CN115672367B - Glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst and preparation method thereof - Google Patents
Glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst and preparation method thereof Download PDFInfo
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- 239000002956 ash Substances 0.000 description 4
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Abstract
The invention discloses a glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst and a preparation method thereof, belonging to the technical field of industrial flue gas treatment. The glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst disclosed by the invention takes a glass fiber plate as a base material, adopts a vacuum impregnation method to coat TiO 2 with a large specific surface area on the glass fiber plate as a carrier, takes K 2CO3 as an active component on the carrier, and takes PEG as an auxiliary agent for modification treatment when the active component is loaded. The catalyst has higher activity of catalyzing and hydrolyzing COS at the temperature of 100-200 ℃, has stronger sulfur resistance stability, and can effectively prolong the service life of the catalyst; meanwhile, the size of the catalyst pore and the size of the catalyst module can be adjusted to meet the requirements of various working conditions, the volume of the reactor is smaller, the system resistance is lower, the amount of carriers and active components used by the catalyst module in unit volume is smaller, and the materials and the cost are saved.
Description
Technical Field
The invention belongs to the technical field of industrial flue gas treatment, and particularly relates to a plate-type carbonyl sulfide hydrolysis catalyst with higher activity and sulfur resistance stability and convenient industrial molding and industrial application and a preparation method thereof.
Background
Blast furnace gas is an important sulfur-containing pollutant emission source in China and forms a great threat to the atmospheric environment. The blast furnace gas generated by steel smelting is a precious gas resource, and can be applied to the subsequent process of steel smelting or connected to civilian use. The ecological environment department issues opinion about ultra-low emission of the advanced implementation steel industry on 22 days 4 months 2019, and steel enterprises formally enter an ultra-low emission era, SO that the average value of emission concentration of SO 2 of a sintering machine head is not higher than 35mg/m 3 and the average value of emission concentration of SO 2 of a hot-blast stove is not higher than 50mg/m 3. Under the new requirement, the original blast furnace gas desulfurization process can not meet the condition, so the fine desulfurization is particularly important before the blast furnace gas is combusted. In order to improve the sulfur removal effect of the gas, sulfur-containing substance carbonyl sulfide in the blast furnace gas is required to be removed.
At present, the main methods for removing COS in industrial gas include direct absorption and removal and indirect conversion absorption and removal. The indirect conversion absorption method has the advantages of high operation temperature, convenient operation, large absorption capacity, economical operation and the like. In the indirect conversion absorption process, COS catalytic conversion is the core. And most of the water vapor required by the COS catalytic hydrolysis process is already present in the raw material gas, and no additional addition is needed; the reaction does not need a hydrogen source, so that the energy consumption is saved; the side reaction is less; the hydrolysis catalyst has relatively low price, and the production cost is reduced. In the hydrolytic conversion process: COS is converted into H 2 S which is easy to remove in a traditional way through hydrolysis and catalysis, and finally, the blast furnace gas fine desulfurization is achieved, and the theory is mature day by day at home and abroad and obtains a certain research result. Thus, the use of hydrolysis catalysis to finely desulphurize blast furnace gas is the best option to solve this problem.
Many students currently conduct research on related aspects in China. For example, the chinese invention with publication No. cn20171019950. X discloses an alumina carbonyl sulfide hydrolysis catalyst and a preparation method thereof, wherein the alumina carbonyl sulfide hydrolysis catalyst is a gamma-Al 2O3 -based carbonyl sulfide hydrolysis catalyst, and has a relative humidity of 14.3%, a space velocity of 1.6 ten thousand h -1, a COS concentration of 800mg/m 3,O2 concentration of 2%, a carbonyl sulfide conversion rate of about 98% at a reaction temperature of 70 ℃, but can only last for about 10h, and has poor sulfur poisoning resistance and stability. The Chinese patent publication No. CN201010551862.5 discloses a carbonyl sulfur hydrolysis catalyst, which comprises (a) 1-5% of alkali metal carbonate, alkaline earth metal oxide or a mixture thereof, (b) 15-25% of rare earth oxide and (c) 70-82% of alumina, wherein the reaction temperature range of the catalyst is wider, the applicable material airspeed is low, but the problem of poor sulfur poisoning resistance is also existed, wherein gamma-Al 2O3 is used as a carrier and La 2O3 is used as an active component, the granular catalyst prepared by dipping Na 2CO3 solution is tested under the conditions that the temperature is 50 ℃, the COS content is 100ppm, the molar ratio of H 2 O to COS is 10:1, the airspeed is 5000hr -1, and the weight percentage of O 2 in the material is 0.3%, and the result shows that the COS conversion rate of the catalyst is about 90%.
For another example, chinese patent publication No. CN 1331596C discloses a COS hydrolysis catalyst in which gamma-Al 2O3 is used as a carrier to support potassium oxalate, and TiO 2 or ZrO 2 is used to modify the catalyst, and the catalyst is extruded to form a 2-4 mm columnar catalyst, so that the COS removal effect of the catalyst with a concentration of about 2500mg/m 3 can reach 95%, and the catalyst activity is only stabilized for about 8 hours. Chinese patent publication No. CN 106824149B discloses a Ti-Si composite carbonyl sulfide hydrolysis catalyst, in which K 2 O is dissolved, impregnated and supported on polystyrene microsphere and calcined at 600 ℃, COS concentration is 800mg/m 3, COS removal efficiency is about 99% at 70 ℃ but only maintained for 12 hours, and active components are rapidly lost. Meanwhile, the two granular and columnar catalysts are in a stacked state in the use process, the catalyst is low in use efficiency and difficult to clean ash, and sulfate generated by the reaction is easy to accumulate on the surface of the catalyst and cover active sites, so that the activity of the catalyst is reduced.
The invention of China with publication number CN 111432924A discloses a titanium dioxide supported barium compound carbonyl sulfide hydrolysis catalyst and a preparation method thereof, wherein barium compound with the weight percent of barium oxide converted into 4 percent is supported on titanium dioxide (TiO 2), the catalyst takes anatase type titanium dioxide as a carrier, is extruded into a honeycomb shape, but has relatively smaller specific surface area, slower reactant export rate and poorer catalyst activity, and test results show that: the space velocity is 12000h -1, the COS concentration is 2300ppm, the COS conversion rate is 62% at the reaction temperature of 150 ℃, the COS conversion rate is about 84% at the reaction temperature of 200 ℃, the COS conversion rate is about 90% at the reaction temperature of 250 ℃, the COS conversion rate is about 92% at the reaction temperature of 300 ℃, the optimal activity temperature of the catalyst is higher, and the window is narrower. In addition, the K 2 O modified TiO 2 is adopted to support the barium oxide honeycomb catalyst, and the result shows that the addition of K 2 O improves the activity of the catalyst, but when the reaction temperature is higher than 250 ℃, the activity of the catalyst is reduced along with the temperature, and the temperature is reduced by about 4% compared with the temperature of 250 ℃ at 300 ℃, so that the addition of K 2 O reduces the stability of an alkaline site.
In summary, the low-temperature catalytic activity of the COS hydrolysis catalyst using gamma-Al 2O3 as a carrier needs to be improved, and the problems of poor stability and sulfur poisoning resistance generally exist. In addition, COS hydrolysis catalysts which are commercially applied at present and take gamma-Al 2O3 as carriers are all in the shape of particles or columns, the running airspeed is low, the filling running resistance is large, the occupied area is large, the installation is complex, ash removal is difficult, fly ash and sulfate generated by reaction are easy to cover the surface of the catalyst, and the catalyst is deactivated. The catalyst taking TiO 2 as a carrier improves the sulfur resistance of COS hydrolysis, but the specific surface area is relatively small (generally about 50-60 m 2/g), which is unfavorable for smooth export of reaction products, and is easy to cause sulfate deposition to be attached to the surface of the catalyst, so that the long-term operation stability of the catalyst is poor. Therefore, research and development of the COS hydrolysis catalyst with high catalytic activity, sulfur resistance and strong alkaline site stability has important theoretical significance and engineering application value for promoting the fine desulfurization of blast furnace gas.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defect that the existing blast furnace gas carbonyl sulfide hydrolysis catalyst is difficult to meet the requirements on catalytic activity and sulfur resistance stability at the same time, and provides a glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst and a preparation method thereof. The catalyst has higher activity of catalyzing and hydrolyzing COS at the temperature of 100-200 ℃, has stronger sulfur resistance stability, and can effectively prolong the service life of the catalyst.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
in order to achieve the above purpose, the technical scheme provided by the invention is as follows:
The invention relates to a glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst, which takes a glass fiber plate as a base material, wherein the glass fiber plate is coated with TiO 2 with large specific surface area as a carrier, K 2CO3 is loaded on the carrier as an active component, and PEG is used as an auxiliary agent for modification treatment when the active component is loaded.
According to the invention, tiO 2 with large specific surface area is taken as a carrier, and PEG is added as an auxiliary agent for modification when active components are loaded, so that the pore channel structure of the surface of TiO 2 can be effectively improved, a large number of step pore structures are formed, the smooth export of reaction products is facilitated, the adhesion of sulfate on the surface of a hydrolysis catalyst can be effectively inhibited, the surface energy of nucleation of active component grains can be reduced, the flocculation of the particles and the aggregation growth of the grains are inhibited, the active components are uniformly dispersed on the carrier, the alkaline sites on the surface of the catalyst are enhanced, good conditions are provided for the adsorption and conversion of COS on the surface of the catalyst, and further, the higher catalyst activity is obtained. In addition, the stepped pore structure of the catalyst is favorable for uniform distribution of alkaline ions, so that the thermal stability of active sites is improved.
The large specific surface area TiO 2 has a certain shrinkage rate when calcined, and the honeycomb-shaped catalyst cannot be prepared by adopting the traditional extrusion molding process, but the invention takes the glass fiber plate as a base material and coats K 2CO3-PEG/TiO2 on the surface of the glass fiber plate, so that on one hand, the special pore characteristics of the catalyst are effectively reserved, and the number of active sites and sulfur resistance stability of the catalyst surface in the industrial molding process are ensured; on the other hand, the catalyst can ensure better mechanical strength and corrosion resistance, can adjust the pore size and the catalyst module size according to actual conditions, is suitable for different working conditions, and improves the reproducibility and the stability of the catalyst. Compared with the honeycomb catalyst formed by extrusion, the catalyst consumption per cubic meter can be reduced by about 250-300 kg, and the catalyst utilization efficiency can be effectively improved by coating the glass fiber plate catalyst, so that the cost is greatly saved.
Further, the loading of the active component is 1-10 wt.%, and the content of the auxiliary agent PEG is 0.5-8 wt.%.
Further, the active component K 2CO3 accounts for 4% of the mass of the mixed material, and the auxiliary agent PEG accounts for 4% of the mass of the mixed material.
Furthermore, the specific surface area of the TiO 2 carrier is not less than 300m 2/g, the surface of the TiO 2 carrier is distributed with a step hole structure, the adsorption binding energy of the large-ratio TiO 2 and H 2 S is relatively low, and the catalyst has high sulfur poisoning resistance under the oxygen-containing atmosphere.
Further, the glass fiber board is of a corrugated plate structure.
The preparation method of the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst comprises the following steps:
(1) Dissolving K 2CO3 powder and PEG in a proper amount of distilled water according to the mass ratio requirement to obtain a mixed solution;
(2) Adding TiO 2 powder into the mixed solution in the step (1), and uniformly stirring and mixing;
(3) Continuously adding carboxymethyl cellulose, polyethylene oxide and glass fibers into the mixed solution, and uniformly stirring and mixing, so that the bonding firmness of the TiO 2 carrier and the corrugated glass fiber plate is guaranteed, falling is prevented, and the overall strength of the catalyst is improved;
(4) Continuously adding ammonia water into the mixed solution to adjust the pH value of the mixed material, and preparing the mixed material with the solid content of 30-65 wt%; acidic substances brought into the catalyst during preparation can be eliminated by ammonia impregnation in the forming process, and alkaline sites on the surface of the catalyst are ensured.
(5) After the obtained mixture is sealed and aged for a certain time, the mixture is uniformly coated on a corrugated glass fiber board by adopting a vacuum impregnation method, and then the catalyst is dried and calcined to obtain the titanium dioxide supported K 2CO3/PEG carbonyl sulfide hydrolysis catalyst, the obtained glass fiber board molding catalyst has small running resistance, low energy consumption and convenient ash removal, and the generated sulfate substances are not easy to adhere to the surface of the catalyst, so that the service life of the catalyst can be greatly prolonged.
Further, in the step (4), the pH value of the mixture is adjusted to 8-10.
Further, the corrugated glass fiber board is prepared by adopting glass fiber paper with the thickness of 0.5-0.8 mm as a base material and adopting corrugated paper preparation technology for the glass fiber paper.
Further, in the step (5), the vacuum degree of the vacuum impregnation method is-0.08 MPa, the drying temperature is 50-80 ℃, the calcining temperature is 450-550 ℃ and the calcining time is 6-8 h.
Further, in the step (3), the mass ratio of the carboxymethyl cellulose to the mixed material is 0.8-1.5%, and the mass ratio of the polyethylene oxide to the mixed material is 0.1-0.3%.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, tiO 2 with large specific surface area is taken as a carrier, and PEG is combined for modification, so that the catalyst has a developed stepped pore structure and a higher specific surface area, thereby ensuring effective contact between reactants and the catalyst and smooth export of reaction products, and also ensuring high oxidation resistance of the catalyst, thereby ensuring high-efficiency and stable hydrolysis catalytic activity of the catalyst. Meanwhile, the vacuum impregnation method can ensure that the active components can penetrate into micropores of the glass fiber and uniformly adhere to the inner surfaces of the micropores, so that the number of effective active sites is increased, and the catalyst has higher activity of catalyzing and hydrolyzing COS and stronger catalytic stability in the temperature range of 100-200 ℃.
(2) The invention takes the glass fiber board as a base material, and the TiO 2 carrier loaded with the active component is coated on the glass fiber board, so that compared with the common granular catalyst and columnar catalyst, the glass fiber board catalyst is convenient for industrial filling and activity regeneration, has high effective utilization rate of the catalyst, has excellent corrosion resistance, and can enable the limited components in the catalyst to efficiently participate in the carbonyl sulfide hydrolysis conversion process. Furthermore, the glass fiber board is processed into a corrugated plate structure, so that the loading rate and the catalytic effect of the catalytic components are improved.
(3) According to the preparation method of the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst, when the K 2CO3 active component is loaded on a carrier, a certain amount of PEG is added into the carrier, so that the pore channel structure of the surface of TiO 2 can be effectively improved, a large number of stepped pore structures are formed, and further the catalyst activity, the catalytic stability and the sulfur poisoning resistance of the catalyst are improved; and K 2CO3-PEG/TiO2 is loaded on the surface of the glass fiber plate in a coating mode, so that the special pore characteristics of the catalyst are effectively reserved, the number of active sites on the surface of the catalyst and the sulfur resistance stability in the industrial molding process are ensured, the utilization efficiency of the catalyst can be effectively improved, and the use amount of the catalyst is reduced.
(4) The preparation method of the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst is simple, glass fiber paper is used as a base material, the corrugated plate structure is formed by high-temperature shaping and compression molding, catalyst carriers with various pore sizes and catalyst module sizes can be prepared by adjusting a die, different working conditions are applicable, the operation resistance is small, the ash removal is convenient, the energy consumption is low, and the service life of the catalyst is long. In addition, the catalyst raw material is easy to obtain, the use amount is small, and the cost is low.
Drawings
FIG. 1 is a schematic diagram of the structure of a catalyst obtained in the present invention;
FIG. 2 is a graph showing the comparison of the CO 2 -TPD characterization of the catalyst of example 1 of the present invention with that of the prior art catalyst (K 2O/Al2O3);
FIG. 3 is an XRD spectrum of the catalyst obtained in example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, wherein the weight percentage of the K 2CO3 to the total catalyst is 4%, the weight percentage of the auxiliary agent PEG to the total catalyst is 4%, then adding the auxiliary agent PEG to the powder of the large-ratio TiO 2 (the specific surface area is 300m 2/g), and stirring for 1h to uniformly mix the materials;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 8, and adjusting the solid content of the mixed material to 40%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
And thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board prepared by a corrugated paper preparation technology by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 60 ℃, and calcining the mixed material at a temperature of 500 ℃ for 8 hours to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 2
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, wherein the weight percentage of the K 2CO3 to the total catalyst is 4%, the weight percentage of the auxiliary agent PEG to the total catalyst is 4%, then adding the mixture into TiO 2 powder with a large proportion, and stirring for 1h to uniformly mix the mixture;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 8, and adjusting the solid content of the mixed material to 50%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
and thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 60 ℃, and calcining the mixed material for 8 hours at a temperature of 500 ℃ to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 3
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, weighing K 2CO3 accounting for 4% of the total catalyst by mass, weighing an auxiliary agent PEG accounting for 4% of the total catalyst by mass, then adding the auxiliary agent PEG into TiO 2 powder with a large proportion table, and stirring for 1h to uniformly mix the components;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 8, and adjusting the solid content of the mixed material to 60%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
and thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 60 ℃, and calcining the mixed material for 8 hours at a temperature of 500 ℃ to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Embodiment 4
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, weighing K 2CO3 accounting for 2% of the total catalyst by mass, weighing an auxiliary agent PEG accounting for 4% of the total catalyst by mass, then adding the auxiliary agent PEG into TiO 2 powder with a large proportion table, and stirring for 1h to uniformly mix the components;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 8, and adjusting the solid content of the mixed material to 40%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
And thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 50 ℃, and calcining the mixed material at a temperature of 450 ℃ for 6 hours to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 5
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, wherein the weight percentage of the K 2CO3 is 6% of the total catalyst, the weight percentage of the auxiliary agent PEG is 4% of the total catalyst, then adding the mixture into TiO 2 powder with a large proportion, and stirring for 1h to uniformly mix the mixture;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 10, and adjusting the solid content of the mixed material to be 40%, wherein the CMC accounts for 0.8% of the mass ratio of the mixed material, and the PEO accounts for 0.1% of the mass ratio of the mixed material;
and thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 60 ℃, and calcining the mixed material at a temperature of 550 ℃ for 7 hours to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 6
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, weighing K 2CO3 accounting for 8% of the total catalyst by mass, weighing an auxiliary agent PEG accounting for 4% of the total catalyst by mass, then adding the auxiliary agent PEG into TiO 2 powder with a large proportion table, and stirring for 1h to uniformly mix the components;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 9, and adjusting the solid content of the mixed material to 65%, wherein the CMC accounts for 1.5% of the mass ratio of the mixed material, and the PEO accounts for 0.3% of the mass ratio of the mixed material;
And thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 80 ℃, and calcining the mixed material for 8 hours at a temperature of 480 ℃ to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 7
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, wherein the weight percentage of the K 2CO3 is 10% of the total catalyst, the weight percentage of the auxiliary agent PEG is 4% of the total catalyst, then adding the mixture into TiO 2 powder with a large proportion, and stirring for 1h to uniformly mix the mixture;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 9, and adjusting the solid content of the mixed material to 40%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
and thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 60 ℃, and calcining the mixed material for 8 hours at a temperature of 500 ℃ to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 8
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, weighing K 2CO3 accounting for 4% of the total catalyst by mass, weighing an auxiliary agent PEG accounting for 2% of the total catalyst by mass, then adding the auxiliary agent PEG into TiO 2 powder with a large proportion table, and stirring for 1h to uniformly mix the components;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 8, and adjusting the solid content of the mixed material to 40%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
And thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 75 ℃, and calcining the mixed material at a temperature of 510 ℃ for 7.5 hours to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 9
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, weighing K 2CO3 accounting for 4% of the total catalyst mass percent, weighing an auxiliary agent PEG accounting for 6% of the total catalyst mass percent, then adding the auxiliary agent PEG into TiO 2 powder with a large proportion table, and stirring for 1.5 hours to uniformly mix the components;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1.5 hours to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 9, and adjusting the solid content of the mixed material to 40%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
and thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 60 ℃, and calcining the mixed material for 8 hours at a temperature of 500 ℃ to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 10
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, weighing K 2CO3 accounting for 4% of the total catalyst by mass, weighing an auxiliary agent PEG accounting for 4% of the total catalyst by mass, then adding the auxiliary agent PEG into TiO 2 powder with a large proportion, and stirring for 50min to uniformly mix the components;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 8, and adjusting the solid content of the mixed material to 40%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
And thirdly, after sealing and ageing the mixed material for 50 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 60 ℃, and calcining the mixed material for 8 hours at a temperature of 450 ℃ to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Example 11
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment comprises the following steps:
Firstly, weighing a proper amount of K 2CO3 and PEG, adding a proper amount of distilled water for dissolution, weighing K 2CO3 accounting for 4% of the total catalyst by mass, weighing an auxiliary agent PEG accounting for 4% of the total catalyst by mass, then adding the auxiliary agent PEG into TiO 2 powder with a large proportion table, and stirring for 1h to uniformly mix the components;
Secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1h to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to 8-10, and adjusting the solid content of the mixed material to 40%, wherein the CMC accounts for 1% of the mass of the mixed material, and the PEO accounts for 0.2% of the mass of the mixed material;
And thirdly, after sealing and ageing the mixed material for 48 hours, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying the mixed material at a constant temperature of 60 ℃, and calcining the mixed material for 8 hours at a temperature of 550 ℃ to obtain the titanium dioxide supported K 2CO3 carbonyl sulfide (COS) hydrolysis catalyst with a large specific surface area.
Activity test of catalyst:
The coated glass fiber plate type catalysts prepared in examples 1 to 11 (as shown in FIG. 1) were prepared to have a specification of 20 mm. Times.20 mm. Times.30 mm, and the catalysts were packed in a fixed bed reactor to test the COS hydrolysis conversion fine desulfurization activity. In the test process, nitrogen is used as carrier gas, the airspeed is controlled to be 6000h -1, the concentration of carbonyl sulfide at the inlet is controlled to be 1500mg/m 3,O2, the volume concentration is controlled to be 0.5%, the entering rate of steam entering the reactor is controlled to be 0.45g/h, the test temperature is in the range of 100-200 ℃, and the results are shown in Table 1.
TABLE 1 catalyst preparation the desulfurization Activity of the catalysts in examples 1 to 11
The data of the activity test examples of the catalysts in Table 1 show that the catalyst shows excellent hydrolysis catalytic activity when the active substance K 2CO3 is loaded on the TiO 2 of the large ratio table and the auxiliary agent PEG is added, the activity shows excellent activity in the temperature range of 100-200 ℃ when the loading amount of K 2CO3 and the PEG is 4wt.% and above, the sustainable hydrolysis conversion rate of the catalyst in the example 1 at 100 ℃ is more than 96%, and the excellent stability is shown; FIG. 2 is a graph showing the characterization of CO 2 -TPD by the enterprise catalyst and the catalyst of example 1, showing that the COS hydrolysis conversion to predominantly weakly basic site-OH (at about 130 ℃ C.) by the catalyst of example 1 is significantly stronger than that by the enterprise catalyst (K-. Gamma. -Al 2O3); fig. 3 is an XRD spectrum of example 1, showing that the intensity of the diffraction peak of the catalyst well matches with the height of the diffraction peak of the TiO 2 crystal, the diffraction peak is sharp, showing that the obtained catalyst has good crystallization, no diffraction peak of active substance K 2CO3 is detected, and showing that the active component is uniformly distributed on the carrier of TiO 2 with a large specific surface. The catalyst activity was best when the solid content of the catalyst mixture in examples 1 to 3 was 40 wt.%; the activity test data of examples 1, 10 and 11 show that the calcination temperature conditions of 450-550 ℃ have almost negligible effect on the catalyst activity.
In conclusion, the blast furnace gas carbonyl sulfide hydrolysis conversion catalyst has extremely high catalytic activity, persistence and stability, has good oxidation resistance to oxygen atmosphere, has high industrial molding feasibility, and can completely meet the requirements of blast furnace gas fine desulfurization.
Claims (10)
1. A glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst is characterized in that: the catalyst is prepared by taking a glass fiber plate as a base material, coating TiO 2 on the glass fiber plate as a carrier by adopting a vacuum impregnation method, taking K 2CO3 as an active component raw material on the carrier, modifying the active component raw material by taking PEG as an auxiliary agent when the active component raw material is loaded, and calcining.
2. A glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to claim 1, characterized in that: the loading of the active component is 1-10 wt.%, and the content of the auxiliary agent PEG is 0.5-8 wt.%.
3. A glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to claim 1, characterized in that: the active component K 2CO3 accounts for 4% of the mass of the mixed material, and the auxiliary agent PEG accounts for 4% of the mass of the mixed material.
4. A glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to any one of claims 1-3, wherein: the specific surface area of the TiO 2 carrier is not less than 300m 2/g.
5. A glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to any one of claims 1-3, wherein: the glass fiber board is of a corrugated plate structure.
6. A method for preparing a glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to any one of claims 1 to 5, comprising the following steps:
(1) Dissolving K 2CO3 powder and PEG in a proper amount of distilled water according to the mass ratio requirement to obtain a mixed solution;
(2) Adding TiO 2 powder into the mixed solution in the step (1), and uniformly stirring and mixing;
(3) Continuously adding carboxymethyl cellulose, polyethylene oxide and glass fiber into the mixed solution, and uniformly stirring and mixing;
(4) Continuously adding ammonia water into the mixed solution to adjust the pH value of the mixed material, and preparing the mixed material with the solid content of 30-65 wt%;
(5) And (3) sealing and ageing the obtained mixture for a certain time, uniformly coating the mixture on a corrugated glass fiber board by adopting a vacuum impregnation method, and drying and calcining the mixture to obtain the titanium dioxide supported K 2CO3/PEG carbonyl sulfide hydrolysis catalyst.
7. The method for preparing the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to claim 6, which is characterized in that: in the step (4), the pH value of the mixed material is adjusted to 8-10.
8. The method for preparing the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to claim 7, which is characterized in that: the corrugated glass fiber board is prepared by adopting glass fiber paper with the thickness of 0.5-0.8 mm as a base material and adopting corrugated paper preparation technology for the glass fiber paper.
9. The method for preparing the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to any one of claims 6 to 8, wherein: in the step (5), the vacuum degree of the vacuum impregnation method is-0.08 MPa, the drying temperature is 50-80 ℃, the calcining temperature is 450-550 ℃ and the calcining time is 6-8 h.
10. The method for preparing the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to any one of claims 6 to 8, wherein: in the step (3), the mass ratio of the carboxymethyl cellulose to the mixed material is 0.8-1.5%, and the mass ratio of the polyethylene oxide to the mixed material is 0.1-0.3%.
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| FR2792547A1 (en) * | 1999-04-23 | 2000-10-27 | Rhodia Chimie Sa | Composition useful as trap for nitrogen oxides emissions in exhaust gases is based on manganese and alkaline earth or rare earth element |
| CN113289602A (en) * | 2021-06-01 | 2021-08-24 | 清华大学 | Catalyst for carbonyl sulfide hydrolysis in blast furnace gas and preparation method and application thereof |
| CN113578329A (en) * | 2021-08-27 | 2021-11-02 | 江苏朗润环保科技有限公司 | Hydrolysis catalyst for removing carbonyl sulfide from blast furnace gas and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2792547A1 (en) * | 1999-04-23 | 2000-10-27 | Rhodia Chimie Sa | Composition useful as trap for nitrogen oxides emissions in exhaust gases is based on manganese and alkaline earth or rare earth element |
| CN113289602A (en) * | 2021-06-01 | 2021-08-24 | 清华大学 | Catalyst for carbonyl sulfide hydrolysis in blast furnace gas and preparation method and application thereof |
| CN113578329A (en) * | 2021-08-27 | 2021-11-02 | 江苏朗润环保科技有限公司 | Hydrolysis catalyst for removing carbonyl sulfide from blast furnace gas and preparation method thereof |
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