CN114130384B - Water-soluble catalyst, preparation method and application thereof, and method for processing residual oil - Google Patents
Water-soluble catalyst, preparation method and application thereof, and method for processing residual oil Download PDFInfo
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- CN114130384B CN114130384B CN202011189898.3A CN202011189898A CN114130384B CN 114130384 B CN114130384 B CN 114130384B CN 202011189898 A CN202011189898 A CN 202011189898A CN 114130384 B CN114130384 B CN 114130384B
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- Prior art keywords
- residual oil
- water
- hydrogen peroxide
- catalyst
- residuum
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000012545 processing Methods 0.000 title claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000002006 petroleum coke Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 30
- 239000011593 sulfur Substances 0.000 claims abstract description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 238000004939 coking Methods 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 230000003111 delayed effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000003502 gasoline Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 abstract description 20
- 239000010937 tungsten Substances 0.000 abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 15
- 239000011733 molybdenum Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 50
- 238000006477 desulfuration reaction Methods 0.000 description 16
- 230000023556 desulfurization Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- -1 and furthermore Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YJEJUIVHAMABCA-UHFFFAOYSA-J molybdenum(4+);oxalate Chemical compound [Mo+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O YJEJUIVHAMABCA-UHFFFAOYSA-J 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
-
- 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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
-
- 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
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a water-soluble catalyst, a preparation method and application thereof, and a method for processing residual oil. The catalyst is a product obtained by mixing and reacting a metal active component with hydrogen peroxide, wherein the metal element in the metal active component is at least one of molybdenum, tungsten and vanadium. The catalyst is obtained by one-step reaction of the metal active component and hydrogen peroxide, and the water-soluble catalyst is used for preparing low-sulfur petroleum coke by processing residual oil, so that the sulfur content in the petroleum coke can be reduced by more than 50 percent, and the catalyst has the advantages of simple preparation process, low synthesis cost and no pollutant emission in the synthesis process.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a water-soluble catalyst, a preparation method and application thereof, and a method for processing residual oil.
Background
With the development of heavy and poor quality of crude oil worldwide and the increasing shortage of crude oil resources, the effective processing of heavy oil and residual oil of crude oil is particularly important, wherein the hydrodesulfurization technology is the most widely applied method for processing residual oil in the petroleum refining industry at present.
However, hydrotreating requires not only a high-temperature and high-pressure reaction environment but also a large amount of noble metal catalyst, and furthermore, hydrogen consumption for hydrotreating is large, and a large burden is imposed on some refineries, both from the viewpoint of the source of hydrogen and economic cost, and therefore, development of other desulfurization technologies is also required.
Non-hydrodesulfurization techniques mainly include extractive desulfurization, biological desulfurization, adsorption desulfurization, complex desulfurization, and the like, and combinations thereof. Compared with the traditional other non-hydrodesulfurization technology, the oxidative desulfurization has the advantages of mild operation conditions, high desulfurization efficiency and the like, and has wide development prospect.
At present, few reports are about research on heavy oil oxidation desulfurization catalysts at home and abroad, and the research is mainly focused on oil-soluble and supported catalysts. The two catalysts have the defects of poor oxidation desulfurization effect, complex preparation process and high synthesis cost. Therefore, a novel residual oil oxidation desulfurization catalyst with good desulfurization effect, simple synthesis process and relatively low cost is developed, and has important significance.
Disclosure of Invention
The invention aims to solve the problems of poor desulfurization effect, complex preparation process and high synthesis cost of the residual oil oxidation desulfurization catalyst in the prior art.
In order to achieve the above object, according to an aspect of the present invention, there is provided a water-soluble catalyst which is a product obtained by mixing a metal active component and hydrogen peroxide, wherein a metal element in the metal active component is at least one selected from molybdenum, tungsten and vanadium.
In a second aspect, the present invention provides a process for preparing a water-soluble catalyst, the process comprising: mixing and reacting a metal active component with hydrogen peroxide, wherein the metal element in the metal active component is at least one selected from molybdenum, tungsten and vanadium.
In a third aspect, the present invention provides the use of a water-soluble catalyst provided in the first aspect of the invention and/or a water-soluble catalyst produced by a process provided in the second aspect in the processing of residuum.
In a fourth aspect, the present invention provides a process for processing residuum comprising:
(1) Mixing residual oil with a solvent to obtain diluted residual oil;
(2) Contacting the diluted residuum with a liquid oxidant in a reactor containing a catalyst; the catalyst is a product obtained by mixing and reacting a metal active component with hydrogen peroxide, wherein a metal element in the metal active component is selected from at least one of tungsten and vanadium, or a combination of molybdenum and at least one of tungsten and vanadium;
(3) Carrying out solvent recovery treatment on the liquid phase material flow obtained after the contact reaction;
(4) And (3) carrying out delayed coking on the oxidized residual oil obtained after the solvent recovery treatment.
The catalyst is obtained by one-step reaction of the hydrogen peroxide and the metal active component containing at least one metal element of molybdenum, tungsten and vanadium, is used for preparing low-sulfur petroleum coke by processing residual oil, has high catalytic efficiency, can reduce the sulfur content in the petroleum coke by more than 50wt%, and has the advantages of simple preparation process, low synthesis cost and no pollutant emission in the synthesis process.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a water-soluble catalyst which is a product obtained by mixing a metal active component and hydrogen peroxide, wherein a metal element in the metal active component is at least one selected from molybdenum, tungsten and vanadium.
Preferably, the conditions of the mixing reaction include at least: the temperature is 25-80 ℃; the time is 1-6h.
More preferably, the conditions of the mixing reaction include at least: the temperature is 25-70 ℃; the time is 2-5h. The inventor finds that in the preferred case, when the prepared catalyst is used for processing residual oil, higher catalytic efficiency can be obtained, and the sulfur content in petroleum coke can be reduced better.
According to a preferred embodiment, the metal active component is selected from at least one of a molybdenum source, a tungsten source, a vanadium source; the method comprises the steps of,
the molybdenum source is at least one selected from simple substance molybdenum and hexavalent molybdenum sources;
the tungsten source is at least one selected from simple substance tungsten and hexavalent tungsten sources;
the vanadium source is at least one selected from simple substance vanadium and pentavalent vanadium source.
Preferably, the weight ratio of the metal active component to the hydrogen peroxide in pure substance is 1:0.6-8.
Preferably, the hexavalent molybdenum source is selected from at least one of molybdenum trioxide, molybdenum oxalate, molybdic acid, molybdate.
Preferably, the hexavalent tungsten source is selected from at least one of tungsten trioxide, tungstic acid, tungstate.
Preferably, the pentavalent vanadium source is selected from at least one of vanadium pentoxide, vanadate and vanadate.
Preferably, the molybdate is at least one selected from ammonium molybdate, ammonium paramolybdate and sodium molybdate.
Preferably, the tungstate is at least one selected from sodium tungstate, calcium tungstate and ammonium tungstate.
Preferably, the vanadate is at least one selected from ammonium metavanadate, sodium metavanadate and potassium metavanadate.
Preferably, the metal active component is a molybdenum source, and the weight ratio of the molybdenum source to the hydrogen peroxide calculated as pure substance is 1:0.6-3.
Preferably, the metal active component is a tungsten source, and the weight ratio of the tungsten source to the hydrogen peroxide calculated as pure substance is 1:0.6-5.
Preferably, the metal active component is a vanadium source, and the weight ratio of the vanadium source to the hydrogen peroxide calculated as pure substance is 1:3-8.
Preferably, the concentration of hydrogen peroxide is 10-30wt%, preferably 10-20wt%, more preferably 10-15wt%.
As previously described, a second aspect of the present invention provides a method of preparing a water soluble catalyst, the method comprising: mixing and reacting a metal active component with hydrogen peroxide, wherein the metal element in the metal active component is at least one selected from molybdenum, tungsten and vanadium.
Preferably, the conditions of the mixing reaction include at least: the temperature is 25-80 ℃; the time is 1-6h.
The water-soluble catalyst has the advantages of simple synthesis process, low synthesis cost, recycling and high efficiency in catalyzing the oxidation reaction of the sulfur-containing compounds in the residual oil.
Unless specifically stated otherwise, the materials, such as metal active components, and the like, involved in the water-soluble catalyst according to the second aspect of the present invention are the same as those of the first aspect of the present invention, and the present invention is not described herein in detail, and those skilled in the art should not understand the limitation of the present invention.
As previously mentioned, a third aspect of the present invention provides the use of the water soluble catalyst provided in the first aspect of the present invention and/or the water soluble catalyst produced by the process provided in the second aspect in the processing of residuum.
As previously mentioned, a fourth aspect of the present invention provides a process for processing residuum, the process comprising:
(1) Mixing residual oil with a solvent to obtain diluted residual oil;
(2) Contacting the diluted residuum with a liquid oxidant in a reactor containing a catalyst; the catalyst is a product obtained by mixing and reacting a metal active component with hydrogen peroxide, wherein a metal element in the metal active component is selected from at least one of tungsten and vanadium, or a combination of molybdenum and at least one of tungsten and vanadium;
(3) Carrying out solvent recovery treatment on the liquid phase material flow obtained after the contact reaction;
(4) And (3) carrying out delayed coking on the oxidized residual oil obtained after the solvent recovery treatment.
Unless otherwise specified, the material raw materials, such as sources of metal elements in the metal active component, and the like, involved in the catalyst according to the fourth aspect of the present invention are the same as those of the first aspect of the present invention, and the present invention is not described herein in detail, and those skilled in the art should not understand the limitation of the present invention.
The inventor discovers that the catalyst and processes such as delayed coking are combined to process residual oil, so that the oxidation reaction of sulfur-containing compounds in the residual oil can be efficiently catalyzed to prepare low-sulfur petroleum coke.
Preferably, in the step (1), the amount of the solvent is controlled so that the resulting diluted residuum has a viscosity of 1 to 500mm at 80 DEG C 2 /s。
Preferably, in step (1), the residual oil and the solvent are used in a weight ratio of 1:0.2 to 5; more preferably 1:0.5 to 2.
Preferably, the residuum is at least one of atmospheric residuum, vacuum residuum, and asphalt, and the sulfur content in the residuum is greater than 2.0 wt.%; more preferably greater than 3.0 wt%.
According to a particularly preferred embodiment, the residuum is a vacuum residuum which is heated to 150-180 ℃ prior to dilution.
Preferably, the solvent is selected from at least one of benzene, toluene, chloroform, tetrahydrofuran, carbon tetrachloride, pyridine, N dimethylformamide, methylene chloride, catalytic diesel, coker diesel, reformed gasoline, and coker gasoline.
According to a particularly preferred embodiment, in step (1), the solvent is a catalytic diesel having an aromatic hydrocarbon content of not less than 30% by weight; the weight ratio of the residual oil to the catalytic diesel oil is 1:0.5-1.
Preferably, in step (2), the conditions of the mixing reaction include at least: the temperature is 25-80 ℃; the time is 1-6h.
According to a preferred embodiment, in step (2), the liquid oxidizing agent is selected from at least one of hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, t-hexyl peroxypivalate, concentrated nitric acid and peracetic acid.
Preferably, the mass ratio of the liquid oxidant to the diluted residual oil is 1:1-5; preferably 1:2.5-5.
According to a particularly preferred embodiment, the liquid oxidizing agent is hydrogen peroxide. In this preferred case, the oxidation reaction rate is high and the safety of operation is high.
According to another particularly preferred embodiment, the hydrogen peroxide is added to the reaction at a flow rate of 0.3 to 0.5 g/min.
According to another preferred embodiment, the reactor is a fully mixed reactor. In this preferred case, the catalyst is led out of the reactor together with the liquid product, and therefore it is preferable to provide a separation unit downstream of the process to effect separation of the catalyst from the liquid product, thereby achieving the objective of recovering the water-soluble catalyst. Preferably, separation of the catalyst and the liquid product is achieved, for example, by standing for delamination, the upper layer being the oil phase and the lower layer being the aqueous phase with the catalyst, the catalyst entering the concentrating unit, the excess water being removed.
Preferably, the conditions of the contact reaction at least satisfy: the reaction temperature is 45-130 ℃, preferably 75-85 ℃; the reaction time is 0.5 to 15 hours, preferably 0.8 to 1.5 hours. The contact reaction according to the present invention may be carried out at normal pressure.
Preferably, the weight ratio of the residual oil to the catalyst is 1:0.05-0.4, preferably 1:0.05-0.2.
Preferably, in step (3), the liquid phase stream obtained after the contact reaction is washed with water before the solvent recovery treatment, and then the washed stream is subjected to the solvent recovery treatment.
Preferably, the operation of the solvent recovery process comprises: and (3) carrying out normal pressure distillation or reduced pressure distillation on the liquid phase stream obtained after the contact reaction.
According to a preferred embodiment, the method further comprises: recycling the recovered solvent obtained after the solvent recovery treatment back to the step (1).
Preferably, the conditions of the delayed coking include at least: the temperature is 480-515 ℃, and the pressure is 0.1-0.25 Mpa.
Particularly, the method can realize more efficient oxidation reaction of sulfur-containing compounds in catalytic residual oil on the premise of applying a small amount of catalyst, so that the sulfur content in petroleum coke prepared by the method can be reduced by more than 50 weight percent. In addition, the catalyst applied in the method can be recycled by a water washing method; in addition, the catalyst has simple obtaining method and low cost, and no pollutant is discharged in the production process.
Unless otherwise indicated, the pressures described herein are gauge pressures.
The invention will be described in detail below by way of examples. In the following examples, various raw materials used without particular explanation were all products manufactured by the national pharmaceutical group chemical reagent company, ltd.
In the following examples, without contrary explanation:
the liquid oxidant adopts 30wt% of hydrogen peroxide;
toluene was used as the solvent.
The feedstock used was vacuum residuum, the properties of which are shown in table 1;
the sulfur content of petroleum coke is measured by an infrared detection method of oxidation combustion developed by China institute of petrochemical industry;
the desulfurization rate calculation method in table 2 is: desulfurization rate of example N% = 100% × (petroleum coke sulfur content in comparative example 1-petroleum coke sulfur content in example N)/petroleum coke sulfur content in comparative example 1.
Table 1: properties of vacuum residuum
Both the preparation examples and the preparation comparative examples were used for preparing the water-soluble catalyst.
Preparation example 1
The preparation embodiment provides a preparation method of a water-soluble catalyst, which comprises the following steps: 1g of tungstic acid is placed in a 50mL three-neck flask, 20g of hydrogen peroxide with the concentration of 10wt% is added, the three-neck flask is placed in a magnetic stirring heating sleeve, a condensing reflux pipe is arranged, heating is carried out to 70 ℃, magnetic stirring is carried out at the same time, mixing reaction is carried out for 2 hours, and the tungstic acid and the hydrogen peroxide completely react to form clear and transparent peroxide solution of tungsten, which is named Cat1.
Preparation example 2
The preparation embodiment provides a preparation method of a water-soluble catalyst, which comprises the following steps: 2g of tungsten powder is placed in a 50mL three-neck flask, 10g of hydrogen peroxide with the concentration of 15wt% is added, a condensing reflux pipe is arranged, magnetic stirring is carried out at the temperature of 25 ℃, and the mixture is reacted for 2 hours until the tungsten powder and the hydrogen peroxide completely react to form clear and transparent tungsten peroxide solution which is named Cat2.
Preparation example 3
The preparation embodiment provides a preparation method of a water-soluble catalyst, which comprises the following steps: 2g of tungsten trioxide is placed in a 50mL three-neck flask, 20g of hydrogen peroxide with the concentration of 30wt% is added, the three-neck flask is placed in a magnetic stirring heating sleeve, a condensing reflux pipe is arranged, heating is carried out to 70 ℃, magnetic stirring is carried out at the same time, mixing reaction is carried out for 5 hours until the tungsten trioxide and the hydrogen peroxide completely react, and a clear and transparent peroxide solution of tungsten is formed, and the clear and transparent peroxide solution is named as Cat3.
Preparation example 4
The preparation embodiment provides a preparation method of a water-soluble catalyst, which comprises the following steps: 2g of molybdenum powder is placed in a 50mL three-neck flask, 20g of hydrogen peroxide with the concentration of 15wt% is added, a condensing reflux pipe is arranged, magnetic stirring is carried out at the temperature of 25 ℃, and the mixing reaction is carried out for 2 hours until the molybdenum powder and the hydrogen peroxide completely react to form a transparent yellow-green molybdenum peroxide solution which is named Cat4.
Preparation example 5
The preparation embodiment provides a preparation method of a water-soluble catalyst, which comprises the following steps: 2g of molybdenum trioxide is placed in a 50mL three-neck flask, 18g of hydrogen peroxide with the concentration of 30wt% is added, the three-neck flask is placed in a magnetic stirring heating sleeve, a condensing reflux pipe is arranged, the temperature is heated to 60 ℃, magnetic stirring is carried out at the same time, and the mixing reaction is carried out for 5 hours until the molybdenum trioxide and the hydrogen peroxide completely react, so that a transparent yellow-green molybdenum peroxide solution is formed, and the transparent yellow-green molybdenum peroxide solution is named as Cat5.
Preparation example 6
The preparation embodiment provides a preparation method of a water-soluble catalyst, which comprises the following steps: 2g of molybdic acid is placed in a 50mL three-neck flask, 5g of hydrogen peroxide with the concentration of 30wt% is added, the three-neck flask is placed in a magnetic stirring heating sleeve, a condensing reflux pipe is arranged, the temperature is heated to 40 ℃, magnetic stirring is carried out at the same time, and the mixing reaction is carried out for 1 hour until the molybdic acid and the hydrogen peroxide completely react, so that a transparent yellow-green molybdenum peroxide solution is formed, and the transparent yellow-green molybdenum peroxide solution is named as Cat6.
Preparation example 7
The preparation embodiment provides a preparation method of a water-soluble catalyst, which comprises the following steps: 1g of vanadium pentoxide is placed in a 100mL three-neck flask, 40g of hydrogen peroxide with the concentration of 15wt% is added, a condensing reflux pipe is arranged, magnetic stirring is carried out at the temperature of 25 ℃, and the mixing reaction is carried out for 2 hours until the vanadium pentoxide and the hydrogen peroxide completely react to form a peroxide solution of red vanadium, and the peroxide solution is named Cat7.
Preparation example 8
The preparation embodiment provides a preparation method of a water-soluble catalyst, which comprises the following steps: 1g of potassium metavanadate is placed in a 50mL three-neck flask, 30g of hydrogen peroxide with the concentration of 15wt% is added, a condensing reflux pipe is arranged, magnetic stirring is carried out at the temperature of 25 ℃, and the mixing reaction is carried out for 1 hour until the potassium metavanadate and the hydrogen peroxide completely react to form a transparent peroxide solution of vanadium, and the transparent peroxide solution is named Cat8.
Preparation example 9
This preparation example was carried out using a procedure similar to preparation example 1, except that: the conditions of the mixing reaction include: the temperature is 30 ℃ and the time is 2 hours; the catalyst prepared in this preparation example was designated Cat9.
The examples are presented to illustrate the process of the present invention for processing residuum.
Example 1
The catalyst prepared in the preparation example was used.
(1) Heating vacuum residuum to 160 ℃, and mixing the heated residuum with solvent-catalyzed diesel oil (the aromatic hydrocarbon content is 35 wt%) according to the weight ratio of 1:1 to obtain diluted residual oil (viscosity of 50mm at 80℃) 2 /s)。
(2) 50g of diluted residual oil, 20g of hydrogen peroxide and a catalyst (the use amount is 20wt% of the residual oil) are added into a full mixing reactor, and the residual oil, the solvent and the catalyst are fully and uniformly mixed by stirring; continuously adding hydrogen peroxide in the reaction process, and controlling the total adding amount by controlling the adding flow rate to be 0.3 g/min; then the fully mixed reactor is heated to 75 ℃ to carry out oxidation reaction, and the reaction time is 1.5h.
(3) After the reaction is finished, washing with water, and then evaporating the solvent in the deslagging oil system to catalyze the diesel oil, so as to obtain oxidized residual oil.
(4) Taking out 2g of oxidized residual oil, placing the oxidized residual oil into a quartz glass test tube, and carrying out a rapid coking experiment in a coking reactor under the protection of nitrogen at the temperature of 515 ℃ and the pressure of 0.1Mpa for 1 hour, thereby obtaining different petroleum cokes according to the types of the used catalysts, and referring to table 2 specifically.
The sulfur content of the petroleum coke obtained was tested, and the sulfur content change in the petroleum coke before and after oxidation was compared, and the specific results are shown in table 2.
Example 2
The catalyst prepared in the preparation example was used.
(1) Heating the vacuum residue to 150 ℃, and mixing the heated residue with toluene solvent according to the weight ratio of 1:1 to obtain diluted residual oil (viscosity of 50mm at 80℃) 2 /s)。
(2) 50g of diluted residual oil and 15g of hydrogen peroxide are added into a full mixing reactor, and the residual oil, the solvent and the catalyst are fully and uniformly mixed by stirring; continuously adding the oxidant in the reaction process, and controlling the total adding amount by controlling the adding flow rate to be 0.3 g/min; then the fully mixed reactor is heated to 80 ℃ to carry out oxidation reaction, and the reaction time is 1h.
(3) After the reaction is finished, washing with water, and then evaporating solvent toluene in the deslagging oil system to obtain oxidized residual oil.
(4) Taking out 2g of oxidized residual oil, placing the oxidized residual oil into a quartz glass test tube, and carrying out a rapid coking experiment in a coking reactor under the protection of nitrogen at the temperature of 500 ℃ and the pressure of 0.2Mpa for 1 hour, so as to obtain different petroleum cokes according to the types of the used catalysts, wherein the specific reference is shown in Table 2.
The sulfur content of the petroleum coke obtained was tested, and the sulfur content change in the petroleum coke before and after oxidation was compared, and the specific results are shown in table 2.
Example 3
The catalyst prepared in the preparation example was used.
(1) Heating the vacuum residue to 180 ℃, and mixing the heated residue with toluene solvent according to a weight ratio of 1:2 to obtain diluted residual oil (viscosity of 50mm at 80deg.C) 2 /s)。
(2) 50g of diluted residual oil and 10g of hydrogen peroxide are added into a full mixing reactor, and the residual oil, the solvent and the catalyst are fully and uniformly mixed by stirring; continuously adding the oxidant in the reaction process, and controlling the total adding amount by controlling the adding flow rate to be 0.3 g/min; then the fully mixed reactor is heated to 85 ℃ for oxidation reaction, and the reaction time is 0.8h.
(3) After the reaction is finished, washing with water, and then evaporating solvent toluene in the deslagging oil system to obtain oxidized residual oil.
(4) Taking out 2g of oxidized residual oil, placing the oxidized residual oil into a quartz glass test tube, and carrying out a rapid coking experiment in a coking reactor under the protection of nitrogen at the temperature of 480 ℃ and the pressure of 0.25Mpa for 1 hour, thereby obtaining different petroleum cokes according to the types of the used catalysts, and referring to table 2 specifically.
The sulfur content of the petroleum coke obtained was tested, and the sulfur content change in the petroleum coke before and after oxidation was compared, and the specific results are shown in table 2.
Comparative example 1
This comparative example is used to illustrate a reference process for preparing petroleum coke from residuum.
2g of vacuum residuum was directly subjected to a rapid coking test, wherein the rapid coking test was the same as the medium rapid coking test procedure of example 1, to obtain petroleum coke PD-1.
The sulfur content of the petroleum coke obtained was tested, and the specific results are shown in table 2.
Comparative example 2
This comparative example is used to illustrate a reference process for preparing petroleum coke from residuum.
This comparative example used the same procedure as in example 1 to process residuum, except that: and (3) a catalyst is not used in the step (2), so that the petroleum coke PD-2 is obtained.
The sulfur content of the petroleum coke obtained was tested, and the specific results are shown in table 2.
Comparative example 3
This comparative example is used to illustrate a reference process for preparing petroleum coke from residuum.
This comparative example used the same procedure as in example 1 to process residuum, except that: the catalyst adopted is formic acid, the use amount is 20wt% of residual oil, and the petroleum coke PD-3 is obtained.
The sulfur content of the petroleum coke obtained was tested, and the specific results are shown in table 2.
Comparative example 4
This comparative example is used to illustrate a reference process for preparing petroleum coke from residuum.
This comparative example used the same procedure as in example 1 to process residuum, except that: the catalyst adopted is acetic acid, the usage amount is 20wt% of residual oil, and the petroleum coke PD-4 is obtained.
The sulfur content of the petroleum coke obtained was tested, and the specific results are shown in table 2.
TABLE 2
From the results, the catalyst can efficiently catalyze the oxidation reaction of the sulfur-containing compounds in the residual oil, and has high catalytic efficiency.
The catalyst in the invention can reduce the sulfur content of the residual oil coking petroleum coke by combining with the residual oil processing method, has high desulfurization rate, and has the advantage of saving the use cost of the catalyst.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (21)
1. A method of processing residuum, the method comprising:
(1) Mixing residual oil with a solvent to obtain diluted residual oil;
(2) Carrying out contact oxidation reaction on the diluted residual oil and a liquid oxidant in a reactor containing a water-soluble catalyst; the water-soluble catalyst is a product obtained by mixing and reacting a metal active component with hydrogen peroxide; the metal active component is tungstic acid, the weight ratio of the metal active component to the hydrogen peroxide calculated as pure substances in the process of preparing the water-soluble catalyst is 1:0.6-8, and the concentration of the hydrogen peroxide is 10-30wt%; the conditions of the mixing reaction at least comprise: the temperature is 25-80 ℃; the time is 1-6h; the liquid oxidant is hydrogen peroxide;
(3) Carrying out solvent recovery treatment on the liquid phase material flow obtained after the contact oxidation reaction;
(4) Performing delayed coking on the oxidized residual oil obtained after the solvent recovery treatment to obtain low-sulfur petroleum coke;
the weight ratio of the residual oil to the water-soluble catalyst is 1:0.05-0.4.
2. The method of claim 1, wherein in step (2), the conditions of the mixing reaction include at least: the temperature is 25-70 ℃; the time is 2-5h.
3. The method according to claim 1, wherein in step (2), in the process of preparing the water-soluble catalyst, the ratio of the metal active component to the hydrogen peroxide in terms of pure substance is 1 by weight: 0.6-5.
4. A process according to any one of claims 1 to 3, wherein in step (2), the hydrogen peroxide is at a concentration of 10 to 20wt% during the preparation of the water soluble catalyst.
5. The method according to claim 4, wherein, in the step (2), the concentration of the hydrogen peroxide is 10 to 15wt% in the process of preparing the water-soluble catalyst.
6. The process according to claim 1, wherein in the step (1), the amount of the solvent is controlled so that the resulting diluted residuum has a viscosity of 1 to 500mm at 80 ℃ 2 /s。
7. The process of claim 1, wherein the residual oil is used in an amount by weight ratio of 1: 0.2-5.
8. The process of claim 7, wherein the residual oil is used in an amount by weight ratio of 1: 0.5-2.
9. The method of claim 1, wherein the residuum is at least one of an atmospheric residuum, a vacuum residuum, and the sulfur content in the residuum is greater than 2.0 wt.%.
10. The process of claim 9, wherein the sulfur content in the residuum is greater than 3.0 wt.%.
11. The method of claim 1, wherein the solvent is selected from at least one of benzene, toluene, chloroform, tetrahydrofuran, carbon tetrachloride, pyridine, N dimethylformamide, methylene chloride, catalytic diesel, coker diesel, reformed gasoline, and coker gasoline.
12. The method according to claim 1, wherein in step (1), the solvent is a catalytic diesel having an aromatic hydrocarbon content of not less than 30% by weight; the weight ratio of the residual oil to the catalytic diesel oil is 1:0.5-1.
13. The process of claim 1, wherein in step (2) the liquid oxidant is used in an amount to mass ratio of 1 to the diluted resid: 1-5.
14. The process of claim 13, wherein in step (2) the liquid oxidant is used in an amount to mass ratio of 1 to the diluted resid: 2.5-5.
15. The method of claim 1, wherein the conditions of the contact oxidation reaction at least satisfy: the reaction temperature is 45-130 ℃; the reaction time is 0.5-1.5h.
16. The method of claim 15, wherein the conditions of the contact oxidation reaction at least satisfy: the reaction temperature is 75-85 ℃; the reaction time is 0.8-1.5h.
17. The process of claim 1, wherein the residual oil is used in an amount by weight ratio to the water soluble catalyst of 1:0.05-0.2.
18. The method according to claim 1, wherein in step (3), the liquid-phase stream obtained after the contact oxidation reaction is subjected to water washing before the solvent recovery treatment, and the water-washed stream is then subjected to the solvent recovery treatment.
19. The method of claim 1, wherein the operation of solvent recovery processing comprises: and (3) carrying out normal pressure distillation or reduced pressure distillation on the liquid phase stream obtained after the contact oxidation reaction.
20. The method of claim 1, wherein the conditions of delayed coking include at least: the temperature is 480-515 ℃, and the pressure is 0.1-0.25 mpa.
21. The method of claim 1, wherein the method further comprises: recycling the recovered solvent obtained after the solvent recovery treatment back to the step (1).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003128619A (en) * | 2001-10-23 | 2003-05-08 | Sumitomo Chem Co Ltd | Method for producing 3-methyladipic acid |
| JP2003300950A (en) * | 2002-02-07 | 2003-10-21 | Sumitomo Chem Co Ltd | Method for producing sulfone compound of sulfoxide compound and catalyst therefor |
| CN110312779A (en) * | 2017-02-20 | 2019-10-08 | 沙特阿拉伯石油公司 | Using coker desulfurization and remove sulfone |
| CN111363588A (en) * | 2018-12-25 | 2020-07-03 | 中国石油化工股份有限公司 | Method and reaction system for producing low-sulfur petroleum coke |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3945914A (en) * | 1974-08-23 | 1976-03-23 | Atlantic Richfield Company | Process for "sulfur reduction of an oxidized hydrocarbon by forming a metal-sulfur-containing compound" |
| FR2818990B1 (en) * | 2000-12-28 | 2004-09-24 | Total Raffinage Distribution | PROCESS AND DEVICE FOR DESULFURIZING HYDROCARBONS FILLED WITH THIOPHENIC DERIVATIVES |
| US6673230B2 (en) * | 2001-02-08 | 2004-01-06 | Bp Corporation North America Inc. | Process for oxygenation of components for refinery blending of transportation fuels |
| JP4200713B2 (en) * | 2002-02-04 | 2008-12-24 | 住友化学株式会社 | Process for producing polyketones and catalyst thereof |
| FR2844518B1 (en) * | 2002-09-16 | 2006-05-12 | Inst Francais Du Petrole | HYDROGEN-FREE DESULFURIZATION PROCESS |
| CN100593531C (en) * | 2006-08-11 | 2010-03-10 | 中国石油化工股份有限公司 | Method for reclaiming and purifying styrene |
| CN101121634B (en) * | 2006-08-11 | 2010-06-16 | 中国石油化工股份有限公司 | Recovery method for styrene from pyrolysis gasoline |
| US9598647B2 (en) * | 2010-09-07 | 2017-03-21 | Saudi Arabian Oil Company | Process for oxidative desulfurization and sulfone disposal using solvent deasphalting |
| SG11201907206YA (en) * | 2017-02-20 | 2019-09-27 | Saudi Arabian Oil Co | Oxidative desulfurization of oil fractions and sulfone management using an fcc |
| SG11201907201VA (en) * | 2017-02-20 | 2019-09-27 | Saudi Arabian Oil Co | Desulfurization and sulfone removal using a coker |
| CN110882690A (en) * | 2019-11-07 | 2020-03-17 | 武汉科技大学 | Silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst and preparation method thereof |
-
2020
- 2020-10-30 CN CN202011189898.3A patent/CN114130384B/en active Active
- 2020-10-30 CN CN202011189894.5A patent/CN114133954B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003128619A (en) * | 2001-10-23 | 2003-05-08 | Sumitomo Chem Co Ltd | Method for producing 3-methyladipic acid |
| JP2003300950A (en) * | 2002-02-07 | 2003-10-21 | Sumitomo Chem Co Ltd | Method for producing sulfone compound of sulfoxide compound and catalyst therefor |
| CN110312779A (en) * | 2017-02-20 | 2019-10-08 | 沙特阿拉伯石油公司 | Using coker desulfurization and remove sulfone |
| CN111363588A (en) * | 2018-12-25 | 2020-07-03 | 中国石油化工股份有限公司 | Method and reaction system for producing low-sulfur petroleum coke |
Non-Patent Citations (1)
| Title |
|---|
| 宋华 ; 冯化林 ; 李国忠 ; 江雪原 ; .V_2O_5催化氧化深度脱硫.化学工程.2011,(06),第84-87页. * |
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| CN114133954B (en) | 2024-08-09 |
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