CN116116409A - Combustion type gas deoxidizing catalyst and preparation method thereof - Google Patents

Combustion type gas deoxidizing catalyst and preparation method thereof Download PDF

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Publication number
CN116116409A
CN116116409A CN202310039134.3A CN202310039134A CN116116409A CN 116116409 A CN116116409 A CN 116116409A CN 202310039134 A CN202310039134 A CN 202310039134A CN 116116409 A CN116116409 A CN 116116409A
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type gas
combustion type
transition metal
catalyst
deoxidizing catalyst
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李玉雪
戚励
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Carbon And Technology Beijing Co ltd
Beijing Feda Geron Air Separating Technique Ltd
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Carbon And Technology Beijing Co ltd
Beijing Feda Geron Air Separating Technique 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/04—Purification or separation of nitrogen
    • C01B21/0405—Purification or separation processes
    • C01B21/0411—Chemical processing only
    • C01B21/0422—Chemical processing only by reduction

Abstract

The invention belongs to the technical field of gas deoxidation and purification, and particularly relates to a combustion type gas deoxidation catalyst and a preparation method thereof. The preparation method of the combustion type gas deoxidizing catalyst comprises the following steps: (1) Soaking a carbon material carrier in a nitric acid solution, performing solid-liquid separation after the soaking is finished, and cleaning and drying the obtained solid to obtain a deoxidized catalyst precursor; (2) Impregnating or spraying the deoxidizing catalyst precursor obtained by the treatment in the step (1) by adopting a solution containing transition metal; (3) And (3) drying and roasting the product obtained by the treatment in the step (2) to obtain the combustion type gas deoxidizing catalyst. The combustion type gas deoxidization catalyst has the advantages of lower deoxidization reaction temperature, less heating heat required by the reaction and low energy consumption.

Description

Combustion type gas deoxidizing catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of gas deoxidation and purification, and particularly relates to a combustion type gas deoxidation catalyst and a preparation method thereof.
Background
Along with the development of modern industry and scientific technology, the requirement on the purity of the gas is higher and higher, and the oxygen in the pure gas is an important index, and the volume fraction of the oxygen in the gas is required to reach 1.0x10 in the production of a plurality of process conditions -6 The following is given. Therefore, the deoxidizer is widely applied to the fields of petrochemical industry, metallurgy, electronics, light industry and the like for removing oxygen in gases with different types and different purposes (shielding gas, reaction gas and carrying gas).
Taking nitrogen as an example, at present, nitrogen deoxidation mainly has 3 major directions, one is hydrodeoxygenation by using air to produce high-purity oxygen and loading noble metals, the noble metals are mainly platinum and palladium, the deoxidization principle is that water is produced by using the reaction of hydrogen and oxygen to remove oxygen in gas, and the catalyst needs to be additionally supplemented with excessive hydrogen in the deoxidization process, so that hydrogen impurities are mixed in the deoxidized gas, and the catalyst cannot be used in the aluminum and magnesium processing industry. The other is combustion type deoxidation, which uses the oxygen in the carbon material and the gas to react to generate CO and CO 2 The catalyst does not introduce hydrogen impurities, but how to reduce the combustion reaction temperature and improve the deoxidization capacity and the deoxidization depth is the key of research.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a combustion type gas deoxidizing catalyst and a preparation method thereof, which are used for solving or improving at least one of the problems of high deoxidizer combustion reaction temperature, low deoxidizing capacity and low deoxidizing depth in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions: a method for preparing a combustion type gas deoxidizing catalyst, comprising the following steps: (1) Soaking a carbon material carrier in a nitric acid solution, performing solid-liquid separation after the soaking is finished, and cleaning and drying the obtained solid to obtain a deoxidized catalyst precursor; (2) Impregnating or spraying the deoxidizing catalyst precursor obtained by the treatment in the step (1) by adopting a solution containing transition metal; (3) And (3) drying and roasting the product obtained by the treatment in the step (2) to obtain the combustion type gas deoxidizing catalyst.
Preferably, the carbon material carrier includes at least one of activated carbon, activated coke, and carbon fiber.
Preferably, the solution containing the transition metal is a transition metal salt solution; the transition metal in the transition metal salt is selected from at least one of iron, copper and zinc; the transition metal salt is selected from at least one of nitrate, carbonate, acetate and hydrochloride.
Preferably, the solution containing the transition metal comprises water and the transition metal immersed in the water; the temperature of water is 90-100 ℃, and the transition metal is copper; the dipping process also comprises the step of introducing carbon dioxide gas into the water.
Preferably, in the step (1), the concentration of the nitric acid solution is 5-10wt%, and the soaking time in the nitric acid solution is 3-5h.
Preferably, in step (1) and/or step (3), the drying temperature is 110-120 ℃ and the drying time is 4-6h.
Preferably, in the step (3), the roasting temperature is 170-200 ℃, and the roasting time is 0.8-1.2h.
The invention also provides a combustion type gas deoxidizing catalyst, which adopts the following technical scheme: the combustion type gas deoxidizing catalyst is prepared by adopting the method; the combustion type gas deoxidizing catalyst comprises a carbon material carrier and an active component; the active component is a transition metal compound.
Preferably, the active component is present in an amount of 0.1wt% to 15wt% on an oxide basis.
Preferably, the active component is present in an amount of 5wt% to 10wt% on an oxide basis.
The beneficial effects are that:
(1) The combustion type gas deoxidization catalyst has the advantages of lower deoxidization reaction temperature, less heating heat required by the reaction and low energy consumption.
(2) The combustion type gas deoxidizing catalyst has low deoxidizing reaction temperature, low equipment requirement and low equipment investment.
(3) The deoxidization reaction product of the combustion type gas deoxidization catalyst of the invention is CO 2 Has polarity, is easy to remove, and is more suitable for the hydrogen production process compared with the gas obtained by hydrodeoxygenation reaction.
(4) The preparation method of the combustion type gas deoxidizing catalyst is simple, the raw material sources are easy to obtain, the preparation cost is low, and the catalyst is suitable for large-scale industrial production.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention provides a preparation method of a combustion type gas deoxidizing catalyst, which aims at least one of the problems of high combustion reaction temperature, low deoxidizing capacity and low deoxidizing depth of deoxidizing agents in the prior art. The preparation method of the combustion type gas deoxidizing catalyst comprises the following steps: (1) Soaking a carbon material carrier in a nitric acid solution, performing solid-liquid separation after the soaking is finished, and cleaning and drying the obtained solid to obtain a deoxidized catalyst precursor; (2) Impregnating or spraying the deoxidizing catalyst precursor obtained by the treatment in the step (1) by adopting a solution containing transition metal; (3) And (3) drying and roasting the product obtained by the treatment in the step (2) to obtain the combustion type gas deoxidizing catalyst.
Through the steps (1) - (3), the transition metal can be fully loaded on the carbon material carrier, the reaction temperature of the carbon material carrier and oxygen molecules is reduced, and further the removal of oxygen can be realized under the condition of reducing the combustion reaction temperature.
In the step (2), the carbon material carrier is soaked in the nitric acid solution, so that the reaming of the carbon material carrier can be realized, and transition metal ions can be absorbed more fully.
In a preferred embodiment of the present invention, step (1) is preceded by the step of sieving and purging the carbon material support. Sieving and purging help to ensure uniformity and cleanliness of the feedstock, and if present, the powder will also absorb transition metals, not only causing waste, but also affecting the absorption of transition metals by the carbon particles.
In a preferred embodiment of the present invention, the carbon material carrier includes at least one of activated carbon, activated coke, and carbon fiber.
In a preferred embodiment of the present invention, the solution containing a transition metal is a transition metal salt solution; the transition metal in the transition metal salt is selected from at least one of iron, copper and zinc; the transition metal salt is selected from at least one of nitrate, carbonate, acetate and hydrochloride.
In a preferred embodiment of the present invention, the solution containing the transition metal includes water and the transition metal immersed in the water; the temperature of water is 90-100deg.C (for example, 90deg.C, 92deg.C, 94deg.C, 98deg.C or 100deg.C), and the transition metal is copper; the dipping process also comprises the step of introducing carbon dioxide gas into the water.
In a preferred embodiment of the invention, in step (1), the concentration of the nitric acid solution is 5wt% to 10wt% (e.g., 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10 wt%), and the time of soaking in the nitric acid solution is 3 to 5 hours (e.g., 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours). If the concentration of the nitric acid is too high, the pore canal of the carbon material carrier is damaged; if the concentration of nitric acid is too low, reaming of the carbon material carrier is not easily achieved.
In a preferred embodiment of the invention, in step (1) and/or step (3), the drying is carried out at a temperature of 110-120 ℃ (e.g. 110 ℃, 112 ℃, 114 ℃, 116 ℃, 118 ℃ or 120 ℃), and the drying time is 4-6 hours (e.g. 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours).
In a preferred embodiment of the invention, in step (3), the temperature of calcination is 170-200deg.C (e.g., 170deg.C, 175 deg.C, 180deg.C, 185 deg.C, 190 deg.C, 195 deg.C or 200deg.C) and the time of calcination is 0.8-1.2h (e.g., 0.8h, 0.9h, 1.0h, 1.1h or 1.2 h). In the step (3), if the baking temperature is too low, decomposition of the transition metal salt (e.g., copper nitrate) cannot be achieved; if the roasting temperature is too high, energy waste is caused. If the roasting time is too short, the transition metal salt is not thoroughly decomposed; if the roasting time is too long, energy waste is caused, and the production efficiency is low.
The invention also provides a combustion type gas deoxidizing catalyst, which is prepared by adopting the method, and comprises a carbon material carrier and an active component, wherein the active component is a transition metal compound (for example, a transition metal oxide).
The deoxidization principle of the combustion type gas deoxidization catalyst of the invention is that the empty d orbit or d orbit electron of the transition metal is utilized to reduce the reaction activation energy, namely the temperature of the reaction of the carbon material and oxygen molecules is reduced, and CO are generated by the combustion of the carbon material and oxygen 2 Thereby achieving the purpose of deoxidization.
In a preferred embodiment of the combustion type gas deoxygenation catalyst of the present invention, the content of the active component is 0.1wt% to 15wt% (e.g., 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 7wt%, 9wt%, 11wt%, 13wt%, 14wt%, 14.9wt% or 15 wt%) in terms of oxide. The higher the content of the transition metal oxide in the combustion type gas deoxidizing catalyst, the more remarkable the catalytic performance of the deoxidizing catalyst, which is shown by lower combustion temperature and higher deoxidizing depth during deoxidization; the lower the deoxidizing combustion temperature is, the lower the energy consumption is, the unsafe of the industrial device is caused, the production cost of the deoxidizer is increased, and the deoxidizing effect cannot be achieved even if the content of the transition metal oxide is too low, so the content of the transition metal oxide is generally in a certain range.
In a preferred embodiment of the combustion type gas deoxygenation catalyst of the present invention, the active component is present in an amount of 5wt% to 10wt% (e.g., 5wt%, 6wt%, 8wt% or 10 wt%) on an oxide basis.
The combustion type gas deoxidizing catalyst of the present invention and the method for preparing the same will be described in detail with reference to specific examples.
Example 1
The preparation method of the combustion type gas deoxidizing catalyst of the present embodiment comprises the following steps:
(1) Weigh 20g of activated carbon in 75mL of HNO with 5% concentration 3 Soaking for 5h, pouring out the solution after 5h, washing for 5 times by using distilled water, pouring wet activated carbon into a Buchner funnel, vacuum filtering, and drying the filtered activated carbon in a baking oven at 110 ℃ for 2h to obtain the deoxidized catalyst precursor.
(2) Placing a deoxidized catalyst precursor into a copper nitrate solution (prepared by weighing 15g of copper nitrate trihydrate, dissolving the copper nitrate trihydrate in 85mL of water, preparing to obtain a 15% copper nitrate solution) with equal volume, and soaking for 6 hours;
(3) After the impregnation was completed, the obtained solid was dried in an oven at 110℃and calcined in a muffle furnace at 170℃for 1 hour to prepare the combustion-type gas deoxidization catalyst of this example.
The copper content of the combustion type gas deoxidizing catalyst of this example was about 5% (in terms of CuO).
Example 2
The preparation method of the combustion type gas deoxidizing catalyst of the present embodiment comprises the following steps:
(1) Weigh 20g of activated carbon in 75mL of HNO with concentration of 10% 3 Soaking for 3 hours, pouring out the solution after 3 hours, washing for 3 times by distilled water, pouring wet activated carbon into a Buchner funnel, vacuum filtering, and drying the filtered activated carbon in a baking oven at 110 ℃ for 2 hours to obtain the deoxidized catalyst precursor.
(2) Placing a deoxidized catalyst precursor into a copper nitrate solution (prepared by weighing 30g of copper nitrate trihydrate, dissolving the copper nitrate trihydrate in 70mL of water, preparing to obtain 30% copper nitrate solution) with equal volume, and soaking for 5h;
(3) After the impregnation was completed, the obtained solid was dried in an oven at 110℃and calcined in a muffle furnace at 170℃for 1 hour to prepare the combustion-type gas deoxidization catalyst of this example.
The copper content of the combustion type gas deoxidizing catalyst of this example was about 10% (in terms of CuO).
Example 3
The preparation method of the combustion type gas deoxidizing catalyst of the present embodiment comprises the following steps:
(1) Weigh 20g of activated carbon in 75mL of HNO with concentration of 10% 3 Soaking for 3 hours, pouring out the solution after 3 hours, washing for 3 times by distilled water, pouring wet activated carbon into a Buchner funnel, vacuum filtering, and drying the filtered activated carbon in a baking oven at 110 ℃ for 2 hours to obtain the deoxidized catalyst precursor.
(2) Placing the deoxidized catalyst precursor into an equal volume of basic copper carbonate solution (preparing the basic copper carbonate solution according to the following method, weighing 30g of basic copper carbonate, dissolving in 70mL of water, preparing to obtain 30% of basic copper carbonate solution), and soaking for 5h;
(3) After the impregnation was completed, the obtained solid was dried in an oven at 110℃and calcined in a muffle furnace at 220℃for 1 hour to prepare the combustion-type gas deoxidization catalyst of this example.
The copper content of the combustion type gas deoxidizing catalyst of this example was about 10% (in terms of CuO).
Example 4
(1) Weigh 20g of activated carbon in 75mL of HNO with concentration of 10% 3 Soaking for 3 hours, pouring out the solution after 3 hours, washing for 3 times by distilled water, pouring wet activated carbon into a Buchner funnel, vacuum filtering, and drying the filtered activated carbon in a baking oven at 110 ℃ for 2 hours to obtain the deoxidized catalyst precursor.
(2) Placing a deoxidizing catalyst precursor into a mixed solution of ferrous nitrate and cupric nitrate (the ferrous nitrate solution is prepared according to the following method, namely, 10g of ferrous nitrate and 20g of cupric nitrate trihydrate are weighed and dissolved in 70mL of water, and the mixed solution of ferrous nitrate and cupric nitrate is prepared) in an equal volume, and immersing for 5 hours;
(3) After the impregnation was completed, the obtained solid was dried in an oven at 110℃and calcined in a muffle furnace at 170℃for 1 hour to prepare the combustion-type gas deoxidization catalyst of this example.
The copper content of the combustion type gas deoxidizing catalyst of this example was about 7% (in terms of CuO) and the iron content was about 3% (in terms of FeO).
Example 5
(1) Weigh 20g of activated carbon in 75mL of HNO with concentration of 10% 3 Soaking for 3 hours, pouring out the solution after 3 hours, washing for 3 times by distilled water, pouring wet activated carbon into a Buchner funnel, vacuum filtering, and drying the filtered activated carbon in a baking oven at 110 ℃ for 2 hours to obtain the deoxidized catalyst precursor.
(2) Placing the deoxidization catalyst precursor in hot water at 90-100 ℃, inserting a copper sheet at the same time, and then introducing carbon dioxide gas for about 1h;
(3) After the reaction was completed, the obtained solid was dried in an oven at 110℃and calcined in a muffle furnace at 220℃for 1 hour to prepare the combustion-type gas deoxidizing catalyst of this example.
The copper content of the combustion type gas deoxidizing catalyst of this example was about 10% (in terms of CuO).
Comparative example 1
This comparative example differs from example 1 only in that: the copper content of the deoxidizer of this comparative example was 2% (in terms of CuO), and the remainder was the same as in example 1.
Comparative example 2
This comparative example differs from example 2 only in that: the deoxidizer of this comparative example had a copper content of 15% (in terms of CuO), and the remainder was identical to example 2.
Experimental example
The deoxidizing effect of the deoxidizing agent of comparative examples 1 to 2 was evaluated by the combustion type gas deoxidizing catalyst of examples 1 to 5, respectively
The testing method comprises the following steps: 1g of combustion type gas deoxidizing catalyst is respectively taken and filled into a reactor, the reactor is heated to 250 ℃, nitrogen with the oxygen content of about 0.2% is introduced, the flow is about 500mL/min, the temperature is continuously raised until the oxygen content at the outlet of the reactor is zero, and the change of the oxygen content at the outlet at different temperatures is recorded. The inlet oxygen content was 2000ppm and the outlet oxygen content was less than 10ppm, the results are given in tables 1-5 below:
table 1 table of deoxidation test experimental results of the combustion type gas deoxidation catalyst of example 1
Reaction time/h 0 1 2 3 4 5
Reaction temperature/. Degree.C 246 298 299 298 298 298
Outlet oxygen content/ppm 49 4 No measurement was made No measurement was made No measurement was made No measurement was made
Table 2 table of deoxidation test experimental results of the combustion type gas deoxidation catalyst of example 2
Reaction time/h 0 1 2 3 4 5
Reaction temperature/. Degree.C 234 269 289 280 272 283
Outlet oxygen content/ppm 16 9 No measurement was made No measurement was made No measurement was made No measurement was made
Table 3 table of deoxidation test experimental results of the combustion type gas deoxidation catalyst of example 3
Reaction time/h 0 1 2 3 4 5
Reaction temperature/. Degree.C 198 241 288 298 295 285
Outlet oxygen content/ppm 162 12 3 No measurement was made No measurement was made No measurement was made
Table 4 table of deoxidation test experimental results of the combustion type gas deoxidation catalyst of example 4
Reaction time/h 0 1 2 3 4 5
Reaction temperature/. Degree.C 232 269 296 287 272 276
Outlet oxygen content/ppm 86 10 No measurement was made No measurement was made No measurement was made No measurement was made
Table 5 table of deoxidation test experimental results of the combustion type gas deoxidation catalyst of example 5
Reaction time/h 0 1 2 3 4 5
Reaction temperature/. Degree.C 240 250 265 260 255 256
Outlet oxygen content/ppm 29 3 No measurement was made No measurement was made No measurement was made No measurement was made
Table 6 shows the results of deoxidation test experiments on the combustion type gas deoxidation catalyst of comparative example 1
Reaction time/h 0 1 2 3 4 5
Reaction temperature/. Degree.C 260 316 338 345 330 340
Outlet oxygen content/ppm 115 27 4 No measurement was made No measurement was made No measurement was made
Table 7 shows the results of deoxidation test experiments on the combustion type gas deoxidation catalyst of comparative example 2
Reaction time/h 0 1 2 3 4 5
Reaction temperature/. Degree.C 225 269 297 267 278 260
Outlet oxygen content/ppm 5 1 No measurement was made No measurement was made No measurement was made No measurement was made
Conclusion of experiment:
it can be seen from tables 1 and 2 that the deoxidizing catalyst having a copper loading of 10% was lower in deoxidizing temperature than the deoxidizing catalyst having a copper loading of 5% and that the deoxidizing catalyst having a copper loading of 5% -10% was reasonable in deoxidizing effect in view of economical applicability.
Compared with Table 2, the deoxidizing catalyst prepared by different methods and different raw materials has small gap in the catalytic reaction, and has good deoxidizing effect.
As can be seen from Table 4, the addition of two transition metals also gives a good deoxidizing effect, but in view of cost and industrial production efficiency, it is recommended to use a single transition metal element.
As can be seen from the data in Table 5, the oxygen scavenger precursor is impregnated in the copper sheet and hot water at the same time in example 5, so that the production efficiency is greatly improved, and compared with other production methods such as example 3, the reaction temperature of the combustion type gas deoxidation catalyst prepared in example 5 is lower (the temperature for completely removing oxygen), and the catalytic effect is better (the combustion type gas deoxidation catalyst in example 5 can realize complete removal of oxygen within 2 hours, and the combustion type gas deoxidation catalyst in example 3 can realize complete removal of oxygen within 3 hours); and the raw materials are available, the price is low, and the preparation method of the embodiment 6 is more suitable for industrial production.
The copper-containing deoxidizing catalyst prepared in comparative example 1 was used, and nitrogen gas having an oxygen content of about 0.2% was introduced, and when the reaction temperature reached 340℃or higher, the outlet oxygen content was less than 5ppm. The comparative example has a catalytic function, but has weak catalytic function, the ignition temperature is reduced to a limited extent, and the energy is not saved.
The copper-containing deoxidizing catalyst produced by the comparative example 2 has very low catalytic temperature and better catalytic depth, but spontaneous combustion phenomenon occurs in the drying process without isolating air, which indicates that the catalyst has too low light-off temperature and too active catalytic performance and cannot be used for industrial production.
Aiming at different preparation methods of the deoxidizing catalyst, the embodiment 5 is more suitable for industrialization because the operation is simple and pollution-free, and in addition, the deoxidizing catalyst has no toxic and harmful gas in the roasting and decomposing process, is harmless to human body and does not pollute the environment. In contrast, examples 1-2 and 4, take-offThe oxygen catalyst generates NO in the roasting decomposition process 2 The gas not only can cause chronic poisoning of human body, but also can pollute the environment and cause acid rain. In addition, the raw materials of examples 1-4 are chemicals, the access is limited, and the storage condition is high; in the embodiment 5, the raw materials are common and easy to obtain, the production and storage requirements are low, and the method is more suitable for large-scale production. Moreover, example 5 can achieve the loading of the transition metal on the carbon material support in a shorter time (shorter time of immersion in the solution containing the transition metal), and the efficiency of the deoxidizing catalyst preparation is higher.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for preparing a combustion type gas deoxidizing catalyst, which is characterized by comprising the following steps:
(1) Soaking a carbon material carrier in a nitric acid solution, performing solid-liquid separation after the soaking is finished, and cleaning and drying the obtained solid to obtain a deoxidized catalyst precursor;
(2) Impregnating or spraying the deoxidizing catalyst precursor obtained by the treatment in the step (1) by adopting a solution containing transition metal;
(3) And (3) drying and roasting the product obtained by the treatment in the step (2) to obtain the combustion type gas deoxidizing catalyst.
2. The method for producing a combustion type gas deoxidizing catalyst according to claim 1, wherein the carbon material carrier comprises at least one of activated carbon, activated coke, and carbon fiber.
3. The method for producing a combustion type gas deoxidizing catalyst according to claim 1, wherein the solution containing a transition metal is a transition metal salt solution;
the transition metal in the transition metal salt is selected from at least one of iron, copper and zinc;
the transition metal salt is selected from at least one of nitrate, carbonate, acetate and hydrochloride.
4. The method for preparing a combustion type gas deoxidizing catalyst according to claim 1, wherein the solution containing a transition metal comprises water and a transition metal immersed in the water;
the temperature of water is 90-100 ℃, and the transition metal is copper;
the dipping process also comprises the step of introducing carbon dioxide gas into the water.
5. The method for preparing a combustion type gas deoxidizing catalyst according to claim 1, wherein in the step (1), the concentration of the nitric acid solution is 5wt% to 10wt%, and the soaking time in the nitric acid solution is 3 to 5 hours.
6. The method for producing a combustion type gas deoxidizing catalyst according to claim 1, wherein in the step (1) and/or the step (3), the drying temperature is 110 to 120 ℃ and the drying time is 4 to 6 hours.
7. The method for producing a combustion type gas deoxidizing catalyst according to claim 1, wherein in the step (3), the baking temperature is 170 to 200 ℃ and the baking time is 0.8 to 1.2 hours.
8. A combustion type gas deoxidizing catalyst, characterized in that the combustion type gas deoxidizing catalyst is prepared by the method of any one of claims 1-7;
the combustion type gas deoxidizing catalyst comprises a carbon material carrier and an active component;
the active component is a transition metal compound.
9. The combustion type gas deoxidizing catalyst according to claim 8, wherein the content of the active component is 0.1 to 15wt% in terms of oxide.
10. The combustion type gas deoxidizing catalyst according to claim 9, wherein the content of the active component is 5 to 10wt% in terms of oxide.
CN202310039134.3A 2023-01-12 2023-01-12 Combustion type gas deoxidizing catalyst and preparation method thereof Pending CN116116409A (en)

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CN117427641A (en) * 2023-12-12 2024-01-23 华能国际电力股份有限公司德州电厂 Low-temperature ceramic catalyst and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117427641A (en) * 2023-12-12 2024-01-23 华能国际电力股份有限公司德州电厂 Low-temperature ceramic catalyst and preparation method and application thereof
CN117427641B (en) * 2023-12-12 2024-04-02 华能国际电力股份有限公司德州电厂 Low-temperature ceramic catalyst and preparation method and application thereof

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