CN109833874B - Nickel catalyst and preparation method and application thereof - Google Patents
Nickel catalyst and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 146
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000007864 aqueous solution Substances 0.000 claims abstract description 50
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 38
- 239000012065 filter cake Substances 0.000 claims abstract description 35
- 239000003513 alkali Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 239000003345 natural gas Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 34
- 229910052759 nickel Inorganic materials 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 description 24
- 238000001556 precipitation Methods 0.000 description 16
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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Abstract
The invention provides a nickel catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) at the constant temperature of 75-90 ℃, simultaneously dripping an aluminum nitrate aqueous solution and an alkali solution into water to obtain a first solution, stirring and standing; 2) filtering the first solution, and washing a filter cake until the pH value of the filtrate is neutral; adding the filter cake into the second solution, stirring, and carrying out ultrasonic treatment for 10-60min to obtain a third solution; wherein the second solution is an aqueous solution of soluble organic fuel and nickel nitrate; 3) heating the third solution to 710-800 ℃ to burn the third solution, and collecting the burnt powder to obtain the oxide of the nickel-based catalyst; 4) and carrying out reduction reaction on the reducing gas and the oxide of the nickel-based catalyst to obtain the nickel catalyst. The nickel catalyst prepared by the method has better Ni dispersibility and larger specific surface area, and can improve the catalytic efficiency of methanation reaction.
Description
Technical Field
The invention relates to a catalyst technology, in particular to a nickel catalyst, a preparation method and application thereof, and belongs to the technical field of methanation reaction catalysts.
Background
Methane is an important fuel and chemical intermediate, and can be used for synthesizing various compounds such as ethylene, acetylene, formaldehyde and the like. In recent years, with the rapid increase of natural gas demand in China, the gap between supply and demand of domestic natural gas resources is gradually increased. The method for producing the substitute natural gas by taking the coal-made synthesis gas as the raw material and carrying out methanation reaction is an effective way for improving the domestic natural gas supply condition. Methanation is the core technology of substitute natural gas, and the reaction refers to CO or CO2Hydrogenation synthesis of CH under the action of catalyst4And H2O, the reaction formula is as follows:
CO+3H2＝CH4+H2O+206KJ/mol (1)
CO2+4H2＝CH4+2H2O+165KJ/mol (2)
at present, large-scale carbon monoxide hydromethanation technology is industrialized, a multi-stage series fixed bed reaction process is mostly adopted, and representative technical schemes comprise German Lurgi (LURGI), British David (DAVY) and Denmark Topyol
Three kinds of the components are adopted. Most of the catalysts adopted in the reaction process are supported Ni-based catalysts, and the methanation activity and stability of the catalysts are main investigation indexes.
In the aspect of methanation reaction activity, the loading amount of Ni in the catalyst needs to be improved, and Ni atoms are fully exposed on the surface of the catalyst, and the methods can increase the methanation activity position of the catalyst and directly improve the catalytic activity; meanwhile, the mass transfer of reaction gas can be improved by increasing the specific surface area of the catalyst, and the methanation activity is improved.
However, stability imposes different requirements on the catalyst properties. The catalyst in the reaction is easy to crush under the blowing of high-speed airflow, and migration and aggregation of Ni particles occur in long-term high-temperature reaction, and finally deactivation is caused. This requires that the catalyst have high mechanical strength, inhibiting pulverization of particles; the Ni in the catalyst should also have highly dispersed properties and have strong interaction with the carrier, inhibiting the migration and agglomeration of Ni particles. However, the degree of close packing of particles in the catalyst having higher mechanical strength is also higher, limiting the increase in specific surface area of the catalyst; the high dispersion of Ni requires a large space interval between Ni particles, so that the Ni loading of the catalyst is limited; the strong interaction between the carrier and Ni requires that part of Ni and the carrier form bonds, so that the atom utilization efficiency of Ni is limited, and part of Ni cannot participate in catalytic reaction in a simple substance form. Because of different requirements of activity and stability on the structure and properties of the catalyst in the reaction process, the methanation catalyst is developed into a 'balanced art', and the characteristics of the catalyst in all aspects are regulated and optimized through the design and innovation of the preparation process and the fine control of the preparation process, so that the catalyst has excellent reaction performance of high activity and high stability.
Disclosure of Invention
The invention provides a nickel catalyst, a preparation method and application thereof, which can ensure that the prepared catalyst has better Ni dispersibility and larger specific surface area while keeping the advantages of the catalyst prepared by a precipitation method, and can improve the catalytic efficiency of methanation reaction.
The invention provides a preparation method of a nickel catalyst, which comprises the following steps:
1) at the constant temperature of 75-90 ℃, simultaneously dripping an aluminum nitrate aqueous solution and an alkali solution into water to obtain a first solution, stirring and standing;
2) filtering the first solution, and washing a filter cake until the pH value of the filtrate is neutral; adding the filter cake into the second solution, stirring, and carrying out ultrasonic treatment for 10-60min to obtain a third solution; wherein the second solution is an aqueous solution of soluble organic fuel and nickel nitrate;
3) heating the third solution to 710-800 ℃ to burn the third solution, and collecting the burnt powder to obtain the oxide of the nickel catalyst;
4) and carrying out reduction reaction on the reducing gas and the oxide of the nickel-based catalyst to obtain the nickel catalyst.
Specifically, the main purpose of the step 1) is to generate precipitate, and aluminum nitrate (Al (NO) is slowly dripped into water with the temperature of 75-90 ℃ at the same time in a constant temperature environment with the temperature of 75-90 DEG C3)3·9H2O) an aqueous solution and an alkali solution to form a precipitate containing aluminum ions. The dropping rate of the aluminum nitrate may be controlled to 50ml/min to 100ml/min in order to facilitate precipitation of the precipitate. In addition, distilled water can be selected as water, and the volume of the water is controlled to be 100-300 ml.
After long-term research, the inventor finds that when the pH value of the mixed solution (namely, the first solution) of the aluminum nitrate aqueous solution and the alkali solution is kept between 10.1 and 11 in the dropping process of the aluminum nitrate aqueous solution and the alkali solution, a good precipitation environment can be provided for precipitation, and the precipitation with a proper pore diameter can be obtained. The pH value can be controlled by the dropping speed of the alkali solution, the pH value of the mixed solution of the aluminum nitrate aqueous solution and the alkali solution needs to be measured continuously in the dropping process, and when the pH value is lower than 10.1-11, the dropping speed of the alkali solution can be improved; when the pH value is higher than 10.1 to 11, the dropping speed of the alkali solution can be reduced. Generally, when the dropping volume of the aqueous aluminum nitrate solution reaches 800-1500ml, the addition of the aqueous aluminum nitrate solution and the alkali solution may be stopped.
During the dropping, continuous stirring is also required to increase the contact area between the aqueous aluminum nitrate solution and the alkali solution. And after the dropwise addition is finished, continuously stirring for 0.5-3h, and then continuously standing and aging the first solution for 10-30h at the constant temperature of 75-90 ℃ to separate out a precipitate.
In step 2), filtering the first solution in the step 1), and repeatedly washing a filter cake with deionized water until the pH value of the filtered washing liquid isThe washing can be stopped at neutral, i.e. pH 7. Collecting the filter cake and adding the filter cake to a mixture containing a soluble organic fuel and nickel nitrate (Ni (NO)3)2·6H2O) is stirred for 24-48h, and ultrasonic treatment is carried out for 10-60min, so that the filter cake is completely dispersed in the second solution, and a third solution is obtained.
In the step 3), the third solution is heated, and because the third solution contains soluble organic fuel, the third solution will burn when the temperature is increased to 710-800 ℃ in the heating process, and then the residual powder after burning, namely the oxide of the nickel catalyst, is collected. In order to make the nickel catalyst produced later suitable for catalyzing methanation reaction in a fixed bed, the powder may be ground and granulated after collecting the residual powder. Generally, the particle size of the grinding is controlled to be 60-80 meshes.
In the step 4), the oxide of the nickel catalyst in the step 3) is subjected to reduction treatment by using a reducing gas, so that the nickel catalyst which can be directly used for catalyzing methanation reaction is generated.
The method for preparing a nickel catalyst as described above, wherein the concentration of the aqueous aluminum nitrate solution is 0.01 to 15 g/ml;
the alkali solution is a mixture of a sodium hydroxide aqueous solution and a sodium carbonate aqueous solution; wherein the concentration of the sodium hydroxide aqueous solution is 0.02-0.5g/ml, and the concentration of the sodium carbonate aqueous solution is 0.01-0.6 g/ml.
The method for preparing a nickel catalyst as described above, wherein the soluble organic fuel and nickel nitrate are added to distilled water and stirred to obtain the second solution;
wherein the mass ratio of the soluble organic fuel to the filter cake is (0.1-0.75): 1, the mass ratio of the nickel nitrate to the filter cake is (1-4): 1, the volume mass ratio of the distilled water to the filter cake is 1: (0.5-1). Wherein the volume mass ratio of the distilled water to the filter cake is such that the dispersed concentration of the precipitate is 0.5-1 g/ml.
The concentration of the reactants and the proportion of the reactants can ensure that the content of nickel oxide is 40-60 percent and the content of aluminum oxide is 40-60 percent in the generated oxide of the nickel catalyst by mass percent, thereby effectively ensuring the loading amount of nickel.
The preparation method of the nickel catalyst is characterized in that the soluble organic fuel is one or more selected from ethylene glycol, n-propanol and glycerol.
The method for preparing the nickel catalyst comprises the following steps of: 2-15% of hydrogen and 85-98% of nitrogen;
in the reduction reaction, the airspeed of the reducing gas is 500-15000/h, the reaction temperature is 400-800 ℃, and the reaction time is 18-36 h.
In addition, the pressure of the reduction reaction was atmospheric pressure.
The invention also provides a nickel catalyst prepared by the preparation method.
The nickel catalyst prepared by the preparation method has the advantages of mechanical strength of (160-2Per g, average pore volume (0.432-0.648) cm3(ii)/g, the average pore diameter is (7.6-8.0) nm.
The invention also provides a preparation method of the substitute natural gas, which comprises the step of injecting hydrogen and carbon monoxide into a fixed bed filled with any one of the nickel catalysts for methanation reaction to obtain the substitute natural gas.
Wherein the volume ratio of the hydrogen to the carbon monoxide is controlled to be (3.8-5.5): 1;
in the methanation reaction, the reaction airspeed is 10000-80000/h, the reaction temperature is 550-750 ℃, and the reaction pressure is 4.2-6.0 MPa.
When the nickel catalyst prepared by the method is used for methanation reaction, the conversion rate of carbon monoxide is not less than 87.9%, and the selectivity of methane is not less than 84.4%.
The invention discloses a method for preparing a nickel catalyst by precipitation and combustion. Compared with the traditional nickel catalyst prepared by an impregnation method, a precipitation method and a combustion method, the nickel catalyst prepared by the method has larger specific surface area. The method is based on a precipitation method, combines the preparation processes of precipitation and combustion, ensures that the catalyst maintains the advantages of stronger binding force between the active component and the carrier of the catalyst prepared by the precipitation method and better stability, and simultaneously increases the specific surface area and reduces the particle size, thereby obtaining higher utilization efficiency of the active metal component and further improving the catalytic efficiency of methanation reaction.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The nickel catalyst of this example was prepared by the following steps:
1) precipitation of the precipitate
Adding 200ml of distilled water into a beaker, heating to 80 ℃ and keeping the temperature constant, simultaneously dropwise adding an aluminum nitrate aqueous solution and an alkali solution into the beaker to prepare a first solution, wherein the dropwise adding speed of the aluminum nitrate aqueous solution is 50ml/min, continuously measuring the pH value of the first solution in the beaker in the dropwise adding process, adjusting the dropwise adding speed of the alkali solution to enable the pH value to be in the range of 10.1-10.3, continuously stirring, and stopping adding the two solutions when the adding amount of the aluminum nitrate aqueous solution reaches 1000 ml.
After the dropwise addition, the stirring is continued for 2h, and then the mixture is kept standing and aged for 15h at constant temperature to separate out a precipitate.
Wherein the concentration of the aluminum nitrate aqueous solution is 2 g/ml-1The alkali solution is a mixture of aqueous sodium hydroxide solution and aqueous sodium carbonate solution, and the concentration of the aqueous sodium hydroxide solution is 0.4 g/ml-1The concentration of the sodium carbonate aqueous solution was 0.02 g/ml-1。
2) Preparation of the third solution
The precipitate is filtered and the filter cake is washed until the pH of the filtrate is close to neutral. Adding the obtained filter cake to the secondIn the solution, the cake was dispersed to a concentration of 0.5g/ml-1And soaking for 24 hours under the stirring condition, and carrying out ultrasonic treatment for 30min to obtain a third solution.
The preparation method of the second solution comprises the following steps: 1577.4ml of distilled water is taken, and ethylene glycol and nickel nitrate are added into the distilled water, wherein the addition amount of the ethylene glycol is 70 percent of the mass of the filter cake, and the addition amount of the nickel nitrate is 1851.6 g.
3) Preparation of oxides of nickel catalysts
And heating and igniting the third solution at 750 ℃, collecting, grinding and granulating the rest powder after combustion to obtain the oxide of the nickel catalyst, wherein the mass content of nickel oxide is 50%, and the mass content of aluminum oxide is 50%.
4) Preparation of nickel catalyst
And introducing reducing gas into the nickel catalyst oxide to perform reduction reaction.
The reducing gas consists of nitrogen and hydrogen, the hydrogen volume is 5%, and the rest is nitrogen. The space velocity of reducing gas is 900h-1And reducing at 750 deg.c and normal pressure for 25 hr to obtain the nickel catalyst.
The specific surface area of the nickel catalyst prepared in this example was found to be 275m2Per g, average pore volume of 0.542cm3G, average pore diameter of 7.8nm, and mechanical strength of 164N/cm.
The nickel catalyst prepared by the embodiment is used for methanation reaction, and specifically, the nickel catalyst is firstly loaded into a fixed bed, then hydrogen and carbon monoxide are introduced, wherein the volume ratio of the hydrogen to the carbon monoxide is 5:1, the reaction temperature is controlled to be 550 ℃, the reaction pressure is 4.2MPa, and the space velocity is 50000h-1. The reaction result showed that the conversion of CO was 98.8%, CH4The selectivity was 89.5%.
Example 2
The nickel catalyst of this example was prepared by the following steps:
1) precipitation of the precipitate
Adding 100ml of distilled water into a beaker, heating to 80 ℃ and keeping the temperature constant, simultaneously dropwise adding an aluminum nitrate aqueous solution and an alkali solution into the beaker to prepare a first solution, wherein the dropwise adding speed of the aluminum nitrate aqueous solution is 60ml/min, continuously measuring the pH value of the first solution in the beaker in the dropwise adding process, adjusting the dropwise adding speed of the alkali solution to enable the pH value to be in the range of 10.2-10.4, continuously stirring, and stopping adding the two solutions when the adding amount of the aluminum nitrate aqueous solution reaches 800 ml.
After the dropwise addition, the stirring is continued for 3h, and then the mixture is kept standing and aged for 25h at constant temperature to separate out a precipitate.
Wherein the concentration of the aluminum nitrate aqueous solution is 1.5 g/ml-1The alkali solution is a mixture of aqueous sodium hydroxide solution and aqueous sodium carbonate solution, and the concentration of the aqueous sodium hydroxide solution is 0.5g/ml-1The concentration of the sodium carbonate aqueous solution was 0.01 g/ml-1。
2) Preparation of the third solution
The precipitate is filtered and the filter cake is washed until the pH of the filtrate is close to neutral. Adding the obtained filter cake to the second solution to make the filter cake disperse to 1g/ml-1And carrying out ultrasonic treatment for 60min, and soaking for 48h under the stirring condition to obtain a third solution.
The preparation method of the second solution comprises the following steps: 439.4ml of distilled water was taken, and n-propanol and nickel nitrate were added thereto, the amount of n-propanol added was 75% by mass of the cake, and the amount of nickel nitrate added was 908.9 g.
3) Preparation of oxides of nickel catalysts
And heating and igniting the third solution at 750 ℃, collecting, grinding and granulating the rest powder after combustion to obtain the oxide of the nickel catalyst, wherein the mass content of nickel oxide is 45%, and the mass content of aluminum oxide is 55%.
4) Preparation of nickel catalyst
And introducing reducing gas into the nickel catalyst oxide to perform reduction reaction.
The reducing gas consists of nitrogen and hydrogen, the hydrogen volume is 15%, and the rest is nitrogen. The space velocity of reducing gas is 13000h-1And reducing at the temperature of 450 ℃ for 24 hours under normal pressure to obtain the nickel catalyst.
The specific surface area of the nickel catalyst prepared in this example was found to be 275m2Per g, average pore volume 0.496cm3G, average pore diameter of 7.4nm, and mechanical strength of 175N/cm.
The nickel catalyst prepared by the embodiment is used for methanation reaction, and specifically, the nickel catalyst is firstly loaded into a fixed bed, and then hydrogen and carbon monoxide are introduced, wherein the volume ratio of the hydrogen to the carbon monoxide is 4.5:1, the reaction temperature is controlled to be 650 ℃, the reaction pressure is 4.6MPa, and the space velocity is 20000h-1. The reaction result showed that the conversion of CO was 96.4%, CH4The selectivity was 85.3%.
Example 3
The nickel catalyst of this example was prepared by the following steps:
1) precipitation of the precipitate
Adding 300ml of distilled water into a beaker, heating to 90 ℃ and keeping the temperature constant, simultaneously dropwise adding an aluminum nitrate aqueous solution and an alkali solution into the beaker to prepare a first solution, wherein the dropwise adding speed of the aluminum nitrate aqueous solution is 70ml/min, continuously measuring the pH value of the first solution in the beaker in the dropwise adding process, adjusting the dropwise adding speed of the alkali solution to enable the pH value to be in the range of 10.6-10.8, continuously stirring, and simultaneously stopping adding the two solutions when the adding amount of the aluminum nitrate aqueous solution reaches 1500 ml.
After the dropwise addition, the stirring is continued for 1h, and then the mixture is kept standing and aged for 10h at constant temperature to separate out a precipitate.
Wherein the concentration of the aluminum nitrate aqueous solution is 0.01 g/ml-1The alkali solution is a mixture of aqueous sodium hydroxide solution and aqueous sodium carbonate solution, and the concentration of the aqueous sodium hydroxide solution is 0.1 g/ml-1The concentration of the sodium carbonate aqueous solution was 0.6g/ml-1。
2) Preparation of the third solution
The precipitate is filtered and the filter cake is washed until the pH of the filtrate is close to neutral. Adding the obtained filter cake into the second solution to make the filter cake disperse to 0.8 g/ml-1And carrying out ultrasonic treatment for 50min, and soaking for 40h under the stirring condition to obtain a third solution.
The preparation method of the second solution comprises the following steps: 6.8ml of distilled water was taken, and ethylene glycol and nickel nitrate were added thereto, the amount of ethylene glycol added being 20% of the mass of the cake, and the amount of nickel nitrate added being 9.25 g.
3) Preparation of oxides of nickel catalysts
And heating and igniting the third solution at 730 ℃, collecting, grinding and granulating the rest powder after combustion to obtain the oxide of the nickel catalyst, wherein the mass content of nickel oxide is 40%, and the mass content of aluminum oxide is 60%.
4) Preparation of nickel catalyst
And introducing reducing gas into the nickel catalyst oxide to perform reduction reaction.
The reducing gas consists of nitrogen and hydrogen, the hydrogen volume is 10%, and the rest is nitrogen. The space velocity of reducing gas is 13000h-1And reducing at 800 ℃ under normal pressure for 24 hours to obtain the nickel catalyst.
The specific surface area of the nickel catalyst prepared in this example was determined to be 290m2Per g, average pore volume of 0.597cm3G, average pore diameter of 7.8nm, mechanical strength of 188N/cm.
The nickel catalyst prepared by the embodiment is used for methanation reaction, and specifically, the nickel catalyst is firstly loaded into a fixed bed, then hydrogen and carbon monoxide are introduced, wherein the volume ratio of the hydrogen to the carbon monoxide is 4.0:1, the reaction temperature is controlled to be 700 ℃, the reaction pressure is controlled to be 4.5MPa, and the space velocity is 40000h-1. The reaction result showed that the conversion of CO was 89.1%, CH4The selectivity was 84.4%.
Example 4
The nickel catalyst of this example was prepared by the following steps:
1) precipitation of the precipitate
Adding 250ml of distilled water into a beaker, heating to 85 ℃, keeping the temperature constant, simultaneously dropwise adding an aluminum nitrate aqueous solution and an alkali solution into the beaker to prepare a first solution, wherein the dropwise adding speed of the aluminum nitrate aqueous solution is 80ml/min, continuously measuring the pH value of the first solution in the beaker in the dropwise adding process, adjusting the dropwise adding speed of the alkali solution to enable the pH value to be in the range of 10.5-10.7, continuously stirring, and stopping adding the two solutions when the adding amount of the aluminum nitrate aqueous solution reaches 1400 ml.
After the dropwise addition, the stirring is continued for 0.5h, and then the mixture is kept standing and aged for 20h at constant temperature to separate out a precipitate.
Wherein the concentration of the aluminum nitrate aqueous solution is 0.5g/ml-1The alkali solution is a mixture of aqueous sodium hydroxide solution and aqueous sodium carbonate solution, and the concentration of the aqueous sodium hydroxide solution is 0.02 g/ml-1The concentration of the sodium carbonate aqueous solution was 0.5g/ml-1。
2) Preparation of the third solution
The precipitate is filtered and the filter cake is washed until the pH of the filtrate is close to neutral. Adding the obtained filter cake into the second solution to make the filter cake disperse to 0.6g/ml-1And carrying out ultrasonic treatment for 45min, and soaking for 30h under the stirring condition to obtain a third solution.
The preparation method of the second solution comprises the following steps: 427.2ml of distilled water was taken, and glycerin and nickel nitrate were added thereto, the amount of glycerin added was 30% by mass of the cake, and the amount of nickel nitrate added was 972.1 g.
3) Preparation of oxides of nickel catalysts
And heating and igniting the third solution at 760 ℃, collecting, grinding and granulating residual powder after combustion to obtain the oxide of the nickel catalyst, wherein the mass content of nickel oxide is 60%, and the mass content of aluminum oxide is 40%.
4) Preparation of nickel catalyst
And introducing reducing gas into the nickel catalyst oxide to perform reduction reaction.
The reducing gas consists of nitrogen and hydrogen, the hydrogen volume is 5%, and the rest is nitrogen. The space velocity of reducing gas is 10000h-1And reducing at 550 ℃ under normal pressure for 20 hours to obtain the nickel catalyst.
The specific surface area of the nickel catalyst prepared in this example was found to be 310m2Per g, average pore volume of 0.616cm3G, average pore diameter of 7.6nm, and mechanical strength of 184N/cm.
The nickel catalyst prepared by the embodiment is used for methanation reaction, specifically, the nickel catalyst is firstly loaded into a fixed bed, then hydrogen and carbon monoxide are introduced, wherein the volume ratio of the hydrogen to the carbon monoxide is 4.8:1, and the reaction is controlledThe reaction temperature is 550 ℃, the reaction pressure is 5.0MPa, and the space velocity is 10000h-1. The reaction result showed that the CO conversion was 87.9%, CH4The selectivity was 87.3%.
Example 5
The nickel catalyst of this example was prepared by the following steps:
1) precipitation of the precipitate
Adding 150ml of distilled water into a beaker, heating to 85 ℃, keeping the temperature constant, simultaneously dropwise adding an aluminum nitrate aqueous solution and an alkali solution into the beaker to prepare a first solution, wherein the dropwise adding speed of the aluminum nitrate aqueous solution is 90ml/min, continuously measuring the pH value of the first solution in the beaker in the dropwise adding process, adjusting the dropwise adding speed of the alkali solution to enable the pH value to be in the range of 10.4-10.6, continuously stirring, and stopping adding the two solutions when the adding amount of the aluminum nitrate aqueous solution reaches 1200 ml.
After the dropwise addition, the stirring is continued for 1.5h, and then the mixture is kept standing and aged for 30h at constant temperature to separate out a precipitate.
Wherein the concentration of the aluminum nitrate aqueous solution is 0.9 g/ml-1The alkali solution is a mixture of an aqueous solution of sodium hydroxide and an aqueous solution of sodium carbonate, and the concentration of the aqueous solution of sodium hydroxide is 0.04 g/ml-1The concentration of the sodium carbonate aqueous solution was 0.3 g/ml-1。
2) Preparation of the third solution
The precipitate is filtered and the filter cake is washed until the pH of the filtrate is close to neutral. Adding the obtained filter cake to the second solution to make the filter cake disperse to 0.7 g/ml-1And carrying out ultrasonic treatment for 40min, and soaking for 35h under the stirring condition to obtain a third solution.
The preparation method of the second solution comprises the following steps: 513.5ml of distilled water was taken, and glycerin and nickel nitrate were added thereto, the amount of glycerin added being 10% of the mass of the cake, and the amount of nickel nitrate added being 666.6 g.
3) Preparation of oxides of nickel catalysts
And heating and igniting the third solution at 780 ℃, collecting, grinding and granulating the rest powder after combustion to obtain the oxide of the nickel catalyst, wherein the mass content of nickel oxide is 40%, and the mass content of aluminum oxide is 60%.
4) Preparation of nickel catalyst
And introducing reducing gas into the nickel catalyst oxide to perform reduction reaction.
The reducing gas consists of nitrogen and hydrogen, the hydrogen volume is 10%, and the rest is nitrogen. The space velocity of the reducing gas is 15000h-1And reducing at 650 ℃ under normal pressure for 23 hours to obtain the nickel catalyst.
The specific surface area of the nickel catalyst prepared in this example was found to be 325m2Per g, average pore volume of 0.515cm3G, average pore diameter of 7.7nm, and mechanical strength of 176N/cm.
The nickel catalyst prepared by the embodiment is used for methanation reaction, and specifically, the nickel catalyst is firstly loaded into a fixed bed, then hydrogen and carbon monoxide are introduced, wherein the volume ratio of the hydrogen to the carbon monoxide is 5.2:1, the reaction temperature is controlled to be 600 ℃, the reaction pressure is controlled to be 5MPa, and the space velocity is 80000h-1. The reaction result showed that the conversion of CO was 88.3%, CH4The selectivity was 86.6%.
Example 6
The nickel catalyst of this example was prepared by the following steps:
1) precipitation of the precipitate
Adding 300ml of distilled water into a beaker, heating to 80 ℃ and keeping the temperature constant, simultaneously dropwise adding an aluminum nitrate aqueous solution and an alkali solution into the beaker to prepare a first solution, wherein the dropwise adding speed of the aluminum nitrate aqueous solution is 100ml/min, continuously measuring the pH value of the first solution in the beaker in the dropwise adding process, adjusting the dropwise adding speed of the alkali solution to enable the pH value to be in the range of 10.8-11, continuously stirring, and simultaneously stopping adding the two solutions when the adding amount of the aluminum nitrate aqueous solution reaches 1000 ml.
After the dropwise addition, the stirring is continued for 2.5h, and then the mixture is kept standing and aged for 20h at constant temperature to separate out a precipitate.
Wherein the concentration of the aluminum nitrate aqueous solution is 1.0 g/ml-1The alkali solution is a mixture of aqueous sodium hydroxide solution and aqueous sodium carbonate solution, and the concentration of the aqueous sodium hydroxide solution is 0.05 g/ml-1Concentration of sodium carbonate aqueous solution was 0.1g·ml-1。
2) Preparation of the third solution
The precipitate is filtered and the filter cake is washed until the pH of the filtrate is close to neutral. Adding the obtained filter cake into the second solution to make the filter cake disperse to 0.9 g/ml-1And carrying out ultrasonic treatment for 45min, and soaking for 24h under the stirring condition to obtain a third solution.
The preparation method of the second solution comprises the following steps: 439.4ml of distilled water was taken, and n-propanol and nickel nitrate were added thereto, the amount of n-propanol added was 50% by mass of the cake, and the amount of nickel nitrate added was 617.2 g.
3) Preparation of oxides of nickel catalysts
And heating and igniting the third solution at 790 ℃, collecting, grinding and granulating the rest powder after combustion to obtain the oxide of the nickel catalyst, wherein the mass content of nickel oxide is 40 percent, and the mass content of aluminum oxide is 60 percent.
4) Preparation of nickel catalyst
And introducing reducing gas into the nickel catalyst oxide to perform reduction reaction.
The reducing gas consists of nitrogen and hydrogen, the hydrogen volume is 15%, and the rest is nitrogen. The space velocity of reducing gas is 7000h-1And reducing at 600 ℃ under normal pressure for 19 hours to obtain the nickel catalyst.
The specific surface area of the nickel catalyst prepared in this example was found to be 278m2Per g, average pore volume of 0.486cm3(iv)/g, average pore diameter 7.9nm, mechanical strength 169N/cm.
The nickel catalyst prepared by the embodiment is used for methanation reaction, and specifically, the nickel catalyst is firstly loaded into a fixed bed, then hydrogen and carbon monoxide are introduced, wherein the volume ratio of the hydrogen to the carbon monoxide is 5:1, the reaction temperature is controlled to be 650 ℃, the reaction pressure is 4.6MPa, and the space velocity is 40000h-1. The reaction result showed that the conversion of CO was 98.8%, CH4The selectivity was 89.5%.
Comparative example
The preparation concentration is 2 g/ml-1The mixed solution of nickel nitrate and aluminum nitrate of (1) is designated as solution A. Preparation ofMixed solution of sodium hydroxide and sodium carbonate, wherein the concentration of the sodium hydroxide and the sodium carbonate is 0.4 g/ml respectively-1And 0.02 g.ml-1And is denoted as solution B.
Adding 200ml of distilled water into a beaker, heating to 50 ℃, keeping the temperature constant, simultaneously and slowly dripping the solution A and the solution B into the beaker, wherein the dripping speed of the solution A is 50ml/min, controlling the pH value of a liquid phase in the beaker to be within the range of 8-8.2 by controlling the dripping speed of the solution B, continuously stirring, and stopping adding the two solutions when the adding amount of the solution A reaches 1000 ml.
And after the dropwise addition is finished, continuously stirring for 2 hours, then continuously aging at constant temperature for 15 hours, and after the obtained precipitate is subjected to suction filtration and washing, enabling the pH value of the filtrate to be close to neutral. Heating and roasting at 600 ℃, collecting powder, grinding and granulating to obtain the oxide of the nickel catalyst, wherein the mass content of nickel oxide is 40%, and the mass content of aluminum oxide is 60%.
And introducing reducing gas into the nickel catalyst oxide to perform reduction reaction. The reducing gas consists of nitrogen and hydrogen, the hydrogen volume is 5%, and the rest is nitrogen. The space velocity of reducing gas is 2000h-1And reducing at 600 ℃ under normal pressure for 18 hours to obtain the nickel catalyst.
The specific surface area of the nickel catalyst prepared in this example was examined to be 180m2Per g, average pore volume of 0.302cm3G, average pore diameter of 8.2nm and mechanical strength of 118N/cm.
The nickel catalyst prepared by the embodiment is used for methanation reaction, and specifically, the nickel catalyst is firstly loaded into a fixed bed, then hydrogen and carbon monoxide are introduced, wherein the volume ratio of the hydrogen to the carbon monoxide is 3:1, the reaction temperature is controlled to be 550 ℃, the reaction pressure is 2.0MPa, and the space velocity is 50000h-1. The reaction result showed that the CO conversion was 82.7%, CH4The selectivity was 76.4%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of a nickel catalyst is characterized by comprising the following steps:
1) dropwise adding an aluminum nitrate aqueous solution and an alkali solution into water at the constant temperature of 75-90 ℃ to obtain a first solution, stirring, and standing for 10-30 h;
the alkali solution is a mixture of a sodium hydroxide aqueous solution and a sodium carbonate aqueous solution; wherein the concentration of the sodium hydroxide aqueous solution is 0.02-0.5g/mL, and the concentration of the sodium carbonate aqueous solution is 0.01-0.6 g/mL;
2) filtering the first solution, and washing a filter cake until the pH value of the filtrate is neutral; adding soluble organic fuel and nickel nitrate into distilled water, and stirring to obtain a second solution; adding the filter cake into the second solution, stirring, and carrying out ultrasonic treatment for 10-60min to obtain a third solution; wherein the mass ratio of the soluble organic fuel to the filter cake is (0.1-0.75): 1, the mass ratio of the nickel nitrate to the filter cake is (1-4): 1, the volume mass ratio of the distilled water to the filter cake is 1: (0.5-1);
3) heating the third solution to 710-800 ℃ to burn the third solution, and collecting the burnt powder to obtain the oxide of the nickel catalyst;
4) and carrying out reduction reaction on the reducing gas and the oxide of the nickel catalyst to obtain the nickel catalyst.
2. The method for preparing a nickel catalyst according to claim 1, wherein the pH of the first solution is controlled to 10.1 to 11 during the dropping in step 1).
3. The method of preparing a nickel catalyst according to claim 1, wherein the concentration of the aqueous aluminum nitrate solution is 0.01 to 15 g/mL.
4. The method of claim 1, wherein the soluble organic fuel is selected from one of ethylene glycol, n-propanol, and glycerol.
5. The method according to claim 1, wherein the reducing gas comprises, in terms of volume percent: 2-15% of hydrogen and 85-98% of nitrogen;
in the reduction reaction, the airspeed of the reducing gas is 500-15000/h, the reaction temperature is 400-800 ℃, and the reaction time is 12-36 h.
6. A nickel catalyst, characterized by being produced by the production method according to any one of the preceding claims 1 to 5.
7. The nickel catalyst as claimed in claim 6, wherein the nickel catalyst has a mechanical strength of (160-200) N/cm and a specific surface area of (250-350) m2Per g, average pore volume (0.432-0.648) cm3(ii)/g, the average pore diameter is (7.6-8.0) nm.
8. Process for the preparation of substitute natural gas, characterized in that hydrogen and carbon monoxide are fed to a fixed bed containing a nickel catalyst according to any of claims 6 to 7 for methanation to give the substitute natural gas.
9. The process according to claim 8, wherein the volume ratio of hydrogen to carbon monoxide is (3.8-5.5): 1;
in the methanation reaction, the reaction airspeed is 10000-80000/h, the reaction temperature is 550-750 ℃, and the reaction pressure is 4.2-6.0 MPa.
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| CN102872874A (en) * | 2012-09-19 | 2013-01-16 | 太原理工大学 | Loaded type nickel-based catalyst used for slurry bed methanation, and preparation method and application thereof |
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| US8637299B2 (en) * | 2011-08-11 | 2014-01-28 | Albert Norman Heichberger | Method for capture carbon and storage (CCS process) from coal fuel gas and the storage as biofuels: oil, gasoline, biodiesel, jet fuel, ethanol, and methane |
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| CN102872874A (en) * | 2012-09-19 | 2013-01-16 | 太原理工大学 | Loaded type nickel-based catalyst used for slurry bed methanation, and preparation method and application thereof |
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