CN106281437A - A kind of method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray - Google Patents
A kind of method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray Download PDFInfo
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- CN106281437A CN106281437A CN201610821090.XA CN201610821090A CN106281437A CN 106281437 A CN106281437 A CN 106281437A CN 201610821090 A CN201610821090 A CN 201610821090A CN 106281437 A CN106281437 A CN 106281437A
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- gasoline
- catalytic oxidation
- visible ray
- photocatalyst
- sulfur
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229930192474 thiophene Natural products 0.000 title claims abstract description 15
- 238000000605 extraction Methods 0.000 title claims abstract description 14
- -1 thiophenes sulfides Chemical class 0.000 title claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 38
- 239000011593 sulfur Substances 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011941 photocatalyst Substances 0.000 claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 claims abstract description 18
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 12
- 230000008313 sensitization Effects 0.000 claims abstract description 12
- UMHFSEWKWORSLP-UHFFFAOYSA-N thiophene 1,1-dioxide Chemical compound O=S1(=O)C=CC=C1 UMHFSEWKWORSLP-UHFFFAOYSA-N 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000006477 desulfuration reaction Methods 0.000 claims description 17
- 230000023556 desulfurization Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000001429 visible spectrum Methods 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 229910002567 K2S2O8 Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses the method for thiophenes sulfides in the removing gasoline of Catalytic Oxidation-Extraction under a kind of visible ray, belongs to oil product processing technique field.The present invention is under visible light, uses dye sensitization photocatalyst, by oxidizing, thiophenic sulfur is catalytically oxidized to thiophene sulfone, then by extractant extract and separate, thus reach to remove the purpose of thiophenic sulfur in gasoline.Described dye sensitization photocatalyst is to be prepared by the preparation method in patent ZL201210553859.6.Dye sensitization photocatalyst specific surface area selected by the present invention is big, dispersion preferable, active site is the most effectively exposed, photocatalyst not easily runs off；And the utilization of visible spectrum part in solar energy is obviously improved.Sulfur method provided by the present invention is simple, with low cost, thiophenic sulfur contained in gasoline can be played effective removal effect.
Description
Technical field
The invention belongs to oil product processing technique field, be specifically related to Catalytic Oxidation-Extraction under a kind of visible ray and remove in gasoline
The method of thiophenes sulfides.
Background technology
Although the growth rate of the GDP in the whole world is persistently slowing down, but overall energy demand is continuing growth.This be because of
For along with the increase of world population and the raising of scientific and technological level, more for the needs energy is supported higher Living Water by the mankind
Gentle living standard and more active socio-economic activity, and next two decades and energy demand later will persistently increase
Long.On the other hand, although due to global warming, the environmental factors of climatic deterioration, the energy resource structure in the whole world, at continued shift, can be held
The accounting of the continuous energy persistently raises, but fossil energy will be to provide the main energy sources of power for World Economics.According to " BP
World energy sources statistical yearbook " 2016 editions reports, fossil energy will provide the energy increment of 2035 60%, and account for the energy and supply
Answer the 80% of total amount.
On the Chinese side, within 2015, China energy consumption increases by 1.5%, and speedup is less than past ten yearly mean level
(5.3%) 1/3rd, but China is still the maximum energy-consuming state in the whole world, and 23% and the whole world that account for global Energy Consumption amount are clean
34% increased.In energy resource structure, coal accounting in China energy consumption drops to 64%, and correspondingly oil consumption
Amount but increases 6.3%.Wherein net import of oil increases by 9.6% to 737 ten thousand barrel per day, reaches a historic high level." BP world energy
Source statistical yearbook " 2016 editions anticipated CNPC's importation dependence in 2035 will rise to 76% by 59% in 2014.
And due to the exhaustion day by day of petroleum resources, the oil of institute of China import mostly is sour crude, correspondingly institute after refining
In the gasoline obtained, sulfur content is the most of a relatively high.Sulfide therein can generate oxysulfide (SO after combustionX), it is to form acid rain
Immediate cause；And oxysulfide (SOXIf) it being converted into sulfate aerosol in an atmosphere, its stimulation also to enter one
Step strengthens, so that the sickness rate of people's respiratory tract system disease raises, more likely induction Human Lung Cancer is formed.Therefore by de-
Sulfur technique, produces and meets the clean gasoline of environmental requirement and have become as the main trend of gasoline industry.
In gasoline, the sulfide of more difficult removing mainly comprises: thiophene, methylthiophene, benzothiophene, dibenzothiophenes etc..Mesh
Before, industrial conventional desulfurization process of gasoline mainly includes hydrodesulfurization, abstraction desulfurization, absorption desulfurization etc., suffers from corresponding
Not enough.If wanting to use traditional hydrodesulfurization technology to continue deep hydrogenation, gasoline is made to meet current low sulfur-bearing standard, it is necessary to
By improving the harsh conditions such as Hydrogen Vapor Pressure and consumption, high temperature, pressure, the consequence thus brought is hydrogen consumption increase, reactor body
Long-pending increase, equipment investment and operating cost sharply increase, and even can bring the quality of gasoline problems such as explosion-proof index reduction.And extract
Desulfurization needs to research and develop efficient extractant, particularly can produce the extractant of weak chemical action with sulfur-containing organic compound, and
The screening of this kind solvent with prepare relatively difficult, cannot industrially be widely used at present.Absorption desulfurization is then to Containing Sulfur
The selectivity of compound is poor, and due to alkene and a large amount of existence of other non-sulfur-bearing benzene homologues, can significantly reduce sulfur-bearing
The adsorption capacity of compound, is not suitable for the deep desulfuration of gasoline.Therefore, new efficient gasoline desulfating method gesture is developed must
OK.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of dye sensitization light to urge
Agent application in gasoline takes off thiophenic sulfur.
Another object of the present invention is to provide Catalytic Oxidation-Extraction under a kind of visible ray to remove thiophenes sulfides in gasoline
Method.
The purpose of the present invention is achieved through the following technical solutions:
The present invention provides the application in gasoline takes off thiophenic sulfur of a kind of dye sensitization photocatalyst.
Under a kind of visible ray, the method for thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline, comprises the steps:
Under visible light, use dye sensitization photocatalyst, by oxidizing, thiophenic sulfur is catalytically oxidized to thiophene
Sulfone, then by extractant extract and separate, thus reach to remove the purpose of thiophenic sulfur in gasoline.
Described dye sensitization photocatalyst is to be prepared by the preparation method in patent ZL201210553859.6.
The wave-length coverage of described visible ray is 450～650nm.
The consumption of described dye sensitization photocatalyst is the 0.3～1wt% of gasoline to be desulfurization.
Described oxidant is potassium permanganate (KMnO4), potassium dichromate (K2Cr2O7), potassium chlorate (KClO3), potassium peroxydisulfate
(K2S2O8), hydrogen peroxide (H2O2One in)；Its consumption (can play equivalent oxygen and the gasoline of Oxidation with oxygen sulfur ratio in oxidant
The mol ratio of middle equivalent sulfur) meter, oxygen sulfur is 20～60 than scope.
The reaction condition of described catalysis oxidation is: reaction temperature is 30～50 DEG C, and photocatalytic oxidation time is
60～180min.
Described extractant is the one in N,N-dimethylformamide, acetonitrile, furfural, ethylenediamine；Its consumption is for waiting to take off
The 10～30wt% of sulfur oil.
The present invention, relative to prior art, has such advantages as and effect:
(1) the dye sensitization photocatalyst specific surface area selected by the present invention is big, dispersion preferable, active site all obtains
Effectively to expose, photocatalyst not easily runs off；And the utilization of visible spectrum part in solar energy is obviously improved.
(2) sulfur method provided by the present invention is simple, with low cost, can play thiophenic sulfur contained in gasoline
To effective removal effect.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
With DCQ/14%-iFe2O3/ SBA-15 is photocatalyst
Take the gasoline 10g that wherein thiophenic sulfur content is about 50ppm, under agitation, add DCQ/14%-iFe2O3/SBA-15
30mg, with KMnO4For oxidant, equivalent oxygen sulfur ratio is 20, it is seen that optical wavelength selectes 450nm, light application time 60min, because
Under the conditions of continuous light, system temperature can rise always, so being 30 by circulating cooling water management catalytic oxidation temperature
℃.After catalytic oxidation terminates, being isolated by filtration photocatalyst, gained gasoline adds 1g DMF and enters
Row extract and separate, the sulfur content recording gained gasoline after separation is 12.2ppm, and desulfurization degree is 75.6%.
Embodiment 2
With DCQ/14%-iFe2O3/ SBA-15 is photocatalyst
Take the gasoline 10g that wherein thiophenic sulfur content is about 50ppm, under agitation, add DCQ/14%-iFe2O3/SBA-15
100mg, with KMnO4For oxidant, equivalent oxygen sulfur ratio is 60, it is seen that optical wavelength selectes 500nm, light application time 180min, catalysis
Oxidizing reaction temperature is 50 DEG C.After catalytic oxidation terminates, being isolated by filtration photocatalyst, gained gasoline adds 2g acetonitrile
Carrying out extract and separate, the sulfur content recording gained gasoline after separation is 4.9ppm, and desulfurization degree is 93.0%.
Embodiment 3
With TCCP/30%-TiO2/ MCM-41 is photocatalyst
Take the gasoline 10g that wherein thiophenic sulfur content is about 50ppm, under agitation, add TCCP/30%-TiO2/MCM-41
60mg, with K2Cr2O7For oxidant, equivalent oxygen sulfur ratio is 40, it is seen that optical wavelength selectes 550nm, light application time 120min, catalysis
Oxidizing reaction temperature is 40 DEG C.After catalytic oxidation terminates, being isolated by filtration photocatalyst, gained gasoline adds 3g furfural
Carrying out extract and separate, the sulfur content recording gained gasoline after separation is 8.3ppm, and desulfurization degree is 83.4%.
Embodiment 4
With TCCP/30%-TiO2/ MCM-41 is photocatalyst
Take the gasoline 10g that wherein thiophenic sulfur content is about 50ppm, under agitation, add TCCP/30%-TiO2/MCM-41
80mg, with K2Cr2O7For oxidant, equivalent oxygen sulfur ratio is 50, it is seen that optical wavelength selectes 600nm, light application time 160min, catalysis
Oxidizing reaction temperature is 50 DEG C.After catalytic oxidation terminates, being isolated by filtration photocatalyst, gained gasoline adds 3g furfural
Carrying out extract and separate, the sulfur content recording gained gasoline after separation is 4.7ppm, and desulfurization degree is 90.6%.
Embodiment 5
With DCQ/15%-TiO2/ HMS is photocatalyst
Take the gasoline 10g that wherein thiophenic sulfur content is about 50ppm, under agitation, add DCQ/15%-TiO2/HMS
90mg, with KClO3For oxidant, equivalent oxygen sulfur ratio is 30, it is seen that optical wavelength selectes 650nm, light application time 180min, is catalyzed oxygen
Changing reaction temperature is 50 DEG C.After catalytic oxidation terminates, being isolated by filtration photocatalyst, gained gasoline adds 1.5g second two
Amine carries out extract and separate, and the sulfur content recording gained gasoline after separation is 4.1ppm, and desulfurization degree is 91.8%.
Embodiment 6
With DCQ/15%-TiO2/ HMS is photocatalyst
Take the gasoline 10g that wherein thiophenic sulfur content is about 50ppm, under agitation, add DCQ/15%-TiO2/HMS
40mg, with K2S2O8For oxidant, equivalent oxygen sulfur ratio is 60, it is seen that optical wavelength selectes 600nm, light application time 130min, is catalyzed oxygen
Changing reaction temperature is 50 DEG C.After catalytic oxidation terminates, being isolated by filtration photocatalyst, gained gasoline adds 2g acetonitrile and enters
Row extract and separate, the sulfur content recording gained gasoline after separation is 6.7ppm, and desulfurization degree is 86.6%.
Embodiment 7
With DCQ/20%-ZnO/13X as photocatalyst
Take the gasoline 10g that wherein thiophenic sulfur content is about 50ppm, under agitation, add DCQ/20%-ZnO/13X
40mg, with H2O2For oxidant, equivalent oxygen sulfur ratio is 30, it is seen that optical wavelength selectes 550nm, light application time 60min, catalysis oxidation
Reaction temperature is 40 DEG C.After catalytic oxidation terminates, being isolated by filtration photocatalyst, gained gasoline adds 2g acetonitrile to be carried out
Extract and separate, the sulfur content recording gained gasoline after separation is 10.6ppm, and desulfurization degree is 78.8%.
Embodiment 8
With DCQ/20%-ZnO/13X as photocatalyst
Take the gasoline 10g that wherein thiophenic sulfur content is about 50ppm, under agitation, add DCQ/20%-ZnO/13X
100mg, with H2O2For oxidant, equivalent oxygen sulfur ratio is 60, it is seen that optical wavelength selectes 500nm, light application time 180min, is catalyzed oxygen
Changing reaction temperature is 50 DEG C.After catalytic oxidation terminates, being isolated by filtration photocatalyst, gained gasoline adds 3g acetonitrile and enters
Row extract and separate, the sulfur content recording gained gasoline after separation is 3.2ppm, and desulfurization degree is 93.6%.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (9)
1. the dye sensitization photocatalyst application in gasoline takes off thiophenic sulfur.
2. the method for thiophenes sulfides during Catalytic Oxidation-Extraction removes gasoline under a visible ray, it is characterised in that include walking as follows
Rapid:
Under visible light, use dye sensitization photocatalyst, by oxidizing, thiophenic sulfur be catalytically oxidized to thiophene sulfone,
Again by extractant extract and separate, thus reach to remove the purpose of thiophenic sulfur in gasoline.
The method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray the most according to claim 2, it is special
Levy and be: the wave-length coverage of described visible ray is 450～650nm.
The method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray the most according to claim 2, it is special
Levy and be: the consumption of described dye sensitization photocatalyst is the 0.3～1wt% of gasoline to be desulfurization.
The method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray the most according to claim 2, it is special
Levy and be: described oxidant is the one in potassium permanganate, potassium dichromate, potassium chlorate, potassium peroxydisulfate, hydrogen peroxide.
6. according to the method for thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under the visible ray described in claim 2 or 5, its
It is characterised by: the consumption of described oxidant is in terms of oxygen sulfur ratio, and oxygen sulfur is 20～60 than scope.
The method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray the most according to claim 2, it is special
Levy and be: the reaction condition of described catalysis oxidation is: reaction temperature is 30～50 DEG C, and photocatalytic oxidation time is 60
～180min.
The method of thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under visible ray the most according to claim 2, it is special
Levy and be: described extractant is the one in N,N-dimethylformamide, acetonitrile, furfural, ethylenediamine.
9. according to the method for thiophenes sulfides in Catalytic Oxidation-Extraction removing gasoline under the visible ray described in claim 2 or 8, its
It is characterised by: the consumption of described extractant is the 10～30wt% of gasoline to be desulfurization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610821090.XA CN106281437B (en) | 2016-09-13 | 2016-09-13 | A kind of method that Catalytic Oxidation-Extraction removes thiophenes sulfides in gasoline under visible ray |
Applications Claiming Priority (1)
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| CN107029731A (en) * | 2017-04-27 | 2017-08-11 | 华南理工大学 | A kind of La doped NiTi compound oxide photocatalyst and its application in photochemical catalytic oxidation desulfurization |
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| CN103055943A (en) * | 2012-12-18 | 2013-04-24 | 华南理工大学 | Dye-sensitization photocatalysis and application thereof in catalytic degradation of ionic liquid under the present of visible light |
| CN103831137A (en) * | 2014-03-05 | 2014-06-04 | 西北大学 | Metal phthalocyanine-sensitized titanium dioxide photocatalyst and preparation method thereof |
| CN103846106A (en) * | 2014-03-07 | 2014-06-11 | 西北大学 | Metal phthalocyanine sensitized tin dioxide photocatalyst and preparation method thereof |
| CN104801347A (en) * | 2015-03-31 | 2015-07-29 | 西安工业大学 | Catalytic desulfurization agent of carboxylic substituent metal phthalocyanine sensitization Zn2SnO4 powder and preparation method for catalytic desulfurization agent |
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| CN103055943A (en) * | 2012-12-18 | 2013-04-24 | 华南理工大学 | Dye-sensitization photocatalysis and application thereof in catalytic degradation of ionic liquid under the present of visible light |
| CN103831137A (en) * | 2014-03-05 | 2014-06-04 | 西北大学 | Metal phthalocyanine-sensitized titanium dioxide photocatalyst and preparation method thereof |
| CN103846106A (en) * | 2014-03-07 | 2014-06-11 | 西北大学 | Metal phthalocyanine sensitized tin dioxide photocatalyst and preparation method thereof |
| CN104801347A (en) * | 2015-03-31 | 2015-07-29 | 西安工业大学 | Catalytic desulfurization agent of carboxylic substituent metal phthalocyanine sensitization Zn2SnO4 powder and preparation method for catalytic desulfurization agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107029731A (en) * | 2017-04-27 | 2017-08-11 | 华南理工大学 | A kind of La doped NiTi compound oxide photocatalyst and its application in photochemical catalytic oxidation desulfurization |
| CN107029731B (en) * | 2017-04-27 | 2019-10-18 | 华南理工大学 | A kind of La doped NiTi compound oxide photocatalyst and its application in photochemical catalytic oxidation desulfurization |
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