CN109772354B - Deoxygenation catalyst and preparation method and application thereof - Google Patents
Deoxygenation catalyst and preparation method and application thereof Download PDFInfo
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- CN109772354B CN109772354B CN201711119022.XA CN201711119022A CN109772354B CN 109772354 B CN109772354 B CN 109772354B CN 201711119022 A CN201711119022 A CN 201711119022A CN 109772354 B CN109772354 B CN 109772354B
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Abstract
The invention discloses a deoxidation catalyst and a preparation method thereof, wherein the preparation method of the deoxidation catalyst comprises the following steps: (1) impregnating silicon oxide with mixed liquid containing Nd and nickel, and then drying and roasting at high temperature to prepare modified silicon oxide; (2) loading cobalt on the modified silicon oxide prepared in the step (1), and drying and roasting to prepare cobalt-loaded silicon oxide; (3) and (4) kneading and molding zirconium sulfate and the cobalt-loaded silicon oxide prepared in the step (3), and drying and roasting to obtain the deoxidation catalyst. The catalyst is used for deoxidizing the coal bed gas and has the advantages of high activity, low reaction temperature, simple preparation method, low cost and the like.
Description
Technical Field
The invention relates to a deoxidation catalyst, a preparation method and application thereof, in particular to a coal bed methane deoxidation composite catalyst, and a preparation method and application thereof.
Background
China is a large coal producing country, coal bed gas with different concentrations can be produced due to coal production every year, and developing effective coal bed gas utilization technology and reducing direct emission of methane are a component part for building an energy-saving and environment-friendly sustainable development mode and building a low-carbon economic system in China. The method has the advantages that the low-grade energy source coal bed gas is practically and reasonably developed by combining energy conservation and emission reduction and improvement of the requirement on the environment, the low-grade energy source coal bed gas is well converted into available resources, the application range and the scale of the coal bed gas are expanded, the utilization efficiency of the coal bed gas is improved, the dual meanings of energy conservation and environmental protection are realized, the national planning on energy policies is met, the control of the international environmental protection organization on the greenhouse effect is met, the strong support of China on the development and the use of the low-grade energy source is better met, and the domestic rapid development of the coal bed gas industry is promoted.
The key point of the development and utilization of the coal bed gas is to remove oxygen in the coal bed gas, and the existing coal bed gas deoxidation technology mainly comprises a pressure swing adsorption separation method, a coke combustion method, a catalytic deoxidation method and the like. Chinese patent ZL85103557 discloses a method for separating and enriching methane from coal bed gas by using a pressure swing adsorption method. Generally, the oxygen content of the exhaust gas discharged in the concentration and purification process of methane is also concentrated and improved, and the exhaust gas inevitably contains 5-15% of methane, so that the discharged exhaust gas is in the explosion limit range of methane, and explosion danger exists, so that the application of the technology is limited.
The deoxidation method by using coke combustion (ZL 02113627.0, 200610021720.1) is characterized in that oxygen in methane-rich gas reacts with coke under the high-temperature condition, and part of methane reacts with oxygen to achieve the aim of deoxidation. The advantage is that about 70% of the oxygen reacts with coke and 30% of the oxygen reacts with methane, so that methane losses are smaller. But the disadvantage is that the precious coke resource is consumed, and the coke consumption cost accounts for about 50 percent of the whole operation cost. In addition, the coke deoxidation method has high labor intensity during coke feeding and slag discharging, large environmental dust and difficulty in realizing self-control operation and large-scale production, and the coke contains sulfides in various forms, so that the sulfur content in the gas after oxygen removal is increased.
The essence of the catalytic deoxidation process is that methane is catalytically combusted under rich-fuel oxygen-poor atmosphere, and CH is subjected to catalytic oxidation under the action of a proper catalyst4Oxidative conversion to CO2And H2And O, the oxygen content in the coal bed gas can be reduced to be below 0.5 percent in the process, and the potential safety hazard in the operation process is thoroughly eliminated. Meanwhile, the process is simple and convenient to operate, automatic control and large-scale expansion are facilitated, equipment is simple, and the technology has a good commercial value in the aspect of economy. Catalytic deoxidation can be divided into two main categories, namely noble metal catalysts and non-noble metal catalysts according to active components of the catalysts.
The technology for researching the supported noble metal catalyst at home and abroad is mature. For example, rare earth cerium component with oxygen storage and release functions is added into a catalyst system for the large-scale ligation of Chinese academy of sciences to prepare the novel supported palladium noble metal catalyst, and the oxygen concentration in produced gas is within 0.1 percent and the oxygen conversion rate is higher than 96 percent after the deoxidation treatment of coal bed gas with the methane concentration of 39.15 percent and the oxygen concentration of 12.6 percent. Since the noble metal catalyst is expensive and has limited resources, the range of application is limited. And the non-noble metal oxide catalyst has low cost and easy availability, so the catalyst is greatly concerned. However, the non-noble metal is limited by activity, and the reaction needs to be carried out at a higher temperature, so that the energy consumption is higher.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a coal bed gas deoxidation catalyst and a preparation method thereof. The catalyst is used for deoxidizing the coal bed gas and has the advantages of high activity, low reaction temperature, simple preparation method, low cost and the like.
A preparation method of a deoxidation catalyst comprises the following steps:
(1) impregnating silicon oxide with mixed liquid containing Nd and nickel, and then drying and roasting at high temperature to prepare modified silicon oxide;
(2) loading cobalt on the modified silicon oxide prepared in the step (1), and drying and roasting to prepare cobalt-loaded silicon oxide;
(3) and (4) kneading and molding zirconium sulfate and the cobalt-loaded silicon oxide prepared in the step (3), and drying and roasting to obtain the deoxidation catalyst.
In the method, in the mixed liquid containing Nd and nickel in the step (1), the molar concentrations of metal ions Nd and nickel are the same, generally 0.1-2.5mol/L, preferably 0.5-1.5mol/L, and the mixed liquid is roasted at 700-1000 ℃ for 1-10 h after being dried, preferably at 800-900 ℃ for 2-8 h after being dried. The impregnation is preferably carried out by an equal volume impregnation method. The silica can be prepared using commercially available products or according to the prior art. Nd and nickel are derived from corresponding salts, such as nitrate, sulfate, chloride and the like. The mixed liquid of Nd and nickel is used for dipping the silicon oxide and then is roasted at high temperature, and the niobium-nickel composite oxide with the perovskite structure is generated on the inner surface and the outer surface of the silicon oxide, and the composite oxide with the perovskite structure can improve the oxygen concentration shown by the silicon oxide and can inhibit the sintering and inactivation of cobalt.
The above method, the preparation of the cobalt-supported silica in the step (2), can employ conventional techniques, including any method of supporting cobalt on silica. Specifically, the cobalt-containing compound is impregnated and loaded on the molded silicon oxide, or the cobalt-containing compound and the silicon oxide powder are kneaded and molded, and then the obtained product is dried and roasted to obtain the cobalt-loaded silicon oxide. The compound carrying cobalt can be one or more of cobalt nitrate, cobalt sulfate, cobalt bromide and cobalt chloride. The drying time is 1-5h, preferably 2-4h, the drying temperature is 90-150 ℃, preferably 100-130 ℃; the roasting time is 3-8h, preferably 4-6h, and the temperature is 300-600 ℃, preferably 400-500 ℃.
In the above method, the impregnation solution supporting cobalt in step (2) contains at least one of 2, 5-dihydroxy-terephthalic acid and 1,3, 5-benzenetricarboxylic acid, and the mass content of at least one of 2, 5-dihydroxy-terephthalic acid and 1,3, 5-benzenetricarboxylic acid in the impregnation solution is 0.5% to 10%, preferably 2% to 7%. The 2, 5-dihydroxy-terephthalic acid or 1,3, 5-benzene tricarboxylic acid added into the mixed solution has stronger coordination effect with cobalt ions, can improve the dispersion degree of copper on alumina, and further improves the activity of the catalyst.
In the method, a proper amount of peptizing agent, pore-forming agent, metal auxiliary agent and the like can be added in the kneading process in the step (3) according to the requirements.
In the method, before the zirconium sulfate is kneaded in the step (3), the cobalt-loaded silicon oxide is preferably treated by using a water vapor nitrogen gas mixture with the water vapor volume content of 1% -15%, preferably 1% -5%, the treatment temperature is 150-. The zirconium sulfate treated by water vapor can improve the hydrophilicity of the surface of the zirconium sulfate, is beneficial to the dispersion of the zirconium sulfate, and further improves the activity.
The catalyst prepared by the method has the weight ratio of silicon oxide to zirconium silicate of 10:1-6:1, and the weight content of cobalt oxide in the catalyst is 5-25%.
Research results show that the mechanism of catalytic combustion of the coal bed gas is that methane is firstly dissociated into CH on the surface of the catalytic combustion catalystxSpecies of which x<4, then carrying out oxidation reaction with the adsorbed oxygen or lattice oxygen. This application will catalyze burning catalyst and have the stronger zirconium sulfate of methane activation ability to mix, methane can be activated on zirconium sulfate molecular sieve, and the methane species after the activation can overflow to the catalytic combustion catalyst on every side and react, burns more easily fast, has showing the activity that has improved the catalyst, and composite metal oxide NdCoO who has perovskite structure that contains in this application catalyst in addition has a perovskite structure3-yHas rich oxygen spaceThe oxygen adsorption capacity is strong, which is beneficial to the enrichment of oxygen and the high-efficiency reaction.
Detailed Description
The action and effect of a deoxygenation catalyst and a preparation method thereof according to the present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the present invention. In this application,% is volume concentration unless otherwise specified.
Example 1
Preparation of modified silica: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g) is soaked in Nd nitrate and nickel nitrate aqueous solution, the molar concentration of Nd and nickel metal ions in the solution is 0.5mol/L, and drying and roasting are carried out after soaking, wherein the drying time is 1h, and the drying temperature is 100 ℃; the roasting time is 2 hours, and the temperature is 900 ℃;
preparation of cobalt-loaded silica: soaking a cobalt nitrate solution on the modified silicon oxide by adopting an isometric soaking method, and drying and roasting after soaking, wherein the drying time is 2 hours, and the drying temperature is 130 ℃; the roasting time is 4 hours, and the temperature is 400 ℃;
kneading and molding zirconium sulfate and cobalt-loaded silicon oxide, and drying and roasting to prepare the deoxidation catalyst, wherein the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 6h, and the temperature is 400 ℃. The weight ratio of silicon oxide to zirconium silicate in the catalyst was 8:1, and the weight content of cobalt oxide in the catalyst was 15%.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)4 20 vol%，O23 vol%, the balance being N2. The reaction temperature is 450 ℃, and the volume space velocity is 11000 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.56%.
Example 2
Preparation of modified silica: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, pore volume of 0.86 ml/g) was immersed in an aqueous solution of Nd nitrate and nickel nitrate, in which Nd and nickel metal ions were presentThe molar concentration of the raw materials is 1.5mol/L, and the raw materials are dried and roasted after being soaked, wherein the drying time is 2 hours and the drying temperature is 100 ℃; the roasting time is 8 hours, and the temperature is 700 ℃;
preparation of cobalt-loaded silica: soaking a cobalt sulfate solution on the modified silicon oxide by adopting an isometric soaking method, drying and roasting after soaking, wherein the drying time is 3 hours, and the drying temperature is 120 ℃; the roasting time is 5 hours, and the temperature is 450 ℃;
kneading and molding zirconium sulfate and cobalt-loaded silicon oxide, and drying and roasting to prepare the deoxidation catalyst, wherein the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 6h, and the temperature is 400 ℃. The weight ratio of silicon oxide to zirconium silicate in the catalyst was 10:1, and the weight content of cobalt oxide in the catalyst was 25%.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)4 20 vol%，O23 vol%, the balance being N2. The reaction temperature is 450 ℃, and the volume space velocity is 14000 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.62%.
Example 3
Preparation of modified silica: an isovolumetric impregnation method was used to impregnate silica (commercially available, having the following properties: specific surface 335 m)2Per g, the pore volume is 0.86 ml/g) is soaked in Nd nitrate and nickel nitrate aqueous solution, the molar concentration of Nd and nickel metal ions in the solution is 1mol/L, and drying and roasting are carried out after soaking, wherein the drying time is 0.5h, and the drying temperature is 130 ℃; the roasting time is 5 hours, and the temperature is 800 ℃;
preparation of cobalt-loaded silica: soaking a cobalt bromide solution on the modified silicon oxide by adopting an isometric soaking method, and drying and roasting after soaking, wherein the drying time is 4 hours and the drying temperature is 100 ℃; the roasting time is 4 hours, and the temperature is 500 ℃;
preparation of cobalt-loaded silica: soaking a cobalt sulfate solution on the modified silicon oxide by adopting an isometric soaking method, drying and roasting after soaking, wherein the drying time is 3 hours, and the drying temperature is 120 ℃; the roasting time is 5 hours, and the temperature is 450 ℃;
kneading and molding zirconium sulfate and cobalt-loaded silicon oxide, and drying and roasting to prepare the deoxidation catalyst, wherein the drying time is 4 hours, and the drying temperature is 100 ℃; the roasting time is 6h, and the temperature is 400 ℃. The weight ratio of silicon oxide to zirconium silicate in the catalyst was 7:1, and the weight content of cobalt oxide in the catalyst was 8%.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)4 20 vol%，O23 vol%, the balance being N2. The reaction temperature is 450 ℃, and the volume space velocity is 12000 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.46%.
Example 4
The process is carried out in the same manner as in example 1 except that the cobalt sulfate solution contains 6% by mass of 2, 5-dihydroxy-terephthalic acid, and the resulting product is impregnated with alumina, dried, and calcined.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)4 20 vol%，O23 vol%, the balance being N2. The reaction temperature is 450 ℃, and the volume space velocity is 11000 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.02%.
Example 5
The same procedure as in example 1 was repeated except that the cobalt sulfate solution contained 3% by mass of 1,3, 5-benzenetricarboxylic acid.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)4 20 vol%，O23 vol%, the balance being N2. The reaction temperature is 450 ℃, and the volume space velocity is 11000 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.
Example 6
The difference from example 1 is that before kneading, the commercially available zirconium sulfate was treated with a steam-nitrogen mixture gas containing 1% by volume of steam at 180 ℃ for 3 min.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)4 20 vol%，O23 vol%, the balance being N2. The reaction temperature is 450 ℃, and the volume space velocity is 11000 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.23%.
Example 7
The difference from example 1 is that before kneading, the commercially available zirconium sulfate was treated with a mixture of steam and nitrogen at a steam volume content of 4% at a temperature of 120 ℃ for a period of 10 min.
The catalyst performance is evaluated by taking coal bed methane deoxidation as a probe reaction, and the feed gas comprises the following components: CH (CH)4 20 vol%，O23 vol%, the balance being N2. The reaction temperature is 450 ℃, and the volume space velocity is 11000 h-1After the reaction is stable, detecting O in tail gas at the outlet of the reactor by on-line chromatography2The concentration was 0.29%.
Claims (12)
1. A method for preparing a deoxygenation catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) impregnating silicon oxide with mixed liquid containing Nd and nickel, and then drying and roasting at high temperature to prepare modified silicon oxide;
(2) loading cobalt on the modified silicon oxide prepared in the step (1), and drying and roasting to prepare cobalt-loaded silicon oxide;
(3) and (4) kneading and molding zirconium sulfate and the cobalt-loaded silicon oxide prepared in the step (3), and drying and roasting to obtain the deoxidation catalyst.
2. The method of claim 1, wherein: in the mixed liquid containing Nd and nickel in the step (1), the molar concentrations of metal ions Nd and nickel are both 0.1-2.5mol/L, the mixed liquid is dried and then roasted at 700-1000 ℃ for 1-10 h, and the impregnation adopts an isometric impregnation method.
3. The method of claim 2, wherein: in the mixed liquid containing Nd and nickel in the step (1), the molar concentrations of metal ions Nd and nickel are the same and are both 0.5-1.5mol/L, and the mixed liquid is roasted for 2-8 h at the temperature of 800-900 ℃ after being dried.
4. The method of claim 1, wherein: in the step (2), the cobalt-loaded silicon oxide is prepared by impregnating a cobalt-containing compound on the molded silicon oxide or kneading the cobalt-containing compound and silicon oxide powder for molding, and then drying and roasting.
5. The method of claim 4, wherein: the cobalt compound is one or more of cobalt nitrate, cobalt sulfate, cobalt bromide and cobalt chloride.
6. The method of claim 4, wherein: the drying time is 1-5h, and the drying temperature is 90-150 ℃; the roasting time is 3-8h, and the temperature is 300-600 ℃.
7. The method of claim 4, wherein: the impregnation liquid for loading cobalt contains at least one of 2, 5-dihydroxy-terephthalic acid and 1,3, 5-benzene tricarboxylic acid, and the mass content of at least one of 2, 5-dihydroxy-terephthalic acid and 1,3, 5-benzene tricarboxylic acid in the impregnation liquid is 0.5-10%.
8. The method of claim 7, wherein: the mass content of at least one of 2, 5-dihydroxy-terephthalic acid or 1,3, 5-benzene tricarboxylic acid in the impregnation liquid is 2-7%.
9. The method of claim 1, wherein: and (4) adding a peptizing agent, a pore-forming agent or a metal auxiliary agent as required in the kneading process in the step (3).
10. The method of claim 1, wherein: before the zirconium sulfate is kneaded in the step (3), the cobalt-loaded silicon oxide is treated by adopting water vapor nitrogen mixed gas with the water vapor volume content of 1-15%, the treatment temperature is 150-.
11. The method of claim 10, wherein: before the zirconium sulfate is kneaded in the step (3), the cobalt-loaded silicon oxide is treated by adopting water vapor nitrogen mixed gas with the water vapor volume content of 1-5%, the treatment temperature is 180-200 ℃, and the treatment time is 5-15 min.
12. A catalyst prepared by the process of any one of claims 1 to 11, wherein: the weight ratio of the silicon oxide to the zirconium silicate in the catalyst is 10:1-6:1, and the weight content of the cobalt oxide in the catalyst is 5-25%.
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