CN113908839A - Preparation method of normal-temperature desulfurizing agent - Google Patents

Preparation method of normal-temperature desulfurizing agent Download PDF

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Publication number
CN113908839A
CN113908839A CN202111262654.8A CN202111262654A CN113908839A CN 113908839 A CN113908839 A CN 113908839A CN 202111262654 A CN202111262654 A CN 202111262654A CN 113908839 A CN113908839 A CN 113908839A
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normal
desulfurizer
desulfurizing agent
gas
temperature
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王贵祥
陆彬
陈卓
周可可
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CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
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CNBM Bengbu Design and Research Institute for Glass Industry Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention relates to a preparation method of a normal-temperature desulfurizer, which is characterized by comprising the following steps: (1) according to Ni2+：Zn2+In a molar ratio of (1: 1) to (6: 1), (Ni)2++Zn2+）：Al3+Dissolving soluble nickel salt, zinc salt and aluminum salt in deionized water at a molar ratio of 2: 1-4: 1, and stirring for dissolving to obtain a solution A; (2) dissolving a precipitator in deionized water to obtain a solution B with the concentration of 0.1-0.5 mol/L; (3) mixing the solution A and the solution B according to a volume ratio of 5: 1-2: 1, then placing the mixed solution of A, B in a hydrothermal kettle for reaction at 80-150 ℃ for 8-24 h to obtain a crude product; (4) and (4) carrying out suction filtration, washing, drying and calcining on the crude product. The invention has the advantages that: the preparation method is simple, easy to operate and easy for industrial amplification production; the hexagonal plate of the normal temperature desulfurizer contains rich mesoporous structures and has the mesoporous structures at the temperature of 10-100 DEG CHigh catalytic performance.

Description

Preparation method of normal-temperature desulfurizing agent
Technical Field
The invention belongs to the field of preparation of environment-friendly materials, and relates to a preparation method of a normal-temperature desulfurizing agent.
Background
At present, a certain amount of H is inevitably generated in the production process of industries such as natural gas and petroleum exploitation, coking, chemical fertilizers, rubber, copper indium gallium selenide thin-film solar cells and the like2S gasTail gas of the body. Due to H2S gas is extremely toxic and corrosive, can not only corrode equipment, but also seriously pollute air and harm human health. Thus, contains H2The tail gas of the S gas can be discharged after strict desulfurization and purification treatment.
Because the dry desulfurization has the advantages of high desulfurization efficiency, convenient operation, small solid waste amount and the like, the dry desulfurization gradually occupies most markets of the desulfurization industry. The most important in dry desulfurization is the development and preparation of the desulfurizing agent, and the performance of the desulfurizing agent determines the final desulfurization efficiency.
The patent publication No. CN106867593B discloses a preparation method of a Zn-Al hydrotalcite-based medium-high temperature coal gas desulfurizer; the preparation process of the desulfurizer comprises the steps of firstly synthesizing a Zn-Al hydrotalcite precursor by microwave with a mixed salt solution, then obtaining Zn-Al hydrotalcite through microwave hydrothermal crystallization reaction, drying and calcining to obtain a desulfurization active component Zn-Al composite oxide, and then adding volcanic rock particles for molding and roasting; the preparation process of the microwave synthesis method is complex and is not beneficial to industrial scale-up production. In addition, the desulfurizer is mainly applied to the field of medium-high temperature gas purification, the temperature required during desulfurization is 400-600 ℃, and the desulfurizer is not suitable for normal-temperature desulfurization and purification treatment of industrial tail gas. In view of this, there is an urgent need for the development of a desulfurizing agent having a simple preparation method and excellent desulfurization performance at normal temperature.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a simple preparation method of a normal-temperature (10-100 ℃) desulfurizing agent, so that H in tail gas is avoided2The S gas corrodes production equipment and pollutes the environment, and the green environmental protection of industrial production is realized.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a normal-temperature desulfurizing agent is characterized by comprising the following steps:
(1) according to Ni2+：Zn2+In a molar ratio of (1: 1) to (6: 1), (Ni)2++Zn2+）：Al3+The molar ratio of the nickel salt to the zinc salt is 2: 1-4: 1Dissolving aluminum salt in deionized water, and stirring for dissolving to obtain a solution A;
(2) dissolving a precipitator in deionized water to obtain a solution B with the concentration of 0.1-0.5 mol/L;
(3) mixing the solution A and the solution B according to a volume ratio of 5: 1-2: 1, then placing the mixed solution of A, B in a hydrothermal kettle for reaction at 80-150 ℃ for 8-24 h to obtain a crude product;
(4) and (3) carrying out suction filtration on the crude product obtained in the step (3), washing for 1-3 times, drying for 10-24 h at the temperature of 60-120 ℃, and calcining for 8-16 h at the temperature of 250-700 ℃ to obtain the normal-temperature desulfurizer.
Further, the soluble nickel salt is any one or combination of nickel nitrate, nickel chloride and nickel sulfate.
Further, the soluble zinc salt is any one or combination of zinc nitrate, zinc chloride and zinc sulfate.
Further, the soluble aluminum salt is any one or combination of aluminum nitrate, aluminum chloride and aluminum sulfate.
Further, the precipitant in step (2) is any one or combination of urea, sodium carbonate, hexamethylenetetramine, ammonia water and sodium bicarbonate.
Furthermore, the normal-temperature desulfurizing agent is regular in shape and hexagonal.
Normal-temperature desulfurizer for purifying H in tail gas2The method for S gas is characterized by comprising the following steps:
putting the normal temperature desulfurizer into a quartz reaction tube, and directly introducing H2S and N2Wherein N in the gas mixture2As carrier gas, reacting at normal temperature and normal pressure; detection of H in gas mixture inlet and outlet by gas chromatography2S gas concentration, as H in the tail gas outlet2When the S gas concentration reaches 1ppm, the desulfurizer is considered to be deactivated, the reaction is stopped, and the sulfur is determined, so that the normal temperature desulfurizer to H is calculated2The purification efficiency of S gas and the penetrating sulfur capacity of a desulfurizer.
The invention firstly prepares the Ni-Zn-Al-III by a hydrothermal methodThe method comprises the steps of preparing a hydrotalcite precursor (by changing the molar ratio of soluble nickel salt, zinc salt and aluminum salt, nickel-zinc-aluminum hydrotalcite precursor with different components and alkaline sites can be prepared), and calcining the hydrotalcite precursor at different temperatures to obtain a normal-temperature desulfurizer with excellent desulfurization performance (by calcining at different temperatures, active components (oxides of zinc and nickel) and AlO can be effectively adjustedxThe interaction force between the substrates, so as to obtain the normal temperature desulfurizer with high activity), and anions and water molecules between the laminates of the hydrotalcite precursor can gradually escape in the calcining process, so that the prepared desulfurizer contains more pore channel structures and larger specific surface area, which is crucial to improving the desulfurization performance of the desulfurizer. The normal-temperature desulfurizer prepared by the invention contains more alkaline sites, has larger specific surface area, and is beneficial to promoting H2S gas adsorption and active component dispersion degree improvement; meanwhile, the zinc oxide in the prepared desulfurizer has small particle size and more exposed active sites, so that H in tail gas can be removed at normal temperature (10-100 ℃)2The S gas is efficiently purified from 500-2000 ppm to 10-50 ppb.
Compared with the prior art, the invention has the following advantages: the preparation method is simple, easy to operate and easy for industrial amplification production; firstly, preparing nickel-zinc-aluminum ternary hydrotalcite as a precursor by a hydrothermal method, and then calcining; the prepared normal-temperature desulfurizer contains rich alkaline sites, high dispersion degree of active components and rich active oxygen vacancies, so that the desulfurizer has high catalytic performance (can remove H in tail gas) at 10-100 DEG C2S gas is efficiently purified from 500-2000 ppm to 10-50 ppb); the normal-temperature desulfurizer has a regular hexagonal sheet structure, and is favorable for exploring the change condition of the desulfurizer before and after reaction and the deposition of sulfur on the surface of the desulfurizer; in addition, the hexagonal plate of the normal temperature desulfurizer contains rich mesoporous structures, which is beneficial to the diffusion of gas and the improvement of the desulfurization performance.
Drawings
FIG. 1 is a NiZn prepared in example 12An X-ray diffraction pattern of the Al-LDH hydrotalcite precursor;
FIG. 2 is a NiZn prepared in example 12Al-LDH hydrotalciteSEM photograph of the precursor;
FIG. 3 is an SEM photograph of the ambient temperature desulfurization agent 1 prepared in example 1;
FIG. 4 shows Ni prepared in example 41Zn1SEM photograph of Al-LDH hydrotalcite precursor;
FIG. 5 is an SEM photograph of the ambient temperature desulfurization agent 4 prepared in example 4.
Detailed Description
A preparation method of a normal-temperature desulfurizing agent comprises the following specific implementation steps:
example 1
A normal-temp desulfurizing agent is prepared from NiZn2Calcining Al-LDH precursor at 350 deg.C for 12 hr to obtain Ni2+And Zn2+In a molar ratio of 1:2, (Ni)2++Zn2+) And Al3+Is 3: 1.
The preparation method of the normal-temperature desulfurizing agent comprises the following specific preparation steps:
(1) 0.6 mmol nickel nitrate, 1.2 mmol zinc nitrate and 0.6 mmol aluminum nitrate were dissolved in 30 mL deionized water to obtain Ni2+Concentration of 20 mmol/L, Zn2+Concentration of 40 mmol/L, Al3+Solution A with the concentration of 20 mmol/L;
(2) dissolving 15 mmol of precipitator urea in 40 mL of deionized water to obtain a solution B with the concentration of the precipitator being 0.375 mol/L;
(3) mixing the solution A and the solution B obtained in the steps (1) and (2), then placing the mixed solution of A, B in a hydrothermal kettle for reaction, carrying out hydrothermal reaction for 10h at 120 ℃, and obtaining a crude product after the reaction is finished;
(4) and (3) filtering the crude product obtained in the step (3), using deionized water for 3 times to obtain a filtered hydrothermal product, drying the hydrothermal product at 80 ℃ for 12 hours, and calcining the dried sample at 350 ℃ for 12 hours to obtain the normal-temperature desulfurizer 1.
Example 2
A normal temperature desulfurizer consisting of Ni1.5Zn1.5Calcining Al-LDH precursor at 350 deg.C for 12 hr to obtain Ni2+And Zn2+In a molar ratio of 1:1, (Ni)2++Zn2+) And Al3+Is 3: 1.
The preparation of a Normal temperature desulfurizing agent described above was carried out in accordance with example 1 except that 0.9 mmol of nickel nitrate and 0.9 mmol of zinc nitrate, Ni, were used in the step (1)2+And Zn2+The molar ratio is 1:1, and the prepared desulfurizer is marked as a normal-temperature desulfurizer 2.
Example 3
A normal temperature desulfurizer consisting of Ni1Zn3Calcining Al-LDH precursor at 500 deg.C for 10h to obtain Ni2+And Zn2 +In a molar ratio of 1:3, (Ni)2++Zn2+) And Al3+Is 4: 1.
The preparation steps of the normal temperature desulfurizer are referred to example 1, and the differences are only that 0.45 mmol of nickel chloride, 1.35 mmol of zinc sulfate and 0.45 mmol of aluminum nitrate are used in step (1), 20 mmol of hexamethylenetetramine is used in step (2), the concentration of a precipitator is 0.5mol/L, the reaction temperature in step (3) is 130 ℃, the calcination is carried out at 500 ℃ for 10 hours in step (4), and the prepared desulfurizer is marked as normal temperature desulfurizer 3.
Example 4
A normal temperature desulfurizer consisting of Ni1Zn1Calcining Al-LDH precursor at 400 deg.C for 15 hr to obtain Ni2+And Zn2 +In a molar ratio of 1:1, (Ni)2++Zn2+) And Al3+In a molar ratio of 2: 1.
Referring to example 1, the preparation steps of the normal temperature desulfurizer are different in that 0.6 mmol of zinc nitrate is used in step (1), 16 mmol of sodium bicarbonate is used in step (2), the concentration of the precipitant is 0.4 mol/L, the reaction temperature in step (4) is 90 ℃, the reaction time is 16h, the dried hydrothermal product is calcined at 400 ℃ for 15h, and the prepared desulfurizer is marked as normal temperature desulfurizer 4.
Example 5
A normal temperature desulfurizer consisting of Ni1Zn5Calcining Al-LDH precursor at 600 deg.C for 8 hr to obtain Ni2+And Zn2+In a molar ratio of 1:5, (Ni)2++Zn2+) And Al3+Is 3: 1.
Referring to example 1, the difference of the preparation steps of the normal temperature desulfurizer is that 0.3 mmol of nickel sulfate and 1.5 mmol of zinc sulfate are used in step (1), the reaction temperature in step (4) is 140 ℃, the reaction time is 12 hours, the dried hydrothermal product is calcined at 600 ℃ for 8 hours, and the prepared desulfurizer is marked as normal temperature desulfurizer 5.
(1) X-ray diffraction test
The phase of the prepared samples was characterized by an X-ray diffractometer of the X' Pert PRO MPD type, manufactured by analytical instruments of the Pasacaceae, the Netherlands (voltage and current during the sample testing were 40 kV and 40 mA, respectively).
(2) SEM test
The microstructure and structure of the prepared room temperature desulfurizing agent are characterized by a scanning electron microscope (SEM, JSM-7001F) produced by Japan Electron company.
(3) Desulfurization Performance test
Tabletting and crushing the prepared normal-temperature desulfurizer 1-5, respectively screening 0.3 g of 60-80-mesh normal-temperature desulfurizer, and placing the normal-temperature desulfurizer in a quartz reaction tube, wherein the bottom and the top of the desulfurizer are respectively filled with quartz wool, so that desulfurizer particles are prevented from entering a gas chromatograph along with gas to damage an instrument; then directly introducing H at normal temperature and normal pressure2S and N2Mixed gas (H in mixed gas)2Concentration of S gas is 1000 ppm), wherein N in the mixed gas2Is a carrier gas. In the performance test experiment process, the reaction temperature is kept at 25 ℃, and the flow rate of the mixed gas is set to be 100 mL/min; detection of H in gas mixture inlet and outlet by gas chromatography2S gas concentration, as H in the tail gas outlet2When the S gas concentration reaches 1ppm, the desulfurizer is considered to be deactivated, the reaction is stopped, and the sulfur is determined, so that the normal temperature desulfurizer to H is calculated2The purification efficiency of S gas and the penetrating sulfur capacity of a desulfurizer. The performance data of different normal temperature desulfurizing agents obtained by the experimental test are shown in table 1.
Figure DEST_PATH_IMAGE001
As can be seen from Table 1, the desulfurizing agents prepared in examples 1, 2, 3, 4 and 5 all have excellent desulfurizing performance, and H in the tail gas after the purification treatment has2The concentration of S gas is 15-22 ppb. In addition, sulfur determination tests are carried out on the reacted desulfurizer, and the normal-temperature desulfurizer prepared by the invention is found to have higher penetrating sulfur capacity (12.5-13.4%). The main reason is that the zinc-based desulfurizer derived from the nickel-zinc-aluminum hydrotalcite precursor has the advantages of high active component content, large specific surface area and the like.
FIG. 1 is a NiZn prepared in example 12X-ray diffraction pattern of Al-LDH hydrotalcite precursor. As a result of XRD test, we found that the product after hydrothermal reaction is indeed NiZn2Al-LDH, and the phase of the product is relatively pure, and no impurity phase is generated. FIG. 2 is a NiZn prepared in example 12SEM photograph of Al-LDH hydrotalcite precursor. According to SEM test results, the prepared hydrotalcite precursor is of a regular hexagonal nano flaky structure, the dispersibility of the hydrotalcite nano sheets is high, and the phenomenon of intercalation and stacking of the nano sheets is avoided. In order to further explore the micro-morphology of the desulfurizing agent prepared in example 1, the normal temperature desulfurizing agent 1 prepared in example 1 was subjected to SEM characterization, and the result is shown in FIG. 3. As can be seen from FIG. 3, NiZn2The hexagonal sheet structure of the Al-LDH hydrotalcite precursor is still kept after the calcination, and some mesoporous structures appear in the nanosheets, so that the prepared normal-temperature desulfurizing agent has a large specific surface area, which is beneficial to improving the desulfurization performance of the normal-temperature desulfurizing agent.
FIGS. 4 and 5 are Ni prepared in example 4, respectively1Zn1SEM photographs of Al-LDH hydrotalcite precursor and the corresponding normal temperature desulfurizing agent 4. According to the SEM characterization result, the molar ratio of nickel and zinc in the hydrotalcite precursor preparation process is changed, the morphology of the hydrotalcite precursor is hardly influenced, and the prepared hydrotalcite still has a hexagonal nano flaky structure. In addition, the normal temperature desulfurizer 4 prepared in example 4 is also a hexagonal nanosheet, and the nanosheet has some mesoporous structures, which is thatCaused by the escape of anions and water molecules between the hydrotalcite laminate during calcination.

Claims (9)

1. A preparation method of a normal-temperature desulfurizing agent is characterized by comprising the following steps:
(1) according to Ni2+：Zn2+In a molar ratio of (1: 1) to (6: 1), (Ni)2++Zn2+）：Al3+Dissolving soluble nickel salt, zinc salt and aluminum salt in deionized water at a molar ratio of 2: 1-4: 1, and stirring for dissolving to obtain a solution A;
(2) dissolving a precipitator in deionized water to obtain a solution B with the concentration of 0.1-0.5 mol/L;
(3) mixing the solution A and the solution B according to a volume ratio of 5: 1-2: 1, then placing the mixed solution of A, B in a hydrothermal kettle for reaction at 80-150 ℃ for 8-24 h to obtain a crude product;
(4) and (4) carrying out suction filtration, washing, drying and calcining on the crude product obtained in the step (3) to obtain the normal-temperature desulfurizer.
2. The method for preparing a normal temperature desulfurizing agent according to claim 1, wherein the method comprises the following steps: the soluble nickel salt is any one or combination of nickel nitrate, nickel chloride and nickel sulfate.
3. The method for preparing a normal temperature desulfurizing agent according to claim 1, wherein the method comprises the following steps: the soluble zinc salt is any one or combination of zinc nitrate, zinc chloride and zinc sulfate.
4. The method for preparing a normal temperature desulfurizing agent according to claim 1, wherein the method comprises the following steps: the soluble aluminum salt is any one or combination of aluminum nitrate, aluminum chloride and aluminum sulfate.
5. A method for preparing a normal temperature desulfurizing agent according to any one of claims 1 to 4, wherein: the precipitator in the step (2) is any one or combination of more of urea, sodium carbonate, hexamethylenetetramine, ammonia water and sodium bicarbonate.
6. The method for preparing a normal temperature desulfurizing agent according to claim 1, wherein the method comprises the following steps: the drying temperature is 60-120 ℃, and the drying time is 10-24 h.
7. The method for preparing a normal temperature desulfurizing agent according to claim 1, wherein the method comprises the following steps: the calcination temperature is 250-700 ℃, and the calcination time is 8-16 h.
8. The method for preparing a normal temperature desulfurizing agent according to claim 1, wherein the method comprises the following steps: the normal-temperature desulfurizing agent is regular in shape and hexagonal.
9. The normal-temperature desulfurizer prepared by the method of claim 1 is used for purifying H in tail gas2The method for S gas is characterized by comprising the following steps:
putting the normal temperature desulfurizer into a quartz reaction tube, and directly introducing H2S and N2Wherein N in the gas mixture2As carrier gas, reacting at normal temperature and normal pressure; detection of H in gas mixture inlet and outlet by gas chromatography2S gas concentration, as H in the tail gas outlet2When the S gas concentration reaches 1ppm, the desulfurizer is considered to be deactivated, the reaction is stopped, and the sulfur is determined, so that the normal temperature desulfurizer to H is calculated2The purification efficiency of S gas and the penetrating sulfur capacity of a desulfurizer.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117282436A (en) * 2023-11-23 2023-12-26 陕西驭腾化学控股发展有限公司 Blast furnace gas fine desulfurization hydrolysis catalyst and preparation method and application thereof

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CN104209084A (en) * 2013-06-05 2014-12-17 中国石油天然气股份有限公司 Claus tail gas SO2 sorbent and preparation and use thereof
CN106867593A (en) * 2017-03-15 2017-06-20 太原理工大学 A kind of preparation method of Zn Al houghites base high temperature gas desulfurizer
CN107626295A (en) * 2017-09-22 2018-01-26 昆明理工大学 A kind of preparation method for being used to remove the houghite catalyst of HCN and COS gases
CN109794251A (en) * 2019-01-07 2019-05-24 太原理工大学 A kind of method of the modified zinc-nickel aluminium cerium houghite precursor preparation hydrolytic catalyst of carbonyl sulfur of complexing agent

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Publication number Priority date Publication date Assignee Title
CN104209084A (en) * 2013-06-05 2014-12-17 中国石油天然气股份有限公司 Claus tail gas SO2 sorbent and preparation and use thereof
CN103691441A (en) * 2013-12-02 2014-04-02 湖南理工学院 Preparation method for photocatalytic material with strong adsorption and high visible light degradation of performance
CN106867593A (en) * 2017-03-15 2017-06-20 太原理工大学 A kind of preparation method of Zn Al houghites base high temperature gas desulfurizer
CN107626295A (en) * 2017-09-22 2018-01-26 昆明理工大学 A kind of preparation method for being used to remove the houghite catalyst of HCN and COS gases
CN109794251A (en) * 2019-01-07 2019-05-24 太原理工大学 A kind of method of the modified zinc-nickel aluminium cerium houghite precursor preparation hydrolytic catalyst of carbonyl sulfur of complexing agent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117282436A (en) * 2023-11-23 2023-12-26 陕西驭腾化学控股发展有限公司 Blast furnace gas fine desulfurization hydrolysis catalyst and preparation method and application thereof
CN117282436B (en) * 2023-11-23 2024-03-01 陕西驭腾化学控股发展有限公司 Blast furnace gas fine desulfurization hydrolysis catalyst and preparation method and application thereof

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Application publication date: 20220111