CN115672367A - 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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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000003054 catalyst Substances 0.000 title claims abstract description 173
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 68
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 68
- 239000003365 glass fiber Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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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 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, and adopts a vacuum impregnation method to coat TiO with large specific surface area on the glass fiber plate 2 As a carrier, and K is loaded on the carrier 2 CO 3 As an active component, PEG is used as an auxiliary agent for modification treatment when the active component is loaded. The catalyst of the invention is in the temperature range of 100-200 DEG CThe catalyst has higher activity of catalyzing and hydrolyzing COS in the enclosure, has stronger sulfur resistance stability, and can effectively prolong the service life of the catalyst; meanwhile, the size of pores and the size of the module of the catalyst can be adjusted to meet various working condition requirements, the reactor volume is smaller, the system resistance is lower, the amount of carriers and active components used by the catalyst module per unit volume is less, and the material 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 which has higher activity and sulfur resistance stability and is convenient for industrial forming and industrial application, and a preparation method thereof.
Background
Blast furnace gas is an important sulfur-containing pollutant emission source in China, and poses great threat to the atmospheric environment. Blast furnace gas produced by iron and steel smelting is a precious gas resource and can be applied to the subsequent process of iron and steel smelting or is connected to civil use. 22.4.2019, the department of ecological environment issued an opinion on promoting implementation of ultra-low emission in the steel industry, and steel enterprises formally entered the ultra-low emission era and required SO at the head of a sintering machine 2 The hourly mean value of the discharge concentration is not higher than 35mg/m 3 Exhaust SO of hot blast stove 2 The hour average value of the discharge concentration is not higher than 50mg/m 3 . Under the new requirement, the original blast furnace gas desulfurization process can not meet the conditions, so that the fine desulfurization before the combustion of the blast furnace gas is particularly important. In order to improve the sulfur removal effect of the gas, the sulfur-containing substance, carbonyl sulfide, in the blast furnace gas needs 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, economic operation and the like. The catalytic conversion of COS is the core in the indirect conversion absorption process. And thenMost of the water vapor required in the COS catalytic hydrolysis process is already in the feed gas, and no additional addition is needed; the reaction does not need a hydrogen source, so that the energy consumption is saved; side reactions are few; the price of the hydrolysis catalyst is relatively low, and the production cost is reduced. In the hydrolytic conversion process: catalytic conversion of COS by hydrolysis to H which is readily removable in conventional manner 2 S, finally achieving the fine desulfurization of blast furnace gas, the theory is matured day by day at home and abroad, and certain research results are obtained. Therefore, the fine desulfurization of blast furnace gas by using a hydrolysis catalysis method is the best choice for solving the problem.
At present, many scholars in China carry out related research. For example, the chinese invention with publication number cn201710119950.x discloses an alumina carbonyl sulfide hydrolysis catalyst and a preparation method thereof, the alumina carbonyl sulfide hydrolysis catalyst is γ -Al 2 O 3 The relative humidity of the catalyst is 14.3 percent, and the space velocity is 1.6 ten thousand h -1 COS concentration of 800mg/m 3 ，O 2 The concentration is 2 percent, the conversion rate of carbonyl sulfide is about 98 percent when the reaction temperature is 70 ℃, but the reaction can only last for about 10 hours, and the sulfur poisoning resistance and the stability are poor. Chinese patent with publication number CN201010551862.5 discloses a carbonyl sulfide hydrolysis catalyst, which comprises (a) 1-5% of alkali metal carbonate, alkaline earth metal oxide or mixture thereof, (b) 15-25% of rare earth oxide in total, and (c) 70-82% of alumina, and the catalyst has a wider reaction temperature range and a low applicable material space velocity, but also has the problem of poor sulfur poisoning resistance, wherein gamma-Al is used 2 O 3 As a carrier and La 2 O 3 As an active ingredient, na 2 CO 3 The granular catalyst prepared by solution impregnation has COS content of 100ppm 2 The molar ratio of O to COS is 10: 1, and the space velocity is 5000hr -1 O in the material 2 The catalyst activity was tested at 0.3 wt% indicating a COS conversion of about 90%.
For another example, chinese patent with publication No. CN 1331596C discloses a pharmaceutical composition comprising gamma-Al 2 O 3 COS hydrolysis catalyst with potassium oxalate as carrier and TiO 2 Or ZrO 2 Modifying, extruding to form 2-4 mm column catalyst with concentration of 2500mg/m 3 The removal effect of the COS can reach 95%, and the activity of the catalyst is only stabilized for about 8 hours. Chinese patent with publication No. CN 106824149B discloses a Ti-Si compound carbonyl sulfide hydrolysis catalyst, K is added 2 Dissolving O, soaking and loading in polystyrene microsphere, and calcining at 600 deg.C with COS concentration of 800mg/m 3 The removal efficiency of COS was about 99% at a reaction temperature of 70 ℃, but the active component was rapidly lost by only 12 hours. Meanwhile, the two granular and columnar catalysts are in a stacked state in the using process, the using efficiency of the catalysts is low, ash is not easy to remove, and simultaneously, sulfate generated by reaction is easy to accumulate on the surfaces of the catalysts to cover active sites, so that the activity of the catalysts is reduced.
Chinese invention with publication No. CN 111432924A discloses a carbonyl sulfide hydrolysis catalyst of barium compound loaded on titanium dioxide and a preparation method thereof, wherein barium compound with the conversion of barium oxide being 4wt% is loaded on titanium dioxide (TiO) 2 ) The catalyst is formed by extrusion molding of a honeycomb shape by using anatase type titanium dioxide as a carrier, but the specific surface area of the catalyst is relatively small, the reactant export rate is relatively slow, the activity of the catalyst is poor, and the test result shows that: controlling airspeed 12000h -1 The concentration of COS is 2300ppm, the conversion rate of COS is 62% at the reaction temperature of 150 ℃, about 84% at the reaction temperature of 200 ℃, about 90% at the reaction temperature of 250 ℃, about 92% at the reaction temperature of 300 ℃, and the optimal activity temperature of the catalyst is high and the window is narrow. In addition, use of K 2 O modified TiO 2 The barium oxide-supported honeycomb catalyst showed K 2 The addition of O increased the catalyst activity, but when the reaction temperature was above 250 ℃ the catalyst activity decreased with increasing temperature, with a decrease of about 4% at 300 ℃ compared to 250 ℃, indicating that K is 2 The addition of O reduces the stability of its basic site.
In conclusion, the above formula is gamma-Al 2 O 3 The low-temperature catalytic activity of the supported COS hydrolysis catalyst needs to be improved, and the problems of poor stability and poor sulfur poisoning resistance exist generally. In addition, it is now commercially availableWith gamma-Al 2 O 3 The COS hydrolysis catalyst serving as a carrier is granular or columnar, the operation airspeed is low, the loading operation resistance is high, the occupied area is large, the installation is complex, ash is not easy to remove, and fly ash and sulfate generated by reaction are easy to cover the surface of the catalyst to cause inactivation of the catalyst. With TiO as a carrier 2 The sulfur resistance of COS hydrolysis is improved by the supported catalyst, but the specific surface area is relatively small (generally about 50-60 m) 2 The concentration of the sulfate is not favorable for smooth discharge of reaction products, and sulfate is easy to deposit and adhere to the surface of the catalyst, so that the stability of the catalyst in long-term operation is poor. Therefore, research and development of a COS hydrolysis catalyst with high catalytic activity, sulfur resistance and strong alkaline site stability have important theoretical significance and engineering application value for promoting blast furnace gas fine desulfurization.
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 within the temperature range of 100-200 ℃, has stronger sulfur resistance stability, and can effectively prolong the service life of the catalyst.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
in order to achieve the 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, and TiO with large specific surface area is coated on the glass fiber plate 2 As a carrier, and K is loaded on the carrier 2 CO 3 As an active component, PEG is used as an auxiliary agent for modification treatment when the active component is loaded.
The invention uses TiO with large specific surface area 2 As a carrier, PEG is added as an auxiliary agent when active components are loaded simultaneouslyIs modified so as to effectively improve TiO 2 The pore structure on the surface forms a large amount of step pore structures, which is beneficial to smoothly guiding out reaction products, can effectively inhibit the attachment of sulfate on the surface of the hydrolysis catalytic catalyst, and simultaneously can reduce the surface energy of active component crystal grain nucleation, inhibit the flocculation of particles and the aggregation growth of crystal grains, uniformly disperse the active components on a carrier, enhance the alkaline sites on the surface of the catalyst, provide good conditions for the adsorption and conversion of COS on the surface of the catalyst, and further obtain higher catalyst activity. In addition, the stepped pore structure of the catalyst is beneficial to the uniform distribution of alkaline ions, so that the thermal stability of active sites is improved.
TiO with large specific surface area 2 The calcination has certain shrinkage, the honeycomb type forming catalyst can not be prepared generally by adopting the traditional extrusion forming process, but the invention takes the glass fiber board as the base material and adopts K as the material 2 CO 3 -PEG/TiO 2 The catalyst is coated on the surface of a glass fiber plate, so that on one hand, the special pore characteristics of the catalyst are effectively retained, and the number of active sites on the surface of the catalyst and the sulfur resistance stability in the industrial forming process are ensured; on the other hand, the catalyst can ensure better mechanical strength and corrosion resistance, can adjust the size of pores and the size of a catalyst module according to actual conditions, is suitable for different working conditions, and improves the reproducibility and the stability of the catalyst. Compared with the extrusion-molded honeycomb catalyst, the amount of the catalyst can be reduced by about 250-300 kg per cubic meter, the utilization efficiency of the catalyst can be effectively improved by coating the glass fiber plate type catalyst, and the cost is greatly saved.
Furthermore, the loading amount of the active component is 1-10 wt.%, and the content of the auxiliary agent PEG is 0.5-8 wt.%.
Furthermore, an active component K 2 CO 3 The PEG additive accounts for 4 percent of the mass ratio of the mixed material, and the PEG additive accounts for 4 percent of the mass ratio of the mixed material.
Further, the TiO is 2 The specific surface area of the carrier is not less than 300m 2 /g, and the surface is distributed with a step pore structure, tiO of large specific surface 2 And H 2 The adsorption binding energy of S is relatively low, and the catalyst is realized to containHas high sulfur poisoning resistance under oxygen atmosphere.
Further, the glass fiber plate is of a corrugated plate structure.
The invention relates to a preparation method of a glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst, which comprises the following steps:
(1) Will K 2 CO 3 Dissolving the powder and PEG in a proper amount of distilled water according to the mass proportion requirement to obtain a mixed solution;
(2) Adding TiO into the mixed solution in the step (1) 2 Stirring and mixing the powder evenly;
(3) Continuously adding the carboxymethyl cellulose, the polyoxyethylene and the glass fiber into the mixed solution, and stirring and mixing uniformly, thereby being beneficial to ensuring that the TiO is 2 The combination firmness of the carrier and the corrugated glass fiber plate prevents the carrier from falling off and improves the overall strength of the catalyst;
(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.%; in the forming process, acidic substances brought into the catalyst during preparation can be eliminated by ammonia water impregnation, and alkaline sites on the surface of the catalyst are ensured.
(5) Sealing and aging the obtained mixed material for a certain time, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, drying and calcining to obtain the titanium dioxide loaded K 2 CO 3 The PEG carbonyl sulfide hydrolysis catalyst has the advantages that the obtained glass fiber plate forming catalyst has small running resistance, low energy consumption and convenient ash removal, and the generated sulfate substance is not easy to attach to the surface of the catalyst, so that the service life of the catalyst can be greatly prolonged.
Furthermore, the pH value of the mixed material is adjusted to 8-10 in the step (4).
Furthermore, the corrugated glass fiber board is prepared by taking glass fiber paper with the thickness of 0.5-0.8 mm as a base material and using corrugated paper as the base material.
Furthermore, 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.
Furthermore, 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 polyoxyethylene to the mixed material is 0.1-0.3%.
In summary, compared with the prior art, the invention has the beneficial effects that:
(1) The invention uses TiO with large specific surface area 2 The catalyst is a carrier and modified by combining PEG, has a developed stepped pore structure and a higher specific surface area, can ensure effective contact of reactants and the catalyst and smooth export of reaction products, and has better oxidation resistance, 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 the micropores of the glass fiber and be uniformly attached to the inner surfaces of the micropores, so that the number of effective active sites is increased, and the catalyst has higher activity for catalyzing and hydrolyzing COS and stronger catalytic stability within the temperature range of 100-200 ℃.
(2) The invention takes a glass fiber board as a substrate and carries TiO with active components 2 The glass fiber plate catalyst is convenient for industrial filling and active regeneration compared with common granular catalysts and columnar catalysts, has high effective utilization rate and excellent corrosion resistance, and can enable limited components in the catalyst to efficiently participate in the hydrolysis conversion process of carbonyl sulfide. Furthermore, the glass fiber plate is processed into a corrugated plate structure, so that the loading rate and the catalytic effect of the catalytic components are further improved.
(3) The invention relates to a preparation method of a glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst, which is characterized in that K is added 2 CO 3 When the active component is loaded on the carrier, a certain content of PEG is added to effectively improve TiO 2 The pore structure on the surface forms a large amount of step pore structures, thereby being beneficial to improving the catalyst activity, the catalytic stability and the sulfur poisoning resistance of the catalyst; and applying K by coating 2 CO 3 -PEG/TiO 2 Loaded onto the surface of a glass fibre sheetThe method effectively maintains the specific pore characteristics of the catalyst, ensures the number of active sites on the surface of the catalyst and the stability of sulfur resistance in the industrial forming process, and can effectively improve the utilization efficiency of the catalyst and reduce the using amount of the catalyst.
(4) The preparation method of the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst is simple, the glass fiber paper is used as a base material, the base material is shaped at high temperature and pressed into a corrugated plate-shaped structure, catalyst carriers and catalyst module sizes with various pore sizes can be prepared by adjusting a mould, the catalyst carrier and the catalyst module are suitable for different working conditions, 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 structural diagram of a catalyst obtained by the present invention;
FIG. 2 shows the catalyst obtained in example 1 of the present invention and a conventional catalyst (K) 2 O/Al 2 O 3 ) CO of 2 -TPD characterization comparison;
FIG. 3 is an XRD spectrum of the catalyst obtained in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
first, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water, and weighing K 2 CO 3 The mass percent of the auxiliary agent PEG in the total catalyst is 4%, the mass percent of the auxiliary agent PEG in the total catalyst is weighed to be 4%, and then TiO in a large proportion table is added 2 (specific surface area 300 m) 2 The powder is stirred for 1 hour simultaneously to be mixed evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 8, and adjusting the solid content of the mixed material to be 40%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, after the mixture is sealed and aged for 48 hours, the mixture is evenly coated on a corrugated glass fiber board prepared by the corrugated paper preparation technology by adopting a vacuum impregnation method, dried at the constant temperature of 60 ℃, and calcined at the temperature of 500 ℃ for 8 hours to obtain the titanium dioxide load K with large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 2
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
firstly, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water, and weighing K 2 CO 3 Accounting for 4 percent of the total catalyst mass, weighing the auxiliary agent PEG accounting for 4 percent of the total catalyst mass, and then adding TiO with a large proportion table 2 Stirring the powder for 1h simultaneously to mix the powder evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 8, and adjusting the solid content of the mixed material to be 50%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, 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 ℃, calcining the dried mixed material at a temperature of 500 ℃ for 8 hours to obtain titanium dioxide load K with a large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 3
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
first, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water to obtain K 2 CO 3 Accounting for 4 percent of the total catalyst mass percent, and weighing the auxiliary agent PEG accounting for the total catalyst massThe percentage is 4%, then TiO with a large scale is added 2 Stirring the powder for 1h simultaneously to mix the powder evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 8, and adjusting the solid content of the mixed material to be 60%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, 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 ℃, calcining the dried mixed material at a temperature of 500 ℃ for 8 hours to obtain titanium dioxide load K with a large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
EXAMPLE 4
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
first, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water to obtain K 2 CO 3 Accounting for 2 percent of the total catalyst by mass, weighing the auxiliary agent PEG accounting for 4 percent of the total catalyst by mass, and then adding TiO with a large proportion table 2 Stirring the powder for 1h simultaneously to mix the powder evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 8, and adjusting the solid content of the mixed material to be 40%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, after the mixture is sealed and aged for 48 hours, the mixture is evenly coated on a corrugated glass fiber board by adopting a vacuum impregnation method, after being dried at the constant temperature of 50 ℃, the mixture is calcined for 6 hours at the temperature of 450 ℃ to obtain the titanium dioxide load K with large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 5
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
firstly, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water to obtain K 2 CO 3 Accounting for 6 percent of the total catalyst by mass, weighing the auxiliary agent PEG accounting for 4 percent of the total catalyst by mass, and then adding TiO with a large specific surface 2 Stirring the powder for 1 hour to mix the powder evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour 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 mass ratio of the CMC to the mixed material is 0.8%, and the mass ratio of the PEO to the mixed material is 0.1%;
thirdly, after the mixture is sealed and aged for 48 hours, the mixture is evenly coated on a corrugated glass fiber board by adopting a vacuum impregnation method, after drying at the constant temperature of 60 ℃, the mixture is calcined for 7 hours at the temperature of 550 ℃, and the titanium dioxide load K with large specific surface is obtained 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 6
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
first, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water to obtain K 2 CO 3 Accounting for 8 percent of the total catalyst by mass, weighing the auxiliary agent PEG accounting for 4 percent of the total catalyst by mass, and then adding TiO with a large specific surface 2 Stirring the powder for 1h simultaneously to mix the powder evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 9, and adjusting the solid content of the mixed material to be 65%, wherein the mass ratio of the CMC to the mixed material is 1.5%, and the mass ratio of the PEO to the mixed material is 0.3%;
thirdly, after the mixture is sealed and aged for 48 hours, the mixture is evenly coated on a wave by adopting a vacuum impregnation methodDrying the textured glass fiber board at the constant temperature of 80 ℃, calcining the dried textured glass fiber board at the temperature of 480 ℃ for 8 hours to obtain titanium dioxide loaded K with large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 7
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
firstly, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water, and weighing K 2 CO 3 Accounting for 10 percent of the total catalyst by mass, weighing the auxiliary agent PEG accounting for 4 percent of the total catalyst by mass, and then adding TiO with a large proportion table 2 Stirring the powder for 1 hour to mix the powder evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 9, and adjusting the solid content of the mixed material to be 40%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, 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 ℃, calcining the dried mixed material at a temperature of 500 ℃ for 8 hours to obtain titanium dioxide load K with a large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 8
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
first, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water to obtain K 2 CO 3 Accounting for 4 percent of the total catalyst mass, weighing the auxiliary agent PEG accounting for 2 percent of the total catalyst mass, and then adding TiO with a large specific surface 2 Stirring the powder for 1 hour to mix the powder evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 8, and adjusting the solid content of the mixed material to be 40%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, 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 ℃, calcining the dried mixed material at a temperature of 510 ℃ for 7.5 hours to obtain titanium dioxide loaded K with a large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 9
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
firstly, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water, and weighing K 2 CO 3 Accounting for 4 percent of the total catalyst mass, weighing the auxiliary agent PEG accounting for 6 percent of the total catalyst mass, and then adding TiO with a large specific surface 2 Stirring the powder for 1.5h simultaneously to mix the powder evenly;
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 be 9, and adjusting the solid content of the mixed material to be 40%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, 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 ℃, calcining the dried mixed material at a temperature of 500 ℃ for 8 hours to obtain titanium dioxide load K with a large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 10
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
firstly, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water to obtain K 2 CO 3 Accounting for 4 percent of the total catalyst mass percentage, and weighing the auxiliary agent PEG accounting for the total4 percent of catalyst by mass percent, and then TiO with large specific surface is added 2 Stirring the powder for 50min to mix uniformly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 8, and adjusting the solid content of the mixed material to be 40%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, sealing and aging 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 ℃, calcining the dried mixed material at a temperature of 450 ℃ for 8 hours to obtain titanium dioxide load K with a large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Example 11
The preparation process of the blast furnace gas carbonyl sulfide (COS) hydrolysis catalyst of the embodiment includes the following steps:
first, weighing a proper amount of K 2 CO 3 Dissolving with PEG and distilled water, and weighing K 2 CO 3 Accounting for 4 percent of the total catalyst mass, weighing the auxiliary agent PEG accounting for 4 percent of the total catalyst mass, and then adding TiO with large specific surface 2 Stirring the powder for 1h simultaneously to mix the powder evenly;
secondly, adding carboxymethyl cellulose (CMC), polyethylene oxide (PEO) and glass fiber, stirring for 1 hour to uniformly mix, then adding a proper amount of ammonia water, mixing and stirring, adjusting the pH value of the mixed material to be 8-10, and adjusting the solid content of the mixed material to be 40%, wherein the mass ratio of the CMC to the mixed material is 1%, and the mass ratio of the PEO to the mixed material is 0.2%;
thirdly, 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 ℃, calcining the dried mixed material at a temperature of 550 ℃ for 8 hours to obtain titanium dioxide load K with a large specific surface 2 CO 3 Carbonyl sulfide (COS) hydrolysis catalyst.
Activity test of the catalyst:
the coated glass fiber plate catalysts prepared in examples 1 to 11 (as shown in fig. 1) were prepared into specifications of 20mm × 20mm × 30mm, and the catalysts were loaded into a fixed bed reactor to test their COS hydrolysis conversion fine desulfurization activity. In the test process, nitrogen is used as carrier gas, and the airspeed is controlled to be 6000h -1 Controlling the concentration of the imported carbonyl sulfide to be 1500mg/m 3 ，O 2 The volume concentration of (2) was 0.5%, the rate of entry of steam into the reactor was controlled at 0.45g/h, the test temperature was in the range of 100 to 200 ℃ and the results are shown in Table 1.
TABLE 1 desulfurization Activity of catalysts in catalyst preparation examples 1 to 11
Activity testing of the catalysts in Table 1 the data of the examples show that TiO is present in a large scale 2 On the active substance K 2 CO 3 And shows excellent hydrolysis catalytic activity when the auxiliary agent PEG is added, and the activity is shown in K 2 CO 3 When the supported amount of PEG is 4wt.% or more, the activity is excellent in the temperature range of 100-200 ℃, and the hydrolysis conversion rate of the catalyst in the embodiment 1 can be more than 96% for 23 hours at 100 ℃, so that the catalyst shows excellent stability; FIG. 2 shows CO for the commercial catalyst and the catalyst of example 1 2 The results of TPD characterization show that the catalyst COS hydrolysis conversion in example 1 has a main weak alkaline site-OH (about 130 ℃) which is obviously better than that of the catalyst of the same enterprise (K-gamma-Al) 2 O 3 ) Strong; FIG. 3 is the XRD spectrum of example 1, which shows that the diffraction peak intensity of the catalyst is well matched with that of TiO 2 The height of a diffraction peak of the crystal is high, and the diffraction peak is sharp, which indicates that the obtained catalyst has good crystallization, and no active substance K is detected 2 CO 3 Diffraction peak of (a), which shows that the active component is distributed more uniformly in TiO with large specific surface 2 On a carrier. In examples 1 to 3, when the solid content of the catalyst mixture was 40wt.%The catalyst activity is best; the activity test data for examples 1, 10 and 11 show that the calcination temperature conditions of 450 to 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, continuity and stability, has good oxidation resistance to oxygen atmosphere, has high industrial forming feasibility, and can completely meet the requirement 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 uses glass fiber board as base material, and TiO is coated on the glass fiber board by vacuum impregnation method 2 As a carrier, and K is loaded on the carrier 2 CO 3 As an active component, PEG is used as an auxiliary agent for modification treatment when the active component is loaded.
2. The fiberglass corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst as set forth in claim 1, characterized in that: the loading amount of the active component is 1-10 wt.%, and the content of the auxiliary agent PEG is 0.5-8 wt.%.
3. The fiberglass corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst as set forth in claim 1, characterized in that: active ingredient K 2 CO 3 Accounting for 4 percent of the mass ratio of the mixed materials, the auxiliary agent PEG accounts for 4% of the mass ratio of the mixed material.
4. The fiberglass corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to any one of claims 1 to 3, wherein: the TiO is 2 The specific surface area of the carrier is not less than 300m 2 And/g, and a step hole structure is distributed on the surface of the material.
5. The fiberglass corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to any one of claims 1 to 3, wherein: the glass fiber plate is of a corrugated plate structure.
6. A method for preparing the glass fiber corrugated plate type blast furnace gas carbonyl sulfide hydrolysis catalyst according to any one of claims 1 to 5, which comprises the following steps:
(1) Will K 2 CO 3 Dissolving the powder and PEG in a proper amount of distilled water according to the mass ratio to obtain a mixed solution;
(2) Adding TiO into the mixed solution in the step (1) 2 Stirring and mixing the powder evenly;
(3) Continuously adding the carboxymethyl cellulose, the polyethylene oxide and the glass fiber into the mixed solution, and stirring and mixing uniformly;
(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) Sealing and aging the obtained mixed material for a certain time, uniformly coating the mixed material on a corrugated glass fiber board by adopting a vacuum impregnation method, and then drying and calcining to obtain the titanium dioxide loaded K 2 CO 3 PEG carbonyl sulfide hydrolysis catalyst.
7. The method for preparing the carbonyl sulfide hydrolysis catalyst for the glass fiber corrugated plate type blast furnace gas according to claim 6, wherein the carbonyl sulfide hydrolysis catalyst comprises: and (4) adjusting the pH value of the mixed material to 8-10.
8. The method for preparing the carbonyl sulfide hydrolysis catalyst for the glass fiber corrugated plate type blast furnace gas according to claim 7, wherein the method comprises the following steps: the corrugated glass fiber board is prepared by taking glass fiber paper with the thickness of 0.5-0.8 mm as a base material and using corrugated paper preparation technology to prepare the glass fiber paper.
9. The method for preparing a 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 a 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 polyoxyethylene 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 |
| US20170056855A1 (en) * | 2014-02-21 | 2017-03-02 | Huntsman P&A Germany Gmbh | TiO2 based catalyst precursor material, production thereof and use thereof |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20170056855A1 (en) * | 2014-02-21 | 2017-03-02 | Huntsman P&A Germany Gmbh | TiO2 based catalyst precursor material, production thereof and use thereof |
| 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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