CN102259027A - Method for preparing cobalt phthalocyanine sulfonamide desulfurization catalyst - Google Patents
Method for preparing cobalt phthalocyanine sulfonamide desulfurization catalyst Download PDFInfo
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- CN102259027A CN102259027A CN201110132008XA CN201110132008A CN102259027A CN 102259027 A CN102259027 A CN 102259027A CN 201110132008X A CN201110132008X A CN 201110132008XA CN 201110132008 A CN201110132008 A CN 201110132008A CN 102259027 A CN102259027 A CN 102259027A
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- phthalic anhydride
- sulfonamide
- chloride
- sulfonic acid
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Abstract
The invention relates to a method for preparing a cobalt phthalocyanine sulfonamide desulfurization catalyst, comprising the steps of: adding chlorosulfonic acid or chlorosulfonic acid into thionyl chloride and carrying out sulfonation through taking phthalic anhydride as a raw material so as to obtain phthalic anhydride sulfonyl chloride; and subjecting the obtained product and pyromellitic formic anhydride, urea, anhydrous cobalt chloride and ammonium molybdate to condensation reaction so as to obtain dinuclear cobalt phthalocyanine sulfonamide. By means of the preparation method provided by the invention, the problems of phthalic anhydride sublimation, sulfuric acid neutralization and separation and the like caused in conventional productive processes of sulfonated cobalt phthalocyanine are avoided and the preparation method has the characteristics of mild production condition, simple production process, recoverability of excessive raw materials and the like. The obtained cobalt phthalocyanine sulfonamide desulfurization catalyst can be applied to catalytic oxidation removing processes of organic sulfur and inorganic sulfur and has the characteristics of high activity, high selectivity, easiness in regeneration and the like.
Description
Technical field
The present invention relates to the preparation method of a kind of novel desulphurization catalyst-phthalocyanine cobalt sulfonamide, belong to the synthesis technical field of Phthalocyanine-like Catalysts.
Background technology
Desulfurization during petrochemical industry and Coal Chemical Industry are produced is handled, and the catalytic oxidation in the wet method is extensively adopted in the particularly desulfurization of coke-stove gas and oil gas at present, wherein pays close attention to the most as the PDS method of catalyst with sulfonated phthalocyanine cobalt especially.The PDS method is a kind of novel sulfur removal technology that developed recently gets up, and for most organic sulfur and inorganic sulfur good removal effect is arranged all.The used phthalocyanine cobalt catalyst series of PDS method is as a kind of efficient catalyst, the desulfurization and the deodorizing that contain low, high-sulfur gas and low-viscosity (mobile) liquid have been widely used in, obvious for technological effects such as hydrogasoline removal of mercaptans, desulfuration of liquefied gas, also be used in the deodourizing of the waste water and gas in the industrial production.Particularly sulfonation (gathering) phthalocyanine cobalt method desulfurization and decyanation technology moves for many years in various gas-liquid sulfur removal technologies, is acknowledged as leading domestic desulfuration and decyanation purification techniques.
But, in the production process of sulfonated phthalocyanine cobalt, as Chinese patent CN1045414A " synthetic method of cobalt phthalocyanine desulfating catalyst ", CN1117049A " preparation method of phthalocyanine cobalt sulfonate desulphurization catalyst ", CN1336253A " production method of binuclear phthalocyanine cobalt desulphurization catalyst ", CN1403459A " preparation method of oxidizing and desulfurizing catalyst phthalocyanine cobalt sulfonate ", method therefor all is to be initiation material with the phthalic anhydride, with oleum or sulfuric acid is sulfonated reagent, at first prepare phthalic anhydride sulfonate at a certain temperature, and then polymerization generates object.This technology is raw materials used cheap, but also has following shortcoming: one, the phthalic anhydride distillation influences productive rate.In the sulfonating reaction process, make solvent with not volatile sulfuric acid, 170～240 ℃ of reaction temperatures are because phthalic anhydride very easily distillation under this temperature causes the part phthalic anhydride to accumulate on still top and the condenser blocking pipe.Its two, intermediate phthalic anhydride sulfonic acid loss is too big or the transpiring moisture energy consumption is too high.Because intermediate phthalic anhydride sulfonic acid is soluble in water, so follow-up separating technology need be used in a large amount of calcium oxide or the calcium hydroxide and as the sulfuric acid of solvent, be commonly called as gypsum and generate calcium sulfate precipitation, when centrifugation, carry the solution of many intermediate phthalic anhydride sulfonate secretly, this is in actual production, perhaps use a large amount of water washing filter cakes, cause the solution of intermediate phthalic anhydride sulfonate rare excessively, follow-up evaporate to dryness mother liquor need consume a large amount of energy and time, perhaps the loss with the part intermediate is a cost, causes the intermediate productive rate low excessively.Usually the two has concurrently.In addition, because calcium sulfate is slightly soluble in water, also makes and contain calcium sulfate in the product and influence product quality.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of phthalocyanine cobalt sulfonamide desulphurization catalyst, preparing product occurs with the form of phthalocyanine cobalt sulfonamide, detect through overtesting, this product can be applicable to the catalytic oxidative desulfurization technology of organic sulfur and inorganic sulfur, has high activity, high selectivity, characteristics such as it is easy to regenerate.
A kind of preparation method of phthalocyanine cobalt sulfonamide desulphurization catalyst comprises that step is as follows:
(1) phthalic anhydride is added chlorosulfonic acid heating backflow sulfonation, recovered under reduced pressure excess chlorine sulfonic acid then; Perhaps phthalic anhydride is added chlorosulfonic acid heating backflow sulfonation, add thionyl chloride after the sulfonation and reflux, and then recovered under reduced pressure excess chlorine sulfonic acid and thionyl chloride;
(2) product that obtains is joined in the frozen water, filter intermediate product phthalic anhydride sulfonic acid chloride;
(3) intermediate product phthalic anhydride sulfonic acid chloride and pyromellitic dianhydride, urea, waterless cobaltous chloride, ammonium molybdate are generated phthalocyanine cobalt sulfonamide through condensation reaction under 150～230 ℃.
Step (1) is preferably: phthalic anhydride is added 180～200 ℃ of following backflow sulfonation of chlorosulfonic acid 6～10 hours, recovered under reduced pressure excess chlorine sulfonic acid then; Perhaps phthalic anhydride is added 180～200 ℃ of following backflow sulfonation of chlorosulfonic acid 6～10 hours, add thionyl chloride after the sulfonation and refluxed 2～4 hours, and then recovered under reduced pressure excess chlorine sulfonic acid and thionyl chloride.
The consumption of reactant is in the above-mentioned steps (1): the molar ratio of phthalic anhydride and chlorosulfonic acid is 1: 1～10 (when reactant is phthalic anhydride and chlorosulfonic acid); Perhaps phthalic anhydride and chlorosulfonic acid and thionyl chloride molar ratio are 1: 1～3: 1～5 (when reactant is phthalic anhydride, chlorosulfonic acid and thionyl chloride).
The phthalic anhydride sulfonic acid chloride is 6～7 with the quality of pyromellitic dianhydride, urea, waterless cobaltous chloride, ammonium molybdate than scope in the step (3): 1: 7～10: 1～2: 0.1～0.3; Described condensation reaction time is 3～5 hours.
The desulfurizing agent of the present invention's preparation is the compound of monokaryon, double-core and multinuclear product, and product is the avy blue microcrystalline powder, and its main component is the binuclear phthalocyanine cobalt sulfonamide, and molecular formula is: C
58H
32Co
2N
22O
12S
6, molecular weight is 1539.27, structural formula is:
The production technology of desulfurizing agent of the present invention compares with the past process for sulfonation, has following advantage:
1, loses owing to the phthalic anhydride that has sulfonic acid chloride to make solvent and in course of reaction, keep backflow, avoided phthalic anhydride to distil the equipment that causes to stop up and to bring thus, make product yield improve work simplification.
2, intermediate products separate to be simplified after the sulfonation, product absorption loss and the follow-up loaded down with trivial details washing of having avoided a large amount of calcium oxide neutralisation of sulphuric acid to generate calcium sulfate causing, operation such as concentrate.
3, excessive sulfonic acid chloride can be recycled.
4, product has the high-efficiency desulfurization activity, and the catalysis cycle is long, simultaneously organic sulfide removal and inorganic sulfur and cyanide, and after testing, desulphurizing activated is 2.2 times of commercial sulfonate phthalocyanine cobalt.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment:
Embodiment 1:
Get phthalic anhydride 300g, chlorosulfonic acid 600g, 180 ℃ of following backflow sulfonation 8 hours, the chlorosulfonic acid that recovered under reduced pressure is excessive, residue joined in the 1000g frozen water, filter intermediate product phthalic anhydride sulfonic acid chloride, productive rate 67.5%.The chlorosulfonic acid that reclaims can be applied mechanically once more.
Get intermediate product phthalic anhydride sulfonic acid chloride 246g, pyromellitic dianhydride 36g, urea 300g, waterless cobaltous chloride 43.3g, ammonium molybdate 6.5g again, 190～220 ℃ generate phthalocyanine cobalt sulfonamide through condensation reaction 4 hours, and product is the avy blue solid.
Embodiment 2:
Get phthalic anhydride 300g, chlorosulfonic acid 400g, 180 ℃～200 ℃ following backflow sulfonation 8 hours, adding people 300g thionyl chloride then continues to reflux 3 hours, thionyl chloride that recovered under reduced pressure is excessive and chlorosulfonic acid, residue joins in the 1000g frozen water, filter intermediate product phthalic anhydride sulfonic acid chloride.Productive rate 87.6%.Thionyl chloride that reclaims and chlorosulfonic acid can be applied mechanically once more through after the simple fractionation separates.
Get intermediate product phthalic anhydride sulfonic acid chloride 246g, pyromellitic dianhydride 36g, urea 300g, waterless cobaltous chloride 43.3g, ammonium molybdate 6.5g, 190～220 ℃ generate phthalocyanine cobalt sulfonamide through condensation reaction 4 hours, and product is the avy blue solid.
Embodiment 3:
Get phthalic anhydride 300g, reclaim chlorosulfonic acid 600g, 180 ℃ of following backflow sulfonation 8 hours, the chlorosulfonic acid that recovered under reduced pressure is excessive, residue joined in the 1000g frozen water, filter intermediate product phthalic anhydride sulfonic acid chloride, productive rate 58.3%.The chlorosulfonic acid that reclaims can be applied mechanically once more.
Get intermediate product phthalic anhydride sulfonic acid chloride 246g, pyromellitic dianhydride 36g, urea 300g, waterless cobaltous chloride 43.3g, ammonium molybdate 6.5g again, 190～220 ℃ generate phthalocyanine cobalt sulfonamide through condensation reaction 4 hours, and product is the avy blue solid.
Embodiment 4:
Get phthalic anhydride 300g, reclaim chlorosulfonic acid 400g, 180 ℃～200 ℃ following backflow sulfonation 8 hours, add people 300g then and reclaim thionyl chloride continuation backflow 3 hours, thionyl chloride that recovered under reduced pressure is excessive and chlorosulfonic acid, residue joins in the 1000g frozen water, filter intermediate product phthalic anhydride sulfonic acid chloride.Productive rate 80.6%.Thionyl chloride that reclaims and chlorosulfonic acid can be applied mechanically once more through after the simple fractionation separates.
Get intermediate product phthalic anhydride sulfonic acid chloride 246g, pyromellitic dianhydride 36g, urea 300g, waterless cobaltous chloride 43.3g, ammonium molybdate 6.5g, 190～220 ℃ generate phthalocyanine cobalt sulfonamide through condensation reaction 4 hours, and product is the avy blue solid.
Embodiment 5:
Prepare 0.25% commercial sulfonate cobalt phthalocyanine desulfating catalyst solution, 0.1M (NH
4)
2Each 200ml is standby for S solution.
In the oxygen consumption tester, add 0.1M (NH
4)
2S solution 50ml, the ammoniacal liquor of 2ml29% adds 1ml commercial sulfonate cobalt phthalocyanine desulfating catalyst solution again, obtains containing desulfurizing agent 50PPm (1.3 * 10
-8Mol) test fluid is carried out the desulfurization test in 30 ℃ of waters bath with thermostatic control, actual measurement oxygen consumption 55ml, desulfurization time 40min.Average OUR is 1.37ml/min.
Embodiment 6:
Prepare phthalocyanine cobalt sulfonamide desulphurization catalyst solution, 0.1M (NH that 0.25% embodiment of the invention obtains
4)
2Each 200ml is standby for S solution.
In the oxygen consumption tester, add 0.1M (NH
4)
2S solution 50ml, the ammoniacal liquor of 2ml29% adds 1ml phthalocyanine cobalt sulfonamide desulphurization catalyst solution again, obtains containing desulfurizing agent 50PPm (1.3 * 10
-8Mol) test fluid is carried out the desulfurization test in 30 ℃ of waters bath with thermostatic control, actual measurement oxygen consumption 56ml, desulfurization time 18.5min.Average OUR is 3.03ml/min.
Claims (5)
1. the preparation method of a phthalocyanine cobalt sulfonamide desulphurization catalyst is characterized in that, comprises that step is as follows:
(1) phthalic anhydride is added chlorosulfonic acid heating backflow sulfonation, recovered under reduced pressure excess chlorine sulfonic acid then; Perhaps phthalic anhydride is added chlorosulfonic acid heating backflow sulfonation, add thionyl chloride after the sulfonation and reflux, and then recovered under reduced pressure excess chlorine sulfonic acid and thionyl chloride;
(2) product that obtains is joined in the frozen water, filter intermediate product phthalic anhydride sulfonic acid chloride;
(3) intermediate product phthalic anhydride sulfonic acid chloride and pyromellitic dianhydride, urea, waterless cobaltous chloride, ammonium molybdate are generated phthalocyanine cobalt sulfonamide through condensation reaction under 150～230 ℃.
2. the preparation method of phthalocyanine cobalt sulfonamide desulphurization catalyst according to claim 1 is characterized in that, step (1) is: phthalic anhydride is added 180～200 ℃ of following backflow sulfonation of chlorosulfonic acid 6～10 hours, recovered under reduced pressure excess chlorine sulfonic acid then; Perhaps phthalic anhydride is added 180～200 ℃ of following backflow sulfonation of chlorosulfonic acid 6～10 hours, add thionyl chloride after the sulfonation and refluxed 2～4 hours, and then recovered under reduced pressure excess chlorine sulfonic acid and thionyl chloride.
3. the preparation method of phthalocyanine cobalt sulfonamide desulphurization catalyst according to claim 1 and 2 is characterized in that, the consumption of reactant is in the step (1): the molar ratio of phthalic anhydride and chlorosulfonic acid is 1: 1～10; Perhaps phthalic anhydride and chlorosulfonic acid and thionyl chloride molar ratio are 1: 1～3: 1～5.
4. the preparation method of phthalocyanine cobalt sulfonamide desulphurization catalyst according to claim 1, it is characterized in that the phthalic anhydride sulfonic acid chloride is 6～7 with the quality of pyromellitic dianhydride, urea, waterless cobaltous chloride, ammonium molybdate than scope in the step (3): 1: 7～10: 1～2: 0.1～0.3.
5. the preparation method of phthalocyanine cobalt sulfonamide desulphurization catalyst according to claim 1 is characterized in that, the described condensation reaction time of step (3) is 3～5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850359A (en) * | 2012-08-22 | 2013-01-02 | 山东科技大学 | Preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst |
| CN103706400A (en) * | 2013-12-19 | 2014-04-09 | 江苏大学 | Monomolecular catalyst for catalyzing water oxidation and synthetic method thereof |
| CN104437658A (en) * | 2014-11-28 | 2015-03-25 | 江苏大学 | Porous silicon oxide nano material as well as preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705108A (en) * | 2009-12-11 | 2010-05-12 | 郝天臻 | Liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705108A (en) * | 2009-12-11 | 2010-05-12 | 郝天臻 | Liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur |
Non-Patent Citations (1)
| Title |
|---|
| B. BASU, ET AL: "Merox and Related Metal Phthalocyanine Catalyzed Oxidation Processes", 《CATALYSIS REVIEWS: SCIENCE AND ENGINEERING》, vol. 35, no. 4, 31 December 1993 (1993-12-31), pages 571 - 609, XP000408832 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850359A (en) * | 2012-08-22 | 2013-01-02 | 山东科技大学 | Preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst |
| CN102850359B (en) * | 2012-08-22 | 2016-04-13 | 山东科技大学 | The preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst |
| CN103706400A (en) * | 2013-12-19 | 2014-04-09 | 江苏大学 | Monomolecular catalyst for catalyzing water oxidation and synthetic method thereof |
| CN103706400B (en) * | 2013-12-19 | 2015-10-28 | 江苏大学 | A kind of monomolecular catalytic agent of catalytic water oxidation and synthetic method thereof |
| CN104437658A (en) * | 2014-11-28 | 2015-03-25 | 江苏大学 | Porous silicon oxide nano material as well as preparation method and application thereof |
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