CN110102302B - Catalyst for carbonyl sulfide purification and preparation method and application thereof - Google Patents
Catalyst for carbonyl sulfide purification and preparation method and application thereof Download PDFInfo
- Publication number
- CN110102302B CN110102302B CN201910439196.7A CN201910439196A CN110102302B CN 110102302 B CN110102302 B CN 110102302B CN 201910439196 A CN201910439196 A CN 201910439196A CN 110102302 B CN110102302 B CN 110102302B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- carbonyl sulfide
- purification
- active component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of environmental protection and air pollution treatment, and particularly relates to a carbonyl sulfide purification catalyst, and a preparation method and application thereof. The invention provides a carbonyl sulfide purification catalyst, which comprises a porous carrier, an active component and alkali metal; the active component is a transition metal; the active component and the alkali metal are supported on the surface and in the pores of the porous carrier. The results of the examples show that the catalyst provided by the invention can be used in CO and/or H 2 In the presence of a reducing atmosphere, the catalytic purification of carbonyl sulfide can be realized in an environment of 100-200 ℃.
Description
Technical Field
The invention belongs to the technical field of sulfur-containing substance purification, and particularly relates to a catalyst for carbonyl sulfide purification and a preparation method and application thereof.
Background
The deep purification of typical low-concentration toxic and harmful gas in an industrial gas source is one of the hot points and difficulties in the international air pollution control engineering technology research, has a wide engineering application background at home, and has great significance. However, the basic research in the field in China is relatively weak, and the technical demand is urgent.
The organic sulfur widely exists in coal gas, petroleum gas, high acid natural gas and unconventional natural gas including shale gas and coal bed gas, the type and concentration of the organic sulfur mainly depend on factors such as producing area, exploitation and processing mode, and the like, and mainly comprises carbonyl sulfide (COS), carbon disulfide (CS) 2 ) Thiol (R-SH), thioether (R-S-R), thiophene (C) 4 H 4 S), and the like, wherein carbonyl sulfide is mainly used. In the process of applying industrial gas sources in chemical industry, catalysts are mostly needed to be used, but carbonyl sulfur can cause sulfur poisoning and inactivation of industrial catalysts and can also cause corrosion of industrial instrument pipelines. Therefore, industrial gas sources require ultra-deep purification of carbonyl sulfide prior to chemical applications.
The main methods for industrially removing carbonyl sulfide include a dry method and a wet method. The dry method is a process of directly removing sulfides by using an adsorbent and a catalyst or removing sulfides after conversion, and mainly includes a hydroconversion method, a hydrolysis conversion method, an oxidation conversion method and the like. The dry method is characterized by high desulfurization precision, low investment, low operation cost and almost no power consumption, and when the sulfur content of the raw material gas is lower or the flow of the gas to be purified is smaller, the dry desulfurization can achieve the aim. Therefore, dry desulfurization is receiving a great deal of attention, wherein the properties of the catalyst are crucial to the desulfurization effect. For example, chinese patent CN1069673 uses a catalyst loaded with rare earth metal oxide or composite metal oxide, which can achieve a certain catalytic effect. However, the catalyst is difficult to realize catalytic conversion of carbonyl sulfide under a reducing atmosphere, and application of the technology is influenced.
Disclosure of Invention
In view of this, the present invention aims to provide a catalyst for carbonyl sulfide purification, a preparation method and applications thereof; the catalyst provided by the invention has high low-temperature activity, and can realize catalytic purification of carbonyl sulfide in a reducing atmosphere.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a carbonyl sulfide purification catalyst, which comprises a porous carrier, an active component and alkali metal; the active component is a transition metal; the active component and the alkali metal are supported on the surface and in the pores of the porous carrier.
Preferably, the porous carrier comprises one or more of porous activated carbon particles, activated carbon fibers, activated alumina, honeycomb cordierite and molecular sieves; the active component comprises one or more of Fe, Mn, Cu and Ni; the alkali metal is Na and/or K.
Preferably, the mass of the active component is 0.5-10% of that of the porous carrier; the mass of the alkali metal is 1-20% of the mass of the porous carrier.
The invention provides a preparation method of the carbonyl sulfide purification catalyst, which comprises the following steps:
(1) heating the strong alkali solution and the porous carrier, and drying the porous carrier to obtain an alkalized carrier;
(2) carrying out contact reaction on the transition metal salt solution and the alkalized carrier obtained in the step (2) in an atomized form to obtain a catalyst precursor; the temperature of the contact reaction is 50-250 ℃;
(3) carrying out deep reaction on the catalyst precursor obtained in the step (2) to obtain a carbonyl sulfide purification catalyst; the temperature of the deep reaction is 300-400 ℃.
Preferably, the solute of the strong alkali solution in the step (1) comprises potassium hydroxide and/or sodium hydroxide; the concentration of the strong alkali solution is 1-3 mol/L.
Preferably, the heating treatment in the step (1) is carried out at the temperature of 50-100 ℃ for 1-5 hours.
Preferably, the solvent in the transition metal salt solution in the step (2) comprises one or more of nitrate, chloride, acetate and formate corresponding to iron, nickel, copper and manganese; the concentration of metal ions in the transition metal salt solution is 0.5-2 mol/L.
Preferably, the atomized solution of the transition metal salt solution in the step (2) is contacted with the alkalized carrier through a carrier gas to react; the carrier gas comprises air, hydrogen or nitrogen;
and (3) the contact reaction time in the step (2) is 1-5 h.
Preferably, the deep reaction of the step (3) is carried out under the condition that the carrier gas is continuously introduced; the carrier gas comprises air, hydrogen or nitrogen; the time of the deep reaction in the step (3) is 3-12 h.
The invention also provides the application of the carbonyl sulfide purification catalyst in the technical scheme or the carbonyl sulfide purification catalyst prepared by the preparation method in the technical scheme in the catalytic purification of carbonyl sulfide.
The technical scheme provided by the invention has the following effects:
the invention provides a carbonyl sulfide purification catalyst, which comprises a porous carrier, an active component and alkali metal; the active component is a transition metal; the active component and the alkali metal are supported on the surface and in the pores of the porous carrier. The active component of the catalyst prepared by the preparation method is uniformly distributed on the surface of the carrier, has small particle size and is in an amorphous state, so that the low-temperature activity is excellent. The catalyst does not need to move frequently in the preparation process, which is beneficial to reducing the production cost.
The results of the examples show that the catalyst provided by the invention can be used in CO and/or H 2 In the presence of a reducing atmosphere, the catalytic purification of carbonyl sulfide is realized at 100-200 ℃.
Drawings
FIG. 1 is a scanning electron microscope photograph of a catalyst obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of the catalyst obtained in example 2 of the present invention;
FIG. 3 is a scanning electron microscope photograph of the catalyst obtained in example 3 of the present invention;
FIG. 4 is a scanning electron microscope photograph of the catalyst obtained in example 4 of the present invention;
FIG. 5 is a graph showing the purification efficiency of carbonyl sulfide with time under a carbon monoxide reducing atmosphere in application example 1;
FIG. 6 is a graph showing the purification efficiency of carbonyl sulfide with time under a carbon monoxide reducing atmosphere in application example 2;
FIG. 7 is a graph showing the purification efficiency of carbonyl sulfide with time under a carbon monoxide reducing atmosphere in application example 3;
FIG. 8 is a graph showing the purification efficiency of carbonyl sulfide with time under a carbon monoxide reducing atmosphere in application example 4.
Detailed Description
In order to more clearly and more deeply illustrate the contents of the present invention, some examples will be further illustrated below, but the present invention is not limited to the illustrated examples. The specific experimental conditions or methods in the following examples were carried out according to the conventional conditions or methods in the art, unless otherwise noted.
The invention provides a carbonyl sulfide purification catalyst, which comprises a porous carrier, an active component and alkali metal. In the present invention, the active component and the alkali metal are supported on the surface and in the pores of the porous support.
In the present invention, the porous carrier preferably comprises one or more of porous activated carbon particles, activated carbon fibers, activated alumina, honeycomb cordierite, and molecular sieves.
In the present invention, the active component is a transition metal; the active component preferably comprises one or more of Fe, Mn, Cu and Ni. In the present invention, the mass of the active ingredient is preferably 0.5% to 10%, more preferably 1.0% to 9.0%, and still more preferably 2.0% to 5.0% of the mass of the porous carrier.
In the present invention, the alkali metal is preferably Na and/or K; when the alkali metal is Na and K, the molar ratio of K to Na is preferably (0.5-2): 1, more preferably (0.8 to 1.6): 1, more preferably (1.0 to 1.2): 1. in the present invention, the mass of the alkali metal is preferably 1% to 20%, more preferably 1.5% to 15%, and still more preferably 5% to 10% of the mass of the porous support.
The invention also provides a preparation method of the carbonyl sulfide purification catalyst, which comprises the following steps:
(1) heating the strong alkali solution and the porous carrier, and drying the porous carrier to obtain an alkalized carrier;
(2) carrying out contact reaction on the transition metal salt solution and the alkalized carrier obtained in the step (2) in an atomized form to obtain a catalyst precursor; the temperature of the contact reaction is 50-250 ℃;
(3) carrying out deep reaction on the catalyst precursor obtained in the step (2) to obtain a carbonyl sulfide purification catalyst; the temperature of the deep reaction is 300-400 ℃.
In the present invention, the starting materials used are commercially available products well known to those skilled in the art, unless otherwise specified.
According to the invention, after a strong alkali solution and a porous carrier are heated, the porous carrier is dried to obtain the alkalized carrier. In the present invention, the solute of the alkali solution preferably includes potassium hydroxide and/or sodium hydroxide; when the solvent is potassium hydroxide and sodium hydroxide, the molar ratio of the potassium hydroxide to the sodium hydroxide is preferably (0.5-2): 1, more preferably (0.8 to 1.6): 1, more preferably (1.0 to 1.2): 1. In the invention, the concentration of the strong alkali solution is preferably 1-3 mol/L; the dosage volume ratio of the strong alkali solution to the porous carrier is preferably 1-1.5.
In the invention, the temperature of the heating treatment is preferably 50-100 ℃, and more preferably 75-90 ℃; the time of the heating treatment is preferably 1 to 5 hours, and more preferably 1.5 to 4 hours. The invention preferably immerses the porous carrier in a strong alkali solution for heating treatment; during the heat treatment, the strong alkali solution is in a boiling state; alkali metal can better enter a micropore pore channel of the catalyst carrier, and meanwhile, hydroxyl interacts with functional groups on the surface of the carrier to form the catalyst carrier rich in hydroxyl, so that the improvement of active sites of the catalyst is facilitated, and the low-temperature activity of the catalyst is improved.
After the heating treatment, the porous carrier is dried to obtain the alkalized carrier. The invention further filters the heated feed liquid, and dries the porous carrier obtained by filtering to obtain the alkalized carrier. In the invention, the drying mode is preferably drying, and the drying temperature is preferably 60-90 ℃, and more preferably 65-80 ℃.
Before the heating treatment, the porous carrier is preferably washed and then dried, and further preferably, the carrier is washed for 3-5 times by sequentially adopting distilled water and absolute ethyl alcohol and then dried.
After the alkalized carrier is obtained, the transition metal salt solution is subjected to contact reaction with the alkalized carrier in an atomized form to obtain the catalyst precursor. In the present invention, the solvent in the transition metal salt solution preferably comprises one or more of nitrate, chloride, acetate and formate corresponding to iron, nickel, copper and manganese; further preferred is one or more of iron nitrate, manganese nitrate, copper nitrate, nickel nitrate, iron chloride, manganese acetate, copper sulfate, and nickel formate. In the invention, the concentration of the metal ions in the transition metal salt solution is preferably 0.5-2 mol/L, more preferably 0.8-1.8 mol/L, and even more preferably 1.0-1.2 mol/L.
The method preferably atomizes the transition metal salt solution by an ultrasonic atomization pool to obtain atomized liquid; the present invention does not require any particular embodiment of the atomization, and may be carried out in any manner known to those skilled in the art.
The invention preferably contacts the atomized liquid of the transition metal salt solution with the alkalization carrier through the carrier gas to react; the carrier gas preferably comprises air, hydrogen or nitrogen; the flow rate of the carrier gas is preferably 100 to 500 mL/min. Under the action of the carrier gas, the transition metal salt solution is fully contacted with the carrier and can react with the carrier, so that oxygen vacancies on the surface of the catalyst are increased, and the catalytic activity is further improved. In the present invention, the contact reaction is preferably carried out in a quartz tube.
In the invention, the temperature of the contact reaction is preferably 50-250 ℃, more preferably 100-200 ℃, and more preferably 120-150 ℃; the time of the contact reaction is preferably 1-5 h, more preferably 1.5-4 h, and even more preferably 2-3 h. The invention realizes the full contact of the atomized liquid and the alkalized carrier by continuously introducing the carrier gas into the atomized liquid.
After the contact reaction, the obtained reaction product is preferably dried in a carrier gas atmosphere. In the invention, the temperature of the drying treatment is preferably 50-250 ℃, more preferably 100-200 ℃, and more preferably 120-150 ℃; the drying reaction time is preferably 10-20 h. In the invention, the drying treatment process does not need to introduce atomized liquid of transition metal salt solution, and only needs to continuously introduce carrier gas in the contact reaction stage.
After the catalyst precursor is obtained, the catalyst precursor is subjected to deep reaction to obtain the carbonyl sulfide purification catalyst. In the invention, the temperature of the deep reaction is 300-400 ℃, preferably 320-380 ℃, and more preferably 350 ℃; the time of the deep reaction is preferably 3-12 h, more preferably 4-10 h, and even more preferably 5-8 h. In the present invention, the deep reaction is preferably carried out in the presence of a carrier gas; specifically, the method is carried out under the condition that the carrier gas is continuously introduced. In the present invention, the carrier gas preferably includes air, hydrogen or nitrogen; the carrier gas is the same as that described in the previous embodiment.
In the present invention, the temperature of the deep reaction is preferably reached by raising the temperature of the contact reaction; the temperature rise process is preferably carried out under the condition of introducing carrier gas; and drying is achieved without introducing the atomized liquid. After the temperature of the deep reaction is reached, the carrier gas is continuously introduced, the heat is preserved at the corresponding temperature, the roasting oxidation is realized, and the catalyst carrier does not move in the whole process. This can save a lot of equipment costs.
The invention also provides the application of the carbonyl sulfide purification catalyst in the technical scheme or the carbonyl sulfide purification catalyst prepared by the preparation method in the technical scheme in the catalytic purification of carbonyl sulfide.
In the present invention, the catalyst for purifying carbonyl sulfide is preferably subjected to catalytic purification treatment of carbonyl sulfide to be purified.
In the present invention, the catalytic purification process is preferably performed in a reducing atmosphere; the reducing atmosphere is preferably CO and/or H 2 The atmosphere present; the temperature of the catalytic purification is preferably 70-200 ℃, more preferably 70-75 ℃ or 80-200 ℃, and more preferably not 110-150 ℃.
In order to further illustrate the present invention, the following detailed description of the carbonyl sulfide purification catalyst, the preparation method and the application thereof are provided in conjunction with the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Weighing 10g of active alumina balls, washing with absolute ethyl alcohol and distilled water for 3 times respectively, and drying at 90 ℃;
(2) the dried alumina ball is put into 100mL KOH aqueous solution (KOH concentration is 1mol/L), immersed for 3 hours at 80 ℃, filtered, dried and put into a quartz tube.
(3) Weighing 1.5g of ferric nitrate and 0.4g of cupric nitrate, and dissolving in 10mL of water; putting the aqueous solution into an ultrasonic atomization pool, carrying the atomized solution into a quartz tube by air, and carrying out contact reaction with an activated alumina ball for 3 hours at 50 ℃;
(4) turning off the power supply of the ultrasonic atomizer, and continuing to react for 10 hours at 80 ℃;
(5) and raising the temperature to 400 ℃ by program, and continuously introducing air to continue the reaction for 3 hours to obtain the catalyst.
Example 2:
(1) weighing 6g of coconut shell activated carbon particles, washing the coconut shell activated carbon particles with absolute ethyl alcohol and distilled water for 3 times respectively, and drying the coconut shell activated carbon particles at 60 ℃;
(2) placing the dried coconut shell activated carbon particles into 100mL of NaOH aqueous solution (the concentration of NaOH is 1.5mol/L), soaking for 2 hours at 100 ℃, filtering, drying the coconut shell activated carbon particles, and placing the coconut shell activated carbon particles into a quartz tube.
(3) Weighing 2.5g of nickel nitrate, and dissolving in 5mL of water; putting the aqueous solution into an ultrasonic atomization pool, carrying 5 wt.% of hydrogen (balance gas is nitrogen) into a quartz tube after the solution is atomized, and carrying out contact reaction with activated carbon for 2 hours at 100 ℃;
(4) turning off the power supply of the ultrasonic atomizer, and continuing to react for 10 hours at 60 ℃;
(5) and raising the temperature to 350 ℃, and continuously introducing 5 wt.% of hydrogen (balance gas is nitrogen) for reacting for 3 hours to obtain the catalyst.
Example 3:
(1) weighing 10g of molecular sieve balls, washing with anhydrous ethanol and distilled water for 3 times, and drying at 100 ℃;
(2) and (3) placing the dried molecular sieve balls into 100mL of mixed aqueous solution of KOH and NaOH (the concentration of KOH is 1mol/L and the concentration of NaOH is 0.5mol/L), soaking for 3 hours at 90 ℃, filtering, drying the molecular sieve balls, and placing the molecular sieve balls into a quartz tube.
(3) Weighing 1g of nickel nitrate and 1.5g of copper nitrate, and dissolving in 10mL of water; putting the aqueous solution into an ultrasonic atomization pool, atomizing the solution, then carrying the atomized solution into a quartz tube by nitrogen, and carrying out contact reaction with molecular sieve balls for 3 hours at 250 ℃;
(4) turning off the power supply of the ultrasonic atomizer, and continuing to react for 10 hours at 80 ℃;
(5) and raising the temperature to 400 ℃ by a program, continuously introducing nitrogen, and continuously reacting for 3 hours to obtain the catalyst.
Example 4
(1) Weighing 5g of activated carbon fiber, washing with anhydrous ethanol and distilled water for 3 times respectively, and drying at 100 ℃;
(2) and (3) placing the dried activated carbon fiber into 100mL of mixed aqueous solution of KOH and NaOH (the concentration of the KOH is 1mol/L and the concentration of the NaOH is 0.5mol/L), soaking for 3 hours at the temperature of 90 ℃, filtering, drying the activated carbon fiber, and placing the dried activated carbon fiber into a quartz tube.
(3) Weighing 1g of manganese nitrate and 1.5g of copper nitrate, and dissolving in 10mL of water; putting the aqueous solution into an ultrasonic atomization pool, atomizing the solution, then introducing the atomized solution into a quartz tube by nitrogen, and carrying out contact reaction with molecular sieve balls for 3 hours at 200 ℃;
(4) turning off the power supply of the ultrasonic atomizer, and continuing to react for 10 hours at 80 ℃;
(5) and raising the temperature to 350 ℃, and continuously introducing nitrogen to continue the reaction for 4 hours to obtain the catalyst.
The catalyst obtained in example 1 was analyzed by scanning electron microscopy, and the results are shown in FIG. 1. From fig. 1, it can be seen that the active component is distributed uniformly on the catalyst support. The catalysts obtained in examples 2-4 were analyzed by scanning electron microscopy, and the results are similar to those in FIG. 1, and can be seen in FIGS. 2, 3 and 4.
Application example 1
The carbonyl sulfide obtained in example 1 is purified by the obtained catalyst to remove the carbonyl sulfide: the catalyst is loaded in a fixed bed reactor (phi 8mm multiplied by 200mm) and the reaction conditions are as follows: the reaction temperature is 100 ℃, and the space velocity is 1000h -1 And COS concentration 300 ppm.
Testing the components of the gas at the outlet of the reactor after different time of purification treatment, and testing the purification rate of the hydroxylated sulfur, wherein the result is shown in figure 5; no H was detected at the reactor outlet 2 S, and the conversion rate of COS is more than 99 percent; with the progress of catalytic purification, the purification rate of sulfur hydroxide was always stably maintained at 99% or more, and it was found that the activity of the catalyst was stable.
Application example 2
The carbonyl sulfide obtained in example 4 is purified by the obtained catalyst to remove the carbonyl sulfide: the catalyst is loaded in a fixed bed reactor (phi 8mm is multiplied by 200mm), and a reaction stripThe parts are as follows: the reaction temperature is 110 ℃, and the space velocity is 1000h -1 And COS concentration 300 ppm.
Testing the components of the gas at the outlet of the reactor after different time of purification treatment, and testing the purification rate of the hydroxylated sulfur, wherein the result is shown in figure 6; no H was detected at the reactor outlet 2 S, and the conversion rate of COS is more than 98%; with the progress of catalytic purification, the purification rate of sulfur hydroxylation is always stably maintained at more than 98%, and the catalyst activity is stable.
Application example 3
The carbonyl sulfide obtained in example 3 is purified by the obtained catalyst to remove the carbonyl sulfide: the catalyst is loaded in a fixed bed reactor (phi 8mm multiplied by 200mm) and the reaction conditions are as follows: the reaction temperature is 150 ℃, and the space velocity is 1000h -1 And COS concentration 300 ppm.
The gas components at the outlet of the reactor after different time of purification treatment are tested, and the purification rate of the sulfur hydroxylation is tested, and the result is shown in figure 7; no H was detected at the reactor outlet 2 S, and the conversion rate of COS is more than 99 percent; with the progress of catalytic purification, the purification rate of sulfur hydroxide was always stably maintained at 99% or more, and it was found that the activity of the catalyst was stable.
Application example 4
The carbonyl sulfide obtained in example 4 is purified by the obtained catalyst to remove the carbonyl sulfide: the catalyst is loaded in a fixed bed reactor (phi 8mm multiplied by 200mm) and the reaction conditions are as follows: the reaction temperature is 200 ℃, and the space velocity is 1000h -1 And COS concentration 300 ppm.
The components of the gas at the outlet of the reactor after different times of purification treatment are tested, and the carbonyl sulfide purification rate is tested, and the result is shown in figure 8; no H was detected at the reactor outlet 2 S, and the conversion rate of COS is more than 99 percent; with the progress of catalytic purification, the purification rate of sulfur hydroxide is stably maintained at 99% or more, and it is seen that the activity of the catalyst is stable.
The embodiment shows that the catalyst provided by the invention is suitable for purifying carbonyl sulfide in a reducing atmosphere and has high catalytic efficiency; the preparation method of the catalyst provided by the invention has the advantages of mild reaction conditions, simplicity, convenience, easiness in operation, lower cost and higher feasibility; the catalyst provided by the invention has good repeatability, and is easy to realize large-scale production; can be widely applied to the deep purification of carbonyl sulfide in reducing atmosphere such as blast furnace gas, coke oven gas, yellow phosphorus tail gas and the like. The catalyst prepared by the invention has low-temperature activity, and can still realize the catalytic degradation of the hydroxy sulfur even under the condition of lower than 80 ℃.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (9)
1. The preparation method of the catalyst for carbonyl sulfide purification is characterized by comprising the following steps:
(1) heating a strong alkali solution and a porous carrier, and drying the porous carrier to obtain an alkalized carrier, wherein solutes of the strong alkali solution comprise potassium hydroxide and/or sodium hydroxide;
(2) carrying out contact reaction on the transition metal salt solution and the alkalized carrier obtained in the step (1) in an atomized form to obtain a catalyst precursor; the temperature of the contact reaction is 50-250 ℃, and solutes in the solution of the transition metal salt comprise one or more of nitrates, chlorides, acetates and formates corresponding to iron, nickel, copper and manganese;
(3) carrying out deep reaction on the catalyst precursor in the step (2) to obtain a catalyst for purifying carbonyl sulfide; the temperature of the deep reaction is 300-400 ℃, and the time of the deep reaction is 3-12 h; the deep reaction is carried out under the condition that carrier gas is continuously introduced; the carrier gases include air, hydrogen and nitrogen.
2. The preparation method according to claim 1, wherein the concentration of the strong alkali solution in the step (1) is 1 to 3 mol/L.
3. The preparation method according to claim 1 or 2, wherein the heating treatment in step (1) is carried out at a temperature of 50 to 100 ℃ for 1 to 5 hours.
4. The method according to claim 1, wherein the concentration of the metal ion in the transition metal salt solution in the step (2) is 0.5 to 2 mol/L.
5. The method for preparing a compound according to claim 1, wherein the atomized liquid of the transition metal salt solution in the step (2) is contacted with the alkalizing carrier by a carrier gas to react; the carrier gas comprises air, hydrogen or nitrogen;
the contact reaction time in the step (2) is 1-5 h.
6. A carbonyl sulfide purification catalyst obtained by the preparation method of any one of claims 1 to 5, which is characterized by comprising a porous carrier, an active component and an alkali metal; the active component is a transition metal; the active component and the alkali metal are loaded on the surface and in the pores of the porous carrier, and the active component comprises one or more of Fe, Mn, Cu and Ni; the alkali metal is Na and/or K.
7. The carbonyl sulfur purification catalyst of claim 6, wherein the porous support comprises one or more of porous activated carbon particles, activated carbon fibers, activated alumina, honeycomb cordierite, and molecular sieves.
8. The carbonyl sulfide purification catalyst according to claim 6, characterized in that the mass of the active component is 0.5-10% of the mass of the porous carrier; the mass of the alkali metal is 1-20% of the mass of the porous carrier.
9. Use of the catalyst for carbonyl sulfide purification according to any one of claims 6 to 8 for the catalytic purification of carbonyl sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910439196.7A CN110102302B (en) | 2019-05-24 | 2019-05-24 | Catalyst for carbonyl sulfide purification and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910439196.7A CN110102302B (en) | 2019-05-24 | 2019-05-24 | Catalyst for carbonyl sulfide purification and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110102302A CN110102302A (en) | 2019-08-09 |
| CN110102302B true CN110102302B (en) | 2022-07-26 |
Family
ID=67492057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910439196.7A Active CN110102302B (en) | 2019-05-24 | 2019-05-24 | Catalyst for carbonyl sulfide purification and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110102302B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111359629B (en) * | 2020-03-19 | 2021-04-23 | 昆明理工大学 | Metal single-atom site catalyst and preparation method and application thereof |
| CN112063422B (en) * | 2020-08-26 | 2021-06-22 | 中国科学院山西煤炭化学研究所 | Blast furnace gas desulfurization and sulfur resource utilization method and device |
| CN115869981A (en) * | 2022-12-08 | 2023-03-31 | 中国科学院山西煤炭化学研究所 | Modified manganese-based spinel carbonyl sulfide hydrolysis catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590392A (en) * | 2008-05-27 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Organic sulfur desulfurizer and preparation method thereof |
| CN103464220A (en) * | 2013-09-13 | 2013-12-25 | 太原理工大学 | Method for modifying catalyst through ultrasonic atomization |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318130A (en) * | 2008-07-10 | 2008-12-10 | 昆明理工大学 | Absorbent charcoal based catalyst for hydrolyzation and catalysis of carbonyl sulphur in low-temperature and preparation method thereof |
| CN102600850B (en) * | 2012-01-13 | 2016-06-22 | 昆明理工大学 | A kind of preparation method of the catalyst of elimination cos and Carbon bisulfide simultaneously |
-
2019
- 2019-05-24 CN CN201910439196.7A patent/CN110102302B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590392A (en) * | 2008-05-27 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Organic sulfur desulfurizer and preparation method thereof |
| CN103464220A (en) * | 2013-09-13 | 2013-12-25 | 太原理工大学 | Method for modifying catalyst through ultrasonic atomization |
Non-Patent Citations (1)
| Title |
|---|
| 羰基中羰基硫的加氢催化转化研究;高成强;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20091015(第10期);第B017-4页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110102302A (en) | 2019-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110102302B (en) | Catalyst for carbonyl sulfide purification and preparation method and application thereof | |
| US4210628A (en) | Removal of nitrogen oxides | |
| CN104772143B (en) | For the preparation method for the support type sludge base catalyst for removing low concentration carbon disulfide | |
| CN102580675A (en) | Modified activated carbon, preparation method thereof and method for adsorbing hydrogen sulfide using modified activated carbon | |
| CN102580525A (en) | Method for using activated carbon load copper oxide composite catalyst to absorb nitrogenous oxide | |
| CN113145103B (en) | Hydrodesulfurization catalyst and preparation method and application thereof | |
| CN113603087A (en) | Nitrogen-rich biomass-based activated carbon with hierarchical pore microchannel structure and application thereof | |
| CN113289583A (en) | Active carbon desulfurizer loaded with metal oxide as well as preparation method and application thereof | |
| CN104888692B (en) | It is a kind of at the same remove hydrogen sulfide, hydrogen phosphide, the preparation method of arsenic hydride adsorbent | |
| CN112337481A (en) | Catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously and preparation method and application thereof | |
| CN114057193A (en) | Nitrogen-doped activated carbon-based desulfurizer as well as preparation method and application thereof | |
| CN110407210A (en) | A kind of active carbon base catalytic desulfurizing process | |
| CN113546644B (en) | Preparation method and application of catalyst for deeply removing organic sulfur from coke oven gas | |
| CN114832838A (en) | Metal/sulfur-persulfate-loaded biochar composite material and preparation and application thereof | |
| CN103028363B (en) | The sulfur method of gas sweetening adsorbent and preparation method thereof and sulfurous gas | |
| CN109721027B (en) | Method for producing hydrogen by reforming reaction of methane and hydrogen sulfide | |
| CN102059094A (en) | Preparation method of sulfur-removal activated carbon containing copper | |
| CN107597183B (en) | Preparation method of denitration catalyst | |
| Yegiazarov et al. | Adsorption-catalytic process for carbon disulfide removal from air | |
| CN114160181B (en) | Core-shell catalyst for removing organic sulfur, preparation method and application thereof | |
| CN115155628A (en) | Carbon-based desulfurization catalyst, preparation method and application | |
| CN101862640A (en) | Method for preparing desulfurizer used for removing H2S from natural gas | |
| CN111001398B (en) | Modified titanium dioxide catalyst with special morphology and preparation method and application thereof | |
| CN109289770B (en) | Preparation method of yttrium modified methyl mercaptan adsorbing material | |
| CN110538668B (en) | Heteroatom-containing nano carbon material, preparation method thereof and cyclohexane oxidation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |