CN102921464A

CN102921464A - Preparation method of sulfonated cobalt phthalocyanine catalyst

Info

Publication number: CN102921464A
Application number: CN 201210421936
Authority: CN
Inventors: 张淑芬
Original assignee: Shaanxi Qiyuan Technology Development Co Ltd
Current assignee: Shaanxi Qiyuan Technology Development Co Ltd
Priority date: 2012-10-30
Filing date: 2012-10-30
Publication date: 2013-02-13

Abstract

The invention relates to a preparation method of a catalyst, in particular to a preparation method of a sulfonated cobalt phthalocyanine catalyst. The preparation method comprises the following steps of: mixing phthalic anhydride with fuming sulfuric acid in a mole ratio of 1:4, reacting at 190 DEG C for 5 hours, diluting the reactant with ice water, leaching the diluted product and taking the filter residue; and mixing cobaltous sulfate heptahydrate, the filter residue, urea and ammonium molybdate in a mole ratio of 0.1:0.354:2.64:2.8, mixing the mixture with 300-350mL of jet fuel and then heating the mixture in a sand bath, reacting at 20-135 DEG C under normal pressure for 0.5 hour, reacting at 135-160 DEG C for 0.5 hour, reacting at 160-185 DEG C for 1 hour, reacting at 185-205 DEG C for 1 hour, reacting at 205-245 DEG C for 2 hours, dissolving the product in 10% of NaOH solution at normal temperature after cooling to prepare an alkaline catalyst solution with mass fraction being 1mu g/g, impregnating activated carbon in the alkaline catalyst solution for 24 hours, taking out the activated carbon and pressing the activated carbon to be dried, and drying the product at 110 DEG C for 6 hours, thus obtaining the sulfonated cobalt phthalocyanine catalyst. The preparation method has the following beneficial effects: the jet fuel with low toxicity is used instead of the traditional solvent benzene trichloride or nitrobenzene which has high toxicity and is easy to cause cancers; and experiments prove that the obtained sulfonated cobalt phthalocyanine catalyst and the contrast agents have the equivalent sweetening effect.

Description

The preparation method of cobalt sulfonated phthalocyanine

Technical field

The present invention relates to a kind of preparation method of catalyst.

Background technology

The mercaptan from gasoline sulfur content of sour crude oil refining is higher.Mercaptan in the gasoline produces stench, has corrosivity, and the plumbous amount of gasoline sense is descended.Simultaneously, mercaptan is again the oxidation initator, can promote that the unstable component oxidative condensation is jelly in the gasoline, causes gasoline storage stability variation.Remove mercaptan sulfur in the light-end products with cobalt sulfonated phthalocyanine, the main physicochemical property of the oil product of processing is constant, and acidity reduces, and is conducive to reduce corrosion and environmental pollution situation.At present, the catalyst that uses in the light oil products deodorizing commercial plant mostly is greatly that sulfonated phthalocyanine bores or the immobilized sulfonated phthalocyanine cobalt of the Activated Carbon Supported that makes with infusion process.

Sulfonated phthalocyanine cobalt synthetic mainly contains two kinds of fusion method and solvent methods: the major defect of fusion method is that raw material is volatile, environmental pollution is sternly smoked, uses water as the situation that medium can produce more serious sticking wall and stop up blast pipe; The major defect of solvent method is that the toxicity of solvent for use is large, during for example take tri-chlorination benzene as solvent, easily generate the strong carcinogen Polychlorinated biphenyls of trace in synthetic sulfonated phthalocyanine cobalt process, and the synthetic technology take nitrobenzene as solvent, solvent refining runs into insoluble problem.

Summary of the invention

The present invention aims to provide a kind of preparation method of cobalt sulfonated phthalocyanine, and use therein solvent toxicity is little, and boiling range is wide.

The preparation method of cobalt sulfonated phthalocyanine of the present invention comprises: with the mixed in molar ratio that phthalic anhydride and oleum are pressed 1:4, then 190 ℃ of lower reaction 5 h with the frozen water dilution, separate out rear suction filtration until solid and get filter residue; Cobalt sulfate, filter residue, urea and ammonium molybdate are pressed the mixed in molar ratio of 0.l:0.354:2.64 and 2.8, then in sand-bath, heat after mixing with the 300-350mL jet fuel, under 20-135 ℃, reacted 0.5 hour under the normal pressure, 135-160 ℃ of lower the reaction 0.5 hour, 160-185 ℃ of lower the reaction 1 hour, 185-205 ℃ of lower the reaction 1 hour, 205-245 ℃ of lower the reaction 2 hours; Be dissolved at normal temperatures after the cooling in 10% the NaOH solution, being made into mass fraction is the catalyst alkaline solution of 1 μ g/g, Immesion active carbon 24 h, and taking-up press dry, and gets final product at 110 ℃ of lower baking 6 h.

The present invention uses the little jet fuel of toxicity to replace carcinogenic conventional solvent tri-chlorination benzene or the nitrobenzene of toxicity Da Yi, and through experimental verification, the cobalt sulfonated phthalocyanine of acquisition and contrast medium have suitable removal of mercaptans effect.

Embodiment one.

With 1 mole of phthalic anhydride and the mole oleum mix, then 190 ℃ of lower reaction 5 h with the frozen water dilution, separate out rear suction filtration until white solid and get filter residue.

0.l mole cobalt sulfate, 0.354 mole of filter residue, 2.64 mole of urea and 2.8 moles of ammonium molybdates are mixed, then in sand-bath, heat after mixing with the 300mL jet fuel, under 20-135 ℃, reacted 0.5 hour under the normal pressure, 135-160 ℃ of lower the reaction 0.5 hour, 160-185 ℃ of lower the reaction 1 hour, 185-205 ℃ of lower the reaction 1 hour, 205-245 ℃ of lower the reaction 2 hours; Obtain the navy blue solid after the cooling, last being dissolved at normal temperatures in 10% the NaOH solution of pulverizing, being made into mass fraction is the catalyst alkaline solution of 1 μ g/g, Immesion active carbon 24 h, taking-up press dry, and gets final product at 110 ℃ of lower baking 6 h.

Its product yield is 67.3%, and wherein C is that 32.2%, H is that 3.25%, N is that 14.71%, S is 12.84%.

Embodiment two.

The cobalt sulfonated phthalocyanine that embodiment one is made is tested in without caustic alkali fixed bed gasoline deodorization technique in that simulation is industrial, tests in without caustic alkali fixed bed gasoline deodorization technique in that same simulation is industrial with contrast medium simultaneously.Test is carried out at miniature fixed bed gasoline deodorization experimental rig, and raw material is catalytically cracked gasoline (mercaptan sulfur content is 102 μ g/g), and 30～32 ℃ of reaction temperatures adopt higher space velocity 18 h ^-1(air speed of commercial plant is generally 1～2 h ^-1), activator is pre-mixed in raw material, and addition is 100 μ g/g, and result of the test shows that the cobalt sulfonated phthalocyanine that embodiment one makes and contrast medium have suitable removal of mercaptans effect.When the reaction time was 11 h, gasoline products corroded the level for 1h by the doctor test, and when 12 h, the mercaptan sulfur content of gasoline products is just above 10 μ g/g.

Claims

1. the preparation method of cobalt sulfonated phthalocyanine is characterized in that comprising:

With the mixed in molar ratio that phthalic anhydride and oleum are pressed 1:4, then 190 ℃ of lower reaction 5 h with the frozen water dilution, separate out rear suction filtration until solid and get filter residue;

Cobalt sulfate, filter residue, urea and ammonium molybdate are pressed the mixed in molar ratio of 0.l:0.354:2.64 and 2.8, then in sand-bath, heat after mixing with the 300-350mL jet fuel, under 20-135 ℃, reacted 0.5 hour under the normal pressure, 135-160 ℃ of lower the reaction 0.5 hour, 160-185 ℃ of lower the reaction 1 hour, 185-205 ℃ of lower the reaction 1 hour, 205-245 ℃ of lower the reaction 2 hours; Be dissolved at normal temperatures after the cooling in 10% the NaOH solution, being made into mass fraction is the catalyst alkaline solution of 1 μ g/g, Immesion active carbon 24 h, and taking-up press dry, and gets final product at 110 ℃ of lower baking 6 h.