CN101058078A - Addend preparation method and process for wet oxidation-desulfurizing catalyst - Google Patents
Addend preparation method and process for wet oxidation-desulfurizing catalyst Download PDFInfo
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- CN101058078A CN101058078A CN 200610076889 CN200610076889A CN101058078A CN 101058078 A CN101058078 A CN 101058078A CN 200610076889 CN200610076889 CN 200610076889 CN 200610076889 A CN200610076889 A CN 200610076889A CN 101058078 A CN101058078 A CN 101058078A
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Abstract
The invention relates to the wet oxidation desulfurization, mainly made of ortho-phthalic anhydride, oleum, ortho-phthalic anhydride, dicarbonic diamide, cobalt chloride, amchlor, titanic chloride, adding or absorbing multi desulfurizer, Ca(OH)2, demineralized water, through dynamic normal pressure heating up and mixing, static constant temperature stratification and activating absorption, greatly shorten reaction cycle, getting rid of the uneven reaction temperature, uneven reaction stratification and degree, with the accelerant being solid particle or activated solution. It applies to wide range of fields, with percentage of desulfurization over 98%. It is particularly suitable for old process remodeling and improvement.
Description
Technical field
A kind of wet oxidation-desulfurizing catalyst Canadian dollar compound method and technology belong to the invention of desulphurization catalyst technical field.
Background technology
Common some are used for the compound oxidizing desulphurization catalyst of wet desulphurization, all exist preparation technique simply can not satisfy the primary condition of prescription chemical reaction in layoutprocedure, cause the product of gained to produce the reaction power defective, and the reaction time is long.Limitation on the prescription also makes production efficiency further not improve simultaneously, and range of application is restricted, and consuming time taking a lot of work, and the unit consumption cost can not reduce, and these drawbacks the present invention just will overcome.
Summary of the invention
Prescription of the present invention is based on being made of sulfonation component, condensation component, chemical combination component, interpolation component, absorption component five parts.The sulfonation component is phthalic anhydride, oleum, and the condensation component is adjacent PMDA, carbonyl diamide, cobalt chloride, ammonium chloride, ammonium molybdate, ammonium nitrate; The chemical combination component is ring fourth alum, titanium tetrachloride; Adding component is polynary desulfurizing agent; Vanadic anhydride; Calcium hydroxide; Absorber component is that ammonia, alkali lye, soft water etc. constitute basic prescription, activate the desulphurization catalyst that absorption technique and Canadian dollar preparation method make by heat up mixings, the condensation reaction of static layering constant temperature, Canadian dollar of dynamic normal pressure, realize the regeneration activating redox reaction by the oxygen enrichment under absorption liquid phase or the gas phase, make the H that adsorbs in the alkalescent working medium solution
2S is oxidized to elemental sulfur or disulphide is separated out, and just will bear the sulphur (S of divalence
2-) be oxidized to elemental sulfur (S
0), disulphide (RSSR) or polysulfide and oxysulfide etc., thereby realize the purpose of multiple liquid phases such as wet oxidation-desulfurizing and wet process of FGD, gas phase high-efficiency desulfurization, decyanation.
The proportioning of material component of the present invention is by phthalic anhydride, oleum; Adjacent PMDA; Carbonyl diamide; Cobalt chloride, ammonium chloride, ammonium molybdate, ammonium nitrate; Ring fourth alum, four titanium oxide; Polynary desulfurizing agent, vanadic anhydride, calcium hydroxide; Ammonia alkali liquid, soft water constitute, and pH value is set up at 8.2-8.8, and its basic proportion proportioning is 90: 10: 98: 21: 7: 20: 2, and the proportioning of wherein adding, absorb component is 5: 2: 20: 100: 1000, the host molecule formula was: C32H12N8Co (SO3NH4) 4.
Description of drawings
The specific embodiment
The present invention is achieved in that phthalic anhydride and oleum are carried out continuously dynamically sulfonating reaction under normal pressure and condition temperature, removes free acid with the aqueous slkali neutralization earlier then, with the ammoniacal liquor neutralization, through the constant temperature thickening filtration, obtains the sulfonic acid ammonium salt product again; Then the adjacent PMDA of sulfonation component and condensation component, carbonyl diamide, cobalt chloride, ammonium chloride, ammonium molybdate, ammonium nitrate proportioning are stirred dried the mixing by heating up continuously, in the presence of chemical combination components such as organic solvent ring fourth alum and catalyst titanium tetrachloride, liquefy mixing, washing, neutralization and get rid of and mix thing, then with the layering of mixture equal portions through the static condensation reaction of secondary constant temperature, generate the phthalocyanine cobalt sulfonate of foaming.Again through dried by hot air stream at high temperature for the third time, obtain dark blue dirty-green powdery intermediate product, then by the Canadian dollar preparation of adding component mix an amount of reaction power element hydrogen calcium oxide fecula, and polynary desulfurizing agent raw material etc. be mixed into dark blue dirty-green zinc white toner shape manufactured goods.Obtain can with the solid-state desulfurization powder of absorbent adapted.Manufactured goods adding absorption component alkali lye, ammoniacal liquor are left standstill the liquid desulfuration liquid that activation obtains directly dripping usefulness by stirring.Add excessive soft water and can obtain smoke-gas wet desulfurization liquid.
Main oxidation desulfur reaction formula of the present invention can be described by following formula:
1, the catalytic oxidation fundamental reaction formula of analysing sulphur can be described as:
2NaHS+O
2＝＝2NaOH+2S↓
Na2Sz+H
2O+1/2O
2＝＝2NaOH+Sz
2, analysing the reaction of Salmon-Saxl formula for the catalytic oxidation of organic sulfur compound can be described as:
2Na
2CO
2S+O
2＝＝2Na
2CO
3+2S↓
4RSNa+O
2+2H
2O＝＝2RSSR+4NaOH
Wherein the chemical combination component is mainly finished washing and neutralization is removed and mixed, regulates acid-base value.Adjust proportioning according to impurity content in the course of reaction and acid-base value.Add, absorb component and be mainly used in the oxidation effect of quickening activation and regulating desulfurizing agent.Can adjust proportioning according to the sulfur content of working medium.
By process chart further describe collocation method of the present invention it is characterized in that with the sulfonation component under 190 ℃ of temperature in reactor continuously the dynamic agitation sulfonation obtain the sulfonic amine salt product, drop in the reactor temperature rate-of-rise by 0.5 ℃ of per minute as required at 25 ℃ with the condensation component again--130 ℃ of temperature sections by one-time continuous heat up stir dried be mixed even, and then the mixing of liquefying, mode can be manual, mechanical type stirring, and process conditions are to carry out in the ceramic cylinder that satisfies continuous intensification condition, native pithos, stainless steel reaction container; Under 135 ℃-145 ℃ continuous intensification, in reactor, carrying out liquefaction mixing in 1-2 hour, washing, neutralization under the participation of chemical combination component organic solvent and catalyst, and getting rid of and mix oxide; Faced the reaction that is situated between again through 2-3 hour, after equitemperature drops to 100 ℃ naturally from 135 ℃, adopt the static layering condensation reaction of 200 ℃ of secondary constant temperature in 3-8 hour then, process conditions are to satisfy the reaction unit or the reactor of the static stratified condition of constant temperature; The product of reaction after finishing again dynamic drying box, also can be dynamically dry through 2-4 hour 250 ℃ of three high-temperature hot-airs in reactor, obtain dark blue dirty-green solid powdery principal product; Principal product is carried out compounding in proportion with the interpolation component obtain the solid granular intermediate product; Intermediate product was left standstill 1-3 hour with absorbing component ammonia, aqueous slkali or soft water liquefaction stirring again, just obtained liquefaction products through overactivation.
Most preferred embodiment of the present invention is to be used for the ammonification desulfurization, adopting quantitative drop thread mode to add in the reaction tank of liquid-phase catalysis equipment the desulfurization activating solution gets final product, it is thrown in the liquid temperature and remains on 40 ℃ ± 2 ℃, injected volume can be thrown in the ratio of 1/1.5-3ppm with the ratio of throwing in the desulfurization activating solution according to carrying sulphur thing sulfur content g/m, service condition: 1, basicity: 0.5-4N 2, pH value: 8.2--8.8,3, temperature: 10 ℃-60 ℃ 4, liquid-gas ratio: 12L/bm.
Another embodiment of the present invention is the smoke-gas wet desulfurization that is used for thermal power generation, the desulfurization activating solution is adopted quantitatively add in the soft water circulatory pool, and to flue gas desulfurization, its effect is better than lime stone flue gas desulfurization by the spray mode.
In sum; Technology that provides according to the present invention and preparation method is characterized in that carrying out equal portions layering condensation reaction under the mixture temperature constant state with raw material, shortened the reaction time, overcome the reaction temperature inequality, the phenomenon of reaction level inequality, extent of reaction inequality.Thereby shortened between the system timing greatly, improved the material work efficiency, reduced the material production cost, prepared desulphurization catalyst, can become the liquid solution product of solid granular or activation, color and luster be dark blue dirty-green, soluble in water, be insoluble in ethanol, ether, do not fire not quick-fried, have no side effect, chemical property is stable.Be mainly used in desulfurization of wet method liquid-phase catalysis and the desulfurization of dry method gas phase catalysis, catalyst is by catalytic oxidation under certain conditions, various sulfide contained in liquid phase or the gas-phase product is converted into elemental sulfur, polysulfide and oxysulfide separates out.Simultaneously because the oxidation catalysis effect of this desulphurization catalyst, be filled in the working medium solution in drop thread mode when adopting wet desulphurization, its intrinsic absorption, active oxidation and absorption regeneration circular response can effectively be eliminated phenomenons such as pipeline adheres to, deposition, plugging.(1) technique effect is good, can simultaneously, at a high speed, efficiently remove H2S, HCN, mercaptan and part organic sulfur; (2) remarkable in economical benefits adopts this technology desulfuration and decyanation, and the solution component is simple, does not need to add any auxiliary agent (except that alkali), and operating cost is lower by about 70% than ADA method, than TV method low about 50%; (3) obvious environment benefit, no noxious material exists in the solution, and does not need to discharge waste liquid in a large number, belongs to nontoxic, pollution-free green environment-protective process.(4) the sulphur foam is easily separated, not stifled tower, and the easy FLOTATION SEPARATION of sulphur foam that in regeneration (oxidation) equipment, forms, the suspension sulfur content in the doctor solution is low, and it is as clear as crystal that solution keeps.
The present invention is applicable to coal gas, natural gas, to the industrialization desulfurization that semiwater gas, synthesis gas, oven gas, cracking gas, sulphide-containing waste water etc. need be deviate from inorganic sulfur and organic sulfur, desulfurization degree can reach more than 98%.Be particularly suitable for the flue gas humidifying desulfurization of industrial liquid phase ammonification desulfurization and thermal power generation.
Claims (3)
1, a kind of wet oxidation-desulfurizing catalyst Canadian dollar compound method and technology are mainly by sulfonation component, condensation component, chemical combination component, interpolation component, absorption component five parts.The sulfonation component is phthalic anhydride, oleum, and the condensation component is adjacent PMDA, carbonyl diamide, cobalt chloride, ammonium chloride, ammonium molybdate, ammonium nitrate; The chemical combination component is ring fourth alum, titanium tetrachloride; Adding component is polynary desulfurizing agent, vanadic anhydride, calcium hydroxide; Absorber component is that ammonia, alkali lye, soft water etc. constitute basic prescription, activate the desulphurization catalyst that absorption technique and Canadian dollar preparation method make by heat up mixings, the condensation reaction of static layering constant temperature, Canadian dollar of dynamic normal pressure, it is characterized in that phthalic anhydride and oleum are carried out continuously dynamically sulfonating reaction under normal pressure and condition temperature, remove free acid with the aqueous slkali neutralization earlier then, neutralize with ammoniacal liquor again, through the constant temperature thickening filtration, obtain the sulfonic acid ammonium salt product; Then the adjacent PMDA of sulfonation component and condensation component, carbonyl diamide, cobalt chloride, ammonium chloride, ammonium molybdate, ammonium nitrate proportioning are stirred dried the mixing by heating up continuously, in the presence of chemical combination components such as organic solvent ring fourth alum and catalyst titanium tetrachloride, liquefy mixing, washing, neutralization and get rid of and mix thing, then with the layering of mixture equal portions through the static condensation reaction of secondary constant temperature, generate the phthalocyanine cobalt sulfonate of foaming.Again through dried by hot air stream at high temperature for the third time, supervised dirty-green powdery intermediate product deeply, then by the Canadian dollar preparation of adding component mix an amount of reaction power element hydrogen calcium oxide fecula, and polynary desulfurizing agent raw material etc. be mixed into dark blue dirty-green zinc white toner shape manufactured goods.Obtain can with the solid-state desulfurization powder of absorbent adapted.Manufactured goods adding absorption component alkali lye, ammoniacal liquor are left standstill the liquid desulfuration liquid that activation obtains directly dripping usefulness by stirring.Add excessive soft water and can obtain smoke-gas wet desulfurization liquid.Thereby constitute independent right of the present invention.
2, according to the described basic prescription of the present invention of claims: the sulfonation component is phthalic anhydride, oleum, and the condensation component is adjacent PMDA, carbonyl diamide, cobalt chloride, ammonium chloride, ammonium molybdate, ammonium nitrate; The chemical combination component is ring fourth alum, titanium tetrachloride; Its basic proportion proportioning is 90: 10: 98: 21: 7: 20: 2 interpolation components are polynary desulfurizing agent, vanadic anhydride, calcium hydroxide; Absorbing component is formations such as ammonia alkali solution, soft water, and it adds the proportion proportioning substantially is 5: 2: 20: 100: 1000.
3, comprise (1), sulfonating reaction according to described its feature of typical process flow of the present invention of claims; (2), do mixed the stirring; (3), liquefaction mixes; (4), washing impurity-removing; (5), acid-base neutralization; (6), face the reaction that is situated between; (7), layering condensation; (8), heated-air drying; (9), Canadian dollar is mixed; (10), dosing activation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760351B (en) * | 2008-12-23 | 2010-12-15 | 李宝利 | High efficiency molybdate ammonium cobalt complex tower-cleaning agent and preparation method thereof |
| CN102659102A (en) * | 2012-05-24 | 2012-09-12 | 兖矿鲁南化肥厂 | Technology and device for preparing industrial carbon monoxide with water gas |
| CN102850359A (en) * | 2012-08-22 | 2013-01-02 | 山东科技大学 | Preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst |
| CN103540378A (en) * | 2012-07-13 | 2014-01-29 | 邹汉平 | Methane-rich gas wet desulphurization comprehensive utilization technology |
| CN113856454A (en) * | 2021-08-14 | 2021-12-31 | 西北大学 | Regeneration tower for hydrogen sulfide removal process by gas-liquid phase catalytic oxidation method |
| CN115006775A (en) * | 2022-05-27 | 2022-09-06 | 内蒙古金陶股份有限公司 | Cyanide tailing decyanation treatment method and decyanation agent composition |
| CN116832873A (en) * | 2023-07-25 | 2023-10-03 | 西北大学 | Complex iron catalyst for removing hydrogen sulfide in industrial gas and preparation method thereof |
-
2006
- 2006-04-18 CN CN 200610076889 patent/CN101058078A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760351B (en) * | 2008-12-23 | 2010-12-15 | 李宝利 | High efficiency molybdate ammonium cobalt complex tower-cleaning agent and preparation method thereof |
| CN102659102A (en) * | 2012-05-24 | 2012-09-12 | 兖矿鲁南化肥厂 | Technology and device for preparing industrial carbon monoxide with water gas |
| CN103540378A (en) * | 2012-07-13 | 2014-01-29 | 邹汉平 | Methane-rich gas wet desulphurization comprehensive utilization technology |
| 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 |
| CN113856454A (en) * | 2021-08-14 | 2021-12-31 | 西北大学 | Regeneration tower for hydrogen sulfide removal process by gas-liquid phase catalytic oxidation method |
| CN113856454B (en) * | 2021-08-14 | 2022-07-15 | 西北大学 | Regeneration tower for hydrogen sulfide removal process by gas-liquid phase catalytic oxidation method |
| CN115006775A (en) * | 2022-05-27 | 2022-09-06 | 内蒙古金陶股份有限公司 | Cyanide tailing decyanation treatment method and decyanation agent composition |
| CN116832873A (en) * | 2023-07-25 | 2023-10-03 | 西北大学 | Complex iron catalyst for removing hydrogen sulfide in industrial gas and preparation method thereof |
| CN116832873B (en) * | 2023-07-25 | 2024-02-27 | 西北大学 | Complex iron catalyst for removing hydrogen sulfide in industrial gas and preparation method thereof |
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