CN115301245A - Carbonyl sulfide hydrolysis catalyst with poisoning resistance and preparation method thereof - Google Patents

Carbonyl sulfide hydrolysis catalyst with poisoning resistance and preparation method thereof Download PDF

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CN115301245A
CN115301245A CN202211023463.0A CN202211023463A CN115301245A CN 115301245 A CN115301245 A CN 115301245A CN 202211023463 A CN202211023463 A CN 202211023463A CN 115301245 A CN115301245 A CN 115301245A
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cuceco
zif
carbonyl sulfide
salt
cerium
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王建国
孔祥宇
谢亮
秦景辉
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Zhejiang University of Technology ZJUT
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    • 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
    • B01J23/83—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 rare earths or actinides
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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Abstract

The invention discloses a carbonyl sulfide hydrolysis catalyst with anti-poisoning capability and a preparation method thereof, wherein the preparation method of the catalyst comprises the following four steps: firstly, quickly synthesizing ZIF-67 from cobalt metal salt and 2-methylimidazole at room temperature; secondly, mixing and dissolving ZIF-67 with cerium metal salt and copper metal salt to prepare CuCeCo-ZIF; the third step is to pyrolyze the CuCeCo-ZIF obtained in the first two steps to obtain CuCeCo 2 O 4 (ii) a The fourth step is to prepare the obtained CuCeCo 2 O 4 Calcining in a tubular furnace under hydrogen-containing atmosphere to obtain CuCeCo 2 O 4‑x The preparation is finished. The carbonyl sulfide hydrolysis catalyst prepared by the invention has high hydrolysis efficiency, is green and environment-friendly and is difficult to inactivate when being applied to the aspect of removing carbonyl sulfide in coal gasAnd the like, and has good application prospect.

Description

Carbonyl sulfide hydrolysis catalyst with poisoning resistance and preparation method thereof
Technical Field
The invention relates to the field of fine desulfurization and purification of coal gas, in particular to a carbonyl sulfide hydrolysis catalyst with poisoning resistance and a preparation method thereof.
Background
Coal gas is used as a byproduct of blast furnace ironmaking, has a high calorific value, and is generally conveyed to various workshops in factories at present to be used as fuel. The coal gas contains a large amount of sulfur-containing components, the most important is carbonyl sulfur, the carbonyl sulfur can be converted into sulfur dioxide after direct combustion and cannot reach the emission standard, secondary treatment is needed to meet the environmental protection requirement, and the prior art mainly carries out SCR (selective catalytic reduction) desulfurization purification technology on the sulfur dioxide generated after the coal gas is combusted, so that the sulfur component content is reduced. However, the method has the disadvantages that the amount of flue gas to be treated is large, and a desulphurization device is built in each workshop needing coal gas, so that the occupied area is large and the cost is high.
Therefore, carbonyl sulfide in the coal gas is treated at the source to realize source fine desulfurization, the coal gas treated by the method is only 60% of the total amount of the flue gas generated after combustion, in addition, only one desulfurization device is required to be built for source treatment, and sulfur dioxide generated after the desulfurized coal gas is conveyed to each workshop and is combusted can reach the standard of direct emission without secondary treatment.
Disclosure of Invention
The invention aims to overcome the defects of easy inactivation, low efficiency and higher reaction temperature of carbonyl sulfide hydrolysis catalysts in the prior art, thereby providing a carbonyl sulfide hydrolysis catalyst with low-temperature hydrolysis, high conversion rate, difficult inactivation, good stability and poisoning resistance and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the carbonyl sulfide hydrolysis catalyst with poisoning resistance comprises the following steps:
the first step is as follows: cobalt salt and imidazole compound are reacted rapidly at room temperature to synthesize a metal organic framework material ZIF-67;
the second step: mixing and dissolving ZIF-67, cerium salt and copper salt, and reacting to prepare CuCeCo-ZIF;
the third step: carrying out pyrolysis on CuCeCo-ZIF obtained in the first two steps to prepare a composite metal oxide CuCeCo 2 O 4 ；
The fourth step: the prepared CuCeCo 2 O 4 Calcining in a tubular furnace under hydrogen-containing atmosphere to obtain CuCeCo 2 O 4 Part of oxygen is lost in the form of oxygen or oxygen atoms in the calcining process, and the product CuCeCo with oxygen vacancy is prepared 2 O 4-x 。
The preparation method of the carbonyl sulfide hydrolysis catalyst specifically comprises the following steps:
1) Dissolving cobalt salt in deionized water and uniformly dispersing by ultrasonic, dissolving imidazole compounds in deionized water and uniformly dispersing by ultrasonic, then dropwise adding the uniformly dispersed imidazole compound solution into the cobalt salt solution, stirring for 1-3min, standing for 15-30 min, collecting a product by centrifugation, washing the product with ethanol for multiple times, and then drying the product in a vacuum drying oven at 60-90 ℃ for 12-24 h to obtain ZIF-67;
2) Dissolving ZIF-67 in ethanol, then adding cerium salt and copper salt, carrying out ultrasonic treatment on the mixed solution for 5min-15min, reacting for 6h-12h in an oil bath environment at the temperature of 60-90 ℃, collecting a product through centrifugation, washing the product with ethanol for multiple times, and drying for 12h-24h in a vacuum drying oven at the temperature of 60-90 ℃ to obtain CuCeCo-ZIF solid powder;
3) Pyrolyzing the prepared CuCeCo-ZIF solid powder in a muffle furnace, heating to 600-900 ℃ from room temperature at a heating rate of 2-10 ℃/min, then pyrolyzing for 1-5 h at 600-900 ℃, and finally cooling to room temperature to obtain CuCeCo 2 O 4 A solid powder;
4) Mixing CuCeCo 2 O 4 Placing the solid powder in a tube furnace, calcining for 1-5 h at 300-500 ℃ in hydrogen-containing atmosphere to obtain CuCeCo 2 O 4-x 。
Further, in the step 1), the cobalt salt is one of cobalt chloride, cobalt nitrate and cobalt acetate, preferably cobalt acetate; the imidazole compound is 2-methylimidazole.
Further, the molar ratio of the cobalt salt to the imidazole compound in the step 1) is (2-5): (14.8-37), preferably 1.3 to 7.5.
Further, the cerium salt in step 2) is one of cerium chloride, cerium nitrate and cerium acetate, preferably cerium chloride; the copper salt is one of copper chloride, copper nitrate and copper acetate, preferably copper chloride.
Further, the molar ratio of the cerium salt to the copper salt in the step 2) is (2-5): (18-45), preferably 1.
Further, in the step 2), the ratio of the total mass of the cerium salt and the copper salt to the mass of the ZIF-67 is 0.2 to 0.3, preferably 0.25 to 0.27.
Further, in the step 4), the hydrogen-containing atmosphere is H 2 And N 2 Mixed gas of H 2 The volume concentration is 10-30%, and the flow of the mixed gas is 30-50 ml/min.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention synthesizes a carbonyl sulfide hydrolysis catalyst with anti-poisoning capability. The reaction mechanism of the carbonyl sulfide hydrolysis catalyst is to convert carbonyl sulfide into thiocarbonate, and the thiocarbonate is decomposed into hydrogen sulfide and carbon dioxide, but the hydrogen sulfide is easily oxidized to form elemental sulfur and sulfate, so that the catalyst is short in service life and poor in stability. The carbonyl sulfide hydrolysis catalyst prepared by the invention has more (111) crystal faces of cerium by doping cerium, so that the retention time of hydrogen sulfide on the surface of the catalyst is shortened, the hydrogen sulfide can quickly leave the surface of the catalyst, and the possibility of catalyst poisoning is reduced.
2. CuCeCo prepared by the invention 2 O 4-x The carbonyl sulfide hydrolysis catalyst has an oxygen vacancy structure, can adsorb surface oxygen and reduce the oxidation effect on hydrogen sulfide, cobalt can be used as an active component to catalyze the hydrolysis of carbonyl sulfide, copper can adsorb water vapor, so that a large amount of hydroxyl groups are accumulated on the surface of the catalyst, and due to the ion dipole effect, the hydroxyl groups are combined with carbonium ions to be converted into an intermediate product thiocarbonate so as to achieve the purpose of removing carbonyl sulfide.
Drawings
FIG. 1 is a scanning electron micrograph of a carbonyl sulfide hydrolysis catalyst obtained in example 1;
FIG. 2 is a graph showing the electron spin resonance comparison of the carbonyl sulfide hydrolysis catalysts obtained in example 1 and comparative example 1.
FIG. 3 is an adsorption isotherm spectrum of the carbonyl sulfide hydrolysis catalyst obtained in example 1.
FIG. 4 is a pore size spectrum of the carbonyl sulfide hydrolysis catalyst obtained in example 1.
FIG. 5 is a graph showing the catalytic conversion of carbonyl sulfide with adsorption time of the carbonyl sulfide hydrolysis catalysts obtained in examples 1 to 5 and comparative examples 1 to 2.
Detailed Description
The invention is further illustrated with reference to the following specific examples, without limiting the scope of the invention thereto.
Example 1
The preparation method of the carbonyl sulfide hydrolysis catalyst with the poisoning resistance comprises the following steps of:
1) Dissolving 1.2 parts of cobalt acetate in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dissolving 4.48 parts of 2-methylimidazole in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dropwise adding the uniformly dispersed 2-methylimidazole solution into the cobalt acetate solution, stirring for 2min, standing for 20min, collecting a product by centrifugation, washing the product with ethanol for multiple times, and drying the product in a vacuum drying oven at 80 ℃ for 24 hours to obtain ZIF-67;
2) Dissolving 0.2 part of ZIF-67 in 100 parts of ethanol, and then adding 0.0515 parts of metal salt (the metal salt consists of cerium chloride and copper chloride, wherein the molar ratio of cerium to copper is 1: 9) Ultrasonically mixing the solution for 10min, reacting in an oil bath at 75 ℃ for 10h, collecting CuCeCo-ZIF solid powder by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h;
3) Pyrolyzing the prepared CuCeCo-ZIF solid powder in a muffle furnace, heating to 800 ℃ from room temperature at a heating rate of 5 ℃/min, then pyrolyzing at 800 ℃ for 3h, and finally cooling to room temperature to obtain CuCeCo 2 O 4 A solid powder;
4) Mixing CuCeCo 2 O 4 The solid powder was placed in a tube furnace and charged with 40ml/min H 2 And N 2 Gas mixture (H) 2 Volume concentration of 20 percent) and calcining for 3 hours at 400 ℃ to prepare CuCeCo 2 O 4-x 。
The scanning electron micrograph of the carbonyl sulfide hydrolysis catalyst with anti-poisoning ability obtained in example 1 is shown in figure 1, the adsorption isotherm chromatogram is shown in figure 3, and the pore size chromatogram is shown in figure 4.
Fig. 1 shows that the CuCeCo2O4-x catalyst contains an octahedral structure and contains more (111) crystal faces of Ce, which makes the catalyst weakly adsorb hydrogen sulfide and can rapidly desorb hydrogen sulfide, and fig. 3 and 4 show that the catalyst has a large specific surface area, can adsorb hydroxyl groups dissociated by water, so that carbonyl sulfide and water form bicarbonate radicals on the surface of the catalyst, and has a large pore diameter, so that the generated elemental sulfur and sulfate are not easy to block pores.
Example 2
The preparation method of the carbonyl sulfide hydrolysis catalyst with the poisoning resistance comprises the following steps of:
1) Dissolving 1.2 parts of cobalt chloride in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dissolving 3.5 parts of 2-methylimidazole in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dropwise adding the uniformly dispersed 2-methylimidazole solution into the cobalt chloride solution, stirring for 2min, standing for 20min, collecting a product by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain ZIF-67;
2) Dissolving 0.2 part of ZIF-67 in 100 parts of ethanol, and then adding 0.0515 parts of metal salt (the metal salt consists of cerium acetate and copper chloride, wherein the molar ratio of cerium to copper is 1: 9) Ultrasonically mixing the solution for 10min, reacting in an oil bath at 75 ℃ for 10h, collecting CuCeCo-ZIF solid powder by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h;
3) Pyrolyzing the prepared CuCeCo-ZIF solid powder in a muffle furnace, heating to 900 ℃ from room temperature at a heating rate of 2 ℃/min, then pyrolyzing at 900 ℃ for 3h, and finally cooling to room temperature to obtain CuCeCo 2 O 4 A solid powder;
4) Mixing CuCeCo 2 O 4 The solid powder was placed in a tube furnace and 40ml/min H was passed through 2 And N 2 Gas mixture (H) 2 Volume concentration of 20 percent) and calcining for 3 hours at 500 ℃ to prepare CuCeCo 2 O 4-x 。
Example 3
The preparation method of the carbonyl sulfide hydrolysis catalyst with the poisoning resistance comprises the following steps of:
1) Dissolving 1.2 parts of cobalt acetate in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dissolving 5.5 parts of 2-methylimidazole in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dropwise adding the uniformly dispersed 2-methylimidazole solution into the cobalt acetate solution, stirring for 2min, standing for 20min, collecting a product by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain ZIF-67;
2) Dissolving 0.2 part of ZIF-67 in 100 parts of ethanol, and then adding 0.0515 parts of metal salt (the metal salt consists of cerium chloride and copper acetate, wherein the molar ratio of cerium to copper is 1: 9) Ultrasonically mixing the solution for 10min, reacting in an oil bath at 75 ℃ for 10h, collecting CuCeCo-ZIF solid powder by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h;
3) Pyrolyzing the prepared CuCeCo-ZIF solid powder in a muffle furnace, heating to 700 ℃ from room temperature at a heating rate of 10 ℃/min, then pyrolyzing for 3h at 700 ℃, and finally cooling to room temperature to obtain CuCeCo-ZIF solid powder 2 O 4 A solid powder;
4) Mixing CuCeCo 2 O 4 The solid powder was placed in a tube furnace and 40ml/min H was passed through 2 And N 2 Mixed gas (H) 2 Volume concentration of 20 percent) and calcining for 3 hours at 300 ℃ to prepare CuCeCo 2 O 4-x 。
Example 4
The preparation method of the carbonyl sulfide hydrolysis catalyst with the poisoning resistance comprises the following steps of:
1) Dissolving 1.2 parts of cobalt acetate in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dissolving 4.48 parts of 2-methylimidazole in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dropwise adding the uniformly dispersed 2-methylimidazole solution into the cobalt acetate solution, stirring for 2min, standing for 30min, collecting a product by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 60 ℃ for 24h to obtain ZIF-67;
2) Dissolving 0.2 part of ZIF-67 in 100 parts of ethanol, and then adding 0.0515 parts of metal salt (the metal salt consists of cerium chloride and copper chloride, wherein the molar ratio of cerium to copper is 1: 1) Ultrasonically mixing the solution for 10min, reacting in an oil bath at 75 ℃ for 10h, collecting CuCeCo-ZIF solid powder by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h;
3) Pyrolyzing the prepared CuCeCo-ZIF solid powder in a muffle furnace, heating to 800 ℃ from room temperature at a heating rate of 5 ℃/min, then pyrolyzing at 800 ℃ for 3h, and finally cooling to room temperature to obtain CuCeCo 2 O 4 A solid powder;
4) Mixing CuCeCo 2 O 4 The solid powder was placed in a tube furnace and charged with 40ml/min H 2 And N 2 Gas mixture (H) 2 Volume concentration of 20 percent) and calcining for 3 hours at 400 ℃ to prepare CuCeCo 2 O 4-x 。
Example 5
The preparation method of the carbonyl sulfide hydrolysis catalyst with the poisoning resistance comprises the following steps of:
1) Dissolving 1.2 parts of cobalt nitrate in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dissolving 4.48 parts of 2-methylimidazole in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dropwise adding the uniformly dispersed 2-methylimidazole solution into the cobalt acetate solution, stirring for 1min, standing for 20min, collecting a product by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 90 ℃ for 12h to obtain ZIF-67;
2) Dissolving 0.2 part of ZIF-67 in 100 parts of ethanol, and then adding 0.0515 parts of metal salt (the metal salt consists of cerium nitrate and copper nitrate, wherein the molar ratio of cerium to copper is 1: 9) Ultrasonically mixing the solution for 10min, reacting in an oil bath at 90 ℃ for 6h, collecting CuCeCo-ZIF solid powder by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h;
3) Pyrolyzing the prepared CuCeCo-ZIF solid powder in a muffle furnace, heating to 800 ℃ from room temperature at a heating rate of 2 ℃/min, then pyrolyzing for 3h at 800 ℃, and finally cooling to room temperature to obtain CuCeCo-ZIF solid powder 2 O 4 A solid powder;
4) Mixing CuCeCo 2 O 4 The solid powder was placed in a tube furnace and 40ml/min H was passed through 2 And N 2 Mixed gas (H) 2 Volume concentration of 20 percent) and calcining for 3 hours at 400 ℃ to prepare CuCeCo 2 O 4-x 。
Comparative example 1
The preparation method of the carbonyl sulfide hydrolysis catalyst with the poisoning resistance comprises the following steps of:
1) Dissolving 1.2 parts of cobalt acetate in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dissolving 4.48 parts of 2-methylimidazole in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dropwise adding the uniformly dispersed 2-methylimidazole solution into the cobalt acetate solution, stirring for 2min, standing for 20min, collecting a product by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain ZIF-67;
2) Dissolving 0.2 part of ZIF-67 in 100 parts of ethanol, then adding 0.0515 parts of copper chloride, ultrasonically mixing the solution for 10min, reacting for 12h in an oil bath at the temperature of 80 ℃, collecting CuCo-ZIF solid powder through centrifugation, washing the CuCo-ZIF solid powder for multiple times by using ethanol, and drying the CuCo-ZIF solid powder in a vacuum drying oven at the temperature of 80 ℃ for 24h;
3) Pyrolyzing the prepared CuCo-ZIF solid powder in a muffle furnace, heating to 800 ℃ from room temperature at a heating rate of 5 ℃/min, then pyrolyzing for 2h at 800 ℃, and finally cooling to room temperature to obtain CuCo 2 O 4 A solid powder;
4) Mixing CuCo 2 O 4 The solid powder was placed in a tube furnace and charged with 40ml/min H 2 And N 2 Mixed gas (H) 2 Volume concentration of 20 percent) and calcining for 3 hours at 300 ℃ to prepare CuCo 2 O 4-x 。
The electron spin resonance contrast of the carbonyl sulfide hydrolysis catalysts obtained in example 1 and comparative example 1 is shown in FIG. 2. As can be seen in fig. 2: the catalyst of example 1 had a distinct peak at g =2.003 and it can be determined that the catalyst prepared contained oxygen vacancies.
Comparative example 2
The preparation method of the carbonyl sulfide hydrolysis catalyst with the poisoning resistance comprises the following steps of:
1) Dissolving 1.2 parts of cobalt acetate in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dissolving 4.48 parts of 2-methylimidazole in 25 parts of deionized water, uniformly dispersing the solution by ultrasonic treatment for 5min, dropwise adding the uniformly dispersed 2-methylimidazole solution into the cobalt acetate solution, stirring for 2min, standing for 20min, collecting a product by centrifugation, washing with ethanol for multiple times, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain ZIF-67;
2) Dissolving 0.2 part of ZIF-67 in 100 parts of ethanol, then adding 0.0515 parts of copper chloride, ultrasonically mixing the solution for 10min, reacting for 12h in an oil bath at the temperature of 80 ℃, collecting CuCeCo-ZIF solid powder through centrifugation, washing the CuCeCo-ZIF solid powder for multiple times by using ethanol, and drying the CuCeCo-ZIF solid powder for 24h in a vacuum drying oven at the temperature of 80 ℃;
3) Pyrolyzing the prepared CuCeCo-ZIF solid powder in a muffle furnace, heating to 800 ℃ from room temperature at a heating rate of 5 ℃/min, then pyrolyzing for 2h at 800 ℃, and finally cooling to room temperature to obtain CuCeCo-ZIF solid powder 2 O 4 And (3) solid powder.
Application example 1:
the catalysts prepared in examples 1-5 and comparative examples 1-2 are applied to catalyze the hydrolysis conversion of carbonyl sulfide, and the specific process is as follows: filling the catalyst into a fixed bed reactor, wherein the bed temperature is 85 ℃, and feeding the catalyst into a catalyst bedCoal gas is introduced into the layer, and the coal gas comprises the following components: 300mg/m 3 Carbonyl sulfur, 25 percent of carbon monoxide, 15 percent of carbon dioxide and the balance of nitrogen, the operation is carried out at normal pressure, and the space velocity is 8000h -1 . The results of experiments on the catalytic conversion of cos by the cos hydrolysis catalysts obtained in examples 1 to 5 and comparative examples 1 to 2 as a function of adsorption time are shown in FIG. 5, in which the results of experiments on the catalytic conversion of cos by hydrolysis at three adsorption times of 5h, 10h and 20h are summarized in Table 1.
Figure DEST_PATH_IMAGE002
As can be seen from the detection data of the examples 1 to 5, the carbonyl sulfide hydrolysis catalyst with anti-poisoning capability provided by the invention has higher desulfurization rate (more than 95%) at low temperature, can be used in a fixed bed reactor or a moving bed reactor, and is suitable for purification treatment of gas containing carbonyl sulfide. It can be seen from the test data of example 1 and examples 2 and 3 that the desulfurization degree is decreased when the molar ratio of the cobalt-based metal salt to 2-methylimidazole is changed to be higher or lower. From the test data of example 1 and example 4, it can be seen that when the molar ratio of cerium to copper is changed, the content of adsorbed water vapor and carbonyl sulfide is reduced due to the reduction of the content of copper, and the desulfurization efficiency is reduced. As can be seen from the test data of example 1 and example 5, the conversion rate slightly decreases when the kind of the metal salt is changed, thereby also demonstrating that the preferable metal salt works best. As can be seen from the detection data of example 1 and comparative example 1, when no cerium salt is added, the hydrolysis efficiency of the catalyst is significantly reduced, because hydrogen sulfide cannot be rapidly desorbed on the surface of the catalyst without cerium, so that hydrogen sulfide is oxidized to form elemental sulfur and metal salt, which greatly affects the stability of the catalyst. From the test data of example 1 and comparative example 2, it can be seen that when calcination was performed without using hydrogen, oxygen vacancies could not be formed, surface oxygen and lattice oxygen of the catalyst could not be transferred to the surface of the catalyst and thus removed, the adsorption ability to hydroxyl groups was weakened, and the hydrolysis efficiency was lowered. It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims (9)

1. A preparation method of carbonyl sulfide hydrolysis catalyst with poisoning resistance is characterized by comprising the following steps:
the first step is as follows: cobalt salt and an imidazole compound are rapidly reacted at room temperature to synthesize a metal organic framework material ZIF-67;
the second step is that: mixing and dissolving ZIF-67, cerium salt and copper salt, and reacting to prepare CuCeCo-ZIF;
the third step: carrying out pyrolysis on CuCeCo-ZIF obtained in the first two steps to prepare a composite metal oxide CuCeCo 2 O 4 ；
The fourth step: the prepared CuCeCo 2 O 4 Calcining in a tubular furnace under hydrogen-containing atmosphere to obtain CuCeCo 2 O 4 Part of oxygen is lost in the form of oxygen or oxygen atoms in the calcining process, and the product CuCeCo with oxygen vacancy is prepared 2 O 4-x 。
2. The method for preparing carbonyl sulfide hydrolysis catalyst with anti-poisoning capability as claimed in claim 1, comprising the following steps:
1) Dissolving cobalt salt in deionized water and uniformly dispersing by ultrasonic, dissolving imidazole compounds in deionized water and uniformly dispersing by ultrasonic, then dropwise adding the uniformly dispersed imidazole compound solution into the cobalt salt solution, stirring for 1-3min, standing for 15-30 min, collecting a product by centrifugation, washing the product with ethanol for multiple times, and then drying the product in a vacuum drying oven at 60-90 ℃ for 12-24 h to obtain ZIF-67;
2) Dissolving ZIF-67 in ethanol, then adding cerium salt and copper salt, carrying out ultrasonic treatment on the mixed solution for 5min-15min, reacting for 6h-12h in an oil bath environment at the temperature of 60-90 ℃, collecting a product through centrifugation, washing the product with ethanol for multiple times, and drying for 12h-24h in a vacuum drying oven at the temperature of 60-90 ℃ to obtain CuCeCo-ZIF solid powder;
3) Pyrolyzing the prepared CuCeCo-ZIF solid powder in a muffle furnace, heating to 600-900 ℃ from room temperature at a heating rate of 2-10 ℃/min, then pyrolyzing for 1-5 h at 600-900 ℃, and finally cooling to room temperature to obtain CuCeCo 2 O 4 A solid powder;
4) Mixing CuCeCo 2 O 4 Placing the solid powder in a tube furnace, calcining for 1-5 h at 300-500 ℃ in the atmosphere containing hydrogen to prepare CuCeCo 2 O 4-x 。
3. The method for preparing carbonyl sulfide hydrolysis catalyst with poisoning resistance as claimed in claim 2, wherein in step 1), the cobalt salt is one of cobalt chloride, cobalt nitrate and cobalt acetate, preferably cobalt acetate; the imidazole compound is 2-methylimidazole.
4. The method for preparing carbonyl sulfide hydrolysis catalyst with poisoning resistance as claimed in claim 2, wherein in step 1), the molar ratio of the cobalt salt to the imidazole compound is (2-5): (14.8-37), preferably 1.3 to 7.5.
5. The method of claim 2, wherein in the step 2), the cerium salt is one of cerium chloride, cerium nitrate and cerium acetate, preferably cerium chloride; the copper salt is one of copper chloride, copper nitrate and copper acetate, preferably copper chloride.
6. The method for preparing carbonyl sulfide hydrolysis catalyst with poisoning resistance according to claim 2, wherein in the step 2), the molar ratio of cerium salt to copper salt is (2-5): (18-45), preferably 1.
7. The method for preparing carbonyl sulfide hydrolysis catalyst with poisoning resistance according to claim 2, wherein in the step 2), the ratio of the total mass of the cerium salt and the copper salt to the mass of the ZIF-67 is 0.2 to 0.3, preferably 0.25 to 0.27.
8. The method for preparing carbonyl sulfide hydrolysis catalyst with poisoning resistance as claimed in claim 2, wherein in step 4), the hydrogen-containing atmosphere is H 2 And N 2 Mixed gas of H 2 The volume concentration is 10-30%, and the flow of the mixed gas is 30-50 ml/min.
9. A carbonyl sulfide hydrolysis catalyst with poisoning resistance prepared by the method of claim 1~8.
CN202211023463.0A 2022-08-25 2022-08-25 Carbonyl sulfide hydrolysis catalyst with poisoning resistance and preparation method thereof Withdrawn CN115301245A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115990493A (en) * 2022-12-28 2023-04-21 电子科技大学 Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial
CN118320811A (en) * 2024-06-14 2024-07-12 北京化工大学 Hydrotalcite-based carbonyl sulfide hydrolysis catalyst, preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115990493A (en) * 2022-12-28 2023-04-21 电子科技大学 Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial
CN115990493B (en) * 2022-12-28 2024-06-07 电子科技大学 Preparation method of cobalt-based multi-metal sulfide heterostructure nanomaterial
CN118320811A (en) * 2024-06-14 2024-07-12 北京化工大学 Hydrotalcite-based carbonyl sulfide hydrolysis catalyst, preparation method and application thereof

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Application publication date: 20221108