CN101474575A - Phthalocyanine iron cobalt sulphonate desulphurization catalyst and preparation method thereof - Google Patents
Phthalocyanine iron cobalt sulphonate desulphurization catalyst and preparation method thereof Download PDFInfo
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- CN101474575A CN101474575A CNA2009100664694A CN200910066469A CN101474575A CN 101474575 A CN101474575 A CN 101474575A CN A2009100664694 A CNA2009100664694 A CN A2009100664694A CN 200910066469 A CN200910066469 A CN 200910066469A CN 101474575 A CN101474575 A CN 101474575A
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Abstract
The invention relates to an iron/cobalt phthalocyanine ammonium sulfonate desulfurization catalyst and a preparation method thereof, comprising steps of using phthalic anhydride as a raw material and fuming sulphuric acid as a sulfonating agent to prepare sulfonate, and then using ammonium molybdate as a catalyst, using sulfonate, cobalt chloride and ferric salt to synthesize Fe-Co phthalocyanine ammonium sulfonate, and then obtaining the inventive catalyst after drying and crushing the Fe-Co phthalocyanine ammonium sulfonate. Compared with currently used cobalt phthalocyanine catalyst, the iron/cobalt phthalocyanine ammonium sulfonate desulfurization catalyst has the advantages of high catalytic activity, capability of removing both organic sulphur and high sulphur, high desulfurization efficiency (more than 99%), low cost and simple processing technique, etc. The desulfurization catalyst can be widely applied to processes for desulfurizing and purifying various sulphur-bearing gases such as semi-water gas, natural gas, ammonia synthesis feed gas and coke oven gas, etc.
Description
Technical field
The present invention discloses a kind of desulphurization catalyst of sulfosalt of phthalocyanine iron cobalt and preparation method thereof, relate to a kind of oxidation-desulfurizing catalyst, can be widely used in various sulfurous gas ground desulfurizing and purifying processes such as semiwater gas, natural gas, syngas for synthetic ammonia, oven gas, belong to the fine chemistry industry technical field of material.
Background technology
The wet oxidation process desulfurization is the method for in liquid phase the sulfur compounds such as hydrogen sulfide in the gas being removed, and has been widely used in various sulfurous gas ground desulfurizing and purifying processes such as natural gas, syngas for synthetic ammonia, oven gas, coal gas.At present, it is phthalocyanine cobalt class that practical Wet-type oxidation sweetening method has multiple, representative catalyst, comprises the independent use of phthalocyanine cobalt and the compound of phthalocyanine cobalt and other composition.Because the continuous rising of the price of cobalt and still undesirable to the removal effect of organic sulfur, therefore, the Phthalocyanine-like Catalysts of developing many metal composite has important practical significance.Synthesis technique for existing phthalocyanine cobalt also needs to improve in addition.
Chinese patent CN1045414 discloses a kind of synthetic method, with pyromellitic dianhydride, industrial urea, cobalt chloride and ammonium molybdate is that raw material mixes according to a certain percentage, be placed on melt foaming and au bleu in the iron pan, in the high temperature furnaces of 250 degree dry 2 hours again, obtain poly-phthalocyanine cobalt.The catalyst of this technology preparation is used for sweetening process, exists the shortcoming that solubility is little, desulfuration efficiency is low.
Chinese patent CN1403459A also discloses and adopted ring fourth maple is that solvent and titanium tetrachloride are the technology that catalyst prepares phthalocyanine cobalt catalyst, but this method exists the problem that reaction utilizes with solvent recovery, and its desulfurization degree needs further to improve in addition.
Summary of the invention
The invention provides a kind of FePC cobalt ichthyodin desulphurization catalyst, it has the catalytic activity height, can take off high-sulfur again by removal of organic sulfur, and the characteristics that desulfuration efficiency is high have overcome the problem that existing synthetic method solubility is little, desulfuration efficiency is low.
The present invention also discloses the preparation method of above-mentioned desulphurization catalyst, has that cost is low, production technology is simple and is applicable to advantage such as suitability for industrialized production.
The structural formula of FePC cobalt ichthyodin desulphurization catalyst is
Molecular formula is C
58H
44O
18S
6N
22FeCo
Technical solution of the present invention may further comprise the steps (following ratio is a ratio of weight and number): with (500 ~ 1000) part phthalic anhydride and (1500 ~ 3000) part oleum under (0.5 ~ 1.5) part vanadium pentoxide catalyst effect, 200 ~ 240 ℃ are carried out sulfonating reaction, 3 ~ 10 hours reaction time, remove unreacted sulfuric acid with the alkaline matter neutralization then, again sulfonated bodies is neutralized with ammoniacal liquor, the neutralized reaction product of gained is obtained the phthalic anhydride ichthyodin through thickening filtration, with itself and urea, cobalt chloride, iron chloride is in (510 ~ 1015) part: (470 ~ 950) part: (27 ~ 54) part: the ratio of (12 ~ 23) part mixes, under the molybdate catalyst of (1.8 ~ 3.7) part and 230-260 ℃ through solid phase synthesis, 3 ~ 5 hours reaction time, obtain purpose product FePC cobalt ichthyodin, obtain navy blue powder after drying and the pulverizing.
Exist two kinds of metals of cobalt and iron in the skeleton of above-mentioned catalyst simultaneously; The mass ratio of molysite and cobalt salt is (4～6): 10.Used cobalt salt is a cobalt chloride; Molysite is iron chloride or ferric sulfate etc.
The molybdate catalyst that uses in the preparation process is ammonium molybdate, and consumption is 0.1～0.8% of a reactant gross weight.
Catalyst of the present invention has following characteristics through using checking in desulfurizing and purifying processes such as semiwater gas, natural gas, syngas for synthetic ammonia, oven gas
1) consumption is few: at concentration 30ppm, under 20 ℃ of conditions, catalyst solution 15min oxygen absorbed is 1.6mL/mL, is higher than the oxygen absorbed of other catalyst.
2) Sulfur capacity height: in solution, with the also increase thereupon of raising Sulfur capacity of catalyst concn, under the practical operation condition, Sulfur capacity can reach 0.25-0.4g/L.
3) applied widely: to processed gas H
2The content wide accommodation of S is from 1g/m
3Pick up g/m to number
3Can both reach satisfied effect.
4) sulfur recovery rate height; Sweetening process side reaction production rate is low, sulfur recovery rate height, Recovered sulphur purity height.The drusen that sweetening process is separated out is by the easily separated recovery of flotation.
5) the organic sulfide removal ability is strong: the removal of organic sulfur ability can reach 50-80%.
6) desulfuration efficiency height: the gas purification degree height, thick desulfurizer can be with H in the purified gas
2S drops to 50mg/Nm
3Below.
Good effect of the present invention is: with cobalt, the iron while is as the coordination element of phthalocyanine, adopt solid-phase synthesis to avoid in course of reaction with an organic solvent simultaneously, make the Preparation of catalysts process more environmentally friendly, in addition owing in the process of reaction, added iron, reduced the cost of catalyst, compare with existing phthalocyanine cobalt class catalyst, has the catalytic activity height, can can take off high-sulfur again by removal of organic sulfur, desulfuration efficiency height (greater than 99%), cost hangs down and reaches advantages such as production technology is simple, can be widely used in semiwater gas, natural gas, syngas for synthetic ammonia, various sulfurous gas such as oven gas ground desulfurizing and purifying process.
The specific embodiment:
Further specify the present invention below in conjunction with embodiment, and do not limit the present invention in any way, under the prerequisite that does not deviate from technical solution of the present invention, any change or change that those of ordinary skills that the present invention did are realized easily all will fall within the claim scope of the present invention.
Embodiment 1:
Get phthalic anhydride 1000g, vanadic anhydride 1.3g, 25% oleum 2980g, putting into reactor constantly stirs, and during heat temperature raising to 30 ℃, after stopping heating, exothermic heat of reaction begins nature and heats up, and keeps reaction to carry out beginning to heat to 235 ℃ after 3 hours, keeps 2 ~ 7 hours laggard line samplings of reaction to detect down at 235 ℃, if it can dissolve in water immediately, then reaction finishes, and adds in the calcium oxide and unreacted sulfuric acid, cools to 50 ℃ of dischargings, after filtration and to be neutralized to pH value with ammoniacal liquor be about 6-7, obtain the solid sulfonated bodies through concentrating again.Take by weighing sulfonated bodies 1015g, urea 950g, cobalt chloride 54g, iron chloride 23g, ammonium molybdate 3.7g slowly heats up, and constantly stirs in the course of reaction, in the hope of be heated and mass transfer even, when being heated to 140-150 ℃, urea melting becomes liquid, when temperature further is increased to 260 ℃, keep reaction to generate the bluish violet solid after 3 hours, discharging was dried 5 hours down at 270 ℃, dried the back taking-up and made catalyst A through grinding, pulverizing.
Embodiment 2:
Get phthalic anhydride 1000g, vanadic anhydride 1.3g, 25% oleum 2980g, putting into reactor constantly stirs, and during heat temperature raising to 30 ℃, after stopping heating, exothermic heat of reaction begins nature and heats up, and keeps reaction to carry out beginning to heat to 235 ℃ after 3 hours, keeps 2 ~ 7 hours laggard line samplings of reaction to detect down at 235 ℃, if it can dissolve in water immediately, then reaction finishes, and adds in the calcium oxide and unreacted sulfuric acid, cools to 50 ℃ of dischargings, after filtration and to be neutralized to pH value with ammoniacal liquor be about 6-7, obtain the solid sulfonated bodies through concentrating again.Take by weighing sulfonated bodies 510g, urea 475g, cobalt chloride 27g, iron chloride 12g, ammonium molybdate 1.8g slowly heats up, and constantly stirs in the course of reaction, in the hope of be heated and mass transfer even, when being heated to 140-150 ℃, urea melting becomes liquid, when temperature further is increased to 260 ℃, keep reaction to generate the bluish violet solid after 3 hours, discharging was dried 5 hours down at 270 ℃, dried the back taking-up and made catalyst B through grinding, pulverizing.
Embodiment 4:
Get phthalic anhydride 500g, vanadic anhydride 0.5g, 25% oleum 1500g, putting into reactor constantly stirs, and during heat temperature raising to 30 ℃, after stopping heating, exothermic heat of reaction begins nature and heats up, and keeps reaction to carry out beginning to heat to 235 ℃ after 3 hours, keeps 2 ~ 7 hours laggard line samplings of reaction to detect down at 235 ℃, if it can dissolve in water immediately, then reaction finishes, and adds in the calcium oxide and unreacted sulfuric acid, cools to 50 ℃ of dischargings, after filtration and to be neutralized to pH value with ammoniacal liquor be about 6-7, obtain the solid sulfonated bodies through concentrating again.Take by weighing sulfonated bodies 765g, urea 710g, cobalt chloride 41g, iron chloride 18g, ammonium molybdate 2.8g slowly heats up, and constantly stirs in the course of reaction, in the hope of be heated and mass transfer even, when being heated to 140-150 ℃, urea melting becomes liquid, when temperature further is increased to 260 ℃, keep reaction to generate the bluish violet solid after 3 hours, discharging was dried 5 hours down at 270 ℃, dried the back taking-up and made catalyst D through grinding, pulverizing.
Embodiment 3: this example is a Preparation of catalysts method as a comparative example.
Get phthalic anhydride 500g, vanadic anhydride 0.5g, 25% oleum 1500g, putting into reactor constantly stirs, and during heat temperature raising to 30 ℃, after stopping heating, exothermic heat of reaction begins nature and heats up, and keeps reaction to carry out beginning to heat to 235 ℃ after 3 hours, keeps 2 ~ 7 hours laggard line samplings of reaction to detect down at 235 ℃, if it can dissolve in water immediately, then reaction finishes, and adds in the calcium oxide and unreacted sulfuric acid, cools to 50 ℃ of dischargings, after filtration and to be neutralized to pH value with ammoniacal liquor be about 6-7, obtain the solid sulfonated bodies through concentrating again.Take by weighing sulfonated bodies 510g, urea 475g, cobalt chloride 27g, ammonium molybdate 1.8g slowly heats up, constantly stir in the course of reaction, in the hope of be heated and mass transfer even, when being heated to 140-150 ℃, urea melting becomes liquid, when temperature further is increased to 260 ℃, keep reaction to generate bluish violet solid, discharging after 3 hours, dried 5 hours down at 270 ℃, dry the back taking-up and make catalyst C through grinding, pulverizing.
Embodiment 5:
This example is the comparison of the desulfurization performance of the catalyst invented and phthalocyanine cobalt catalyst
| The mensuration project | Comparative catalyst C | Catalyst A | Catalyst B | Catalyst D |
| Air inflow/L | 40.01 | 40.01 | 40.01 | 40.01 |
| Inlet H 2S/g | 0.2611 | 02611 | 0.2611 | 0.2611 |
| Outlet H 2S/mg/ | 4.41 | 1.75 | 1.79 | 1.72 |
| Work Sulfur capacity/g/L | 1.0272 | 1.0380 | 1.0376 | 1.0378 |
| Desulfuration efficiency/% | 98.43 | 99.35 | 99.31 | 99.34 |
| Recovered sulphur/g | 0.1420 | 0.1832 | 0.1826 | 0.1836 |
| Sulfur recovery rate/% | 57.76 | 74.37 | 74.28 | 74.72 |
Condition determination: gas speed 1000ml/min; Circulation fluid 5mL/min; Inlet H
2S concentration 0.43%; 40 ℃ of desulfurization reaction temperatures; 42 ℃ of regeneration temperatures; Catalyst concn is 20ppm, and alkali source is the sodium carbonate liquor of 0.2N.
By the data of embodiment 5 gained as can be seen, the desulfurization performance of catalyst of the present invention is significantly better than used titanium cyanines Co catalysts at present.Its work Sulfur capacity, desulfuration efficiency, sulfur recovery rate all are significantly improved.
Claims (5)
1, a kind of FePC cobalt ichthyodin desulphurization catalyst, preparation by the following method: phthalic anhydride and oleum carry out sulfonating reaction at 200～240 ℃, 3～6 hours reaction time, remove unreacted sulfuric acid with the alkaline matter neutralization then, again sulfonated bodies is neutralized with ammoniacal liquor, the neutralized reaction product of gained is obtained the phthalic anhydride ichthyodin through thickening filtration, with itself and urea, cobalt chloride, molysite and ammonium molybdate under 230-260 ℃ through solid phase synthesis, in 2～5 hours reaction time, after dry under 250-280 ℃ and pulverizing, obtain navy blue powder;
The structural formula of its product is
Molecular formula is C
58H
44O
18S
6N
22FeCo.
2, claim 1 is narrated FePC cobalt ichthyodin Preparation of catalysts method, it is characterized in that (following ratio is a ratio of weight and number): with 500 ~ 1000 parts of phthalic anhydrides and 1500 ~ 3000 part of 25% oleum under 0.5 ~ 1.5 part of vanadium pentoxide catalyst effect, 200 ~ 240 ℃ are carried out sulfonating reaction, 3 ~ 10 hours reaction time, remove unreacted sulfuric acid with the alkaline matter neutralization then, again sulfonated bodies is neutralized with ammoniacal liquor, the neutralized reaction product of gained is obtained the phthalic anhydride ichthyodin through thickening filtration, with itself and urea, cobalt chloride, iron chloride is in (510 ~ 1015) part: (470 ~ 950) part: (27 ~ 54) part: the ratio of (12 ~ 23) part mixes, the molybdate catalyst that adds (1.8 ~ 3.7) part again, under 230-260 ℃ through solid phase synthesis, in 3 ~ 5 hours reaction time, obtain navy blue powder after drying and the pulverizing.
3, claim 2 is narrated FePC cobalt ichthyodin Preparation of catalysts method, it is characterized in that: exist two kinds of metals of cobalt and iron in the skeleton of catalyst simultaneously, used cobalt salt is a cobalt chloride, and molysite is iron chloride or ferric sulfate.
4, claim 2 is narrated FePC cobalt ichthyodin Preparation of catalysts method, it is characterized in that: the mass ratio of molysite and cobalt salt is (4～6): 10.
5, claim 2 is narrated FePC cobalt ichthyodin Preparation of catalysts method, and it is characterized in that: the catalyst that uses in the preparation process is ammonium molybdate, and consumption is 0.1～0.8% of a reactant gross weight.
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| CNA2009100664694A CN101474575A (en) | 2009-01-21 | 2009-01-21 | Phthalocyanine iron cobalt sulphonate desulphurization catalyst and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633842A (en) * | 2012-03-28 | 2012-08-15 | 北京化工大学 | Preparation method and application of ionic liquid desulfurizer with bimetal reactivity center |
| CN113285081A (en) * | 2021-05-28 | 2021-08-20 | 昆明理工大学 | FeCo-PPc catalyst and preparation method and application thereof |
| CN114904532A (en) * | 2022-06-06 | 2022-08-16 | 河南美源环保新材料有限公司 | Preparation method of desulfurization catalyst |
-
2009
- 2009-01-21 CN CNA2009100664694A patent/CN101474575A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633842A (en) * | 2012-03-28 | 2012-08-15 | 北京化工大学 | Preparation method and application of ionic liquid desulfurizer with bimetal reactivity center |
| CN102633842B (en) * | 2012-03-28 | 2015-02-04 | 北京化工大学 | Preparation method and application of ionic liquid desulfurizer with bimetal reactivity center |
| CN113285081A (en) * | 2021-05-28 | 2021-08-20 | 昆明理工大学 | FeCo-PPc catalyst and preparation method and application thereof |
| CN113285081B (en) * | 2021-05-28 | 2023-11-10 | 昆明理工大学 | FeCo-PPc catalyst and preparation method and application thereof |
| CN114904532A (en) * | 2022-06-06 | 2022-08-16 | 河南美源环保新材料有限公司 | Preparation method of desulfurization catalyst |
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Open date: 20090708 |