CN107029731B - A kind of La doped NiTi compound oxide photocatalyst and its application in photochemical catalytic oxidation desulfurization - Google Patents
A kind of La doped NiTi compound oxide photocatalyst and its application in photochemical catalytic oxidation desulfurization Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 34
- 230000023556 desulfurization Effects 0.000 title claims abstract description 33
- 229910001000 nickel titanium Inorganic materials 0.000 title claims abstract description 21
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 229930192474 thiophene Natural products 0.000 abstract description 6
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- -1 thiophenes sulfides Chemical class 0.000 abstract description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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- Thermal Sciences (AREA)
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Abstract
The present invention discloses a kind of La doped NiTi compound oxide photocatalyst and its application in photochemical catalytic oxidation desulfurization, belongs to oil product processing technique field.The photochemical catalyst is LaxNi1‑xTiO3Photochemical catalyst, wherein 0.01≤x≤0.15.The present invention uses metal salt for raw material, and hydro-thermal method synthesizes photochemical catalyst, and preparation method process is simple, time-consuming short, and condition is also more mild.Photochemical catalyst of the invention enhances the photoresponse in visible-range, improves the utilization rate to light, enhances the removal effect to thiophenes sulfides in gasoline.Photochemical catalyst shows the excellent results such as reaction condition is mild, desulfurization effect is good, oil product loses less, recycling effect is good in the present invention.The photochemical catalytic oxidation abstraction desulfurization of gasoline is used for using photochemical catalyst of the invention, dibenzothiophenes removal efficiency to can reach 95% or more after reacting 3h, thiophene sulfur content in gasoline can be reduced to 2.5ppm or less.
Description
Technical field
The invention belongs to oil product processing technique fields, are related to a kind of visible light catalyst for gasoline desulfurization, specifically relate to
And a kind of La doped NiTi compound oxide photocatalyst and its application in photochemical catalytic oxidation desulfurization, in particular to it is a kind of
LaxNi1-xTiO3Oxidation-extraction removes the application in gasoline in terms of thiophenes sulfides to photochemical catalyst under visible light.
Background technique
Since 21st century, explosive growth is presented in auto industry, and global auto recoverable amount constantly increases, the energy
Consume sharp increase.Gasoline occupies higher share as important power fuel in various countries' fuel structure.China's vapour in 2016
Oily demand has reached 1.18 hundred million tons, and since passenger car upgrade requirement and small and medium-sized cities automobile popularity rate are continuously improved, not
The consumption for carrying out gasoline in a period of time also will continue to increase.Thus caused exhaust emissions also will be increasingly tight to the harm of environment
Weight, the contradiction between energy demand and environmental protection become increasingly conspicuous.
The presence of sulfide will cause very big harm in automobile, and the sulfide in gasoline can not only generate sulphur after combustion
Oxide directly pollutes environment, can also make the catalyst poisoning in vehicle exhaust converter, reduce the conversion of catalytic converter
Ability increases three kinds of harmful substances HC, CO, NO in vehicle exhaustXDischarge amount, aggravate environmental degradation indirectly.In view of gasoline
The drawbacks of high sulfur-bearing is brought, countries in the world one after another according to the economic and technical condition of itself, formulated stringent marine fuels specification and
Discharge standard is to improve fuel qualities.
The technology of gasoline desulfurization at present mainly includes two class of hydrodesulfurization (HDS) and non-hydrodesulfurization.HDS refers in catalyst
Under the action of, using hydrogen as reducing agent, the organic sulfur compound in oil product is reduced to hydrogen sulfide first, then through gas-liquid separation and vapour
It the technologies such as proposes and carries out gas-liquid separation to obtain a kind of method of sweet oil.In general the organic sulfur compound in gasoline fraction
It mainly include mercaptan, thioether and thiophene derivant etc., wherein mercaptan and thioether are easy to plus hydrogen removes, and thiophene-type sulfide is stablized
Property is higher, it is difficult to be removed by hydrodesulfurization.These sulfide, which are removed, with hydrodesulfurization needs more stringent reaction condition,
Desulphurization cost is significantly increased.Therefore people start to be dedicated to various non-hydrodesulfurizations.Adsorb desulfurization, abstraction desulfurization, oxidation
Desulfurization and biological desulphurization etc. are received extensive attention because reaction condition is mild and higher desulfurization degree.Wherein, photochemical catalytic oxidation
Desulfurization becomes a research hotspot as a kind of novel oxidized desulfurization technology, because low energy consumption for it.In numerous photochemical catalysts, titanium
Base composite oxidate (such as calcium titanium composite oxide, barium titanium composite oxide, NiTi composite oxides) has relatively stable calcium
Perovskite like structure, and it is easily prepared.
Summary of the invention
In order to overcome the disadvantages and deficiencies of the prior art, the primary purpose of the present invention is that provide a kind of La doped NiTi multiple
Close oxidation photocatalyst.
Another object of the present invention is to provide the applications of above-mentioned La doped NiTi compound oxide photocatalyst.
The purpose of the invention is achieved by the following technical solution:
A kind of La doped NiTi compound oxide photocatalyst is to synthesize to obtain La by hydro-thermal methodxNi1-xTiO3Photocatalysis
Agent, wherein 0.01≤x≤0.15.
Preferably, 0.05≤x≤0.15；
It is further preferred that 0.1≤x≤0.15；
Most preferably, x=0.1.
The preparation method of the La doped NiTi compound oxide photocatalyst, includes the following steps:
Nickel salt and lanthanum salt are dissolved in deionized water, under vigorous stirring, butyl titanate is added dropwise dropwise into solution, then
Solid sodium hydroxide is added, stirs at room temperature；Then solution is heated and is reacted；Cold filtration, and washed with deionized water, ethyl alcohol
It washs, it is dry, obtain La doped NiTi compound oxide photocatalyst.
The nickel salt is one kind of nickel nitrate and nickel chloride；
The lanthanum salt is one kind of lanthanum nitrate and lanthanum chloride.
The concentration of the nickel salt is 0.17~0.2mol/L；
The volume fraction of the butyl titanate in the reaction system is 5~10%；Preferably 6.4%.
The dosage of the sodium hydroxide is 2~20g/L；More preferably 16g/L.
The time stirred at room temperature is 0.5~3h, preferably 1h；
The condition of the heating reaction is 180~300 DEG C of 18~30h of reaction；Preferably 200 DEG C reactions are for 24 hours.
The condition of the drying is 80~120 DEG C of dry 8~12h, preferably 80 DEG C dry 12h.
Application of the La doped NiTi compound oxide photocatalyst in photochemical catalytic oxidation desulfurization；Further,
The application in thiophenic sulfur is taken off in gasoline.
Catalytic Oxidation-Extraction removes thiophene in gasoline to the La doped NiTi compound oxide photocatalyst under visible light
The method of pheno sulfide, includes the following steps:
Under visible light, using LaxNi1-xTiO3Thiophenic sulfur is catalytically oxidized to thiophene by oxidizing by photochemical catalyst
Pheno sulfone, then by extractant extraction and separation, to achieve the purpose that remove thiophenic sulfur in gasoline.
Mechanism of the invention is: NiTi composite oxides have biggish potentiality, the doping of lanthanoid metal in terms of photocatalysis
Its photoresponse in visible-range can be enhanced.LaxNi1-xTiO3Photochemical catalyst is good with that can have in photochemical catalytic oxidation desulfurization
Effect.
The present invention compared with the existing technology, have following advantages and effects
(1) present invention uses metal salt for raw material, and hydro-thermal method synthesizes photochemical catalyst, and preparation method process is simple, time-consuming short,
Condition is also more mild.
(2) from desulfurization result it can be concluded that, NiTi composite oxides have a good desulfurization effect, and La doped at
Function enhances photoresponse of the photochemical catalyst in visible-range, improves the utilization rate to light, enhances to thiophene in gasoline
The removal effect of pheno sulfide.
(3) present invention in La doped NiTi compound oxide photocatalyst show reaction condition is mild, desulfurization effect is good,
The excellent results such as oil product loses less, recycling effect is good.
(4) it is extracted using La doped NiTi compound oxide photocatalyst of the invention for the photochemical catalytic oxidation of gasoline de-
Sulphur, dibenzothiophenes removal efficiency can reach 95% or more after reacting 3h, thiophene sulfur content in gasoline can be reduced to
2.5ppm following.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
La0.01Ni0.99TiO3Photochemical catalyst prepares and its is used for gasoline desulfurization
(1) Nickelous nitrate hexahydrate 2.88g (9.9mmol) is weighed, is weighed lanthanum nitrate hexahydrate 0.044g (0.1mmol), it is molten
In 50mL deionized water, under vigorous stirring, 3.4mL butyl titanate is added dropwise dropwise into solution, solid hydrogen-oxygen is then added
Change sodium 0.8g, stirs 1h at room temperature.Then solution is transferred in ptfe autoclave and is heated to 200 DEG C, reaction is for 24 hours.Instead
Cold filtration after answering, and with deionized water, ethanol washing, 80 DEG C of dry 12h obtain La0.01Ni0.99TiO3。
(2) using the dibenzothiophenes of removing more difficult in hydrodesulfurization as target sulphide, dibenzothiophenes is dissolved in just pungent
Alkane is configured to the analog gasoline that sulfur content is 50ppm.Take analog gasoline 10mL, photochemical catalyst NiTiO30.0315g and simulation
Gasoline mixing.Hydrogen peroxide and 10mL acetonitrile is added, using hydrogen peroxide as oxidant, acetonitrile is that extractant is added to fuel gasoline and light
In the mixed liquor of catalyst, under visible light illumination, temperature is controlled at 30 DEG C, stirs 180min.O and simulation vapour in hydrogen peroxide
The molar ratio of S in oil is 15.Stratification after suction filtration, take upper layer analog gasoline with high performance liquid chromatography measure sulfur content be
10.4ppm, desulfurization degree reach 81%.
Embodiment 2
La0.05Ni0.95TiO3Photochemical catalyst prepares and its is used for gasoline desulfurization
Compared with Example 1 compared with difference is to weigh Nickelous nitrate hexahydrate 2.76g (9.5mmol), weighs six nitric hydrates
La is made in lanthanum 0.22g (0.5mmol)0.05Ni0.95TiO3Photochemical catalyst, desulfurization degree reaches under reaction condition same as Example 1
82.5%.
Embodiment 3
La0.1Ni0.9TiO3Photochemical catalyst prepares and its is used for gasoline desulfurization
Compared with Example 1 compared with difference is to weigh Nickelous nitrate hexahydrate 2.62g (9mmol), weighs lanthanum nitrate hexahydrate
La is made in 0.43g (1mmol)0.1Ni0.9TiO3Photochemical catalyst, desulfurization degree reaches under reaction condition same as Example 1
95.2%.
Embodiment 4
La0.15Ni0.85TiO3Photochemical catalyst prepares and its is used for gasoline desulfurization
Compared with Example 1 compared with difference is to weigh Nickelous nitrate hexahydrate 2.47g (8.5mmol), weighs six nitric hydrates
La is made in lanthanum 0.65g (1.5mmol)0.15Ni0.85TiO3Photochemical catalyst, desulfurization degree reaches under reaction condition same as Example 1
90.6%.
Comparative example 1
NiTiO3Photochemical catalyst prepares and its is used for gasoline desulfurization
Compared with Example 1 compared with difference is to weigh Nickelous nitrate hexahydrate 2.91g (10mmol), and NiTiO is made3Light is urged
Agent, desulfurization degree reaches 79.2% under reaction condition same as Example 1.
Embodiment 5
The preparation of photochemical catalyst and desulfurization step are with embodiment 3, after the photochemical catalyst after reaction is recycled
It recycles, investigates the reusability of photochemical catalyst, the results are shown in Table 1.Desulfurizing agent has good it can be seen from table
Repeat performance, after 5 circulations, desulfurization degree still can reach 85% or more.
Table 1La0.1Ni0.9TiO3The repetition desulfurization effect of photochemical catalyst
| Experimentai batches | 1 | 2 | 3 | 4 | 5 |
| Desulfuration efficiency % | 95.2 | 93.4 | 90.9 | 88.7 | 87.6 |
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (7)
1. a kind of application of La doped NiTi compound oxide photocatalyst in photochemical catalytic oxidation desulfurization, it is characterised in that: institute
The La doped NiTi compound oxide photocatalyst stated is to synthesize to obtain La by hydro-thermal methodxNi1-xTiO3Photochemical catalyst, wherein
0.1≤x≤0.15。
2. application according to claim 1, it is characterised in that:
The La doped NiTi compound oxide photocatalyst takes off the application in thiophenic sulfur in gasoline.
3. application according to claim 1 or 2, it is characterised in that: the La doped NiTi composite oxides photocatalysis
The preparation method of agent, includes the following steps:
Nickel salt and lanthanum salt are dissolved in deionized water, under vigorous stirring, butyl titanate is added dropwise dropwise into solution, is then added
Solid sodium hydroxide stirs at room temperature；Then solution is heated and is reacted；Cold filtration, and with deionized water, ethanol washing, it does
It is dry, obtain La doped NiTi compound oxide photocatalyst.
4. application according to claim 3, it is characterised in that:
The nickel salt is one kind of nickel nitrate and nickel chloride；
The lanthanum salt is one kind of lanthanum nitrate and lanthanum chloride.
5. application according to claim 3, it is characterised in that:
The concentration of the nickel salt is 0.17~0.2mol/L.
6. application according to claim 3, it is characterised in that:
The volume fraction of the butyl titanate in the reaction system is 5~10%；
The dosage of the sodium hydroxide is 2~20g/L.
7. application according to claim 3, it is characterised in that:
The time stirred at room temperature is 0.5~3h；
The condition of the heating reaction is 180~300 DEG C of 18~30h of reaction；
The condition of the drying is 80~120 DEG C of dry 8~12h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962068A (en) * | 2012-11-08 | 2013-03-13 | 浙江理工大学 | Nickel titanate catalyst for organic dyestuff degradation by visible light and preparation method thereof |
| CN104230378A (en) * | 2014-08-29 | 2014-12-24 | 华北水利水电大学 | Perovskite-type superfine yellow ceramic pigment and preparation method thereof |
| CN105582939A (en) * | 2016-03-15 | 2016-05-18 | 河北工业大学 | Preparation method of visible-light response nano La/Ni-SrTiO3 |
| CN105905940A (en) * | 2016-04-12 | 2016-08-31 | 渤海大学 | Preparation method of nickel titanate/titanium dioxide composite nanomaterial |
| CN106281437A (en) * | 2016-09-13 | 2017-01-04 | 华南理工大学 | A kind of method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962068A (en) * | 2012-11-08 | 2013-03-13 | 浙江理工大学 | Nickel titanate catalyst for organic dyestuff degradation by visible light and preparation method thereof |
| CN104230378A (en) * | 2014-08-29 | 2014-12-24 | 华北水利水电大学 | Perovskite-type superfine yellow ceramic pigment and preparation method thereof |
| CN105582939A (en) * | 2016-03-15 | 2016-05-18 | 河北工业大学 | Preparation method of visible-light response nano La/Ni-SrTiO3 |
| CN105905940A (en) * | 2016-04-12 | 2016-08-31 | 渤海大学 | Preparation method of nickel titanate/titanium dioxide composite nanomaterial |
| CN106281437A (en) * | 2016-09-13 | 2017-01-04 | 华南理工大学 | A kind of method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray |
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