CN100587036C - Method for desulfurization of fuel oil by oxidation process with modified titanium silicon molecular sieve as catalyst - Google Patents
Method for desulfurization of fuel oil by oxidation process with modified titanium silicon molecular sieve as catalyst Download PDFInfo
- Publication number
- CN100587036C CN100587036C CN200610200318A CN200610200318A CN100587036C CN 100587036 C CN100587036 C CN 100587036C CN 200610200318 A CN200610200318 A CN 200610200318A CN 200610200318 A CN200610200318 A CN 200610200318A CN 100587036 C CN100587036 C CN 100587036C
- Authority
- CN
- China
- Prior art keywords
- fuel oil
- catalyzer
- reaction
- hts
- silicon molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 69
- 239000000295 fuel oil Substances 0.000 title claims abstract description 60
- 230000003647 oxidation Effects 0.000 title claims abstract description 48
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 39
- 230000023556 desulfurization Effects 0.000 title claims abstract description 32
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical class [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 title claims description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 title claims description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- 230000004048 modification Effects 0.000 claims description 31
- 238000012986 modification Methods 0.000 claims description 31
- 238000002444 silanisation Methods 0.000 claims description 28
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 7
- 150000003457 sulfones Chemical class 0.000 claims description 5
- 150000003462 sulfoxides Chemical class 0.000 claims description 5
- -1 alkyl silicate Chemical compound 0.000 claims description 3
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 63
- 238000007654 immersion Methods 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 6
- 230000003252 repetitive effect Effects 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 66
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 46
- 238000004088 simulation Methods 0.000 description 40
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 32
- 230000001590 oxidative effect Effects 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 21
- 230000003247 decreasing effect Effects 0.000 description 20
- 230000006698 induction Effects 0.000 description 20
- 239000007800 oxidant agent Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 16
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 238000006424 Flood reaction Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000005055 methyl trichlorosilane Substances 0.000 description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- NFKMSYOEMWGTMW-UHFFFAOYSA-N 5-sulfanylidenedibenzothiophene Chemical class C1=CC=C2S(=S)C3=CC=CC=C3C2=C1 NFKMSYOEMWGTMW-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
An oxidation sweetening method for fuel oil selecting modified titanium-silicon molecular screen as accelerating agent belongs to technical sphere of petroleum process. The invention provides an accelerating agent of modified titanium-silicon molecular screen which can be used in oxidation sweetening of fuel oil. The charge number of earth silicon in this invention adopting immersion method is 1.0wt%-3.0wt%. The obtained modified titanium-silicon molecular screen is used for catalytic and oxidation desulfurization of fuel oil. The significance effect of this invention is that it improves the repetitive use of accelerating agent in oxidation sweetening reaction. The method includes selecting modified titanium-silicon molecular screen as accelerating agent and removing sulfidization of fueloil by hydrocarbonylation, which can reduce the sulfur content of fuel oil to 29.7 mu/g from 226.1 mu/g and reach deep desulfuration, and the accelerating agent can be recovered and the catalytic oxidation susceptibility of the recovered accelerating agent is good. The invention is of mild reaction condition, simple equipment and no consumption of hydrogen gas.
Description
Technical field
The invention belongs to the Petroleum Processing Technology field.Relate to a kind of method that adopts silanization modifying titanium-silicon molecular sieve catalyzer to carry out the fuel oil oxidation desulfurization.
Background technology
The burning of sulfocompound can cause environmental pollution in the liquid fuel.In the clean fuel standards that formulate countries in the world, to the wherein more and more strictness of restriction of sulphur content.Adopt traditional hydrodesulfurizationprocess process that removing of macromole sulfide faced very big difficulty.Catalytic oxidation removes organic sulfide in the liquid fuel, and it is effective particularly to remove macromole sulfide, is a kind of new technology little, that reaction conditions is gentle of investing, and also can be used as the follow-up deep desulfuration of hydrodesulfurization.The catalyzer that the catalytic oxidation desulfurization is adopted has liquid acid, heteropolyacid, molecular sieve etc.Wherein, adopting molecular sieve is that catalyzer has been avoided the influence of liquid acid catalyst to fuel qualities, has application promise in clinical practice.
Document [J.Catal., 2001,198:179] has been reported and has been adopted titanium-silicon molecular sieve TS-1, Ti-Suan i-HMS catalysis hydrogen peroxide oxidation to remove thionaphthene, dibenzothiophene sulfides in the kerosene.Document [J.Chem.Eng.Jpn., 2002,35:1305] has been reported thionaphthene, the dibenzothiophene sulfides that adopts in the HTS Ti-HMS catalytic oxidative desulfurization solar oil.
But, the easy inactivation of molecular sieve catalyst during diesel oxidation desulfurizing, this is that this technology realizes the problem that industrialization need solve.
Document [Chem.Commun., 1998,325] has been reported the inactivation that adopts silanization modification Ti-MCM-41 catalyzer to reduce catalyzer.
P.20030183555, it is that catalyst oxidation removes sulfide in petrol that U.S. Pat adopts silanization modified molecular screen Ti-MCM-41, can reach 96% desulfurization degree.
Up to now, Shang Weiyou is used for catalytic oxidative desulfurization diesel oil macromole sulfide 4 with the silanization modifying titanium-silicon molecular sieve, 6-dimethyl Dibenzothiophene (DMDBT) and improve the report of catalyzer repeat performance.
Summary of the invention
The purpose of this invention is to provide that a kind of to adopt the HTS of silanization modification be catalyzer, macromole sulfide in the catalyzed oxidation fuel oil, as thionaphthene, dibenzothiophene and alkyl substituent thereof, reach the purpose of fuel desulfuration, and solve the reusability of catalyzer.
Technical solution of the present invention is, a kind of silanization modifying titanium-silicon molecular sieve that adopts is the method that catalyzer carries out the fuel oil oxidation desulfurization, and processing step is:
(a) to have adopted a kind of silanization modifying titanium-silicon molecular sieve be catalyzer to catalytic oxidation, and the silanization modification has improved the reusability of catalyzer in the sulfide oxidation reaction;
(b) thionaphthene in the catalyzed oxidation fuel oil, dibenzothiophene and 4, the 6-dimethyl Dibenzothiophene, this oxidising process changes into sulfone, sulfoxide with sulfide;
(c) after the fuel oil oxide treatment, the sulfide oxidation product with oil phase and catalyst separating, is realized fuel desulfuration by solvent extraction, and the solvent extraction operation can be carried out with oxide treatment or carry out after oxide treatment simultaneously.
Silanization modifying titanium-silicon molecular sieve catalyzer can adopt pickling process or vapour deposition process preparation.The pickling process solution impregnation HTS of silylating reagent, 298K then? the 23K oven dry, 673K? the 73K roasting.The solvent of used silylating reagent can be benzene, toluene, n-Octanol, normal hexane or hexanaphthene.Is the strength of solution of silylating reagent 0.0216mol/L? 0.0415mol/L.
The silylating reagent that is used for modification can be alkyl silicate (wherein alkyl can be methyl, ethyl and sec.-propyl), methyl chlorosilane Si (CH
3)
4-nCl
n(n=1,2,3) and ((CH
3)
3Si)
2NH etc.Silanization modifying titanium-silicon molecular sieve SiO
2Charge capacity is 1.0wt%～3.0wt%, and is wherein preferred: 1.0wt%～2.5wt%.
HTS is Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, wherein preferred Ti-HMS, Ti-MCM-41.
It is catalyzer that the fuel oil catalytic oxidation desulfurization adopts the HTS of silanization modification.Oxygenant can be hydrogen peroxide, tertbutyl peroxide, hydrogen phosphide cumene, wherein preferred hydrogen peroxide.Temperature of reaction 293K? 73K.The oxidation products of the sulfide in the fuel oil is sulfoxide, sulfone etc.Oxidation goes out the wherein oxidation products of sulfide with solvent extraction simultaneously or after the oxidation.The solvent that adopts is water, the trimethyl carbinol, methyl alcohol, acetonitrile, dimethyl sulfoxide (DMSO) etc., wherein particular methanol.
Effect of the present invention is: by adopting silylating reagent HTS is carried out modification, improved the reusability of catalyst oxidation desulfurization.HTS with modification is a catalyzer, remove sulfide in the fuel oil by oxidation style, the sulphur content in the fuel oil is dropped to 29.7 He/g from 226.1 He/g, reach deep desulfuration, catalyzer is recyclable, and the catalytic oxidation performance of recovery rear catalyst is good.The reaction conditions gentleness, equipment is simple, does not consume hydrogen.
Embodiment
Embodiment 1.
Present embodiment illustrates the preparation method of the HTS of a kind of silanization modification provided by the invention.HTS Ti-HMS is a template with the amino dodecane, is the silicon source with the tetraethoxy, presses document [Chin J Catal, 2004,25 (2): 89] preparation.With the tetraethoxy is the HTS that silylating reagent adopts the immersion process for preparing modification.The cyclohexane solution of 1g HTS Ti-HMS and 8mL 4.33g/L tetraethoxy is stirred, the tetraethoxy charge capacity is 3.47wt% on the HTS, floods 10h under the room temperature then, dries back temperature programming dry 6h under 363K, roasting 5h makes SiO under 810K
2Charge capacity is the SiO of 1.0wt%
2/ Ti-HMS catalyzer.
Embodiment 2.
Present embodiment illustrates the preparation method of the HTS of a kind of silanization modification provided by the invention.HTS Ti-HMS is a template with the amino dodecane, is the silicon source with the tetraethoxy, presses document [Chin J Catal, 2004,25 (2): 89] preparation.With the tetraethoxy is the HTS that silylating reagent adopts the immersion process for preparing modification.The cyclohexane solution of 1g HTS Ti-HMS and 8mL 5.63g/L tetraethoxy is stirred, the tetraethoxy charge capacity is 4.51wt% on the HTS, floods 10h under the room temperature then, dries back temperature programming dry 6h under 363K, roasting 5h makes SiO under 810K
2Charge capacity is the SiO of 1.3wt%
2/ Ti-HMS catalyzer.
Embodiment 3.
Present embodiment illustrates the preparation method of the HTS of a kind of silanization modification provided by the invention.HTS Ti-HMS is a template with the amino dodecane, is the silicon source with the tetraethoxy, presses document [Chin J Catal, 2004,25 (2): 89] preparation.With the tetraethoxy is the HTS that silylating reagent adopts the immersion process for preparing modification.The cyclohexane solution of 1g HTS Ti-HMS and 8mL 8.66g/L tetraethoxy is stirred, the tetraethoxy charge capacity is 6.94wt% on the HTS, floods 10h under the room temperature then, dries back temperature programming dry 6h under 363K, roasting 5h makes SiO under 810K
2Charge capacity is the SiO of 2.0wt%
2/ Ti-HMS catalyzer.
Embodiment 4.
Present embodiment illustrates the preparation method of the HTS of a kind of silanization modification provided by the invention.HTS Ti-HMS is a template with the amino dodecane, is the silicon source with the tetraethoxy, presses document [Chin J Catal, 2004,25 (2): 89] preparation.With the tetraethoxy is the HTS that silylating reagent adopts the immersion process for preparing modification.The cyclohexane solution of 1g HTS Ti-HMS and 8mL 10.87g/L tetraethoxy is stirred, the tetraethoxy charge capacity is 8.68wt% on the HTS, floods 10h under the room temperature then, dries back temperature programming dry 6h under 363K, roasting 5h makes SiO under 810K
2Charge capacity is the SiO of 2.5wt%
2/ Ti-HMS catalyzer.
Embodiment 5.
Present embodiment illustrates the preparation method of the HTS of a kind of silanization modification provided by the invention.HTS Ti-MCM-41 is a template with the hexadecyl trimethyl ammonium bromide, is the silicon source with the tetraethoxy, presses document [J Chem Soc, Chem.Commun, 1994, (2): 147] preparation.With the tetraethoxy is the HTS that silylating reagent adopts the immersion process for preparing modification.The cyclohexane solution of 1g HTS Ti-MCM-41 and 8mL 8.66g/L tetraethoxy is stirred, the tetraethoxy charge capacity is 6.94wt% on the HTS, floods 10h under the room temperature then, dries back temperature programming dry 6h under 363K, roasting 5h makes SiO under 810K
2Charge capacity is the SiO of 2.0wt%
2/ Ti-MCM-41 catalyzer.
Embodiment 6.
Present embodiment illustrates the preparation method of the HTS of a kind of silanization modification provided by the invention.HTS Ti-HMS is a template with the amino dodecane, is the silicon source with the tetraethoxy, presses document [Chin J Catal, 2004,25 (2): 89] preparation.With the METHYL TRICHLORO SILANE is the HTS that silylating reagent adopts the immersion process for preparing modification.The cyclohexane solution of 1g HTS Ti-HMS and 8mL 6.23g/L METHYL TRICHLORO SILANE is stirred, the METHYL TRICHLORO SILANE charge capacity is 4.98wt% on the HTS, floods 10h under the room temperature then, dries back temperature programming dry 6h under 363K, roasting 5h makes SiO under 810K
2Charge capacity is the SiO of 2.0wt%
2/ Ti-HMS catalyzer.
Comparative Examples 1.
This Comparative Examples explanation catalytic oxidation desulfurization performance of the HTS of silanization modification.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor, oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g Ti-HMS catalyzer also join in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 86.51% of DMDBT.
Comparative Examples 2.
Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back in the Comparative Examples 1, and the cooling back is as this contrast experiment's catalyzer.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor, oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and reclaim back 0.1g Ti-HMS catalyzer and also join in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 48.2% of DMDBT.
Comparative Examples 3.
This Comparative Examples explanation catalytic oxidation desulfurization performance of the HTS of silanization modification.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor, oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g Ti-MCM-41 catalyzer also join in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 81.72% of DMDBT.
Comparative Examples 4.
Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back in the Comparative Examples 3, and the cooling back is as this contrast experiment's catalyzer.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor, oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and reclaim back 0.1g Ti-MCM-41 catalyzer and also join in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 45.4% of DMDBT.
Embodiment 7.
The catalytic oxidation desulfurization performance of the HTS of present embodiment explanation embodiment 1 silanization modification.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 84.58% of DMDBT.
Embodiment 8.
The catalytic oxidation desulfurization performance of catalyzer is reclaimed in the reaction back among the present embodiment explanation embodiment 7.Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back among the embodiment 7, and the cooling back is as the catalyzer of present embodiment.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation diesel oil of 10mL is joined in the reactor, oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and reclaim back 0.1g Ti-HMS catalyzer and also join in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 87.0% of DMDBT.
Embodiment 9.
The catalytic oxidation desulfurization performance of the HTS of present embodiment explanation embodiment 2 silanization modifications.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 85.58% of DMDBT.
Embodiment 10.
The catalytic oxidation desulfurization performance of catalyzer is reclaimed in the reaction back among the present embodiment explanation embodiment 9.Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back among the embodiment 9, and the cooling back is as the catalyzer of present embodiment.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation diesel oil of 10mL is joined in the reactor, oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and reclaim back 0.1g Ti-HMS catalyzer and also join in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 81.61% of DMDBT.
Embodiment 11.
The catalytic oxidation desulfurization performance of the HTS of present embodiment explanation embodiment 3 silanization modifications.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane that (sulphur content is 226.1 He/g) as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is that (sulphur content is 29.7 He/g) for the decreasing ratio 86.85% of DMDBT.Sulphur content in the fuel oil can be dropped to 29.7 He/g from 226.1 He/g by this experiment, reach deep desulfuration.
Embodiment 12.
The catalytic oxidation desulfurization performance of catalyzer is reclaimed in the reaction back among the present embodiment explanation embodiment 11.Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back among the embodiment 11, and the cooling back is as the catalyzer of present embodiment.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor, oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and reclaim back 0.1g Ti-HMS catalyzer and also join in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 86.34% of DMDBT.
Embodiment 13.
The catalytic oxidation desulfurization performance of the HTS of present embodiment explanation embodiment 4 silanization modifications.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 80.63% of DMDBT.
Embodiment 14.
The catalytic oxidation desulfurization performance of catalyzer is reclaimed in the reaction back among the present embodiment explanation embodiment 13.Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back among the embodiment 13, and the cooling back is as the catalyzer of present embodiment.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor, oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and reclaim back 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 81.97% of DMDBT.
Embodiment 15.
The catalytic oxidation desulfurization performance of the HTS of present embodiment explanation embodiment 5 silanization modifications.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-MCM-41 catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 86.91% of DMDBT
Embodiment 16.
The catalytic oxidation desulfurization performance of catalyzer is reclaimed in the reaction back among the present embodiment explanation embodiment 15.Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back among the embodiment 15, and the cooling back is as the catalyzer of present embodiment.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-MCM-41 catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 87.10% of DMDBT.
Embodiment 17.
The catalytic oxidation desulfurization performance of the HTS of present embodiment explanation embodiment 3 silanization modifications.7.8mg dibenzothiophene (DBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 1 hour.Reaction result is the decreasing ratio 100% of DBT.
Embodiment 18.
The catalytic oxidation desulfurization performance of catalyzer is reclaimed in the reaction back among the present embodiment explanation embodiment 17.Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back among the embodiment 17, and the cooling back is as the catalyzer of present embodiment.7.8mg dibenzothiophene (DBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 1 hour.Reaction result is the decreasing ratio 100% of DBT.
Embodiment 19.
The catalytic oxidation desulfurization performance of the HTS of present embodiment explanation embodiment 3 silanization modifications.6.5mg thionaphthene (BT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 1 hour.Reaction result is the decreasing ratio 100% of BT.
Embodiment 20.
The catalytic oxidation desulfurization performance of catalyzer is reclaimed in the reaction back among the present embodiment explanation embodiment 19.Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back among the embodiment 19, and the cooling back is as the catalyzer of present embodiment.6.5mg thionaphthene (BT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 96.46% of BT.
Embodiment 21.
The catalytic oxidation desulfurization performance of the HTS of present embodiment explanation embodiment 6 silanization modifications.With 10.2mg 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 84.88% of DMDBT.
Embodiment 22.
The catalytic oxidation desulfurization performance of catalyzer is reclaimed in the reaction back among the present embodiment explanation embodiment 21.Catalyzer dry 4h in the baking oven of 373K is reclaimed in reaction back among the embodiment 21, and the cooling back is as the catalyzer of present embodiment.With 4,6-dimethyl Dibenzothiophene (DMDBT) is dissolved in the 10mL octane as the simulation fuel oil.In three mouthfuls of reactors of band water-bath chuck, carry out the selective oxidation reaction, the water-bath temperature control.The above-mentioned simulation fuel oil of 10mL is joined in the reactor oxidant hydrogen peroxide (30wt.%) 50 Teng, solvent methanol 10mL, and 0.1g SiO
2/ Ti-HMS catalyzer also joins in the reactor successively.H
2O
2/ sulfide mol ratio is 4: 1.60 ℃ of temperature of reaction.Induction stirring 6 hours.Reaction result is the decreasing ratio 84.34% of DMDBT.
Claims (3)
1, a kind of modifying titanium-silicon molecular sieve that adopts is the method that catalyzer carries out the fuel oil oxidation desulfurization, it is characterized in that processing step is:
(a) alkyl silicate, methyl chlorosilane or ((CH
3)
3Si)
2NH is a silylating reagent; Alkyl in the alkyl silicate is methyl, ethyl or sec.-propyl; Methyl chlorosilane is Si (CH
3)
3Cl, Si (CH
3)
2Cl
2Or Si (CH
3) Cl
3
(b) with aforementioned silylating reagent modifying titanium-silicon molecular sieve, adopting the HTS of silanization modification is catalyzer; HTS is Ti-HMS, Ti-MCM-41, Ti-MCM-48 or Ti-SBA-15; SiO wherein
2Charge capacity be 1.0wt%～3.0wt%;
(c) through the catalytic oxidation treatment fuel oil, thionaphthene, dibenzothiophene and 4 in the fuel oil, the 6-dimethyl Dibenzothiophene changes into sulfoxide and sulfone;
(d) after sulfoxide and sulfone are extracted,, realize fuel desulfuration with oil phase and catalyst separating.
2, a kind of modifying titanium-silicon molecular sieve that adopts according to claim 1 is the method that catalyzer carries out the fuel oil oxidation desulfurization, it is characterized in that sulfone and sulfoxide extracting operation and oxide treatment are carried out simultaneously or carried out after oxide treatment.
3, a kind of modifying titanium-silicon molecular sieve that adopts according to claim 1 is the method that catalyzer carries out the fuel oil oxidation desulfurization, it is characterized in that the HTS of modification is reusable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610200318A CN100587036C (en) | 2006-04-06 | 2006-04-06 | Method for desulfurization of fuel oil by oxidation process with modified titanium silicon molecular sieve as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610200318A CN100587036C (en) | 2006-04-06 | 2006-04-06 | Method for desulfurization of fuel oil by oxidation process with modified titanium silicon molecular sieve as catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1844321A CN1844321A (en) | 2006-10-11 |
| CN100587036C true CN100587036C (en) | 2010-02-03 |
Family
ID=37063291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610200318A Expired - Fee Related CN100587036C (en) | 2006-04-06 | 2006-04-06 | Method for desulfurization of fuel oil by oxidation process with modified titanium silicon molecular sieve as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100587036C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502807B (en) * | 2009-03-05 | 2011-06-01 | 天津大学 | Modified nano molecular sieve catalyst for cracking endothermic hydrocarbon fuels and preparation method |
| CN101602647B (en) * | 2009-06-25 | 2012-07-25 | 江苏扬农化工集团有限公司 | Method for removing sulphur from coking benzol |
| CN102757811B (en) * | 2011-04-26 | 2014-10-15 | 中国石油化工股份有限公司 | Diesel oil oxidative desulphurization method |
| CN102807537B (en) * | 2011-06-02 | 2014-08-06 | 中国石油化工股份有限公司 | Method for preparing propylene oxide |
| CN102807538B (en) * | 2011-06-02 | 2014-08-06 | 中国石油化工股份有限公司 | Method for preparing propylene oxide |
| CN103012366B (en) * | 2011-09-28 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method of thiophene-type sulfide oxidation |
| CN102502690A (en) | 2011-10-31 | 2012-06-20 | 大连理工大学 | Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base |
| CN102557066B (en) * | 2011-12-30 | 2013-11-06 | 大连理工大学 | Tetraethoxysilane modified datolite molecular sieve and preparation method and application thereof |
| CN107500310B (en) * | 2017-09-05 | 2020-05-12 | 吉林大学 | High-performance nano hierarchical pore TS-1 molecular sieve, preparation method and application thereof |
| CN110681414B (en) * | 2019-12-09 | 2020-05-08 | 山东国瓷功能材料股份有限公司 | Copper-containing loaded molecular sieve with high hydrothermal stability, and preparation method and application thereof |
| CN111085265B (en) * | 2019-12-27 | 2021-04-23 | 中国科学院大连化学物理研究所 | Catalyst for improving para-selectivity of phenol hydroxylation reaction product and preparation method and application thereof |
-
2006
- 2006-04-06 CN CN200610200318A patent/CN100587036C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1844321A (en) | 2006-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100587036C (en) | Method for desulfurization of fuel oil by oxidation process with modified titanium silicon molecular sieve as catalyst | |
| Rang et al. | Advances in desulfurization research of liquid fuel | |
| CN100569917C (en) | The method of a kind of oxidation sweetening of light-end products and deodorization | |
| CN100348701C (en) | Organosulfur oxidation process | |
| KR20070091297A (en) | Oxidative desulfurization process | |
| CN101717659A (en) | Deep desulfurization method for diesel by coupling of oxidation and extraction | |
| CN100379841C (en) | Highly sulfur removal method of diesel oil | |
| CN102925198A (en) | Method of applying modified catalyst to catalytic oxidation DBT (dibenzothiophene) removal | |
| CN101255352A (en) | Method for removing sulfides in gasoline by oxidation-absorption under mild conditions | |
| CN105419853B (en) | A kind of method of ionic liquid intermediate fuel oil bionic oxidation desulfurization | |
| CN103184068B (en) | Hydrogen peroxide-hydrochloric acid oxidation and desulfurization method | |
| CN102294236B (en) | Preparation method for supported Mo-based oxidation and desulfurization catalyst | |
| CN110157467B (en) | Method for deep desulfurization of fuel oil by catalytic oxidation of hydrogen peroxide | |
| CN103525453A (en) | Oxidative coupling extraction desulfurization of petroleum product as well as ionic liquid and preparation method thereof | |
| CN101255353A (en) | Method for removing sulfides in diesel by oxidation-absorption | |
| CN101063044B (en) | Diesel oxidation desulfurizing method | |
| CN110252384B (en) | Sub-nano cluster transition metal oxide/MCM-41 composite material, preparation method and application thereof | |
| CN102757811B (en) | Diesel oil oxidative desulphurization method | |
| CN104694151A (en) | An oxidation regeneration method for a thiolate-containing alkali solution | |
| CN107570139B (en) | A kind of vanadic anhydride nanometer sheet catalyst and the preparation method and application thereof | |
| CN101962567B (en) | Method for catalytically oxidizing sulfocompound in petroleum product | |
| CN101302441A (en) | Method for removing sulfide in catalytically cracked gasoline by oxidation-extraction | |
| WO2014030964A1 (en) | Oxidative desulphurisation method for hydrocarbons | |
| CN112044425B (en) | Hydrochloric acid acidified kaolin loaded vanadium oxidation desulfurization catalyst and preparation and application thereof | |
| CN105038841A (en) | Method for catalyzing fuel oil oxidation desulphurization by polyether type oxovanadium heteropolyacid ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100203 Termination date: 20130406 |