CN101797477B - Method for reducing concentration of carbonyl sulfide on outlet of hydrogen sulfide (H2S) desulfurizer - Google Patents
Method for reducing concentration of carbonyl sulfide on outlet of hydrogen sulfide (H2S) desulfurizer Download PDFInfo
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- CN101797477B CN101797477B CN201010133676XA CN201010133676A CN101797477B CN 101797477 B CN101797477 B CN 101797477B CN 201010133676X A CN201010133676X A CN 201010133676XA CN 201010133676 A CN201010133676 A CN 201010133676A CN 101797477 B CN101797477 B CN 101797477B
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Abstract
The invention provides a method for preparing hydrogen sulfide desulfurizer with dry process, in particular to a method for reducing the concentration of carbonyl sulfide on the outlet of the hydrogen sulfide (H2S) desulfurizer, belonging to the filed of the preparation and the application of the desulfurizer. The invention is characterized in that the desulfurizer which has high H2S desulfurizing rate and can reduce the concentration of carbonyl sulfide on the outlet of the H2S at moderate temperature is prepared by adding desulfurizer alkaline modifier K2CO3 to modify the alkaline of the desulfurizer and adding desulfurizer pore structure modifier Gamma-Al2O3 to modify the pore structure of the desulfurizer. The invention solves the problem existing in the prior art that a large amount of carbonyl sulfide is left on the outlet of the desulfurizer when the desulfurizer is used for desulfurizeing with dry process at moderate temperature. The invention is provided mainly for desulfurizing and purifying the H2S in the gases containing the carbon monoxide, the carbon dioxide and the like and has very considerable applicable, economic and social benefits.
Description
Technical field
A kind of method that reduces concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer of the present invention; Belong to desulfurizing agent preparation and application; The preparation method who relates to a kind of dry method hydrogen sulfide desulphurization agent; Specifically a kind of reduce in the dry desulfurization process in the method for warm Zinc oxide-base concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer, the desulfurizing agent that this method makes is mainly used in removing of hydrogen sulfide in the unstripped gas such as containing carbon monoxide, carbon dioxide.
Background technology
World industry and economic fast development cause energy supply anxiety and environmental problem outstanding.Positive relevant policy is all being taked in countries in the world, to alleviate the contradiction between use of energy resource supply and demand and the energy and the environmental pollution.Especially be in developing China, country has formulated strict energy-saving and emission-reduction and the policy and the measure that improve energy utilization rate, and solving China is the main environmental problem that energy resource structure caused with the coal.Fossil feedstock is clean to be transformed and utilizes, and has become the developing direction that national cleaner production is done one's utmost to advocate, and particularly fossil feedstock low-carbon (LC) utilization has at present become novel technology in national science and technology, economy, the industrial development, obtains vigorously supporting of national policy.Advanced technology during clean conversions of fossil feedstock such as integrated gasification combined cycle plants (IGCC) generating, carbonate fusion fuel cell (CMFC) generate electricity, the coal-based Poly-generation of two gas heads (DCPG) are produced alcohol-ether fuel and utilization or fossil feedstock low-carbon (LC) utilize is at present by extensive research and development and industry demonstration.Coal conversion is one of its critical process in these technology.As everyone knows, the original sulfide of coal is partly moved in the coal gas product of preparation in the coal conversion processes.Sulfide can cause process equipment, corrosive pipeline, catalyst poisoning inactivation and product quality to descend in technical process in the coal gas, and production process efficient is obviously descended, even causes production to be difficult to carry out.Sulfide is discharged in the atmosphere in the coal gas simultaneously, can cause environmental pollution, causes that social economy's loss and social life quality descend.Therefore desulfurizing and purifying is one of key technology essential in the clean conversion of coal and utilization or the utilization of fossil feedstock low-carbon (LC).Gas desulfurization and purification is divided into wet method and dry method two big classes based on the form of absorbent usually.Wet method is under normal temperature or low temperature, to adopt liquid-absorbant to remove sulfide in the gas, has that the gas flow of processing is big, a hydrogen sulfide content advantages of higher in the gas, but serviceability temperature is low, complicated operation is its unvanquishable deficiency.Dry method is to adopt solid absorbent to remove sulfide in the gas, compares with wet desulphurization, and dry method has that the serviceability temperature zone is wide, desulfuration efficiency is high, characteristics such as low, simple to operate, the low equipment investment of sulfide concentration in the gas after the desulfurization.Dry desulfurization has been widely used in the deep removal or meticulous the removing of different shape sulphur under complicated atmosphere, the complex operations condition.Since dry desulfurization is used, gas purification with separate in brought into play huge effect, for condition has been created in the improvement of industrial production environment and people's lives environment.Dry desulfurization mainly contains according to the desulfurizing agent type difference of using at present: active carbon, iron oxide, manganese oxide, zinc oxide and composite metal oxide etc.Along with the rapid exploitation of new technology and the continuous development of new catalyst, desulfurization by dry method presses for further development, and the dry desulfurization range of application also must further be expanded.
But along with dry desulfurization research deeply with the expansion of range of application, find appearance " putting sulphur " phenomenon in the dry desulfurization process.So-called " putting sulphur " phenomenon be in the sweetening process in certain period desulfurization outlet sulfide concentration be higher than the import sulfide concentration or the desulfurization outlet discharges sulfide with the form that is different from import sulfide." put sulphur " in the dry desulfurization process and show seemingly desulfurizing agent and run counter to its basic function; Desulfurizing agent is not in desulfurization; But discharging sulfide, or even be converted into the sulfide that is difficult to remove to the sulfide that removes easily, as the hydrogen sulfide (H that removes easily in the gas
2S) be converted into the cos (COS) that is difficult to remove.Desulfurizing agent in the dry desulfurization process " is put sulphur " and in industry use, engineering development, scientific research, is familiar with by people.The unstring technological process of normal temp zinc oxide desulfurization of two sections water at low temperature has been adopted in certain Methanol Plant decarbonization gas smart desulfurization, after the operation, removes H
2S is respond well, but is another kind of situation to COS, produces to analyze data and show that through the hydrolyst bed, COS is converted into H
2S, its concentration descends significantly, but the hydrogen sulfide that generates is not removed, on the contrary H through the normal temp zinc oxide desulfurization bed
2S changes into COS again, outlet COS (7.60mg/m
3～14.76mg/m
3) often be higher than (the 0.07mg/m of import
3～6.70mg/m
3), " putting sulphur " phenomenon has appearred, i.e. import H
2S is converted into COS.Document is also found when the research Zinc oxide desulfurizer; In the time of 400～500 ℃, from contain CO gas, removing in the hydrogen sulfide process Zinc oxide desulfurizer outlet has COS to generate [Sasaoka etc.; Characterization of reaction between zinc oxide and hydrogen sulfide; Energy & Fuel, 1994,8:1100-1105].Document find that also the desulfurizing agent outlet has COS to occur, and COS concentration is with H at research zinc ferrite desulfurizing agent for high-temp gas
2The increase of S concentration and increase [Liang etc., Bench-scale testing of zinc ferrite sorbent forhot gas clean-up, Journal of Natural Gas Chemistry, 2007,16:204-209].We find in the temperature coal gas desulfurizing agent research that in zinc oxide temperature is at 300～400 ℃, and in the simulation coal gas hydrogen sulfide stripping process, import does not have COS, and outlet has nearly 100mg/m unexpectedly
3COS, so-called " putting sulphur " phenomenon has appearred.
Along with the use of advanced analysis instrument in industrial process, having detected in many dry desulfurization processes the desulfurizing agent outlet has COS to occur.Cos is a kind ofly to cause the sulfide of catalyst poisoning more easily than hydrogen sulfide, and cos is difficult for again removing through direct method simultaneously, need be through removing after the indirect reformer, and the technology relative complex removes the condition harshness.The desulfurizing agent outlet has COS to occur in the dry desulfurization process, and is also shorter from the present domestic synthetic catalyst life-span, is mainly sulfur poisoning, but detects less than H in the catalyst inlet gas
2S confirms.
Many dry-desulphurizers are being arranged aspect the meticulous desulfurization, and wherein Zinc oxide desulfurizer is used as main desulfurizing agent type.This is that it is more favourable than other desulfurizing agent on thermodynamics, to adopt zinc oxide to remove hydrogen sulfide because hydrogen sulfide and zinc oxide reaction equilibrium constant are bigger, and the Zinc oxide desulfurizer desulfurization precision is higher relatively.The replacement is being brought in constant renewal in the exploitation of Zinc oxide desulfurizer both at home and abroad.An important development direction is exactly to add the intensity that structural promoter improves desulfurizing agent; A kind of normal temp zinc oxide desulfuriging agent and preparation method have been invented like the patent ZL93111222.2 of SINOPEC Qilu Petro-Chemical Corp; Be characterized in ZnO composition and structural promoter iron aluminous cement mixed-forming are formed, can be used for removing of hydrogen sulfide under the normal low temperature (≤200 ℃); The patent ZL01111032.2 of Institutes Of Technology Of Taiyuan has invented a kind of desulfurizing agent of zinc ferrite for high-temp gas and preparation, adopts the layer column compound of Different Silicon aluminum ratio to be used for zinc ferrite desulfurization agent preparation, has overcome the efflorescence of desulfurizing agent.Another important focus is to prepare through Zinc oxide desulfurizer active component Zinc oxide particles nanoscale to improve the activity that desulfurizing agent removes hydrogen sulfide; Invent a kind of nano zine oxide and nano-sized iron oxide preparation method like the patent CN1907544A of Harbin Institute of Technology, obtained a kind of nano oxidized zinc base desulfurizing agent; The patent ZL200610012811.9 of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences has invented a kind of nano-desulfurizer and method for making and application that is used for gas sweetening, is characterized in adopting sol-gel-obtain the desulfurizer active component zinc ferrite from combustion process.All these patented technologies all are to investigate desulfurizer activity with the hydrogen sulfide stripping ability, and performance assessment criteria is the Sulfur capacity that penetrates when being several ppm with the outlet concentration of hydrogen sulfide.
Zinc oxide desulfurizer plays last " checking on " effect as meticulous desulfurizing agent in the gas desulfurization and purification process, and the content very low (requiring total sulfur content usually below 0.1ppm) of the gas purification of advanced technologies requirement at present after cure thing.So, only exporting concentration of hydrogen sulfide as purification standard with desulfurizing agent, and ignore the existence of desulfurizing agent outlet COS, is present desulfurizing and purifying production management, the ubiquitous mindset of scientific research personnel.Thus, including outlet COS concentration in the purification requirement is scientific progress.
We study for a long period of time and think, desulfurizing agent outlet COS exists chief reason to have in the dry desulfurization process: atmosphere effect (H
2S, CO, CO
2, H
2, H
2O), three types of factors of operating condition (temperature, air speed, pressure) and desulfurizing agent character (composition, structure).But owing to atmosphere, operating condition are closely related with industrial use; Malleable not normally; Therefore when above-mentioned two factors, one timing; Reducing the method for desulfurizing agent outlet cos concentration in the dry desulfurization process should innovate in the desulfurizing agent preparation, just carries out the desulfurizing agent property modification.
Summary of the invention
A kind of method that reduces concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer of the present invention; Purpose is to solve in the dry desulfurization process desulfurizing agent and puts the sulphur problem and improve the desulfurizing agent desulfurization performance, discloses a kind of technical scheme that reduces the method for concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer in the dry desulfurization process.
A kind of method that reduces concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer of the present invention; It is characterized in that it being a kind of method of cos concentration in the warm hydrogen sulfide desulphurization agent exit gas that reduces in the sweetening process in the dry method; Particularly be to add structure modifier in a kind of employing desulfurizing agent, improve the desulfurizing agent pore structure, improve hydrogen sulfide diffusion rate in desulfurizing agent; Accelerate the absorption of desulfurizing agent to hydrogen sulfide; Reduce hydrogen sulfide and generate the cos chance and adopt interpolation cos catalyzed conversion activating agent in the desulfurizing agent, improve the cos catalysis alkaline nature of desulfurizing agent, improve the cos conversion speed of generation; Reduce cos is accumulated production rate in desulfurizing agent method, the concrete processing step of this method is:
The preparation of I, activating agent, alkaline modifier and structure modifier
Select for use zinc oxide (ZnO) as activating agent, select potash (K for use
2CO
3) as alkaline modifier, select gama-alumina (γ-Al for use
2O
3) as structure modifier, select for use carboxymethyl cellulose and graphite as pore creating material and select water for use or nitric acid as binding agent; The predecessor of wherein said activating agent zinc oxide preparation is a basic zinc carbonate, and the predecessor of wherein said structure modifier gama-alumina preparation is a boehmite;
The composition of raw materials of II, preparation hydrogen sulfide desulphurization agent
The composition of raw materials of preparation hydrogen sulfide desulphurization agent is:
Basic zinc carbonate 112～126g
Potash 7～13g
Boehmite 4～10g
Carboxymethyl cellulose+graphite 4～6g
Carboxymethyl cellulose: graphite 15wt: 1wt;
III, preparation dry method hydrogen sulfide desulphurization agent
Composition of raw materials according to Step II; Accomplish the mixing of the activating agent of being prepared by step I, alkaline modifier, structure modifier through one step of mechanical mixing; Just activating agent, alkaline modifier, structure modifier, pore creating material, water are mixed, room temperature extruded moulding, high-temperature activation are accomplished preparation successively, particularly at room temperature behind the predecessor boehmite and pore creating material mixing with the predecessor basic zinc carbonate of activating agent zinc oxide, alkaline modifier potash, structure modifier gama-alumina; Add behind the binding agent extruded moulding at room temperature; At room temperature placed 12～24 hours, and descended dry 2～4 hours at 100～150 ℃ then, at last 500～700 ℃ of following roastings 2～4 hours; Obtain the finished product desulfurizing agent, the hydrogen sulfide desulphurization agent chemical composition and the physical arrangement of preparation are: N
2Absorption BET surface area is at 15～25m
2/ g, particle size is φ 2～3mm * 3～5mm, its chemical composition is:
ZnO 80～90wt.％
K
2CO
3 7～13wt.％
γ-Al
2O
3 3～7wt.％；
IV, reduction concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer
Adopt the prepared desulfurizing agent of Step II I to be used for removing of hydrogen sulfide gas in the synthesis material gas that temperature time contains carbon monoxide and carbon dioxide; Temperature is in 200～400 ℃ of scopes in wherein said, and desulfurizing agent is at normal pressure～4.0MPa, 200～400 ℃ of reaction temperatures, air speed 1000～4000h
-1, import H
2S concentration is less than 300mgS/m
3Service condition under, when the outlet H
2S concentration and outlet COS concentration are all less than 0.1mgS/m
3The time, desulfurizing agent penetrate Sulfur capacity at 12～15wt.%.
A kind of advantage that reduces the method for concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer of the present invention is, overcome prior art under mesophilic condition in the dry desulfurization process desulfurizing agent outlet have the problem of a large amount of cos, through adding desulfurizing agent alkalescence modifier K
2CO
3Change desulfurizing agent alkalescence, add desulfurizing agent structure modifier γ-Al
2O
3Change the desulfurizing agent pore structure, obtained a kind of middle temperature and had high H down
2The desulfurizing agent of S removal efficiency and low outlet cos concentration, the middle temperature that the present invention is primarily aimed at hydrogen sulfide in the gases such as containing carbon monoxide, carbon dioxide removes and purifies and develop, and using value, economic benefit and social benefit are all very considerable.
The desulfurizer activity test is in the glass reactor of 20 millimeters of internal diameters, to carry out, and the desulfurizing agent granularity is φ 2～3mm * 3～5mm, and loadings is 10 milliliters, 200～400 ℃ of reaction temperatures, air speed 1000～4000h
-1, normal pressure, the hydrogen sulfide inlet concentration is less than 300mgS/m
3, test in test the concentration of desulfurizing agent outlet concentration of hydrogen sulfide, cos and penetrate Sulfur capacity.
Description of drawings
Shown in Figure 1 is two kinds of desulfurizing agent pore structure characterization result figure of embodiment of the present invention 2 and Comparative Examples 2 preparations.
The specific embodiment
Through the specific embodiment desulfurizing agent of the present invention, preparation method and result of use are described below.
Embodiment 1:
Take by weighing the basic zinc carbonate of about 112g, in basic zinc carbonate, add the potash mixing of 13g, then in basic zinc carbonate and potassium carbonate mixtures, add the boehmite of about 9.5g again; The carboxymethyl cellulose and the 0.25g graphite mixture that add about 3.75g at last; All raw materials are formed mixing, add deionized water, mediate after the room temperature extrusion; Obtain being of a size of the particle of φ 2～3mm * 3～5mm; After the room temperature held 24 hours, drying is 4 hours under 120 ℃, and dried sample is warm Zinc oxide desulfurizer in 550 ℃ of following roastings promptly got in 4 hours.Desulfurizing agent is 300 ℃ in temperature, and air speed is 2000h
-1, inlet gas is formed: 30Vol.%CO, 20Vol.%CO
2, 40Vol.%H
2, 1Vol.%H
2O, N
2Balance, import H
2S concentration is less than 300mgS/m
3Under the condition, record outlet H
2S concentration and outlet COS concentration are all less than 0.1mgS/m
3The time, desulfurizing agent penetrate Sulfur capacity about 13wt.%.
Embodiment 2:
Take by weighing the basic zinc carbonate of about 119g, in basic zinc carbonate, add the potash mixing of 10g, then in basic zinc carbonate and potassium carbonate mixtures, add the boehmite of about 7g again; Add carboxymethyl cellulose and 0.36g graphite mixture at last with 5.4g; All raw materials are formed mixing, add deionized water, mediate after the room temperature extrusion; Obtain being of a size of the particle of φ 2～3mm * 3～5mm; After the room temperature held 24 hours, drying is 4 hours under 120 ℃, and dried sample is warm Zinc oxide desulfurizer in 550 ℃ of following roastings promptly got in 4 hours.Desulfurizing agent is 300 ℃ in temperature, and air speed is 2000h
-1, inlet gas is formed: 30Vol.%CO, 20Vol.%CO
2, 40Vol.%H
2, 1Vol.%H
2O, N
2Balance, import H
2S concentration is less than 300mgS/m
3, record outlet H
2S concentration and outlet COS concentration are all less than 0.1mgS/m
3The time, desulfurizing agent penetrate Sulfur capacity about 15wt.%.
Embodiment 3:
Take by weighing the basic zinc carbonate of about 126g, in basic zinc carbonate, add the potash mixing of 7g, then in basic zinc carbonate and potassium carbonate mixtures, add the boehmite of about 4g again; Add carboxymethyl cellulose and 0.5g graphite mixture at last with 7.5g; All raw materials are formed mixing, add deionized water, mediate after the room temperature extrusion; Obtain being of a size of the particle of φ 2～3mm * 3～5mm; After the room temperature held 24 hours, drying is 4 hours under 120 ℃, and dried sample is warm Zinc oxide desulfurizer in 550 ℃ of following roastings promptly got in 4 hours.Desulfurizing agent is 300 ℃ in temperature, and inlet gas is formed: 30Vol.%CO, 20Vol.%CO
2, 40Vol.%H
2, 1Vol.%H
2O, N
2Balance, import H
2S concentration is less than 300mgS/m
3, record outlet H
2S concentration and outlet COS concentration are all less than 0.1mgS/m
3The time, desulfurizing agent penetrate Sulfur capacity about 14wt.%.
Embodiment 4:
According to the desulfurizing agent of embodiment 2 preparations, form in normal pressure, 300 ℃ of temperature, inlet gas: 30Vol.%CO, 20Vol.%CO
2, 40Vol.%H
2, 1Vol.%H
2O, N
2Balance, import H
2S concentration is less than 300mgS/m
3Condition under, record air speed and be respectively 1000h
-1, 2000h
-1, 3000h
-1, 40000h
-1During four different numerical value, outlet H
2S concentration and outlet COS concentration are all less than 0.1mgS/m
3The time, desulfurizing agent penetrate Sulfur capacity about 13～15wt.%.
Embodiment 5:
According to the desulfurizing agent of embodiment 2 preparations, at normal pressure, air speed 2000h
-1, inlet gas forms: 30Vol.%CO, 20Vol.%CO
2, 40Vol.%H
2, 1Vol.%H
2O, N
2Balance, import H
2S concentration is less than 300mgS/m
3Condition under, when recording temperature and being respectively the different numerical value of 250 ℃, 300 ℃, 350 ℃, 400 ℃ four, outlet H
2S concentration and outlet COS concentration are all less than 0.1mgS/m
3The time, desulfurizing agent penetrate Sulfur capacity about 12～14wt.%.
Comparative Examples 1:
Take by weighing the basic zinc carbonate of about 130g, in basic zinc carbonate, add the boehmite of about 7g, add carboxymethyl cellulose and the 0.36g graphite mixture of 5.4g at last; All raw materials are formed mixing, add deionized water, mediate after the room temperature extrusion; Obtain being of a size of the particle of φ 2～3mm * 3～5mm; After the room temperature held 24 hours, drying is 4 hours under 120 ℃, and dried sample is warm Zinc oxide desulfurizer in 550 ℃ of following roastings promptly got in 4 hours.In temperature is 300 ℃, and air speed is 2000h
-1, inlet gas is formed: 30Vol.%CO, 20Vol.%CO
2, 40Vol.%H
2, 1Vol.%H
2O, N
2Balance, import H
2S concentration is less than 300mgS/m
3, record outlet H
2S concentration is less than 0.1mgS/m
3, but outlet COS concentration is less than 0.1～8mgS/m
3, desulfurizing agent hydrogen sulfide stripping performance can meet essence and remove requirement, but does not reach the requirement of meticulous desulfurization to carbonyl sulfide removal.
Comparative Examples 2:
Take by weighing the basic zinc carbonate of about 130g, in basic zinc carbonate, add the potash mixing of 11g, add carboxymethyl cellulose and 0.36g graphite mixture at last with 5.4g; All raw materials are formed mixing, add deionized water, mediate after the room temperature extrusion; Obtain being of a size of the particle of φ 2～3mm * 3～5mm; After the room temperature held 24 hours, drying is 4 hours under 120 ℃, and dried sample is warm Zinc oxide desulfurizer in 550 ℃ of following roastings promptly got in 4 hours.Desulfurizing agent is 300 ℃ in temperature, and air speed is 2000h
-1, inlet gas is formed: 30Vol.%CO, 20Vol.%CO
2, 40Vol.%H
2, 1Vol.%H
2O, N
2Balance, import H
2S concentration is less than 300mgS/m
3, record outlet H
2S concentration and outlet COS concentration are all less than 0.1mgS/m
3The time, desulfurizing agent penetrate Sulfur capacity about 10wt.%, but compare with the desulfurizing agent of embodiment 2 preparation, desulfurization precision is lower, it is also less to penetrate Sulfur capacity.
The desulfurizing agent K for preparing respectively according to embodiment 2 and Comparative Examples 2
2CO
3-Al
2O
3-ZnO and K
2CO
3Two kinds of desulfurizing agents of-ZnO adopt Tristar3000 nitrogen isothermal physical adsorption appearance that physical parameters such as its specific surface, pore volume, pore size distribution are characterized.Characterization result such as table 1 are with shown in Figure 1.
Table 1 K
2CO
3-Al
2O
3-ZnO and K
2CO
3Two kinds of desulfurizing agent physical parameters of-ZnO
| Desulfurizing agent | Color | Particle diameter (mm) | Bulk density (g/ml) | Surface area (m 2/g) | Pore volume (cm 3/g) | Average pore size (nm) |
| K 2CO 3-ZnO | Greyish white | 2-3 | 1.03 | 9.2316 | 0.00687 | 31.9049 |
| K 2CO 3-Al 2O 3-ZnO | Greyish white | 2-3 | 0.925 | 20.1650 | 0.00689 | 23.2691 |
Desulfurizing agent surface area of the present invention number of perforations big, 10～70nm aperture is many, and these all help, and hydrogen sulfide spreads in its hole and the surface adsorption reaction.
Claims (1)
1. method that reduces concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer; It is characterized in that it being a kind of method of cos concentration in the warm hydrogen sulfide desulphurization agent exit gas that reduces in the sweetening process in the dry method; Particularly be to add structure modifier in a kind of employing desulfurizing agent, improve the desulfurizing agent pore structure, improve hydrogen sulfide diffusion rate in desulfurizing agent; Accelerate the absorption of desulfurizing agent to hydrogen sulfide; Reduce hydrogen sulfide and generate the cos chance and adopt interpolation cos catalyzed conversion activating agent in the desulfurizing agent, improve the cos catalysis alkaline nature of desulfurizing agent, improve the cos conversion speed of generation; Reduce cos is accumulated production rate in desulfurizing agent method, the concrete processing step of this method is:
The preparation of I, activating agent, alkaline modifier and structure modifier
Select for use zinc oxide (ZnO) as activating agent, select potash (K for use
2CO
3) as alkaline modifier, select gama-alumina (γ-Al for use
2O
3) as structure modifier, select for use carboxymethyl cellulose and graphite as pore creating material and select water for use or nitric acid as binding agent; The predecessor of wherein said activating agent zinc oxide preparation is a basic zinc carbonate, and the predecessor of wherein said structure modifier gama-alumina preparation is a boehmite;
The composition of raw materials of II, preparation hydrogen sulfide desulphurization agent
The composition of raw materials of preparation hydrogen sulfide desulphurization agent is:
III, preparation dry method hydrogen sulfide desulphurization agent
Composition of raw materials according to Step II; Accomplish the mixing of the predecessor boehmite of the predecessor basic zinc carbonate of the activating agent zinc oxide of being prepared by step I, alkaline modifier potash, structure modifier gama-alumina through one step of mechanical mixing; Just the predecessor basic zinc carbonate of activating agent zinc oxide, alkaline modifier potash, the predecessor boehmite of structure modifier gama-alumina, pore creating material, water are mixed; Room temperature extruded moulding, high-temperature activation are accomplished preparation successively; Particularly at room temperature behind the predecessor boehmite and pore creating material mixing with the predecessor basic zinc carbonate of activating agent zinc oxide, alkaline modifier potash, structure modifier gama-alumina, add behind the binding agent extruded moulding at room temperature, at room temperature placed 12～24 hours; Following dry 2～4 hours at 100～150 ℃ then; 500～700 ℃ of following roastings 2～4 hours, obtain the finished product desulfurizing agent at last, the hydrogen sulfide desulphurization agent chemical composition and the physical arrangement of preparation are: N
2Absorption BET specific area is at 15～25m
2/ g, particle size is φ 2～3mm * 3～5mm, its chemical composition is:
ZnO 80～90wt.％
K
2CO
3 7～13wt.％
γ-A1
2O
3 3～7wt.％；
IV, reduction concentration of carbonyl sulfide on outlet of hydrogen sulfide (H 2 S) desulfurizer
Adopt the prepared desulfurizing agent of Step II I to be used for removing of hydrogen sulfide gas in the synthesis material gas that temperature time contains carbon monoxide and carbon dioxide; Temperature is in 200～400 ℃ of scopes in wherein said, and desulfurizing agent is at normal pressure～4.0MPa, 200～400 ℃ of reaction temperatures, air speed 1000～4000h
-1, import H
2S concentration is less than 300mgS/m
3Service condition under, when the outlet H
2S concentration and outlet COS concentration are all less than 0.1mgS/m
3The time, desulfurizing agent penetrate Sulfur capacity at 12～15wt.%.
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| CN102381924B (en) * | 2010-09-06 | 2013-11-27 | 中国石油化工股份有限公司 | Method for purifying propylene coarse product containing sulfur-containing compound |
| CN102381923B (en) * | 2010-09-06 | 2013-11-27 | 中国石油化工股份有限公司 | Method for acquiring propylene from liquid hydrocarbon containing propylene and sulfur-containing compound |
| CN102000505A (en) * | 2010-11-16 | 2011-04-06 | 湖北双雄催化剂有限公司 | Novel middle-temperature carbonyl sulfide hydrolysis method |
| CN104190242B (en) * | 2014-08-29 | 2016-08-24 | 深圳中纺滤材科技有限公司 | A kind of hydrogen sulfide scavenging material and preparation method thereof |
| CN105858604B (en) * | 2016-03-31 | 2018-06-29 | 四川天采科技有限责任公司 | A kind of full temperature journey pressure swing adsorption method of enriched gas source removing hydrogen sulfide |
| CN108479827B (en) * | 2018-04-03 | 2021-06-15 | 太原理工大学 | Mid-temperature hydrolysis conversion carbonyl sulfide and deoxidation bifunctional coupling catalyst and preparation method thereof |
| CN114433006B (en) * | 2020-10-20 | 2023-10-31 | 中国石油化工股份有限公司 | Normal-temperature COS adsorbent, and preparation method and application thereof |
| CN114196448B (en) * | 2022-02-16 | 2022-05-10 | 北京中航天业科技有限公司 | Full-flow dry type blast furnace gas fine desulfurization system and method |
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| US5439867A (en) * | 1994-03-04 | 1995-08-08 | Phillips Petroleum Company | Fluidizable sulfur sorbent and fluidized sorption process |
| CN1283669A (en) * | 2000-07-14 | 2001-02-14 | 太原理工大学 | Desulfurizing agent for high-temp gas and its preparing process |
| 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 |
| CN100493699C (en) * | 2007-07-25 | 2009-06-03 | 太原理工大学 | Intermediate temperate carbonyl sulfur hydrolyst and method of preparing the same and use thereof |
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