CN1680025A - Low-temperature hydrolyst for high concentrated organosulfur and preparation thereof - Google Patents
Low-temperature hydrolyst for high concentrated organosulfur and preparation thereof Download PDFInfo
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- CN1680025A CN1680025A CN 200510012331 CN200510012331A CN1680025A CN 1680025 A CN1680025 A CN 1680025A CN 200510012331 CN200510012331 CN 200510012331 CN 200510012331 A CN200510012331 A CN 200510012331A CN 1680025 A CN1680025 A CN 1680025A
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Abstract
A low-temp hydrolyzing catalyst for high-concentration organic sulfur, especially the carbonyl sulfur, contains proportionally gamma-Al2O3, TiO2, ZrO2 and K2O. Its preparing process includes such steps as proportionally mixing carrier, active components and pore-forming agent together, adding water or nitric acid, kneading, extruding for shaping, drying at 100-150 deg.C, and activating at 500-700 deg.C. Its advantages are high activity to hydrolyze carbonyl sulfur, high resistance to sulfur and oxygen, and high conversion rate of carbonyl sulfur (more than 95%).
Description
One, technical field
The invention belongs to a kind of catalyst of organic sulfide removal, relate in particular to a kind of hydrolytic catalyst of carbonyl sulfur and preparation method.
Two, technical background
As everyone knows, organic sulfur particularly cos extensively to be present in coal, natural gas and oil be in the Chemical Manufacture unstripped gas of raw material, its existence can cause catalyst poisoning inactivation in the subsequent production process.Along with colm and oven gas are used for the production of synthesis gas, the cos that removes high concentration is paid much attention to, and the cos catalyzing hydrolysis is to remove the effective method of cos.
The patented technology of relevant cos catalyzing hydrolysis is many both at home and abroad, external have Fr.2236555, UK1307875, US4500668, a WO9943195 etc., in these patents, catalyst mainly is used in the Sulfur Recovery Unit process, serviceability temperature is all more than 100 ℃, and great majority are more than 200 ℃.Catalyst is operated the shortcoming that the following aspects is arranged under higher temperature: the one, and sulfation easily takes place and poisons in hydrolyst; The 2nd, equilibrium conversion is low under the high temperature; The 3rd, the operating cost height.And be low temperature at the optimal catalyst serviceability temperature of gas purification.The patented technology of domestic carbonyl sulfide hydrolysis has the CN1095309 of Qilu Petroleum Chemical Corporation Institute, in this patent with TiO
2As carrier A l
2O
3Modifier, carry out the preparation of carrier in the catalyst preparation process earlier, and then with the KOH activity component impregnation on carrier, preparation technology is comparatively complicated, the cos concentration of handling gas is below 200ppm.The CN1189394 of Institutes Of Technology Of Taiyuan and the CN1069673 of Hubei Prov. Chemical Research Inst select γ-Al for use
2O
3Load active component on the carrier, at all be the fine desulfurizing technology of low concentration, cos content all is lower than 10mgS/m
3The CN1403197 of East China University of Science is as active component with rare earth oxysulfide, though this catalyst has sulfur resistance preferably, but 100～250 ℃ of operations down, have the high problem of operating cost equally, and the concentration of treatment of its cos is also only at 150～300ppm.The CN1304781 of Shanxi coal chemistry institute also is at γ-Al with activity component impregnation
2O
3, the concentration of treatment of the cos that it is the highest also is no more than 800mg/m
3This shows, what above several patents was handled all is the gas of low concentration cos and low oxygen content, with this understanding, the catalyst poisoning phenomenon that hydrogen sulfide and oxygen reaction cause is not obvious, so low concentration uses good catalyst to show serious deactivation phenomenom down when handling high concentration cos gas.The CN1134312 patent of Nanjing chemical industry group company is introduced its processing gas cos concentration can reach 5000mg/m
3, its catalyst composition is 4～20% titanium dioxide and gama-alumina, operating temperature is more than 200 ℃, and catalyst sulfur poisoning-resistant ability improves under the high temperature though the existence of titanium oxide makes, and also has the malaria on the explained hereafter, and operating cost is increased.
In a word, except that above-mentioned deficiency, a common feature of above patent is to select carrier or preparation carrier earlier for use, floods active component again, complicated process of preparation like this, preparation cost raising.How these patents all only mention the carbonyl sulfide hydrolysis conversion ratio when mentioning catalytic activity simultaneously, do not illustrate that carbonyl sulfide hydrolysis transforms the situation that the back generates hydrogen sulfide.We know that hydrogen sulfide can catalytic oxidation be elemental sulfur when aerobic, the further again oxidation of elemental sulfur generates sulfur dioxide and sulfur trioxide.It is two reasons that cause the catalyst sulfur poisoning that elemental sulfur stops up duct and oxysulfide and active component reacting generating salt.Therefore, there are not the hydrogen sulfide data after the hydrolysis can cause the explanation of catalyst anti-sulfur poisonous performance unclear.
Three, summary of the invention
The present invention purifies and develops at the cryogenic industrial gases that contains the high concentration cos.When handling the gas of high concentration cos, the concentration of hydrolysate hydrogen sulfide is equally very high, and under high-concentration hydrogen sulfide, oxygen and hydrogen sulfide reaction are accelerated, the elemental sulfur that reaction generates stops up also serious more to the catalyst duct, cause that catalyst activity reduction is also obvious more.It is considered herein that to overcome high concentration carbonyl sulfide hydrolysis product hydrogen sulfide to the poisoning of catalyst with keep the catalyst hydrolysing activity, should consider Preparation of catalysts from following two aspects.The one, make the constituent of catalyst itself have the ability that suppresses hydrogen sulfide and oxygen reaction generation elemental sulfur, the 2nd, the pore passage structure that makes hydrogen sulfide be diffused into cushionila gas body smoothly from catalyst surface be arranged.Purpose of the present invention is exactly to obtain a kind of like this catalyst and preparation technology who has high hydrolyzation catalysis activity and import and export sulfur balance under the high concentration cos.
The present invention realizes by following method on aspect three of carrier component, active component and pore creating material components.
1. support modification.Adopt two components or three components as carrier component, improve one-component carrier catalytic activity shortcoming not high or that generation is adsorbed to hydrogen sulfide, strengthen the performance of carrier.Pass through TiO
2, ZrO
2And Al
2O
3The use of two components or three component carriers obtains under identical COS inlet concentration, and the outlet hydrogen sulfide content is obviously improved than single carrier.
2. activity of such catalysts constituent content.We are by discovering active component K
2The content of O is low excessively, too high all bad.K
2It is not high that the content of O is crossed when low the carbonyl sulfide hydrolysis conversion ratio; K
2Then because catalyst surface alkalescence is strong excessively, product hydrogen sulfide is difficult for desorption and causes catalyst poisoning at catalyst surface the too high levels of O, so catalyst has the content range an of the best.
3. preparation process.What patent CN1095309, CN1189394, CN1069673, CN1304781 adopted all is to flood active component on carrier, this method for making makes active component mainly be distributed in catalyst surface, and can be along with the loss that active component takes place service time by the active component of this load.Simultaneously, if employing is commercially available ball type carrier, in catalyst preparation process, can not transform its duct especially.In high concentration carbonyl sulfide hydrolysis process, suitable duct not only helps the diffusion of high concentration cos, also is beneficial to hydrolysate hydrogen sulfide and is diffused into cushionila gas body smoothly, reduces hydrogen sulfide in the time of staying of catalyst surface, reduces the chance of catalyst poisoning.Adopt dry pigmentation one step preparation among the present invention, be about to all powder raw materials, comprise that active component, carrier component, pore creating material etc. are fully mixed in blender to scale, add binding agent then and mediate, extruded moulding, primary drying, the bakes to burn the article catalyst that gets product.
The molecular structure and the molecular weight of organic matter and inorganic matter vary in size, formed pore passage structure is also different, in the present invention, in conjunction with the characteristics of the two, use organic matter pore creating material and inorganic matter pore creating material simultaneously, the organic matter pore creating material that uses has cellulose family and polymer class, is specially carboxymethyl cellulose, methylcellulose, the plain class of hydroxyethyl cellulose and polyacrylamide, polyethylene glycol, polyvinyl alcohol polymer class, and inorganic matter class pore creating material is ammonium nitrate, carbon ammonium, urea etc.
Specifically, catalyst of the present invention is a kind of high concentrated organosulfur low temperature hydrolysis catalyst, it is characterized in that with γ-Al
2O
3, TiO
2Two components or γ-Al
2O
3, ZrO
2Two components or γ-Al
2O
3, TiO
2, ZrO
2Three components are carrier, alkali metal oxide K
2O is an active component, and its each weight percentages of components consists of:
γ-Al
2O
3 73～89wt％
TiO
2 5～15wt％
ZrO
2 5～15wt％
K
2The catalyst of O 6～12wt%.
The preparation method is with carrier component boehmite 85～105g, titanium oxide 5～15g, hydrous zirconium oxide(HZO) 6～17g, active component potash 9～17g and pore creating material 10～15g evenly mix, adding water or nitric acid mediates, be extruded into diameter at normal temperatures and be about the cylindricality of 2～4mm, drying is 2～4 hours under 100～150 ℃, 500～700 ℃ of following roastings 2～4 hours, obtain finished catalyst at last.
The described pore creating material of method of a kind of high concentrated organosulfur low temperature hydrolysis of above-mentioned preparation catalyst, it is characterized in that being two or more the mixture in cellulose family, polymer class, the inorganic matter class, the cellulose family pore creating material is carboxymethyl cellulose, methylcellulose, hydroxyethylcellulose; The polymer class pore creating material is polyacrylamide, polyethylene glycol, polyvinyl alcohol; Inorganic matter class pore creating material is ammonium nitrate, carbon ammonium, urea.
Catalyst characteristics of the present invention are low temperature conversion rate height when handling high concentration cos gas, and product hydrogen sulfide is derived smoothly, and the anti-sulphur of catalyst, antioxygen poisoning capability are strong.
The catalyst activity property testing is to carry out in the glass reactor of 20 millimeters of internal diameters.Catalyst grain size is φ 3mm * 5mm, and loadings is 20 milliliters, 60 ℃ of reaction temperatures, air speed 2000h
-1, normal pressure.For the antitoxin performance of detecting catalyst, in activity rating, the concentration of regulating oxygen is 12%, and the cos inlet concentration is 2500mgS/m
3, and the concentration of testing in test outlet hydrogen sulfide.
Table 1 is that catalyst of the present invention is at 60 ℃ of reaction temperatures, air speed 2000h
-1, the concentration of oxygen is the evaluation result under 12% condition.
Table 1 catalyst activity of the present invention is estimated
This shows that it is basic identical with the carbonyl sulfur content of outlet hydrogen sulfide amount and hydrolysis that catalyst of the present invention has high hydrolysis conversion.
Four, the specific embodiment
Below by the specific embodiment catalyst of the present invention, preparation and result of use are described.
Embodiment 1:
Take by weighing three parts of weight and be respectively the boehmite of 100g, 94g, 88g, the potash mixing that in three parts of boehmites, adds 7.5g, 15g, 22.5g successively respectively, the titanium oxide that in every part, adds 10g then again, add the pore creating material that three kinds of components of polyvinyl alcohol of carbon ammonium, the 3g of methylcellulose with 4g, 6g are formed at last, all raw materials are formed mixing, add deionized water, mediate after the normal temperature extrusion, drying is 4 hours under 100 ℃, promptly gets K in 4 hours 550 ℃ of following roastings
2O content is respectively three kinds of hydrolytic catalyst of carbonyl sulfur of 5%, 10% and 15%.The catalyst carbonyl sulfide hydrolysis is reflected at 40 ℃ of temperature, air speed 1000h
-1, oxygen concentration 12%, import COS concentration 2500mgS/m
3Carry out hydrolysis conversion and hydrogen sulfide adsorption rate the results list 2 under the condition.
The catalyst hydrolysis conversion of the different potassium contents of table 2 and hydrogen sulfide adsorption rate
As seen, having high hydrolysis conversion is K with the essentially identical catalyst of carbonyl sulfur content that exports hydrogen sulfide amount and hydrolysis
2The O weight content is 10% catalyst.
Embodiment 2:
Take by weighing boehmite 105g, titanium oxide 5g, potash 15g, pore creating material carboxymethyl cellulose and each 7g of carbon ammonium two components are mixed, and add 1% rare nitric acid, normal temperature is mediated the back extrusion, 120 ℃ of dryings 3 hours, at 550 ℃ of following roastings catalyst that got product in 4 hours.This catalyst activity property testing is at import COS concentration 2500mgS/m
3, 60 ℃ of reaction temperatures, air speed 2000h
-1, carry out under oxygen content 12% condition, the COS conversion ratio reaches more than 95%, the carbonyl sulfur content of outlet hydrogen sulfide amount and hydrolysis is basic identical.
Embodiment 3:
Take by weighing boehmite 84g, titanium oxide 15g, potash 15g, pore creating material methylcellulose, ammonium nitrate, polyvinyl alcohol three composition weight are 4g, 5g, 6g, be mixed, add deionized water, normal temperature is mediated the back extrusion, 150 ℃ dry 2 hours down, at 600 ℃ of following roastings catalyst that got product in 3 hours.This catalyst activity property testing is at import COS concentration 2500mgS/m
3, 60 ℃ of reaction temperatures, air speed 2000h
-1, carry out under oxygen content 12% condition, the COS conversion ratio reaches more than 95%, the carbonyl sulfur content of outlet hydrogen sulfide amount and hydrolysis is basic identical.
Embodiment 4:
Take by weighing boehmite 94g, titanium oxide 10g, potash 15g, pore creating material hydroxyethylcellulose, urea, polyethylene glycol three composition weight are 4g, 5g, 6g, be mixed, add deionized water, normal temperature is mediated the back extrusion, 150 ℃ dry 2 hours down, at 600 ℃ of following roastings catalyst that got product in 3 hours.This catalyst activity property testing is at import COS concentration 2500mgS/m
3, 60 ℃ of reaction temperatures, air speed 2000h
-1, carry out under oxygen content 12% condition, the COS conversion ratio reaches more than 95%, the carbonyl sulfur content of outlet hydrogen sulfide amount and hydrolysis is basic identical.
Embodiment 5:
Take by weighing boehmite 84g, titanium oxide 7g, hydrous zirconium oxide(HZO) 7g, potash 15g, pore creating material methylcellulose, carbon ammonium, polyvinyl alcohol three composition weight are 4g, 6g, 3g, are mixed, add deionized water, normal temperature is mediated the back extrusion, 120 ℃ dry 3 hours down, at 550 ℃ of following roastings catalyst that got product in 4 hours.This activity of such catalysts test is at import COS concentration 2500mgS/m
3, 60 ℃ of reaction temperatures, air speed 2000h
-1, carry out under oxygen content 12% condition, the COS conversion ratio reaches more than 95%, the carbonyl sulfur content of outlet hydrogen sulfide amount and hydrolysis is basic identical.
Claims (3)
1, a kind of high concentrated organosulfur low temperature hydrolysis catalyst is characterized in that with γ-Al
2O
3, TiO
2Two components or γ-Al
2O
3, ZrO
2Two components or γ-Al
2O
3, TiO
2, ZrO
2Three components are carrier, alkali metal oxide K
2O is an active component, and its each weight percentages of components consists of:
γ-Al
2O
3 73～89wt％
TiO
2 5～15wt％
ZrO
2 5～15wt％
K
2The catalyst of O 6～12wt%.
2, prepare the method for the described a kind of high concentrated organosulfur low temperature hydrolysis catalyst of claim 1, it is characterized in that:
With carrier component boehmite 85～105g, titanium oxide 5～15g, hydrous zirconium oxide(HZO) 6～17g, active component potash 9～17g and pore creating material 10～15g evenly mix, adding water or nitric acid mediates, be extruded into diameter at normal temperatures and be about the cylindricality of 2～4mm, drying is 2～4 hours under 100～150 ℃, 500～700 ℃ of following roastings 2～4 hours, obtain finished catalyst at last.
3, it is characterized in that according to the method for a kind of high concentrated organosulfur low temperature hydrolysis of the described preparation of claim 2 catalyst described pore creating material is two or more the mixture in cellulose family, polymer class, the inorganic matter class, the cellulose family pore creating material is carboxymethyl cellulose, methylcellulose, hydroxyethylcellulose; The polymer class pore creating material is polyacrylamide, polyethylene glycol, polyvinyl alcohol; Inorganic matter class pore creating material is ammonium nitrate, carbon ammonium, urea.
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| CN1331596C CN1331596C (en) | 2007-08-15 |
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| CN101121123B (en) * | 2007-07-25 | 2010-05-19 | 太原理工大学 | Medium temperature carbon bisulfide hydrolytic catalyst and preparation method and application thereof |
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| CN102463033A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for hydrolyzing carbonyl sulphide (COS) |
| CN103007939A (en) * | 2012-12-13 | 2013-04-03 | 北京化工大学常州先进材料研究院 | Preparation method of Cu/ZrO2 catalyst |
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| CN103992831A (en) * | 2014-05-22 | 2014-08-20 | 中国石油天然气集团公司 | Low-temperature hydrolysis method for removing carbonyl sulfide in liquefied petroleum gas |
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| CN110639494A (en) * | 2019-10-31 | 2020-01-03 | 北京北科环境工程有限公司 | Blast furnace gas carbonyl sulfide hydrolytic agent and preparation method thereof |
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| CN1056096C (en) * | 1994-02-21 | 2000-09-06 | 中国石化齐鲁石油化工公司 | Sulfur carbonyl hydrolytic catalyzer |
| CN1048916C (en) * | 1995-08-16 | 2000-02-02 | 南京化学工业(集团)公司催化剂厂 | Organic sulfur hydrolyst and its preparation |
| CN1102420C (en) * | 2000-07-11 | 2003-03-05 | 中国科学院山西煤炭化学研究所 | Hydrolytic catalyst of carbonyl sulfur and its preparing process and application |
| JP2007245843A (en) * | 2006-03-15 | 2007-09-27 | Hitachi Ltd | Tie rod structure of steering system |
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