CN104801347A - Catalytic desulfurization agent of carboxylic substituent metal phthalocyanine sensitization Zn2SnO4 powder and preparation method for catalytic desulfurization agent - Google Patents

Abstract

The invention discloses a catalytic desulfurization agent of carboxylic substituent metal phthalocyanine sensitization Zn2SnO4 powder. The catalytic desulfurization agent contains tetra-carboxylic phthalocyanine complex TcPcM and Zn2SnO4 powder, wherein TcPc is tetra-carboxylic phthalocyanine; M is one or more metal ion combinations of Mn<2+>, Fe<2+>, Co<2+>, Ni<2+>, Cu<2+> and Zn<2+>. The invention further discloses a preparation method for the catalytic desulfurization agent. The prepared catalytic desulfurization agent is a photocatalyst of tetra-carboxylic substituent metal phthalocyanine sensitization Zn2SnO4 powder, and can be used for testing in a light fuel simulation system with an air source as a catalyst, so that the desulfurization effect is obvious, no additional oxygen is needed for oxidation and the practicability is very high.

Description

Carboxyl substituted metal phthalocyanine sensitization Zn 2snO 4catalytic desulfurizing agent of powder and preparation method thereof

Technical field

The invention belongs to light fuel technical field of desulfurization, particularly relate to a kind of carboxyl substituted metal phthalocyanine sensitization Zn ₂snO ₄catalytic desulfurizing agent of powder and preparation method thereof.

Background technology

Auto industry is fast-developing, and the pollution of vehicle exhaust to environment becomes principal element.Sulfur-containing compound burning in gasoline generates SOx, is not only the main source of acid rain, and can significantly reduce auto-exhaust catalyst to the transformation efficiency of NOx, imperfect combustion hydro carbons and particle etc., aggravation environmental pollution.The restriction of the sulphur emissions index in succession put 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, cuts 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 be used for the effective environmentally friendly desulfurization new method of various fluid (liquids and gases) fuel and raw material and Desulfurization Technology imperative.

Current various countries and various worldwide organization are in the world all in the standard formulating gasoline sulfure content.Mainly contain Europe, Japan, U.S.'s three major controls, other various countries formulate according to respective national conditions reference substantially.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 allowed at technology and economic condition, each state is all improving constantly the requirement to sulfur content in gasoline.As the U.S. requires gasoline mean content of sulfur 30 μ gg in 2006 ^-1, most 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; Use 10 μ gg carried out in 2003 in Germany ^-1low-sulphur oil, and the motion about using " without sulphur " fuel in 2007 has been have submitted in February, 2000 to European Union; China's gasoline requires that from 2003 sulfur content is 800 μ gg ^-1, strive integrating with international standard for 2010.But generally speaking, the research of fuel desulfuration catalyst is still in the starting stage in China.

In order to reduce Sulfur Content in Petroleum Products, most people selective hydrodesulfrization.Hydrodesulfurization removes relatively easily to the mercaptan in oil product cut, thioether, but there is the problems such as one-time investment is large, operating cost is high, consumption amounts of hydrogen is large, and be difficult to remove dibenzothiophenes and alkyl substituted diphenylamine bithiophene series sulfide, deep desulfuration requirement can not be met; The sulphur be removed in addition exists with the form of hydrogen sulfide, also can pollute environment.The features such as the simple to operate and cost that photochemical oxidation method has because of it is low, become a kind of emerging desulfur technology, and get more and more people's extensive concerning.Photochemical Oxidative Desulfurization of Fluidized method utilizes semiconductor to carry out sulfur-containing compound in catalytic oxidation fuel oil exactly, reduces fuel oil sulfur content, realizes the deep desulfuration technology of fuel oil.Mainly concentrate on degraded organic pollutants to the research of photochemical oxidation method both at home and abroad, the research being applied to reduce sulfur content in fuel oil just just starts, imperfection is gone back in the research of reaction mechanism and dynamics characteristic aspect, also there is many problems needing to solve.There is following problem in the preparation aspect of current dye-sensitized semiconductor catalyst: the sol-gal process that (1) is traditional and coprecipitation are prepared oxide powder and all will at high temperature be heat-treated to promote crystallization, and its photoresponse scope to be improved and photocatalysis characteristic just must carry out doping vario-property, dye sensitization is that one compares effective method, but general dyestuff can decompose at oxide crystallization temperature, cannot realize effective compound.(2) research of another aspect is that the catalyst prepared by this method is physisorption again by infusion process carried dye after oxide powder is successfully prepared, can desorption in degradation process.Meanwhile, the metal phthalocyanine of area load is just adsorbed on semiconductor surface with physical action, cannot realize the effective transfer of the photoelectron on metal phthalocyanine to the valence band of oxide, effectively cannot improve catalytic performance.

Summary of the invention

In view of this, main purpose of the present invention is to provide a kind of carboxyl substituted metal phthalocyanine sensitization Zn ₂snO ₄catalytic desulfurizing agent of powder and preparation method thereof.

For achieving the above object, technical scheme of the present invention is achieved in that

The embodiment of the present invention provides a kind of carboxyl substituted metal phthalocyanine sensitization Zn ₂snO ₄powder catalytic desulfurizing agent, described catalytic desulfurizing agent contains tetracarboxylic phthalocyanine complex TcPcM and Zn ₂snO ₄powder, TcPc is tetracarboxylic phthalocyanine, and M is Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺one or more combination in metal ion.

In such scheme, described Zn ₂snO ₄the apparent mole ratios of powder and TcPcM is 50 ~ 150:1.

In such scheme, described Zn ₂snO ₄be 100:1 with the optimum apparent mole ratios of TcPcM.

The embodiment of the present invention also provides a kind of carboxyl substituted metal phthalocyanine sensitization Zn ₂snO ₄the preparation method of the catalytic desulfurizing agent of powder, reaction raw materials comprises ZnSO ₄7H ₂o and SnCl ₄5H ₂o and tetracarboxylic phthalocyanine complex TcPcM, at room temperature stirs 0.5-1.5 hour, proceeds in hydrothermal reaction kettle, be progressively warmed up to 170 degree, and hydro-thermal reaction 3-5 hour, naturally cool, obtain catalytic desulfurizing agent; Wherein, TcPc is tetracarboxylic phthalocyanine, and M is Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺one or more combination in metal ion.

In such scheme, described ZnSO ₄7H ₂o is 0.01-0.03mol, SnCl ₄5H ₂o is 0.005-0.015mol, and described tetracarboxylic phthalocyanine complex TcPcM is ZnSO ₄7H ₂1% of the amount of substance of O.

In such scheme, described hydro-thermal reaction is carried out in the mixed solution of DMF, NaOH aqueous solution and absolute ethyl alcohol.

In such scheme, described TcPcM obtains by the following method: be 2.0molL by 100mL concentration by four formamido phthalocyanines at 100 DEG C ^-1sodium hydroxide solution hydrolysis 12h after filter, filtrate regulates pH=1 with hydrochloric acid, by G4 sand core funnel suction filtration after leaving standstill, with deionized water rinsing filter cake to neutral, then chloroform, ethanol, ether, acetone, THF flush cake is used successively, by the solid product that obtains 100 DEG C of vacuum drying, finally with DMF, gained crude product is recrystallized, obtains TcPcM;

The molecular formula of described TcPcM is (COOH) ₄pcM, structural formula is

In such scheme, described four formamido phthalocyanines obtain by the following method: take 1, 2, 4-benzenetricarboxylic anhydride 2.0496g, urea 6.0533g, ammonium molybdate 0.1260g, in mortar, grinding evenly, be that 4:1 adds zinc acetate grinding evenly according to mol ratio again, solid is proceeded in 100mL round-bottomed flask, oil bath is heated to 140 DEG C, the round-bottomed flask that condenser pipe is housed is placed in oil bath, open condensed water, quick magnetic agitation, urea starts to dissolve, as the solvent of solid phase reaction, continue to be heated to 210 DEG C, after 30min, solution colour becomes blackish green, and start solidification, 6h is incubated after becoming fluffy dark green solid completely, naturally cool, take out reactant mixture grinding evenly, go in round-bottomed flask, by its in 100mL secondary deionized water in 100 DEG C backflow 8h, filter while hot, by a large amount of absolute ethyl alcohol and hot secondary deionized water flush cake, dry, the product refluxed by secondary deionized water is joined the 1.0molL of 80mL ^-1in HCl solution, reflux 5h, while hot suction filtration in the oil bath of 100 DEG C, and by a large amount of boiling water and absolute ethyl alcohol flush cake, then use chloroform, oxolane, washed with ether product successively, obtains four formamido phthalocyanines,

The molecular formula of described four formamido phthalocyanines is (CONH ₂) ₄pcM, structural formula is

Compared with prior art, beneficial effect of the present invention:

The present invention is by prepared tetracarboxylic substituted metal phthalocyanine sensitization Zn ₂snO ₄powder photocatalyst is that catalyst is used for testing in light fuel simulated system with air-source, has obvious desulfurized effect, and is oxidized without the need to outer oxygen, have very strong practicality.

Accompanying drawing explanation

Fig. 1 is the comparing result of different desulfurization method.

Detailed description of the invention

Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.

The embodiment of the present invention provides a kind of carboxyl substituted metal phthalocyanine sensitization Zn ₂snO ₄the catalytic desulfurizing agent of powder, described catalytic desulfurizing agent contains tetracarboxylic phthalocyanine complex TcPcM and Zn ₂snO ₄powder, TcPc is tetracarboxylic phthalocyanine, and M is Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺one or more combination in metal ion.

Described Zn ₂snO ₄the apparent mole ratios of powder and TcPcM is 50 ~ 150:1.

Described Zn ₂snO ₄the apparent mole ratios of powder and TcPcM is preferably 100:1.

The embodiment of the present invention also provides a kind of carboxyl substituted metal phthalocyanine sensitization Zn ₂snO ₄the preparation method of the catalytic desulfurizing agent of powder, reaction raw materials comprises ZnSO ₄7H ₂o and SnCl ₄5H ₂o and tetracarboxylic phthalocyanine complex TcPcM, at room temperature stirs 0.5-1.5 hour, proceeds in hydrothermal reaction kettle, by temperature programming, be progressively warmed up to 170 degree, and hydro-thermal reaction 3-5 hour, naturally cool, obtain catalytic desulfurizing agent; Wherein, TcPc is tetracarboxylic phthalocyanine, and M is Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺one or more combination in metal ion.

Described ZnSO ₄7H ₂o is 0.01-0.03mol, SnCl ₄5H ₂o is 0.005-0.015mol, and described tetracarboxylic phthalocyanine complex TcPcM is ZnSO ₄7H ₂1% of the amount of substance of O.

Described hydro-thermal reaction is carried out in the mixed solution of DMF, NaOH aqueous solution and absolute ethyl alcohol.

Described TcPcM obtains by the following method: be 2.0molL by 100mL concentration by four formamido phthalocyanines at 100 DEG C ^-1sodium hydroxide solution hydrolysis 12h after filter, filtrate regulates pH=1 with hydrochloric acid, by G4 sand core funnel suction filtration after leaving standstill, with deionized water rinsing filter cake to neutral, then chloroform, ethanol, ether, acetone, THF flush cake is used successively, by the solid product that obtains 100 DEG C of vacuum drying, finally with DMF, gained crude product is recrystallized, obtains TcPcM;

The molecular formula of described TcPcM is MPc (COOH) ₄, structural formula is

Described four formamido phthalocyanines obtain by the following method: take 1, 2, 4-benzenetricarboxylic anhydride 2.0496g, urea 6.0533g, ammonium molybdate 0.1260g, in mortar, grinding evenly, be that 4:1 adds zinc acetate grinding evenly according to mol ratio again, solid is proceeded in 100mL round-bottomed flask, oil bath is heated to 140 DEG C, the round-bottomed flask that condenser pipe is housed is placed in oil bath, open condensed water, quick magnetic agitation, urea starts to dissolve, as the solvent of solid phase reaction, continue to be heated to 210 DEG C, after 30min, solution colour becomes blackish green, and start solidification, 6h is incubated after becoming fluffy dark green solid completely, naturally cool, take out reactant mixture grinding evenly, go in round-bottomed flask, by its in 100mL secondary deionized water in 100 DEG C backflow 8h, filter while hot, by a large amount of absolute ethyl alcohol and hot secondary deionized water flush cake, dry, the product refluxed by secondary deionized water is joined the 1.0molL of 80mL ^-1in HCl solution, reflux 5h, while hot suction filtration in the oil bath of 100 DEG C, and by a large amount of boiling water and absolute ethyl alcohol flush cake, then use chloroform, oxolane, washed with ether product successively, obtains four formamido phthalocyanines,

The molecular formula of described four formamido phthalocyanines is (CONH ₂) ₄pcM, structural formula is

The preparation process of described four formamido phthalocyanines and TcPcM represents as follows:

Embodiment:

The synthesis of described tetracarboxylic substituted metal phthalocyanine:

Take 1, 2, 4-benzenetricarboxylic anhydride 2.0496g, urea 6.0533g, ammonium molybdate 0.1260g, in mortar, grinding evenly, be that 4:1 adds zinc acetate grinding evenly according to mol ratio again, solid is proceeded in 100mL round-bottomed flask, oil bath is heated to 140 DEG C, the round-bottomed flask that condenser pipe is housed is placed in oil bath, open condensed water, quick magnetic agitation, urea starts to dissolve, as the solvent of solid phase reaction, continue to be heated to 210 DEG C, after 30min, solution colour becomes blackish green, and start solidification, 6h is incubated after becoming fluffy dark green solid completely, naturally cool, take out reactant mixture grinding evenly, go in round-bottomed flask, by its in 100mL secondary deionized water in 100 DEG C backflow 8h, filter while hot, by a large amount of absolute ethyl alcohol and hot secondary deionized water flush cake, dry, the product refluxed by secondary deionized water is joined the 1.0molL of 80mL _- ¹in HCl solution, reflux 5h, while hot suction filtration in the oil bath of 100 DEG C, and by a large amount of boiling water and absolute ethyl alcohol flush cake, then use chloroform, oxolane, washed with ether product successively, obtains four formamido phthalocyanines.

Be 2.0molL by 100mL concentration by the four formamido phthalocyanines that obtain at 100 DEG C _- ¹sodium hydroxide solution hydrolysis 12h after filter, filtrate regulates pH=1 with hydrochloric acid, have after leaving standstill and precipitate generation in a large number, G4 sand core funnel suction filtration, with deionized water rinsing filter cake to neutral, then use chloroform, ethanol, ether, acetone, THF flush cake successively, by the solid product that obtains 100 DEG C of vacuum drying, with DMF, gained crude product is recrystallized, obtains tetracarboxylic phthalocyanine complex.

The synthesis of described catalytic desulfurizing agent:

Take the ZnSO of 0.02mol respectively ₄7H ₂the SnCl of O, 0.01mol ₄5H ₂o, adds few distilled water as far as possible and makes it dissolve mixing, then take the PcTcM of 0.2mmol, i.e. ZnSO ₄7H ₂1% of O amount of substance, dissolves with a small amount of DMF, mixes with above-mentioned mixed solution; Take the NaOH of 0.12mol again, add 30ml distilled water and dissolve, be mixed with 4.0mol/LNaOH solution, regulate the PH of above-mentioned mixed solution to be about 7 by this NaOH solution, suction filtration, and with a large amount of distilled water washing to there is no SO ₄ ^2-and Cl ^?residual.

Be transferred in hydrothermal reaction kettle by above-mentioned product, the DMF adding 20ml absolute ethyl alcohol and 10ml, as solvent, puts into thermostatic drying chamber, keeps 24h at 170 DEG C, suction filtration after cooling, with absolute ethanol washing, is ground to thin after drying, weigh, bottle, same method is obtained TcPcM and Zn respectively ₂snO ₄sample.

The test of nature of devulcanization:

Adopt the experimental provision of photocatalytic degradation instrument and equipment, in order to ensure the accuracy of testing, avoid external light source on the impact of experimental result, in actual mechanical process, whole device is put in the large carton of inwall blacking, to guarantee that in reactor, solution is only subject to the irradiation of this device light source.

Get 5.3ml thiophene and be dissolved in 1000ml normal octane that to be made into sulfur content be 2000 μ LL ^-1model gasoline, measure model gasoline 2 parts of each 125ml and put into 200ml quartz reactor, 0.125g catalyst and P25 is added in reactor, stir 30min under lucifuge condition and reach adsorption-desorption balance, then photocatalytic reaction device is put into, under magnetic stirring, under the iodine-tungsten lamp illumination of 300W, air is passed into reactor with air pump, carry out photocatalytic degradation reaction experiment, 30min gets a sample, degradation solution is proceeded in clean centrifuge tube, put into centrifuge and be separated 30min, get supernatant liquor to be measured, sulfur content adopts gas-chromatography test, the peak area change of the thiophene before and after observing response calculates sulfur content, as shown in Figure 1, found by contrast, catalyst can make desulfuration efficiency be up to 97.95%, than the Zn of non-sensitization ₂snO ₄the highlyest improve 30.68%.

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 improve and convert the protection domain that all should belong to claims of the present invention.

Claims (8)

1. a carboxyl substituted metal phthalocyanine sensitization Zn ₂snO ₄powder catalytic desulfurizing agent, is characterized in that: described catalytic desulfurizing agent contains tetracarboxylic phthalocyanine complex TcPcM and Zn ₂snO ₄powder, TcPc is tetracarboxylic phthalocyanine, and M is Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺one or more combination in metal ion.

2. carboxyl substituted metal phthalocyanine sensitization Zn according to claim 1 ₂snO ₄the agent of powder catalytic desulfurizing agent sulphur, is characterized in that: described Zn ₂snO ₄the apparent mole ratios of powder and TcPcM is 50 ~ 150:1.

3. carboxyl substituted metal phthalocyanine sensitization Zn according to claim 1 and 2 ₂snO ₄powder catalytic desulfurizing agent, is characterized in that: described Zn ₂snO ₄be 100:1 with the optimum apparent mole ratios of TcPcM.

4. a carboxyl substituted metal phthalocyanine sensitization Zn ₂snO ₄the preparation method of the catalytic desulfurizing agent of powder, is characterized in that: reaction raw materials comprises ZnSO ₄7H ₂o and SnCl ₄5H ₂o and tetracarboxylic phthalocyanine complex TcPcM, at room temperature stirs 0.5-1.5 hour, proceeds in hydrothermal reaction kettle, be progressively warmed up to 170 degree, and hydro-thermal reaction 3-5 hour, naturally cool, obtain catalytic desulfurizing agent; Wherein, TcPc is tetracarboxylic phthalocyanine, and M is Mn ²⁺, Fe ²⁺, Co ²⁺, Ni ²⁺, Cu ²⁺, Zn ²⁺one or more combination in metal ion.

5. the preparation method of the catalytic desulfurizing agent sulphur agent of carboxyl substituted metal phthalocyanine sensitization Zn2SnO4 powder according to claim 4, is characterized in that: described ZnSO ₄7H ₂o is 0.01-0.03mol, SnCl ₄5H ₂o is 0.005-0.015mol, and described tetracarboxylic phthalocyanine complex TcPcM is ZnSO ₄7H ₂1% of the amount of substance of O.

6. the carboxyl substituted metal phthalocyanine sensitization Zn according to claim 4 or 5 ₂snO ₄the preparation method of powder catalytic desulfurizing agent, is characterized in that: described hydro-thermal reaction is carried out in the mixed solution of DMF, NaOH aqueous solution and absolute ethyl alcohol.

7. carboxyl substituted metal phthalocyanine sensitization Zn according to claim 6 ₂snO ₄the preparation method of powder catalytic desulfurizing agent, is characterized in that, described TcPcM obtains by the following method: be 2.0molL by 100mL concentration by four formamido phthalocyanines at 100 DEG C ^-1sodium hydroxide solution hydrolysis 12h after filter, filtrate regulates pH=1 with hydrochloric acid, by G4 sand core funnel suction filtration after leaving standstill, with deionized water rinsing filter cake to neutral, then chloroform, ethanol, ether, acetone, THF flush cake is used successively, by the solid product that obtains 100 DEG C of vacuum drying, finally with DMF, gained crude product is recrystallized, obtains TcPcM;

The molecular formula of described TcPcM is (COOH) ₄pcM, structural formula is

8. carboxyl substituted metal phthalocyanine sensitization Zn according to claim 7 ₂snO ₄the preparation method of powder catalytic desulfurizing agent, it is characterized in that, described four formamido phthalocyanines obtain by the following method: take 1, 2, 4-benzenetricarboxylic anhydride 2.0496g, urea 6.0533g, ammonium molybdate 0.1260g, in mortar, grinding evenly, be that 4:1 adds zinc acetate grinding evenly according to mol ratio again, solid is proceeded in 100mL round-bottomed flask, oil bath is heated to 140 DEG C, the round-bottomed flask that condenser pipe is housed is placed in oil bath, open condensed water, quick magnetic agitation, urea starts to dissolve, as the solvent of solid phase reaction, continue to be heated to 210 DEG C, after 30min, solution colour becomes blackish green, and start solidification, 6h is incubated after becoming fluffy dark green solid completely, naturally cool, take out reactant mixture grinding evenly, go in round-bottomed flask, by its in 100mL secondary deionized water in 100 DEG C backflow 8h, filter while hot, by a large amount of absolute ethyl alcohol and hot secondary deionized water flush cake, dry, the product refluxed by secondary deionized water is joined the 1.0molL of 80mL ^-1in HCl solution, reflux 5h, while hot suction filtration in the oil bath of 100 DEG C, and by a large amount of boiling water and absolute ethyl alcohol flush cake, then use chloroform, oxolane, washed with ether product successively, obtains four formamido phthalocyanines,

The molecular formula of described four formamido phthalocyanines is (CONH ₂) ₄pcM, structural formula is