CN103846106A - Metal phthalocyanine sensitized tin dioxide photocatalyst and preparation method thereof - Google Patents
Metal phthalocyanine sensitized tin dioxide photocatalyst and preparation method thereof Download PDFInfo
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- CN103846106A CN103846106A CN201410083052.XA CN201410083052A CN103846106A CN 103846106 A CN103846106 A CN 103846106A CN 201410083052 A CN201410083052 A CN 201410083052A CN 103846106 A CN103846106 A CN 103846106A
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- desulfurizing agent
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Abstract
The invention discloses a metal phthalocyanine sensitized tin dioxide photocatalyst and a preparation method of the photocatalyst. The desulfurization catalyst contains MPc/SnO2 powder, wherein Pc represents phthalocyanine, and M is one or a combination of more of metal ions such as Mn<2+>, Fe<2+>, Co<2+>, Ni<2+>, Cu<2+> and Zn<2+>. After the dye-sensitized semiconductor photocatalytic desulfurizer is used for desulfuration for 3h, the removal rate of thiophene reaches up to 89% and is increased by 50% compared with that of a semiconductor which is not sensitized.
Description
Technical field
The present invention relates to light fuel desulfur technology field, relate in particular to a kind of preparation method and the application of this catalyst in oxidation sweetening of metal phthalocyanine sensitization tin ash visible light catalyst.
Background technology
Auto industry fast development, vehicle exhaust becomes principal element to the pollution of environment.The burning of sulfur-containing compound in gasoline generates SOx, is not only the main source of acid rain, and can significantly reduce the transformation efficiency of auto-exhaust catalyst to NOx, imperfect combustion hydro carbons and particle etc., aggravation environmental pollution.The restriction of the sulphur emissions index of in succession putting into effect along with enhancing and the various countries of people's environmental consciousness, production super-low sulfur even, without the clean fuel of sulphur, is cut down the harm that sulfur-containing compound causes environment from source, become the urgent cry of people's protection of the environment.Given this, research and development is imperative for effective environmentally friendly desulfurization new method and the Desulfurization Technology of various fluids (liquids and gases) fuel and raw material.
Current various countries in the world and various worldwide organization are all in the standard of formulating gasoline sulfure content.Mainly contain Europe, Japan, the large system of the U.S. three, other various countries substantially according to national conditions separately with reference to formulation.New standard-required content of sulfur in gasoline is from 450 μ gg
-1be reduced to 50 μ gg
-1, hydrocarbon emission amount will reduce by 18%, CO and reduce 19%, NOx minimizing 9%, and Toxic reduces 16%.Therefore under the prerequisite of technology and economic condition permission, each state is all in the requirement improving constantly sulfur content in gasoline.As the U.S. requires gasoline mean content of sulfur 30 μ gg in 2006
-1, high sulfur content 80 μ gg
-1; Canada production mean content of sulfur 30 μ gg in 2005
-1low-sulphur oil; European Union member countries produce sulfur-bearing 50 μ gg for 2005
-1low-sulphur oil; 10 μ gg carried out using in Germany in 2003
-1low-sulphur oil, and submitted in February, 2000 to European Union about the motion that used " without sulphur " fuel in 2007; China's gasoline required sulfur content from 2003 be 800 μ gg
-1, strive integrating with international standard for 2010.But generally speaking, the research of fuel desulfuration catalyst in China still in the starting stage.
In order to reduce Sulfur Content in Petroleum Products, most people is selected hydrodesulfurization.Hydrodesulfurization removes relatively easily the mercaptan in oil product cut, thioether, but exist, one-time investment is large, operating cost is high, consume the problems such as amounts of hydrogen is large, and be difficult to remove dibenzothiophenes and alkyl substituted diphenylamine bithiophene series sulfide, can not meet deep desulfuration requirement; The sulphur being removed in addition exists with the form of hydrogen sulfide, also can pollute environment.
Metal phthalocyanine sensitization SnO
2the application aspect of visible light catalytic deep desulfuration does not have report at home.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of metal phthalocyanine sensitization tin ash visible light catalytic to remove the preparation scheme of thiophene sulfocompounds catalyst, and this scheme desulfuration efficiency is high, and preparation is simple.
One aspect of the present invention relates to a kind of dye-sensitized semiconductor photocatalysis desulfurizing agent, it is characterized in that described desulphurization catalyst contains MPc/SnO
2powder, Pc represents phthalocyanine, M is for selecting white Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+the combination of one or more in metal ion, preferably Cu
2+.
In a preferred embodiment of the present invention, it is characterized in that SnO
2be greater than 10: 1 with the apparent mole ratios of MPc, be preferably greater than 50: 1, be further preferably greater than 80: 1.
In a preferred embodiment of the present invention, it is characterized in that metal phthalocyanine complex is bonded on nano-stannic oxide, by new collosol and gel hydrothermal synthesis method, metal phthalocyanine is bonded on tin ash.
The present invention also relates to the preparation method of dye-sensitized semiconductor photocatalysis desulfurizing agent on the other hand, it is characterized in that first by Sn (OH)
4superfine powder and absolute ethyl alcohol and DMF are mixed together and obtain collosol and gel presoma, then join in collosol and gel presoma and react preparing the raw material phthalonitrile of metal phthalocyanine and the soluble-salt of metal M.
In a preferred preparation method of the present invention, it is characterized in that reacting and undertaken by temperature programmed control, first at room temperature stir 0.5-1.5 hour, in hydrothermal reaction kettle, react 1-2 hour, be warmed up to 180 degree and react above 3-5 hour, naturally cooling.
The present invention also relates to the application of dye-sensitized semiconductor photocatalysis desulfurizing agent on the other hand, and described application is the application in oxidation sweetening.
In a preferred embodiment of the present invention, it is characterized in that described oxidation sweetening refers to for gasoline carries out oxidation sweetening.
In a preferred embodiment of the present invention, it is characterized in that described dye-sensitized semiconductor photocatalysis desulfurizing agent is photochemical catalyst to be aided with air-source be that oxidant carries out oxidation sweetening.
The present invention tests take air-source as catalyst prepared metal phthalocyanine sensitization tin dioxide photocatalyst for light fuel simulated system, have obvious desulfurized effect, and be oxidized without outer oxygen, has very strong practicality.
Accompanying drawing explanation
Fig. 1: the structural representation of metal phthalocyanine sensitization tin ash desulphurization catalyst
Fig. 2: photocatalytic degradation instrument and equipment schematic diagram:
1.300W iodine-tungsten lamp
2. optical filter (not adding in this experiment)
3. fan
4. thermostat water bath
5. light degradation reactor
6. air pump
7. magnetic stirrer
8. magneton
9,10. thermostatted water intake-outlet
Fig. 3: the comparing result of different desulfurization methods.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Synthesizing of collosol and gel presoma:
Mol ratio is the SnCl of 1: 2
45H
2o and urea are dissolved in distilled water, in 60 ℃ of water-baths, add hot reflux 4h, slowly drip to adjust to make system pH=9 with the ammonia spirit of 2mol/L, and adularescent precipitation generates, and the precipitation obtaining is repeatedly washed until there is no Cl with distilled water
-, dry at 80 ℃, the Sn (OH) obtaining
4powder is in Muffle furnace, and sintering 4h at 200 ℃, obtains SnO
2superfine powder.Take 2g Sn (OH)
4powder, is dissolved in 20ml absolute ethyl alcohol, then adds 5mlDMF to stir, and obtains collosol and gel presoma.
Synthesizing of metal phthalocyanine sensitization tin ash desulphurization catalyst:
By prepare the raw material phthalonitrile of phthalocyanine complex and transition metal salt add to reaction in tin ash collosol and gel presoma prepare metal phthalocyanine complex MPc (M=Cu) slaine and, under room temperature, stir 1h and form homogeneous system, the mixed liquor obtaining adds 2mL redistilled water, proceeds in 100mL hydrothermal reaction kettle after stirring.After 90min, be warming up to 200 ℃, be incubated naturally coolingly after 4 hours, after taking-up, the upper strata stillness of night is outwelled, gained solid washing 2 times, ethanol washes twice, and the drying box of putting into 1 () () ℃ is dried, and grinds to form powdery, obtains MPc/SnO
2sample, color sample is turquoise.
The test of nature of devulcanization:
Adopt the experimental provision shown in Fig. 2, in order to guarantee the accuracy of experiment, avoid the impact of external light source on experimental result, in actual mechanical process, whole device is put in the large carton of inwall blacking, to guarantee that solution in reactor is only subject to the irradiation of this device light source.
Get 5.3ml thiophene and be dissolved in that in 1000ml normal octane, to be made into sulfur content be 2000 μ LL
-1model gasoline.Measure 2 parts of each 125ml of model gasoline and put into 200ml quartz reactor, in reactor, add 0.125g catalyst and SnO
2, under lucifuge condition, stir 30min and reach adsorption-desorption balance.Then put into photocatalytic reaction device (seeing Fig. 2), under magnetic agitation, under the iodine-tungsten lamp illumination of 300W, pass into air to reactor with air pump, carry out photocatalytic degradation reaction experiment.30min gets sample one time, and degradation solution is proceeded in clean centrifuge tube, puts into centrifuge centrifugation 30min, gets supernatant liquor to be measured.Sulfur content adopts gas-chromatography test, and the peak area of the thiophene before and after observing response changes to calculate sulfur content.Find by contrast, catalyst can make desulfuration efficiency be up to 90%, than pure SnO
2improve 50%.
When what understand be; specific embodiments of the invention are only the objects for exemplary illustration; it limits protection scope of the present invention never in any form; those skilled in the art can be improved according to the above description or be converted, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (8)
1. a dye-sensitized semiconductor photocatalysis desulfurizing agent, is characterized in that described desulphurization catalyst contains MPc/SnO
2powder, Pc represents phthalocyanine, M is for selecting white Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+the combination of one or more in metal ion, preferably Cu
2+.
2. dye-sensitized semiconductor photocatalysis desulfurizing agent according to claim 1, is characterized in that SnO
2be greater than 10: 1 with the apparent mole ratios of MPc, be preferably greater than 50: 1, be further preferably greater than 80: 1.
3. according to the dye-sensitized semiconductor photocatalysis desulfurizing agent described in right 2, it is characterized in that metal phthalocyanine complex is bonded on nano-stannic oxide, by new collosol and gel hydrothermal synthesis method, metal phthalocyanine is bonded on tin ash.
4. the preparation method of the dye-sensitized semiconductor photocatalysis desulfurizing agent described in claim 1-3 any one, is characterized in that first by Sn (OH)
4powder and absolute ethyl alcohol and DMF are mixed together and obtain collosol and gel presoma, then join in collosol and gel presoma and react preparing the raw material phthalonitrile of metal phthalocyanine and the soluble-salt of metal M.
5. the preparation method of dye-sensitized semiconductor photocatalysis desulfurizing agent according to claim 4, it is characterized in that reacting and undertaken by temperature programmed control, first at room temperature stir 0.5-1.5 hour, in hydrothermal reaction kettle, react 1-2 hour, be warmed up to 180 degree and react above 3-5 hour, naturally cooling.
6. the application of the dye-sensitized semiconductor photocatalysis desulfurizing agent described in claim 1-3 any one, described application is the application in oxidation sweetening.
7. the application of dye-sensitized semiconductor photocatalysis desulfurizing agent according to claim 6, the oxidation sweetening described in it is characterized in that refers to for gasoline and carries out oxidation sweetening.
8. according to the application of the dye-sensitized semiconductor photocatalysis desulfurizing agent described in claim 6 or 7, it is characterized in that described dye-sensitized semiconductor photocatalysis desulfurizing agent is photochemical catalyst to be aided with air-source be that oxidant carries out oxidation sweetening.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277870A (en) * | 2014-10-16 | 2015-01-14 | 大连理工大学 | Photodissociation reaction method of benzothiophene compound for oxidative desulfurization |
| 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 |
| 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 |
| CN108404994A (en) * | 2018-03-16 | 2018-08-17 | 常州大学 | A kind of preparation method of the phthalocyanine-sensitized indium sulfide tin composite visible light catalyst of nitro cobalt |
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| CN103288838A (en) * | 2013-05-09 | 2013-09-11 | 西北大学 | Preparation method of di-nuclear sub-phthalocyanine substance and application thereof |
| CN103447094A (en) * | 2013-04-08 | 2013-12-18 | 西北大学 | Preparation method of desulfurization catalyst |
| CN103480414A (en) * | 2013-04-23 | 2014-01-01 | 西北大学 | Preparation method and application of subphthalocyanine bonded graphene oxide |
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2014
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Patent Citations (3)
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| CN103447094A (en) * | 2013-04-08 | 2013-12-18 | 西北大学 | Preparation method of desulfurization catalyst |
| CN103480414A (en) * | 2013-04-23 | 2014-01-01 | 西北大学 | Preparation method and application of subphthalocyanine bonded graphene oxide |
| CN103288838A (en) * | 2013-05-09 | 2013-09-11 | 西北大学 | Preparation method of di-nuclear sub-phthalocyanine substance and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张改: "酞菁配合物-TiO2/SnO2复合材料的制备及脱硫性能研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277870A (en) * | 2014-10-16 | 2015-01-14 | 大连理工大学 | Photodissociation reaction method of benzothiophene compound for oxidative desulfurization |
| CN104277870B (en) * | 2014-10-16 | 2017-04-12 | 大连理工大学 | Photodissociation reaction method of benzothiophene compound for oxidative desulfurization |
| 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 |
| 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 |
| CN106281437B (en) * | 2016-09-13 | 2018-06-22 | 华南理工大学 | A kind of method that Catalytic Oxidation-Extraction removes thiophenes sulfides in gasoline under visible ray |
| CN108404994A (en) * | 2018-03-16 | 2018-08-17 | 常州大学 | A kind of preparation method of the phthalocyanine-sensitized indium sulfide tin composite visible light catalyst of nitro cobalt |
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Application publication date: 20140611 |