nitrate solution and mix evenly to obtain the second solution;
将207.32g无水碳酸钾溶于去离子水中,定容至1000ml,配制成1.5mol/L的碳酸钾溶液,量取1.5mol/L碳酸钾溶液665.3ml为第三溶液。207.32g of anhydrous potassium carbonate was dissolved in deionized water, and the volume was adjusted to 1000ml to prepare a 1.5mol/L potassium carbonate solution, and 665.3ml of the 1.5mol/L potassium carbonate solution was measured as the third solution.
步骤2、将第一浆液加入到反应釜中,开启搅拌速度200rmp、加热至反应温度60℃,向反应釜加入1.3ml的第三溶液,调节第一浆液的pH至10,形成第一混合体系; Step 2. Add the first slurry to the reaction kettle, turn on the stirring speed of 200rmp, heat to the reaction temperature of 60°C, add 1.3ml of the third solution to the reaction kettle, adjust the pH of the first slurry to 10, and form the first mixing system ;
在搅拌条件下,分别以35ml/min和109.2ml/min向第一混合体系并流加入第二溶液和第三溶液,控制pH值恒定为10,第二溶液和第三溶液滴加完毕后,得到第二混合体 系。Under stirring conditions, add the second solution and the third solution concurrently to the first mixing system at 35ml/min and 109.2ml/min respectively, and control the pH value to be constant at 10. After the second solution and the third solution are added dropwise, A second mixed system is obtained.
步骤3、将第二混合体系在60℃下搅拌老化2h,老化结束后,过滤得到滤饼并洗涤至中性,将滤饼置于120℃烘箱内干燥4h,研磨后经500℃的马弗炉焙烧5h,得到镍加氢催化剂。 Step 3. Stir and age the second mixed system at 60°C for 2 hours. After aging, filter the filter cake and wash it until neutral. Dry the filter cake in an oven at 120°C for 4 hours. After grinding, pass through a muffle at 500°C Furnace roasting for 5h to obtain nickel hydrogenation catalyst.
上述加氢催化剂中,镍的氧化物的质量含量为60%,镁的氧化物的质量含量为5%。In the above hydrogenation catalyst, the mass content of nickel oxide is 60%, and the mass content of magnesium oxide is 5%.
对本实施例的催化剂测试,得到Ni金属分散度为15.08%,比表面积为251m
2/g、所述加氢催化剂的孔容为0.41cm
3/g。
The test of the catalyst in this example shows that the dispersion degree of Ni metal is 15.08%, the specific surface area is 251 m 2 /g, and the pore volume of the hydrogenation catalyst is 0.41 cm 3 /g.
实施例1bExample 1b
本实施例提供了一种加氢催化剂,其制备方法包括:Present embodiment provides a kind of hydrogenation catalyst, and its preparation method comprises:
步骤1、将16.10g拟薄水铝石粉体(含70wt%的Al
2O
3)、2.30g氧化硅与55ml去离子水混合搅拌均匀得到第一浆液;
Step 1. Mix and stir 16.10g of pseudo-boehmite powder (containing 70wt% Al 2 O 3 ), 2.30g of silicon oxide and 55ml of deionized water to obtain the first slurry;
将72.70g六水硝酸镍溶于去离子水中,定容至500ml,配制成0.5mol/L硝酸镍溶液;将4.33g六水硝酸镧溶于去离子水中,定容至20ml,配制成0.5mol/L的硝酸镧溶液。量取0.5mol/L硝酸镍溶液246.3ml与0.5mol/L硝酸镧溶液2.8ml混合均匀得到第二溶液;Dissolve 72.70g of nickel nitrate hexahydrate in deionized water, set the volume to 500ml, and prepare 0.5mol/L nickel nitrate solution; dissolve 4.33g of lanthanum nitrate hexahydrate in deionized water, set the volume to 20ml, and prepare 0.5mol /L of lanthanum nitrate solution. Measure 246.3ml of 0.5mol/L nickel nitrate solution and 2.8ml of 0.5mol/L lanthanum nitrate solution and mix evenly to obtain the second solution;
将15.81g碳酸氢铵溶于去离子水中,定容至200ml,配制成1mol/L碳酸氢铵溶液。量取1mol/L碳酸氢铵溶液191.1ml为第三溶液。15.81g of ammonium bicarbonate was dissolved in deionized water, and the volume was adjusted to 200ml to prepare a 1mol/L ammonium bicarbonate solution. Measure 191.1ml of 1mol/L ammonium bicarbonate solution as the third solution.
步骤2、将第一浆液加入到反应釜中,开启搅拌速度200rmp、加热至反应温度80℃,向反应釜加入1.2ml第三溶液,调节第一浆液的pH至8,形成第一混合体系; Step 2. Add the first slurry to the reaction kettle, turn on the stirring speed of 200rmp, heat to the reaction temperature of 80°C, add 1.2ml of the third solution to the reaction kettle, adjust the pH of the first slurry to 8, and form the first mixed system;
在搅拌条件下,分别以20ml/min和15ml/min向第一混合体系并流加入第二溶液和第三溶液,控制pH值恒定为8,第二溶液和第三溶液滴加完毕后,得到第二混合体系。Under stirring conditions, add the second solution and the third solution concurrently to the first mixing system at 20ml/min and 15ml/min respectively, and control the pH value to be constant at 8. After the second solution and the third solution are added dropwise, the obtained Second mixing system.
步骤3、将第二混合体系在80℃下搅拌老化3h,老化结束后,过滤得到滤饼并洗涤至中性,将滤饼置于120℃烘箱内干燥4h,研磨后经500℃的马弗炉焙烧5h,得到镍加氢催化剂。 Step 3. Stir and age the second mixed system at 80°C for 3 hours. After aging, filter the filter cake and wash it until neutral. Dry the filter cake in an oven at 120°C for 4 hours. After grinding, pass through a 500°C muffle Furnace roasting for 5h to obtain nickel hydrogenation catalyst.
上述加氢催化剂中,镍的氧化物的质量含量为40%,镧的氧化物的质量含量为1%。In the above hydrogenation catalyst, the mass content of nickel oxide is 40%, and the mass content of lanthanum oxide is 1%.
对本实施例的催化剂测试,得到Ni金属分散度为16.18%,比表面积为246m
2/g、所述加氢催化剂的孔容为0.40cm
3/g。
The test of the catalyst in this example shows that the dispersion degree of Ni metal is 16.18%, the specific surface area is 246 m 2 /g, and the pore volume of the hydrogenation catalyst is 0.40 cm 3 /g.
实施例1cExample 1c
本实施例提供了一种加氢催化剂,其制备方法包括:Present embodiment provides a kind of hydrogenation catalyst, and its preparation method comprises:
步骤1、将11.50g拟薄水铝石粉体(含70wt%的Al
2O
3)与40ml去离子水混合搅拌均匀得到第一浆液;
Step 1. Mix and stir 11.50g of pseudo-boehmite powder (containing 70wt% Al 2 O 3 ) and 40ml of deionized water to obtain the first slurry;
将58.16g六水硝酸镍溶于去离子水中,定容至200ml,配制成1mol/L硝酸镍溶液;将4.83g三水硝酸铜溶于去离子水中,定容至20ml,配制成1mol/L的硝酸铜溶液;量取1mol/L硝酸镍溶液184.7ml与1mol/L硝酸铜溶液14.5ml混合均匀得到第二溶液;Dissolve 58.16g of nickel nitrate hexahydrate in deionized water, dilute to 200ml, and prepare 1mol/L nickel nitrate solution; dissolve 4.83g of copper nitrate trihydrate in deionized water, dilute to 20ml, and prepare 1mol/L Copper nitrate solution; Measure 184.7ml of 1mol/L nickel nitrate solution and mix with 14.5ml of 1mol/L copper nitrate solution to obtain the second solution;
将207.32g无水碳酸钾溶于去离子水中,定容至1000ml,配制成1.5mol/L的碳酸钾溶液,量取1.5mol/L碳酸钾溶液621.4ml为第三溶液。Dissolve 207.32g of anhydrous potassium carbonate in deionized water, set the volume to 1000ml, and prepare a 1.5mol/L potassium carbonate solution. Measure 621.4ml of the 1.5mol/L potassium carbonate solution as the third solution.
步骤2、将第一浆液加入到反应釜中,开启搅拌速度100rmp、加热至反应温度60℃,向反应釜加入1.3ml的第三溶液,调节第一浆液的pH至10,形成第一混合体系; Step 2. Add the first slurry to the reaction kettle, turn on the stirring speed of 100rmp, heat to the reaction temperature of 60°C, add 1.3ml of the third solution to the reaction kettle, adjust the pH of the first slurry to 10, and form the first mixing system ;
在搅拌条件下,分别以35ml/min和109ml/min向第一混合体系并流加入第二溶液和第三溶液,控制pH值恒定为10,第二溶液和第三溶液滴加完毕后,得到第二混合体系。Under stirring conditions, add the second solution and the third solution concurrently to the first mixing system at 35ml/min and 109ml/min respectively, and control the pH value to be constant at 10. After the second solution and the third solution are added dropwise, the obtained Second mixing system.
步骤3、将第二混合体系在60℃下搅拌老化2h,老化结束后,过滤得到滤饼并洗涤至中性,将滤饼置于120℃烘箱内干燥4h,研磨后经500℃的马弗炉焙烧5h、在高纯H
2下,在400℃还原10h,得到镍加氢催化剂。
Step 3. Stir and age the second mixed system at 60°C for 2 hours. After aging, filter the filter cake and wash it until neutral. Dry the filter cake in an oven at 120°C for 4 hours. After grinding, pass through a muffle at 500°C Furnace calcination for 5h, and reduction in high-purity H2 at 400°C for 10h to obtain a nickel hydrogenation catalyst.
上述加氢催化剂中,镍的氧化物的质量含量为60%,铜的氧化物的质量含量为5%。In the above hydrogenation catalyst, the mass content of nickel oxide is 60%, and the mass content of copper oxide is 5%.
对本实施例的催化剂测试,得到Ni金属分散度为14.74%,比表面积为248m
2/g、所述加氢催化剂的孔容为0.42cm
3/g。
The test of the catalyst in this example shows that the Ni metal dispersion is 14.74%, the specific surface area is 248 m 2 /g, and the pore volume of the hydrogenation catalyst is 0.42 cm 3 /g.
实施例2a至实施例2e中重整抽余油生产溶剂油的方法是在如图1所示的系统中进行的,该系统包括脱附脱硫反应器1、加氢反应器2、第一气液分离器3、第一精馏塔4、第二精馏塔5、第三精馏塔6、正构化反应器7、第二气液分离器8、循环氢压缩机9。The method for reforming raffinate to produce solvent oil in embodiment 2a to embodiment 2e is carried out in the system as shown in Figure 1, and this system comprises desorption desulfurization reactor 1, hydrogenation reactor 2, the first gas Liquid separator 3, first rectification tower 4, second rectification tower 5, third rectification tower 6, normalization reactor 7, second gas-liquid separator 8, circulating hydrogen compressor 9.
其中,脱附脱硫反应器1的塔顶设有入口,塔底设有出口;加氢反应器2的塔顶设有入口、塔底设有出口;第一气液分离器3的测线设有入口,塔底和塔顶分别设有出口;第一精馏塔4的测线设有入口,塔顶和塔底分别设有出口;第二精馏塔5的测线设有入口,塔顶和塔底分别设有出口;第三精馏塔6的测线设有入口,塔顶和塔底分别设有出口;正构化反应器7的塔顶设有入口、塔底设有出口;第二气液分离器8的测线设有入口,塔顶和塔底分别设有出口。循环氢压缩机9设有入口和出口。Wherein, the top of the desorption desulfurization reactor 1 is provided with an inlet, and the bottom of the tower is provided with an outlet; the top of the hydrogenation reactor 2 is provided with an inlet, and the bottom of the tower is provided with an outlet; There is an inlet, and an outlet is respectively provided at the bottom and the top of the tower; the measuring line of the first rectifying tower 4 is provided with an inlet, and the tower top and the tower bottom are respectively provided with an outlet; the measuring line of the second rectifying tower 5 is provided with an inlet, and the measuring line of the tower The top and the bottom of the tower are respectively provided with an outlet; the measuring line of the third rectification tower 6 is provided with an inlet, and the tower top and the tower bottom are respectively provided with an outlet; the tower top of the normalization reactor 7 is provided with an inlet, and the tower bottom is provided with an outlet ; The measuring line of the second gas-liquid separator 8 is provided with an inlet, and the top and the bottom of the tower are respectively provided with an outlet. The circulating hydrogen compressor 9 is provided with an inlet and an outlet.
具体地,各装置之间的连接关系为:所述脱附脱硫反应器1位于塔底的出口与加氢反应器2的入口(位于塔顶)连接;所述加氢反应器2位于塔底的出口与第一气液分离器3的入口连接;所述第一气液分离器3的位于塔底的出口与第一精馏塔4的入口连接;所述第一精馏塔4位于测线的出口与第二精馏塔5的入口连接;所述第二精馏塔5位于塔顶的出口与第三精馏塔6的入口连接;所述第三精馏塔6位于塔顶的出口与正构化反应器7的入口连接;正构化反应器7位于塔底的出口与第二气液分离器8的入口连接, 第二气液分离器8位于塔顶的出口以及第一气液分离器3位于塔顶的出口分别与循环氢压缩机9的入口连接;循环氢压缩机9的出口与加氢反应器2的入口、正构化反应器7的入口分别连接。Specifically, the connection relationship between each device is: the outlet of the desorption and desulfurization reactor 1 at the bottom of the tower is connected with the inlet of the hydrogenation reactor 2 (at the top of the tower); the hydrogenation reactor 2 is at the bottom of the tower The outlet of the first gas-liquid separator 3 is connected to the inlet; the outlet at the bottom of the first gas-liquid separator 3 is connected to the inlet of the first rectification tower 4; the first rectification tower 4 is located at the The outlet of the line is connected with the inlet of the second rectifying tower 5; the outlet of the second rectifying tower 5 at the top of the tower is connected with the inlet of the third rectifying tower 6; the third rectifying tower 6 is positioned at the top of the tower Outlet is connected with the inlet of normalization reactor 7; The outlet of the gas-liquid separator 3 at the top of the tower is respectively connected to the inlet of the circulating hydrogen compressor 9; the outlet of the circulating hydrogen compressor 9 is connected to the inlet of the hydrogenation reactor 2 and the inlet of the normalization reactor 7 respectively.
实施例2a至实施例2e中采用的重整抽余油生产溶剂油的方法流程如图1所示,具体包括:The process flow of the method for producing solvent oil from the reformed raffinate adopted in embodiment 2a to embodiment 2e is as shown in Figure 1, specifically comprising:
S1、将重整抽余油输送至吸附反应器进行脱硫、脱水;S1. Transport the reformed raffinate to the adsorption reactor for desulfurization and dehydration;
S2、脱硫、脱水产物与氢气混合进入加氢反应器脱苯、脱烯烃,其中,加氢反应器中装填的加氢催化剂为本发明提供的加氢催化剂;S2. Desulfurization and dehydration products are mixed with hydrogen into a hydrogenation reactor to remove benzene and deolefins, wherein the hydrogenation catalyst loaded in the hydrogenation reactor is the hydrogenation catalyst provided by the present invention;
S3、将加氢反应产物输送至气液分离器进行气液分离,分离出的液体产物由气液分离器的塔底排出,分离的富氢气体由气液分离器顶部排出,该富氢气可以与新氢混合,经循环氢压缩机升压后作为循环氢使用;S3. Transport the hydrogenation reaction product to the gas-liquid separator for gas-liquid separation. The separated liquid product is discharged from the bottom of the gas-liquid separator, and the separated hydrogen-rich gas is discharged from the top of the gas-liquid separator. The hydrogen-rich gas can be It is mixed with fresh hydrogen and used as circulating hydrogen after being boosted by a circulating hydrogen compressor;
S4、将气液分离出的液体产物进入第一精馏塔,塔顶为C5组分(戊烷发泡剂),侧线为C6组分,塔底为C7及以上组分(120#溶剂油);S4, the liquid product that gas-liquid separation is separated enters the first rectifying tower, and tower top is C5 component (pentane blowing agent), and side line is C6 component, and tower bottom is C7 and above component (120# solvent oil );
S5、第一精馏塔侧线出来的C6组分进入第二精馏塔进行分馏,塔顶为正己烷和异己烷混合物,塔底为环己烷;S5, the C6 component coming out of the side line of the first rectification tower enters the second rectification tower for fractionation, the top of the tower is a mixture of n-hexane and isohexane, and the bottom of the tower is cyclohexane;
S6、正己烷和异己烷混合物再进入第三精馏塔进行分馏,塔顶为异己烷,塔底为正己烷;S6, the mixture of normal hexane and isohexane enters the third rectification tower for fractionation, the top of the tower is isohexane, and the bottom of the tower is normal hexane;
S7、异己烷进入正构化反应器进行反应,得到的产物进入分离器气液分离,分离器底部产物为高浓度正己烷,再与第三精馏塔塔底正己烷产物混合,进一步提高正己烷收率。S7. Isohexane enters the normalization reactor for reaction, and the obtained product enters the separator for gas-liquid separation, and the bottom product of the separator is high-concentration n-hexane, which is then mixed with the n-hexane product at the bottom of the third rectification tower to further increase the n-hexane alkane yield.
表1为以下实施例2a至实施例2e、对比例1、对比例2中重整抽余油原料组成。Table 1 shows the raw material composition of the reformed raffinate in the following examples 2a to 2e, comparative example 1 and comparative example 2.
表1Table 1
实施例2aExample 2a
本实施例提供了一种重整抽余油生产溶剂油的方法,包括:This embodiment provides a method for reforming raffinate oil to produce solvent oil, including:
S1、以表1重整抽余油为原料,重整抽余油进入吸附反应器进行脱硫、脱水,所用催化剂为工业5A分子筛吸附剂;S1, using the reformed raffinate in Table 1 as raw material, the reformed raffinate enters the adsorption reactor for desulfurization and dehydration, and the catalyst used is an industrial 5A molecular sieve adsorbent;
S2、脱硫、脱水产物与氢气混合进入加氢反应器脱苯、脱烯烃,所用催化剂为实施例1a制备的高镍加氢催化剂(Ni金属分散度大于10%);S2, desulfurization, dehydration product and hydrogen are mixed into the hydrogenation reactor to remove benzene and deolefins, and the catalyst used is the high-nickel hydrogenation catalyst prepared in Example 1a (Ni metal dispersion is greater than 10%);
吸附脱硫反应条件:常温,常压,空速为3h
-1,产品S≤1mg/kg;
Adsorption desulfurization reaction conditions: normal temperature, normal pressure, space velocity of 3h -1 , product S≤1mg/kg;
S3、加氢反应器产物进入分离器进行气液分离,塔底排出液体产物,顶部排出富氢气体,该富氢气体可以与重整装置新氢混合,经循环氢压缩机升压后作为循环氢使用;S3. The product of the hydrogenation reactor enters the separator for gas-liquid separation, the liquid product is discharged from the bottom of the tower, and the hydrogen-rich gas is discharged from the top. The hydrogen-rich gas can be mixed with the new hydrogen of the reforming unit, and is used as a cycle after being boosted by the circulating hydrogen compressor. Hydrogen use;
固定床加氢反应器反应条件:反应温度120℃、反应压力1.0MPa、氢油体积比100:1、体积空速3.0h
-1,测得苯脱除率100%;
Reaction conditions of fixed bed hydrogenation reactor: reaction temperature 120°C, reaction pressure 1.0MPa, hydrogen-to-oil volume ratio 100:1, volume space velocity 3.0h -1 , the measured benzene removal rate is 100%;
S4、分离器底部液体产物进入第一精馏塔,塔顶为C5组分,测线排出C6组分,塔底为C7及以上组分;S4, the liquid product at the bottom of the separator enters the first rectification tower, the top of the tower is the C5 component, the measuring line discharges the C6 component, and the bottom of the tower is the C7 and above components;
第一精馏塔操作条件:塔内压力0.1MPa,塔顶温度35℃,塔底温度95℃,塔顶C5组分为戊烷发泡剂,塔底C7及以上组分为120#溶剂油,侧线排出C6组分;采用溴价溴指数测定仪根据微库仑滴定原理进行溴指数测定,C5组分的溴指数5.1mgBr/100g,C7及以上组分的溴指数9.8mgBr/100g;The operating conditions of the first rectification tower: the pressure inside the tower is 0.1MPa, the temperature at the top of the tower is 35°C, and the temperature at the bottom of the tower is 95°C. , the C6 component is discharged from the side line; the bromine index is measured by a bromine index analyzer according to the principle of microcoulomb titration, the bromine index of the C5 component is 5.1mgBr/100g, and the bromine index of the C7 and above components is 9.8mgBr/100g;
S5、侧线出来的C6组分进入第二精馏塔进行分馏,塔顶为正己烷和异己烷混合物,塔底为环己烷;S5, the C6 component coming out of the side line enters the second rectification tower for fractionation, the top of the tower is a mixture of n-hexane and isohexane, and the bottom of the tower is cyclohexane;
第二精馏塔操作条件:塔顶压力0.1MPa,塔顶温度60℃,塔底温度72℃,塔底环己烷的纯度97wt%;Operating conditions of the second rectifying tower: tower top pressure 0.1MPa, tower top temperature 60°C, tower bottom temperature 72°C, tower bottom cyclohexane purity 97wt%;
S6、正己烷和异己烷混合物再进入第三精馏塔进行分馏,塔顶为异己烷,塔底为正己烷;S6, the mixture of normal hexane and isohexane enters the third rectification tower for fractionation, the top of the tower is isohexane, and the bottom of the tower is normal hexane;
第三精馏塔操作条件:塔顶压力0.1MPa,塔顶温度55℃,塔底温度65℃,塔底正己烷纯度87%;Operating conditions of the third rectification tower: tower top pressure 0.1MPa, tower top temperature 55°C, tower bottom temperature 65°C, bottom n-hexane purity 87%;
S7、塔顶产物异己烷进入正构化反应器进行反应,得到的产物进入分离器气液分离,分离器底部产物为高浓度正己烷,再与第三精馏塔塔底正己烷产物混合,进一步提高正己烷收率。S7. The isohexane product at the top of the tower enters the normalization reactor for reaction, and the obtained product enters the separator for gas-liquid separation, and the bottom product of the separator is high-concentration n-hexane, which is then mixed with the n-hexane product at the bottom of the third rectification tower, Further increase the yield of n-hexane.
正构化反应器反应条件为:反应温度380℃、反应压力2.0MPa、氢油体积比200:1、体积空速1.5h
-1,转化率91%,选择性>99wt%;
The reaction conditions of the normalization reactor are: reaction temperature 380°C, reaction pressure 2.0MPa, hydrogen oil volume ratio 200:1, volume space velocity 1.5h -1 , conversion rate 91%, selectivity >99wt%;
其中,正构化反应所用的催化剂为分子筛催化剂,该分子筛催化剂由分子筛载体、非分子筛载体和第三活性金属组分构成,其中,分子筛载体为丝光分子筛MOR、在催化剂中的重量含量是80%;第三活性金属组分为钯的氧化物、在催化剂中的重量占比为0.35%;余量为作为非分子筛催化剂的氧化铝。Wherein, the catalyst used in the normalization reaction is a molecular sieve catalyst, and the molecular sieve catalyst is composed of a molecular sieve carrier, a non-molecular sieve carrier and a third active metal component, wherein the molecular sieve carrier is a mercerized molecular sieve MOR, and the weight content in the catalyst is 80% ; The third active metal component is palladium oxide, which accounts for 0.35% by weight in the catalyst; the balance is alumina as a non-molecular sieve catalyst.
本实施例得到产品:正己烷纯度83wt%,收率54%;环己烷的纯度>97wt%;C5组分满足戊烷发泡剂标准要求;C7及以上组分满足120#溶剂油标准要求。The product obtained in this embodiment: the purity of n-hexane is 83wt%, and the yield is 54%; the purity of cyclohexane is >97wt%; the C5 component meets the standard requirements of pentane blowing agent; the C7 and above components meet the 120# solvent oil standard requirements .
以上的苯脱除率、转化率、选择性、产品中各成分的纯度和收率均通过气相色谱法进行原料和产品族组成分析得到。The above benzene removal rate, conversion rate, selectivity, purity and yield of each component in the product are all obtained by analyzing the composition of raw materials and product groups by gas chromatography.
实施例2bExample 2b
本实施例提供了一种重整抽余油生产溶剂油的方法,包括:This embodiment provides a method for reforming raffinate oil to produce solvent oil, including:
其中,所用原料、工艺流程、吸附脱硫反应、加氢反应和正构化反应条件与实施例2a完全相同,不同的是改变三个精馏塔的操作条件。Among them, the raw materials used, process flow, adsorption desulfurization reaction, hydrogenation reaction and normalization reaction conditions are exactly the same as those in Example 2a, the difference is that the operating conditions of the three rectification towers are changed.
第一精馏塔操作条件:塔内压力0.1MPa,塔顶温度40℃,塔底温度102℃,塔顶C5组分为戊烷发泡剂,溴指数5.8mgBr/100g,塔底C7及以上组分为120#溶剂油,溴指数8.3mgBr/100g;The operating conditions of the first rectification tower: the pressure inside the tower is 0.1MPa, the temperature at the top of the tower is 40°C, the temperature at the bottom of the tower is 102°C, the C5 component at the top of the tower is pentane foaming agent, the bromine index is 5.8mgBr/100g, and the bottom C7 and above The component is 120# solvent oil, the bromine index is 8.3mgBr/100g;
第二精馏塔操作条件:塔顶压力0.1MPa,塔顶温度66℃,塔底温度78℃,塔底环己烷的纯度99wt%;Operating conditions of the second rectifying tower: tower top pressure 0.1MPa, tower top temperature 66°C, tower bottom temperature 78°C, purity of cyclohexane at the bottom of the tower 99wt%;
第三精馏塔操作条件:塔顶压力0.1MPa,塔顶温度60℃,塔底温度71℃,塔底正己烷纯度91%;Operating conditions of the third rectification tower: tower top pressure 0.1MPa, tower top temperature 60°C, tower bottom temperature 71°C, bottom n-hexane purity 91%;
本实施例得到产品:正己烷纯度88wt%,收率53%;环己烷的纯度>99wt%;C5组分满足戊烷发泡剂标准要求;C7及以上组分满足120#溶剂油标准要求。The product obtained in this embodiment: the purity of n-hexane is 88wt%, and the yield is 53%; the purity of cyclohexane is >99wt%; the C5 component meets the standard requirements of pentane blowing agent; the C7 and above components meet the 120# solvent oil standard requirements .
实施例2cExample 2c
本实施例提供了一种重整抽余油生产溶剂油的方法,包括:This embodiment provides a method for reforming raffinate oil to produce solvent oil, comprising:
其中,所用原料、工艺流程、吸附脱硫反应、加氢反应和正构化反应条件与实施例2b完全相同,不同的是改变三个精馏塔操作条件。Among them, the raw materials used, process flow, adsorption desulfurization reaction, hydrogenation reaction and normalization reaction conditions are exactly the same as those in Example 2b, the difference is that the operating conditions of the three rectification towers are changed.
第一精馏塔操作条件:塔内压力0.1MPa,塔顶温度50℃,塔底温度110℃,塔顶C5组分为戊烷发泡剂,溴指数7.8mgBr/100g,塔底C7及以上组分为120#溶剂油,溴指数8.9mgBr/100g;The operating conditions of the first rectification tower: the pressure inside the tower is 0.1MPa, the temperature at the top of the tower is 50°C, and the temperature at the bottom of the tower is 110°C. The component is 120# solvent oil, the bromine index is 8.9mgBr/100g;
第二精馏塔操作条件:塔顶压力0.1MPa,塔顶温度75℃,塔底温度90℃,塔底环己烷的纯度98wt%;Operating conditions of the second rectifying tower: tower top pressure 0.1MPa, tower top temperature 75°C, tower bottom temperature 90°C, tower bottom cyclohexane purity 98wt%;
第三精馏塔操作条件:塔顶压力0.1MPa,塔顶温度65℃,塔底温度78℃,塔底正己烷纯度88%;Operating conditions of the third rectification tower: tower top pressure 0.1MPa, tower top temperature 65°C, tower bottom temperature 78°C, bottom n-hexane purity 88%;
本实施例得到产品:正己烷纯度85wt%,收率51%;环己烷的纯度>98wt%;C5组分满足戊烷发泡剂标准要求;C7及以上组分满足120#溶剂油标准要求。The product obtained in this embodiment: the purity of n-hexane is 85wt%, and the yield is 51%; the purity of cyclohexane is >98wt%; the C5 component meets the standard requirements of pentane blowing agent; the C7 and above components meet the 120# solvent oil standard requirements .
实施例2dExample 2d
本实施例提供了一种重整抽余油生产溶剂油的方法:This embodiment provides a method for reforming raffinate to produce solvent oil:
其中,所用原料、工艺流程、精馏塔操作条件、吸附脱硫反应和正构化反应条件与实施例2b完全相同,不同的是固定床加氢反应条件。Among them, the raw materials used, the process flow, the operation conditions of the rectification tower, the conditions of the adsorption desulfurization reaction and the normalization reaction are exactly the same as those of Example 2b, and the difference is the fixed bed hydrogenation reaction conditions.
固定床加氢反应器反应条件:反应温度180℃、反应压力1.0MPa、氢油体积比100:1、体积空速3.0h
-1,苯脱除率100%;
Reaction conditions of fixed bed hydrogenation reactor: reaction temperature 180°C, reaction pressure 1.0MPa, hydrogen oil volume ratio 100:1, volume space velocity 3.0h -1 , benzene removal rate 100%;
第一精馏塔产品:塔顶C5组分溴指数1.2mgBr/100g,满足戊烷发泡剂的要求,塔底C7及以上组分溴指数3.5mgBr/100g,满足120#溶剂油的要求;The product of the first rectification tower: the bromine index of C5 component at the top of the tower is 1.2mgBr/100g, which meets the requirements of pentane blowing agent; the bromine index of C7 and above components at the bottom of the tower is 3.5mgBr/100g, which meets the requirements of 120# solvent oil;
得到产品:正己烷的纯度88wt%,收率53%;环己烷的纯度>99wt%;C5组分满足戊烷发泡剂标准要求;C7及以上组分满足120#溶剂油标准要求。The obtained product: the purity of n-hexane is 88wt%, and the yield is 53%; the purity of cyclohexane is >99wt%; the C5 component meets the standard requirement of pentane blowing agent; the C7 and above components meet the standard requirement of 120# solvent oil.
实施例2eExample 2e
本实施例提供了一种重整抽余油生产溶剂油的方法:This embodiment provides a method for reforming raffinate to produce solvent oil:
其中,所用原料、工艺流程、精馏塔操作条件、吸附脱硫反应和固定床加氢反应条件与实施例2b完全相同,不同的是正构化反应条件。Among them, the raw materials used, the process flow, the operating conditions of the rectification tower, the conditions of the adsorption desulfurization reaction and the fixed bed hydrogenation reaction are exactly the same as those of Example 2b, and the difference is the normalization reaction conditions.
正构化反应器反应条件为:反应温度300℃、反应压力2.0MPa、氢油体积比200:1、体积空速1.5h
-1,转化率73%,选择性>99wt%;
The reaction conditions of the normalization reactor are: reaction temperature 300°C, reaction pressure 2.0MPa, hydrogen oil volume ratio 200:1, volume space velocity 1.5h -1 , conversion rate 73%, selectivity >99wt%;
得到产品:正己烷纯度82wt%,收率52%;环己烷的纯度>99wt%;C5组分满足戊烷发泡剂标准要求;C7及以上组分满足120#溶剂油标准要求。The obtained product: the purity of n-hexane is 82wt%, and the yield is 52%; the purity of cyclohexane is >99wt%; the C5 component meets the standard requirement of pentane blowing agent; the C7 and above components meet the standard requirement of 120# solvent oil.
对比例1Comparative example 1
本对比例提供了一种重整抽余油生产溶剂油的方法:This comparative example provides a kind of method of reforming raffinate production solvent oil:
其中,所用原料、工艺流程、精馏塔操作条件、吸附脱硫反应和正构化反应条件与实施例2b完全相同,不同的是固定床加氢反应条件。Among them, the raw materials used, the process flow, the operation conditions of the rectification tower, the conditions of the adsorption desulfurization reaction and the normalization reaction are exactly the same as those of Example 2b, and the difference is the fixed bed hydrogenation reaction conditions.
固定床加氢反应器反应条件:反应温度80℃、反应压力1.0MPa、氢油体积比100:1、体积空速3.0h
-1,苯脱除率83%;
Reaction conditions of fixed bed hydrogenation reactor: reaction temperature 80°C, reaction pressure 1.0MPa, hydrogen oil volume ratio 100:1, volume space velocity 3.0h -1 , benzene removal rate 83%;
第一精馏塔产品:塔顶C5组分溴指数121.2mgBr/100g,不满足戊烷发泡剂的要求,塔底C7及以上组分溴指数133.7mgBr/100g,不满足120#溶剂油的要求;The product of the first rectification tower: the bromine index of C5 component at the top of the tower is 121.2mgBr/100g, which does not meet the requirements of pentane blowing agent; the bromine index of C7 and above components at the bottom of the tower is 133.7mgBr/100g, which does not meet the requirements of 120# solvent oil Require;
本对比例得到产品:正己烷的纯度76wt%,收率53%;环己烷的纯度>99w%。The product obtained in this comparative example: the purity of n-hexane is 76wt%, and the yield is 53%; the purity of cyclohexane is >99w%.
对比例2Comparative example 2
本对比例提供了一种重整抽余油生产溶剂油的方法,所用原料与实施例2b相同,该方法包括:This comparative example provides a kind of method for reforming raffinate to produce solvent oil, and used raw material is identical with embodiment 2b, and this method comprises:
1、重整抽余油原料先加氢反应器进行脱苯、脱烯烃,所用催化剂为常规加氢脱烯烃催化剂;1. The raw material of reformed raffinate is first debenzene and deolefinization in a hydrogenation reactor, and the catalyst used is a conventional hydrogenation deolefination catalyst;
加氢反应器反应条件为:反应温度120℃、反应压力1.0MPa、氢油体积比100:1、体积空速3.0h
-1,苯脱除率82%;
The reaction conditions of the hydrogenation reactor are: reaction temperature 120°C, reaction pressure 1.0MPa, hydrogen oil volume ratio 100:1, volume space velocity 3.0h -1 , benzene removal rate 82%;
制备方法如下:称取九水硝酸铝82.9g,定容240ml,配制成1mol/L硝酸铝溶液。量取1mol/L硝酸镍溶液190ml与1mol/L硝酸镁溶液30ml与1mol/L硝酸铝溶液170ml混合均匀为金属混合溶液,待用。量取1.5mol/L碳酸钾为沉淀剂溶液1000ml,待用。在反应釜中加入40ml净水,开启搅拌速度250rmp、加热至反应温度50℃。在搅拌条件下,分别以35ml/min和71ml/min并流加入金属混合溶液和沉淀剂溶液,控制pH值恒定为9。溶液滴加完毕后,在50℃下搅拌老化2h。将所得物料过滤、洗涤至滤液为中性。将滤饼置于烘箱120℃干燥4h,研磨后经马弗炉500℃焙烧5h、研磨得到催化剂The preparation method is as follows: Weigh 82.9 g of aluminum nitrate nonahydrate, make it into a constant volume of 240 ml, and prepare a 1 mol/L aluminum nitrate solution. Measure 190ml of 1mol/L nickel nitrate solution, 30ml of 1mol/L magnesium nitrate solution and 170ml of 1mol/L aluminum nitrate solution and mix them evenly to form a mixed metal solution for use. Measure 1.5mol/L potassium carbonate as 1000ml of precipitant solution and set it aside. Add 40ml of clean water into the reaction kettle, turn on the stirring speed of 250rmp, and heat to the reaction temperature of 50°C. Under stirring conditions, the mixed metal solution and the precipitant solution were added in parallel at 35ml/min and 71ml/min respectively, and the pH value was kept constant at 9. After the solution was added dropwise, it was stirred and aged at 50° C. for 2 h. The resulting material was filtered and washed until the filtrate was neutral. The filter cake was dried in an oven at 120°C for 4 hours, and after grinding, it was roasted in a muffle furnace at 500°C for 5 hours and ground to obtain the catalyst
2、加氢反应产物进入分离器进行气液分离,底部排出液体产物,顶部排出的富氢气体与重整装置新氢混合,经循环氢压缩机升压后作为循环氢使用;2. The hydrogenation reaction product enters the separator for gas-liquid separation, the liquid product is discharged from the bottom, and the hydrogen-rich gas discharged from the top is mixed with the new hydrogen of the reforming unit, and is used as circulating hydrogen after being boosted by the circulating hydrogen compressor;
3、分离器底部液体产物进入第一精馏塔进行分馏,塔顶排出C5组分,侧线排出C6组分,塔底排出C7及以上组分;3. The liquid product at the bottom of the separator enters the first rectification tower for fractionation, the C5 component is discharged from the top of the tower, the C6 component is discharged from the side line, and the C7 and above components are discharged from the bottom of the tower;
第一精馏塔操作条件:塔内压力0.1MPa,塔顶温度40℃,塔底温度102℃,塔顶C5组分为戊烷发泡剂,溴指数131.1mgBr/100g,不满足戊烷发泡剂的要求,塔底C7及以上组分溴指数138.9mgBr/100g,不满足120#溶剂油的要求;The operating conditions of the first rectification tower: the pressure inside the tower is 0.1MPa, the temperature at the top of the tower is 40°C, the temperature at the bottom of the tower is 102°C, the C5 component at the top of the tower is a pentane blowing agent, and the bromine index is 131.1mgBr/100g, which does not meet the requirements of pentane blowing agent. Foaming agent requirements, the bromine index of C7 and above components at the bottom of the tower is 138.9mgBr/100g, which does not meet the requirements of 120# solvent oil;
4、C6组分进入第二精馏塔进行分馏,塔顶为正己烷和异己烷混合物,塔底为环己 烷;4. The C6 component enters the second rectification tower for fractionation, the top of the tower is a mixture of n-hexane and isohexane, and the bottom of the tower is cyclohexane;
第二精馏塔操作条件:塔顶压力0.1MPa,塔顶温度66℃,塔底温度78℃,塔底环己烷的纯度98wt%;Operating conditions of the second rectifying tower: tower top pressure 0.1MPa, tower top temperature 66°C, tower bottom temperature 78°C, tower bottom cyclohexane purity 98wt%;
5、正己烷和异己烷混合物再进入第三精馏塔进行分馏,塔顶为异己烷,塔底为正己烷;5. The mixture of n-hexane and isohexane enters the third rectification tower for fractionation, the top of the tower is isohexane, and the bottom of the tower is n-hexane;
第三精馏塔操作条件:塔顶压力0.1MPa,塔顶温度60℃,塔底温度71℃。Operating conditions of the third rectification tower: tower top pressure 0.1MPa, tower top temperature 60°C, tower bottom temperature 71°C.
本对比例得到产品:正己烷的纯度88wt%,收率31%;异己烷的纯度91wt%(可作为6#溶剂油),环己烷的纯度>99wt%。This comparative example obtains the product: the purity of normal hexane is 88wt%, and the yield is 31%; The purity of isohexane is 91wt% (can be used as 6# solvent oil), and the purity of cyclohexane>99wt%.
表2为对实施例2a-实施例2e与对比例1至对比例2的产物的评价结果。Table 2 shows the evaluation results of the products of Example 2a-Example 2e and Comparative Example 1 to Comparative Example 2.
表2Table 2
从表2可以看出,实施例2a至实施例2e的评价结果明显好于对比例1、对比例2的评价结果。原因在于:It can be seen from Table 2 that the evaluation results of Examples 2a to 2e are obviously better than those of Comparative Example 1 and Comparative Example 2. the reason is:
对比例2采用先加氢再切割的工艺流程,以常规加氢催化剂处理重整抽余油,由于催化剂加氢性能略差,烯烃和苯的脱除率较低,C5组分由于存在烯烃不能满足戊烷发泡剂溴指数的标准要求,C7及以上组分由于环丁砜未进行脱除不能满足120#溶剂油硫含量的要求;同时,由于未设置异己烷正构化反应单元,无法将异己烷转化为正己烷,降低了正己烷的收率,未能实现重整抽余油的高效利用。Comparative Example 2 adopts the process of hydrogenation first and then cutting, and treats the reformed raffinate with a conventional hydrogenation catalyst. Due to the slightly poor hydrogenation performance of the catalyst, the removal rate of olefins and benzene is low, and the C5 component cannot be recovered due to the presence of olefins. It meets the standard requirements of the bromine index of pentane foaming agent, and the C7 and above components cannot meet the requirements of the sulfur content of 120# solvent oil because the sulfolane has not been removed; at the same time, because the isohexane normalization reaction unit is not installed, the isohexane Alkanes are converted into n-hexane, which reduces the yield of n-hexane and fails to realize the efficient utilization of reformed raffinate.
相比之下,实施例2a至-实施例2e采用本发明的工艺流程处理重整抽余油,通过增设吸附脱硫单元及正构化反应单元,实现了重整抽余油的高效利用。In contrast, Example 2a to -Example 2e adopt the technological process of the present invention to treat the reformed raffinate, and realize the efficient utilization of the reformed raffinate by adding an adsorption desulfurization unit and a normalization reaction unit.
其中,实施例2a至实施例2c通过调整精馏塔塔顶、塔底操作温度,可以实现对正己烷纯度和收率的调控;实施例2b和实施例2d通过改变加氢催化剂操作温度,可以实 现苯和烯烃不同程度的脱除,相比之下,对比例1中加氢催化剂的操作温度没有达到90℃-200℃,对苯和烯烃的脱除不彻底;实施例2b、实施例2e通过改变正构化反应条件,可以实现异己烷不同程度正构化生成正己烷,调变正己烷的纯度。Among them, embodiment 2a to embodiment 2c can realize the regulation and control of the purity and yield of n-hexane by adjusting the operating temperature of the rectifying tower top and bottom; embodiment 2b and embodiment 2d can be achieved by changing the operating temperature of the hydrogenation catalyst To achieve different degrees of removal of benzene and olefins. In contrast, the operating temperature of the hydrogenation catalyst in Comparative Example 1 did not reach 90°C-200°C, and the removal of benzene and olefins was not complete; Example 2b, Example 2e By changing the normalization reaction conditions, different degrees of normalization of isohexane can be achieved to generate n-hexane, and the purity of n-hexane can be adjusted.
以上结果说明,本发明提供的重整抽余油生产溶剂油的方法适用于苯和烯烃含量偏高的重整抽余油的分离和利用,生产得到的溶剂油纯度和收率高,利用效果好,可有效提升重整抽余油附加值。The above results show that the method for producing solvent oil from reformed raffinate provided by the present invention is suitable for the separation and utilization of reformed raffinate with high benzene and olefin content, and the obtained solvent oil has high purity and yield, and the utilization effect is high. Well, it can effectively increase the added value of reformed raffinate.
Claims (36)
- 一种重整抽余油生产溶剂油的方法,该方法包括:A method for reforming raffinate to produce solvent oil, the method comprising:S2、利用加氢催化剂,催化经过脱硫脱水后的重整抽余油进行加氢脱苯、脱烯烃反应,得到反应产物;S2. Using a hydrogenation catalyst to catalyze the desulfurization and dehydration of the reformed raffinate to undergo hydrogenation, debenzene, and deolefination reactions to obtain a reaction product;S3、对S2得到的反应产物进行气液分离;S3, performing gas-liquid separation on the reaction product obtained in S2;S4、将分离得到的液体进行精馏,分别馏出C5组分、C6组分和C7以上组分;S4, performing rectification on the separated liquid, respectively distilling out C5 components, C6 components and C7 or more components;S5、对所述C6组分进行精馏,分别馏出环己烷以及正己烷和异己烷的混合物;S5, performing rectification on the C6 component, and distilling off the mixture of cyclohexane and n-hexane and isohexane respectively;S6、对所述正己烷和异己烷的混合物进行精馏,分别馏出异己烷和正己烷,完成溶剂油的生产;S6. Rectifying the mixture of n-hexane and isohexane to distill out isohexane and n-hexane respectively to complete the production of solvent oil;其中,所述加氢催化剂包括载体、负载于载体的第一活性金属组分和第二活性金属组分,其中,所述第一活性金属组分的金属元素包括镍,以催化剂总重量为100%计,所述第一活性金属组分在所述催化剂中的重量含量为40-70%,所述载体在所述催化剂中的重量含量为20-59%,余量为所述第二活性金属组分。Wherein, the hydrogenation catalyst includes a carrier, a first active metal component and a second active metal component loaded on the carrier, wherein the metal element of the first active metal component includes nickel, and the total weight of the catalyst is 100 %, the weight content of the first active metal component in the catalyst is 40-70%, the weight content of the carrier in the catalyst is 20-59%, and the balance is the second active metal component. metal components.
- 根据权利要求1所述的方法,其中,S2中,所述加氢脱苯、脱烯烃反应的条件为:温度90-200℃、反应压力1.0-3.0MPa、氢油体积比100-300:1、体积空速1.0-3.0h -1; The method according to claim 1, wherein, in S2, the conditions for the hydrodebenzene and deolefination reactions are: temperature 90-200°C, reaction pressure 1.0-3.0MPa, hydrogen-to-oil volume ratio 100-300:1 , volumetric space velocity 1.0-3.0h -1 ;S4中,所述精馏的压力为0-0.2MPa;In S4, the pressure of the rectification is 0-0.2MPa;S5中,所述精馏的压力为0-0.1MPa;In S5, the pressure of the rectification is 0-0.1MPa;S6中,所述精馏的压力为0-0.1MPa。In S6, the pressure of the rectification is 0-0.1 MPa.
- 根据权利要求1或2所述的方法,其中,S2中,所述反应产物中,苯含量≤0.01%,溴指数≤50mgBr/100g。The method according to claim 1 or 2, wherein, in S2, in the reaction product, the benzene content is ≤0.01%, and the bromine index is ≤50mgBr/100g.
- 根据权利要求1或2所述的方法,其中,S4的精馏过程在精馏塔内完成,精馏塔的塔顶温度为30-50℃、塔底温度为90-110℃。The method according to claim 1 or 2, wherein the rectification process of S4 is completed in a rectification tower, the temperature at the top of the rectification tower is 30-50°C, and the temperature at the bottom of the tower is 90-110°C.
- 根据权利要求1或2所述的方法,其中,S5的精馏过程在精馏塔内完成,精馏塔的塔顶温度为55-75℃、塔底温度为70-90℃。The method according to claim 1 or 2, wherein the rectification process of S5 is completed in a rectification tower, the temperature at the top of the rectification tower is 55-75°C, and the temperature at the bottom of the tower is 70-90°C.
- 根据权利要求1或2所述的方法,其中,S6的精馏过程在精馏塔内完成,精馏塔的塔顶温度为50-70℃、塔底温度为60-80℃。The method according to claim 1 or 2, wherein the rectification process of S6 is completed in a rectification tower, the temperature at the top of the rectification tower is 50-70°C, and the temperature at the bottom of the tower is 60-80°C.
- 根据权利要求1-6任一项所述的方法,其中,在未经脱硫、脱水的重整抽余油中,硫含量为20mg/kg以下,苯含量为3-5v%,烯烃含量为1-3v%,正己烷与异己烷的总含量大于50v%。The method according to any one of claims 1-6, wherein, in reformed raffinate without desulfurization and dehydration, the sulfur content is below 20mg/kg, the benzene content is 3-5v%, and the olefin content is 1 -3v%, the total content of n-hexane and isohexane is greater than 50v%.
- 根据权利要求1所述的方法,其中,所述加氢催化剂中Ni金属的分散度为10% 以上;The method according to claim 1, wherein the dispersion of Ni metal in the hydrogenation catalyst is more than 10%;所述第二活性金属组分的金属元素包括铜、镧、镁中的一种或两种以上的组合;The metal element of the second active metal component includes one or a combination of two or more of copper, lanthanum, and magnesium;所述载体包括氧化铝、氧化硅、氧化钛、氧化铈中的一种,和/或,氧化硅、氧化钛、氧化铈中的至少一种与氧化铝的混合物。The carrier includes one of alumina, silica, titania, and ceria, and/or a mixture of at least one of silica, titania, and ceria with alumina.
- 根据权利要求1所述的方法,其中,所述加氢催化剂的比表面积为200-500m 2/g、所述加氢催化剂的孔容为0.3-0.6cm 3/g。 The method according to claim 1, wherein the specific surface area of the hydrogenation catalyst is 200-500m 2 /g, and the pore volume of the hydrogenation catalyst is 0.3-0.6cm 3 /g.
- 根据权利要求1、8-9任一项所述的方法,其中,所述加氢催化剂的制备方法包括:The method according to any one of claims 1,8-9, wherein the preparation method of the hydrogenation catalyst comprises:使载体前驱体的浆液的温度达到沉淀反应温度,并调节载体前驱体的浆液的pH值达到碱性pH值,得到第一混合体系;Make the temperature of the slurry of the carrier precursor reach the precipitation reaction temperature, and adjust the pH value of the slurry of the carrier precursor to an alkaline pH value to obtain the first mixed system;向所述第一混合体系并流加入第一活性金属组分前驱体、第二活性金属组分前驱体、沉淀剂,保持体系pH为碱性pH值,得到第二混合体系;Adding the first active metal component precursor, the second active metal component precursor, and the precipitant to the first mixed system in parallel to keep the pH of the system at an alkaline pH value to obtain a second mixed system;将第二混合体系进行老化处理,将老化产物焙烧,得到所述加氢催化剂。The second mixed system is subjected to aging treatment, and the aged product is roasted to obtain the hydrogenation catalyst.
- 根据权利要求10所述的方法,其中,所述碱性pH值为8-11。The method according to claim 10, wherein the alkaline pH value is 8-11.
- 根据权利要求10所述的方法,其中,所述沉淀反应温度为40-90℃。The method according to claim 10, wherein the precipitation reaction temperature is 40-90°C.
- 根据权利要求10所述的方法,其中,所述老化处理的温度为40-90℃。The method according to claim 10, wherein the temperature of the aging treatment is 40-90°C.
- 根据权利要求10所述的方法,其中,所述焙烧的温度为300-600℃。The method according to claim 10, wherein the temperature of the calcination is 300-600°C.
- 根据权利要求10所述的方法,其中,所述第一活性金属组分前驱体是第一活性金属组分中金属元素的化合物;The method according to claim 10, wherein the first active metal component precursor is a compound of a metal element in the first active metal component;所述第二活性金属组分前驱体是第二活性金属组分中金属元素的化合物;The precursor of the second active metal component is a compound of metal elements in the second active metal component;所述沉淀剂包括碱性沉淀剂。The precipitating agent includes an alkaline precipitating agent.
- 根据权利要求10所述的方法,其中,所述第一活性金属组分前驱体包括第一活性金属组分中金属元素的金属盐。The method according to claim 10, wherein the first active metal component precursor comprises a metal salt of a metal element in the first active metal component.
- 根据权利要求10所述的方法,其中,所述第二活性金属组分前驱体包括第二活性金属组分中金属元素的金属盐。The method according to claim 10, wherein the precursor of the second active metal component comprises a metal salt of a metal element in the second active metal component.
- 根据权利要求10所述的方法,其中,所述沉淀剂包括可溶性碳酸盐。The method of claim 10, wherein the precipitating agent comprises a soluble carbonate.
- 根据权利要求1-18任一项所述的方法,其中,所述方法还包括:S1、对重整抽余油进行脱硫、脱水处理,产品S≤1mg/kg。The method according to any one of claims 1-18, wherein the method further comprises: S1, performing desulfurization and dehydration treatment on the reformed raffinate, and the product S≤1 mg/kg.
- 根据权利要求19所述的方法,其中,S1中,所述脱硫、脱水过程中的空速为1-10h -1。 The method according to claim 19, wherein, in S1, the space velocity in the desulfurization and dehydration process is 1-10h -1 .
- 根据权利要求19所述的方法,其中,S1中,所述脱硫、脱水采用的吸附剂包括分子筛吸附剂。The method according to claim 19, wherein, in S1, the adsorbent used in the desulfurization and dehydration includes a molecular sieve adsorbent.
- 根据权利要求21所述的方法,其中,所述分子筛吸附剂包括3A分子筛、4A分子筛、5A分子筛和13A分子筛中的一种或两种以上的组合。The method according to claim 21, wherein the molecular sieve adsorbent comprises one or a combination of two or more of 3A molecular sieves, 4A molecular sieves, 5A molecular sieves and 13A molecular sieves.
- 根据权利要求21或22所述的方法,其中,所述分子筛吸附剂的比表面积为400-700m 2/g、孔容为0.05-0.30cm 3/g。 The method according to claim 21 or 22, wherein the molecular sieve adsorbent has a specific surface area of 400-700m 2 /g and a pore volume of 0.05-0.30cm 3 /g.
- 根据权利要求1-23任一项所述的方法,其中,该方法还包括:S7、将S6得到的异己烷通过正构化反应转化为正己烷。The method according to any one of claims 1-23, wherein the method further comprises: S7, converting the isohexane obtained in S6 into normal hexane through a normalization reaction.
- 根据权利要求24所述的方法,其中,S7中,所述正构化反应的条件为:反应温度200-400℃、反应压力1.0-3.0MPa、氢油体积比100-300:1、体积空速1.0-3.0h -1。 The method according to claim 24, wherein, in S7, the conditions of the normalization reaction are: reaction temperature 200-400°C, reaction pressure 1.0-3.0MPa, hydrogen-oil volume ratio 100-300:1, volume empty Speed 1.0-3.0h -1 .
- 根据权利要求24所述的方法,其中,S7中,所述异己烷的纯度为90%以上。The method according to claim 24, wherein, in S7, the purity of the isohexane is above 90%.
- 根据权利要求24所述的方法,其中,S7中,所述异己烷的纯度为95%以上。The method according to claim 24, wherein, in S7, the purity of the isohexane is above 95%.
- 根据权利要求24-27任一项所述的方法,其中,所述正构化反应的催化剂包括分子筛催化剂,该分子筛催化剂包括第三活性金属组分、分子筛载体和非分子筛载体。The method according to any one of claims 24-27, wherein the catalyst for the normalization reaction comprises a molecular sieve catalyst, and the molecular sieve catalyst comprises a third active metal component, a molecular sieve carrier and a non-molecular sieve carrier.
- 根据权利要求28所述的方法,其中,所述分子筛载体包括MOR、MCM-41、ZSM-22、SAPO-11的一种或两种以上的组合。The method according to claim 28, wherein the molecular sieve carrier comprises one or a combination of two or more of MOR, MCM-41, ZSM-22, and SAPO-11.
- 根据权利要求28所述的方法,其中,所述第三活性金属组分中的金属元素包括第VIB和/或第VIII族中的元素。The method according to claim 28, wherein the metal elements in the third active metal component include elements in Group VIB and/or Group VIII.
- 根据权利要求28所述的方法,其中,所述非分子筛载体包括氧化铝。The method of claim 28, wherein the non-molecular sieve support comprises alumina.
- 根据权利要求28所述的方法,其中,以所述分子筛催化剂的总重量为100%计,所述分子筛载体的重量占催化剂总重的10-80%、所述第三活性金属组分的重量占催化剂总重的0.01-5%,余量为非金属载体。The method according to claim 28, wherein, based on the total weight of the molecular sieve catalyst as 100%, the weight of the molecular sieve carrier accounts for 10-80% of the total weight of the catalyst, and the weight of the third active metal component It accounts for 0.01-5% of the total weight of the catalyst, and the balance is non-metal carrier.
- 根据权利要求28所述的方法,其中,所述第三活性金属组分的重量占催化剂总重的0.1-0.5%。The method according to claim 28, wherein the weight of the third active metal component accounts for 0.1-0.5% of the total weight of the catalyst.
- 一种重整抽余油生产溶剂油的系统,该系统能够实现权利要求1-33任一项所述的重整抽余油生产溶剂油的方法。A system for producing solvent oil by reforming raffinate oil, which can realize the method for producing solvent oil by reforming raffinate oil according to any one of claims 1-33.
- 根据权利要求34所述的系统,其中,所述重整抽余油生产溶剂油的系统包括依次连接的脱附脱硫反应器、加氢反应器、气液分离器、第一精馏塔、第二精馏塔、第三精馏塔。The system according to claim 34, wherein the system for producing solvent oil from the reforming raffinate comprises a desorption and desulfurization reactor, a hydrogenation reactor, a gas-liquid separator, a first rectification tower, and a second desulfurization reactor connected in sequence. The second rectification tower and the third rectification tower.
- 根据权利要求35所述的系统,其中,所述重整抽余油生产溶剂油的系统还包括 正构化反应器和气液分离器,所述正构化反应器的入口与所述第三精馏塔的出口连接,所述正构化反应器的出口与所述气液分离器的入口连接。The system according to claim 35, wherein the system for producing solvent oil from the reformed raffinate further comprises a normalization reactor and a gas-liquid separator, the inlet of the normalization reactor is connected to the third refining The outlet of the distillation tower is connected, and the outlet of the normalization reactor is connected with the inlet of the gas-liquid separator.
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