CN104056634A - Preparation method of catalyst applied to methanation of fixed bed and application thereof - Google Patents
Preparation method of catalyst applied to methanation of fixed bed and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst applied to methanation of a fixed bed. The preparation method of the catalyst comprises the following steps: preprocessing nickel powder by using dilute acid, preprocessing aluminum powder by using an organic solvent, uniformly mixing the nickel powder with the aluminum powder, fusing in a high-temperature furnace of an external magnetic field, cooling to room temperature in the presence of inert gas, grinding into particles with size being 80-200 meshes, putting a container filled with NaOH solution into an ultrasonic constant-temperature water bath, stirring while adding nickel-aluminium alloy powder into the NaOH solution for reacting, removing upper alkaline liquid after the reaction is ended, washing the solution with deionized water till the solution is neutral, then adding absolute ethyl alcohol, and thus obtaining the catalyst. The preparation method of the catalyst has the advantages of simple process and easiness in control of the process. The prepared catalyst has the advantages of uniform particle diameter, high mechanical strength, good catalytic effect and applicability to large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of Raney's nickel catalyst, be specifically related to a kind of preparation method of Raney's nickel catalyst and application of Raney's nickel catalyst of applicable fixed bed methanation.
Background technology
Raney's nickel (Raney Ni) catalyst is a kind of very important industrial catalyst, has higher activity and selectivity and lower production and application cost, has been widely used in catalytic organism hydrogenation reaction.Raney's nickel (Raney Ni) catalyst is found by Murray Raney at first, and is applied for a patent with nineteen twenty-five.When prepared by catalyst, first with NaOH solution, dissolve the Al in alumel, then washing, residue is for being similar to spongiform skeleton structure, and catalyst mainly contains Ni and Al, and total specific surface area is 50-130m
2/ g.
The method that tradition is prepared Raney's nickel is that the nickel alumin(i)um alloy making is carried out to extracting with certain density aqueous slkali, and then washing, except alkali, obtains the Raney's nickel particle of porous.But these catalyst ubiquity catalytic efficiencies are low, the problem that environmental pollution is serious.Therefore need to develop a kind of catalytic activity high, pollute little novel Raney's nickel catalyst.
China's " rich coal; oil-poor; the resources characteristic of weak breath ", especially the natural gas resource utmost point is rare, cannot meet the demand of country to clean energy resource, therefore, the imbalance between supply and demand of natural gas is outstanding, utilize coal especially colm methanation to produce natural gas be the new way that using energy source transforms, contribute to make full use of the coal resources that China's output is abundant, alleviate the situation of natural gas deficiency, it both can improve resource utilization, also can reduce the pollution of colm to environment, convenience and the security that also can increase transportation and use.
Current industrial methanation catalyst is mainly German Shandong strange (LURGI), and Britain wears three kinds, dimension (DAVY) and Denmark Top rope (TOPSOE), and it is catalyst based that above-mentioned technology catalyst is support type Ni.Patent CN200810051416.0 has introduced a kind of preparation method of Raney's nickel catalyst, the concrete alumel that adopts evenly mixes for 2:1-1:2 in mass ratio with solid NaOH, slowly drip distilled water reaction, the upper strata alkali lye that inclines, successively uses the Raney's nickel catalyst of distilled water and absolute ethanol washing system.But in catalyst preparation process, I haven't seen you for ages produces a large amount of NaAlO4 and make troubles to washing for the addition of NaOH; cause the activity of catalyst very low; the rate of addition of distilled water and dripping quantity are also not easy to control simultaneously; because course of reaction is exothermic reaction; can produce a large amount of heat and gas; what distilled water dripped causes produced hydrogen deficient with guard catalyst excessively slowly, and the too fast mistake dripping can produce at most a large amount of bubbles and makes catalyst excessive.Therefore, utilize this kind of method Kaolinite Preparation of Catalyst process to be difficult to control, be unsuitable for large-scale production, main is that the Raney's nickel catalyst duct of preparing is inhomogeneous, and specific area is little, and catalytic activity is low, selectively not high.
The preparation method of a patent CN200810301493.7 Raney's nickel catalyst of fixed bed, adopt nickel foam as nickel source, after soaking with ketones solvent, being immersed in dipping in aluminum salt solution aluminizes, then wash, be dried, 600-1000 ℃ of roasting, finally with the Raney's nickel catalyst of making after strong base solution leaching aluminium.But the particle diameter of this kind of preparation method's nickel foam is fixing, floods aluminium in nickel foam, then there is substantial variation with particle diameter and the pore passage structure of nickel foam after alkali extraction aluminium.
The disclosed methanation catalyst of above-mentioned two patent is fixed bde catalyst, but it is less about Raney's nickel, to be applied to the report of methanation.
Summary of the invention
The object of this invention is to provide a kind of technique simple, process is easily controlled, to have particle diameter even for the catalyst of preparation, and mechanical strength is high, the good and preparation method and Raney's nickel catalyst and its application that are suitable for the fixed bed methanation Raney's nickel catalyst of large-scale production of catalytic activity.Its concrete steps are as follows:
(1) pretreatment: nickel powder is soaked to 5-60min with dilute acid soln, then use soaked in absolute ethyl alcohol 5-10min, with deionized water washing 2-4 time, standby at 50-110 ℃ of dry 1-8 hour afterwards;
Aluminium powder is soaked to 5-30 minute with organic solvent, then with deionized water washing 2-4 time, standby at 50-110 ℃ of dry 1-8 hour;
(2) Nickel Aluminium Alloy Powder preparation: nickel powder and aluminium powder are mixed, fuse in the high temperature furnace of externally-applied magnetic field, cool to room temperature under inert gas shielding, grinds to form 40-100 object particle by Nickel Aluminium Alloy Powder standby;
(3) Raney's nickel catalyst preparation: in advance the rustless steel container that NaOH solution is housed is placed in ultrasonic thermostatic water bath groove, regulate constant temperature water bath temperature and ultrasonic intensity, the Nickel Aluminium Alloy Powder preparing is joined to above-mentioned NaOH solution while stirring, then at 0-70 ℃ of constant temperature, stir 3-12h, after reaction finishes, remove upper strata alkali lye, by deionized water, repeatedly rinse to neutrality, with absolute ethyl alcohol, rinse 2-4 time again, obtain Raney's nickel catalyst.
As described in above-mentioned steps (1), pretreated nickel powder is technical grade nickel powder.
As described in above-mentioned steps (1), pretreated aluminium powder is technical grade aluminium powder.
Dilute acid soln as described in above-mentioned steps (1) is a kind of in watery hydrochloric acid, dilute sulfuric acid, rare nitric acid.
Step (1) organic solvent is a kind of in benzene, toluene, ether or acetone as mentioned above.
As described in above-mentioned steps (1), nickel powder, aluminium powder is dried as vacuum drying.
In the nickel powder of the mixing as described in above-mentioned steps (2), aluminium powder, to account for the percentage of gross mass be between 15-90% to nickel powder.
When prepared by the Nickel Aluminium Alloy Powder as described in above-mentioned steps (2), externally-applied magnetic field intensity is 1-40T, is preferably 5-30T.
When the Nickel Aluminium Alloy Powder preparation as described in above-mentioned steps (2) fuses, high temperature furnace temperature is 900-1600 ℃, is preferably 1250-1400 ℃.
Nickel Aluminium Alloy Powder preparation fusion time under fusion temperature as described in above-mentioned steps (2) is 1-5h, is preferably 2-3h.
It is N that Nickel Aluminium Alloy Powder as described in above-mentioned steps (2) passes into inert gas while preparing
2, a kind of in Ar.
The NaOH solution molar concentration of dress in advance as described in above-mentioned steps (3) is between 3-10mol/L, is preferably between 4-6mol/L.
It is 0-70 ℃ that Water Tank with Temp.-controlled as described in above-mentioned steps (3) is controlled temperature.
Hyperacoustic power as described in above-mentioned steps (3) is 100-2000W, is preferably 400-1300W.
NaOH solution as described in above-mentioned steps (3) and the ratio of nickel alumin(i)um alloy are: 3-10ml:1g.
Stir speed (S.S.) as described in above-mentioned steps (3) is 100-900r/min.
Adopting the nickel content of the catalyst of above-mentioned preparation is 85-97wt%, and specific area is at 100-230m
2between/g.
Raney's nickel catalyst prepared by the inventive method can be used for fixed bed methanation reaction, can improve conversion ratio and selective.CO conversion ratio can reach more than 98.0%, and methane selectively can reach more than 98.5%.
Raney's nickel catalyst of the present invention comprises the steps: in the application application of synthesis gas fixed bed methanation
Raney's nickel catalyst is evenly added in fixed bed bed reactor, and synthesis gas is at H
2/ CO mol ratio is 3.0-3.5, and pressure is 1.0-4.0MPa, and temperature is 400-650 ℃, and volume space velocity is under 7000-9000L/hkg condition, to carry out methanation reaction.
The present invention is applied in externally-applied magnetic field in nickel alumin(i)um alloy preparation process first, also be using ultrasonic technology in caustic extraction process first, in nickel powder, aluminium powder alloying process, the use of externally-applied magnetic field can make Coulomb force directly act on atomic nucleus and electron outside nucleus, fusion contact is tightr naturally under gravity condition to make original of nickel al atomic ratio, and the grid frame structure of nickle atom is more carefully firmer; In nickel alumin(i)um alloy caustic extraction process, adding ultrasonic technology advantage is, utilize hyperacoustic strong micro-vibration to make aluminium more easily depart from nickel alumin(i)um alloy, so that and NaOH reaction is converted into sodium aluminate, and be unlikely to block Raney's nickel duct, stop sodium hydroxide solution to enter the path of nickel alumin(i)um alloy, thereby cause Raney's nickel catalyst loose structure specific area to diminish.Raney's nickel catalyst prepared by the present invention more particle diameter is even, and catalytic activity and selectively higher compared with prior art has substantive distinguishing features and technical advantage is as follows:
(1) pore passage structure is more even:
Innovative point of the present invention is to have introduced additional high-intensity magnetic field in the fusion preparation process of Raney's nickel, and atom is comprised of atomic nucleus and electron outside nucleus.Electronics can produce Coulomb force and do orderly motion in magnetic field, and the particle under magnetic field is more orderly.Charged particle particularly can change in high-intensity magnetic field in magnetic field as the motion of electronics and ion etc. and some polar molecule.And the effect in magnetic field can change bond energy, thereby change interfacial structure, fusion contact is tightr naturally under gravity condition to make original of nickel al atomic ratio, and the grid frame structure of nickle atom is more carefully firmer.Introduce the crystallization velocity that particle has been accelerated in magnetic field, the decentralization of magnetic particle is improved, size distribution is more even, therefore make catalyst duct structure more even.
Innovative point of the present invention is also to have used ultrasonic technology in aluminium extracting and washing process, this is because nickel alumin(i)um alloy is prepared in fusion under high-intensity magnetic field condition, it is tightr that nickel aluminium contacts, general whipping process is difficult to make aluminium to depart from nickel alumin(i)um alloy completely, and also easily make aluminium part in duct excessive and produce aluminum hydroxide precipitation and stop up duct to NaOH solution, cause Raney's nickel specific area to reduce.The ultrasonic technology of introducing can produce strong motion in tiny scope, can impel surperficial aluminium to react with NaOH in time and depart from nickel alumin(i)um alloy, main is strong motion makes the inside, duct NaOH solution phase is excessive and do not produce precipitation for aluminium, even if produced aluminum hydroxide precipitation very among a small circle, because being also difficult to allow, hyperacoustic strong motion aluminium hydroxide is deposited in duct, so just can guarantee that the aluminium in duct can be extracted completely, also just because of this has improved the catalytic activity of Raney's nickel catalyst.
(2) particle diameter is evenly controlled:
In the preparation process of Raney's nickel catalyst, by the granularity of grinding control Nickel Aluminium Alloy Powder, thus the granularity of control Raney's nickel after alkali extracting, the epigranular having realized under the even prerequisite of Raney's nickel catalyst pore passage structure is controlled.
(3) mechanical strength is higher:
In nickel powder, aluminium powder fusion, in preparing nickel alumin(i)um alloy process, add the magnetic field of varying strength, realization is to the miniature adjustment of Raney's nickel crystal grain-growth and duct, can fill up nickel alumin(i)um alloy and because mixing is inhomogeneous, cause the tiny cavity forming in aluminium extractive process, make the skeleton structure of Raney's nickel catalyst more firm, therefore catalyst mechanical strength obtained by this method is higher.Can reduce the loss of catalyst mechanical wear.
(4) specific area is larger:
Because the high-intensity magnetic field adding in nickel alumin(i)um alloy preparation process can change bond energy, thereby change interfacial structure, can make the tightr of nickel aluminium contact, the grid frame structure of nickle atom is more carefully firmer, and pore passage structure is more even.The application of ultrasonic technology in aluminium extracting and washing process, the caustic extraction of comparing traditional Raney's nickel catalyst more easily makes aluminium atom by caustic extraction out, makes in pore passage structure that more nickle atom is naked spills.Therefore the specific surface area of catalyst that, prepared by the method is larger than traditional.
(5) reduce carbon distribution, can mass production
The Raney's nickel catalyst of this invention preparation can reduce the disproportionation activity of CO in methanation reaction, and the carbon deposit on catalyst is reduced, and has reduced rate of catalyst deactivation, has improved the conversion ratio of CO.Catalyst preparation process is simple, easy to operate simultaneously, and preparation condition is reliable and stable, is suitable for industrialized mass.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but be interpreted as, and these embodiment are only for specifically describing more in detail the present invention, and the scope that should not be construed as the above-mentioned theme of the present invention only limits to the restriction of following embodiment.
Embodiment 1
(1) pretreatment: by nickel powder, with dilute hydrochloric acid solution, soak 35min, then use soaked in absolute ethyl alcohol 20min, afterwards with deionized water washing 4 times, 80 ℃ dry 4 hours standby;
Ether for aluminium powder is soaked 25 minutes, then with deionized water washing 3 times, 70 ℃ dry 4 hours standby.
(2) Nickel Aluminium Alloy Powder preparation: the mass percent (nickel powder/nickel powder+aluminium powder) that nickel powder is accounted for to gross mass is 35% to mix, and passes into inert gas N
2gas protection, is that 35T, high temperature furnace temperature are to fuse 3h under 1350 ℃ of conditions in additional magnetic field intensity, and cool to room temperature under inert gas shielding grinds to form 60 object particles by Nickel Aluminium Alloy Powder standby.
(3) Raney's nickel catalyst preparation: the rustless steel container of the NaOH solution that is 5mol/L by the concentration that 85.0ml is housed is in advance placed in 20 ℃ of ultrasonic thermostatic water bath grooves, adjusting ultrasonic intensity is 600W, the Nickel Aluminium Alloy Powder that 17.5g is prepared joins above-mentioned NaOH solution when stir speed (S.S.) is 400r/min, then at 15 ℃ of constant temperature, stir 6h, after reaction finishes, remove upper strata alkali lye, by deionized water, repeatedly rinse to neutrality, with absolute ethyl alcohol, rinse 3 times again, (nickel content is 87wt%, and specific area is 150m to obtain Raney's nickel catalyst
2/ g).
Raney's nickel catalyst is as follows for the synthesis of the application of gas-solid fixed bed methanation: 6.0g Raney's nickel catalyst is evenly joined in fixed bed reaction still, at H
2/ CO=3.3 (mol ratio), pressure is 1.5MPa, and temperature is 450 ℃, and volume space velocity is 8000L/hkg, carries out the evaluation of 6h methanation activity, and evaluation procedure utilizes Shimadzu GC-9160 chromatography of gases to carry out quantitative analysis to product.
It is 98.8% that the Raney's nickel catalyst of the fixed bed methanation making can obtain CO conversion ratio through activity rating, and methane selectively is 98.6%.
Embodiment 2
(1) pretreatment: by nickel powder, with dilution heat of sulfuric acid, soak 40min, then use soaked in absolute ethyl alcohol 20min, afterwards with deionized water washing 4 times, 70 ℃ dry 5 hours standby;
Ether for aluminium powder is soaked 20 minutes, then with deionized water washing 3 times, 80 ℃ dry 4 hours standby.
(2) Nickel Aluminium Alloy Powder preparation: the mass percent (nickel powder/nickel powder+aluminium powder) that nickel powder is accounted for to gross mass is 45% to mix, and passes into inert gas N
2gas protection, is that 30T, high temperature furnace temperature are to fuse 4h under 1100 ℃ of conditions in additional magnetic field intensity, and cool to room temperature under inert gas shielding grinds to form 40 object particles by Nickel Aluminium Alloy Powder standby.
(3) Raney's nickel catalyst preparation: the rustless steel container of the NaOH solution that is 8mol/L by the concentration that 90.0ml is housed is in advance placed in 20 ℃ of ultrasonic thermostatic water bath grooves, adjusting ultrasonic intensity is 800W, the Nickel Aluminium Alloy Powder that 21.0g is prepared joins above-mentioned NaOH solution when stir speed (S.S.) is 600r/min, then at 20 ℃ of constant temperature, stir 7h, after reaction finishes, remove upper strata alkali lye, by deionized water, repeatedly rinse to neutrality, with absolute ethyl alcohol, rinse 3 times again, (nickel content is 91wt%, and specific area is 180m to obtain Raney's nickel catalyst
2/ g).
Raney's nickel catalyst is as follows for the synthesis of the application of gas-solid fixed bed methanation: 5.5g Raney's nickel catalyst is evenly joined in fixed bed reaction still, at H
2/ CO=3.5 (mol ratio), pressure is 2.5MPa, and temperature is 550 ℃, and volume space velocity is 7500L/hkg, carries out the evaluation of 5h methanation activity, and evaluation procedure utilizes Shimadzu GC-9160 chromatography of gases to carry out quantitative analysis to product.
It is 98.6% that the Raney's nickel catalyst of the fixed bed methanation making can obtain CO conversion ratio through activity rating, and methane selectively is 99.3%.
Embodiment 3
(1) pretreatment: by nickel powder, with dilute nitric acid solution, soak 25min, then use soaked in absolute ethyl alcohol 20min, afterwards with deionized water washing 3 times, 90 ℃ dry 4 hours standby;
Acetone for aluminium powder is soaked 20 minutes, then with deionized water washing 3 times, 70 ℃ dry 5 hours standby.
(2) Nickel Aluminium Alloy Powder preparation: the mass percent (nickel powder/nickel powder+aluminium powder) that nickel powder is accounted for to gross mass is 60% to mix; pass into the protection of inert gas Ar gas; in additional magnetic field intensity, be that 28T, high temperature furnace temperature are to fuse 3h under 1450 ℃ of conditions; cool to room temperature under inert gas shielding, grinds to form 80 object particles by Nickel Aluminium Alloy Powder standby.
(3) Raney's nickel catalyst preparation: the rustless steel container of the NaOH solution that is 7mol/L by the concentration that 100.0ml is housed is in advance placed in 30 ℃ of ultrasonic thermostatic water bath grooves, adjusting ultrasonic intensity is 1300W, the Nickel Aluminium Alloy Powder that 20.0g is prepared joins above-mentioned NaOH solution when stir speed (S.S.) is 650r/min, then at 15 ℃ of constant temperature, stir 6h, after reaction finishes, remove upper strata alkali lye, by deionized water, repeatedly rinse to neutrality, with absolute ethyl alcohol, rinse 4 times again, (nickel content is 93wt%, and specific area is 210m to obtain Raney's nickel catalyst
2/ g).
Raney's nickel catalyst is as follows for the synthesis of the application of gas-solid fixed bed methanation: 7.0g Raney's nickel catalyst is evenly joined in fixed bed reaction still, at H
2/ CO=3.1 (mol ratio), pressure is 3.0MPa, and temperature is 500 ℃, and volume space velocity is 8200L/hkg, carries out the evaluation of 4h methanation activity, and evaluation procedure utilizes Shimadzu GC-9160 chromatography of gases to carry out quantitative analysis to product.
It is 98.4% that the Raney's nickel catalyst of the fixed bed methanation making can obtain CO conversion ratio through activity rating, and methane selectively is 98.9%.
Embodiment 4
(1) pretreatment: by nickel powder, with dilute nitric acid solution, soak 45min, then use soaked in absolute ethyl alcohol 30min, afterwards with deionized water washing 4 times, 95 ℃ dry 5 hours standby;
Toluene for aluminium powder is soaked 25 minutes, then with deionized water washing 4 times, 50 ℃ dry 8 hours standby.
(2) Nickel Aluminium Alloy Powder preparation: the mass percent (nickel powder/nickel powder+aluminium powder) that nickel powder is accounted for to gross mass is 80% to mix; pass into the protection of inert gas Ar gas; in additional magnetic field intensity, be that 25T, high temperature furnace temperature are to fuse 3h under 950 ℃ of conditions; cool to room temperature under inert gas shielding, grinds to form 100 object particles by Nickel Aluminium Alloy Powder standby.
(3) Raney's nickel catalyst preparation: the rustless steel container of the NaOH solution that is 8mol/L by the concentration that 75.0ml is housed is in advance placed in 40 ℃ of ultrasonic thermostatic water bath grooves, adjusting ultrasonic intensity is 1500W, the Nickel Aluminium Alloy Powder that 18.0g is prepared joins above-mentioned NaOH solution when stir speed (S.S.) is 700r/min, then at 25 ℃ of constant temperature, stir 8h, after reaction finishes, remove upper strata alkali lye, by deionized water, repeatedly rinse to neutrality, with absolute ethyl alcohol, rinse 3 times again, (nickel content is 95wt%, and specific area is 220m to obtain Raney's nickel catalyst
2/ g).
Raney's nickel catalyst is as follows for the synthesis of the application of gas-solid fixed bed methanation: 7.5g Raney's nickel catalyst is evenly joined in fixed bed reaction still, at H
2/ CO=3.5 (mol ratio), pressure is 3.5MPa, and temperature is 600 ℃, and volume space velocity is 8100L/hkg, carries out the evaluation of 4h methanation activity, and evaluation procedure utilizes Shimadzu GC-9160 chromatography of gases to carry out quantitative analysis to product.
It is 98.5% that the Raney's nickel catalyst of the fixed bed methanation making can obtain CO conversion ratio through activity rating, and methane selectively is 99.1%.
Embodiment 5
(1) pretreatment: by nickel powder, with dilute hydrochloric acid solution, soak 50min, then use soaked in absolute ethyl alcohol 15min, afterwards with deionized water washing 4 times, 55 ℃ dry 8 hours standby;
Benzene for aluminium powder is soaked 25 minutes, then with deionized water washing 4 times, 70 ℃ dry 6 hours standby.
(2) Nickel Aluminium Alloy Powder preparation: the mass percent (nickel powder/nickel powder+aluminium powder) that nickel powder is accounted for to gross mass is 65% to mix, and passes into inert gas N
2gas protection, is that 18T, high temperature furnace temperature are to fuse 2h under 1300 ℃ of conditions in additional magnetic field intensity, and cool to room temperature under inert gas shielding grinds to form 100 object particles by Nickel Aluminium Alloy Powder standby.
(3) Raney's nickel catalyst preparation: the rustless steel container of the NaOH solution that is 9mol/L by the concentration that 60.0ml is housed is in advance placed in 45 ℃ of ultrasonic thermostatic water bath grooves, adjusting ultrasonic intensity is 1500W, the Nickel Aluminium Alloy Powder that 17.5g is prepared joins above-mentioned NaOH solution when stir speed (S.S.) is 750r/min, then at 20 ℃ of constant temperature, stir 8h, after reaction finishes, remove upper strata alkali lye, by deionized water, repeatedly rinse to neutrality, with absolute ethyl alcohol, rinse 3 times again, (nickel content is 94wt%, and specific area is 220m to obtain Raney's nickel catalyst
2/ g).
Raney's nickel catalyst is as follows for the synthesis of the application of gas-solid fixed bed methanation: 7.0g Raney's nickel catalyst is evenly joined in fixed bed reaction still, at H
2/ CO=3.4 (mol ratio), pressure is 4.0MPa, and temperature is 500 ℃, and volume space velocity is 8600L/hkg, carries out the evaluation of 5h methanation activity, and evaluation procedure utilizes Shimadzu GC-9160 chromatography of gases to carry out quantitative analysis to product.
It is 99.1% that the Raney's nickel catalyst of the fixed bed methanation making can obtain CO conversion ratio through activity rating, and methane selectively is 99.4%.
Embodiment 6
(1) pretreatment: by nickel powder, with dilution heat of sulfuric acid, soak 30min, then use soaked in absolute ethyl alcohol 15min, afterwards with deionized water washing 3 times, 90 ℃ dry 8 hours standby;
Acetone for aluminium powder is soaked 30 minutes, then with deionized water washing 4 times, 100 ℃ dry 6 hours standby.
(2) Nickel Aluminium Alloy Powder preparation: the mass percent (nickel powder/nickel powder+aluminium powder) that nickel powder is accounted for to gross mass is 20% to mix, and passes into inert gas N
2gas protection, is that 10T, high temperature furnace temperature are to fuse 3h under 1350 ℃ of conditions in additional magnetic field intensity, and cool to room temperature under inert gas shielding grinds to form 40 object particles by Nickel Aluminium Alloy Powder standby.
(3) Raney's nickel catalyst preparation: the rustless steel container of the NaOH solution that is 5mol/L by the concentration that 120.0ml is housed is in advance placed in 35 ℃ of ultrasonic thermostatic water bath grooves, adjusting ultrasonic intensity is 1500W, the Nickel Aluminium Alloy Powder that 32.5g is prepared joins above-mentioned NaOH solution when stir speed (S.S.) is 800r/min, then at 25 ℃ of constant temperature, stir 6h, after reaction finishes, remove upper strata alkali lye, by deionized water, repeatedly rinse to neutrality, with absolute ethyl alcohol, rinse 3 times again, (nickel content is 96wt%, and specific area is 230m to obtain Raney's nickel catalyst
2/ g).
Raney's nickel catalyst is as follows for the synthesis of the application of gas-solid fixed bed methanation: 8.0g Raney's nickel catalyst is evenly joined in fixed bed reaction still, at H
2/ CO=3.3 (mol ratio), pressure is 3.0MPa, and temperature is 500 ℃, and volume space velocity is 8500L/hkg, carries out the evaluation of 6h methanation activity, and evaluation procedure utilizes Shimadzu GC-9160 chromatography of gases to carry out quantitative analysis to product.
It is 99.0% that the Raney's nickel catalyst of the fixed bed methanation making can obtain CO conversion ratio through activity rating, and methane selectively is 99.4%.
Claims (23)
1. be applicable to a preparation method for fixed bed methanation catalyst, it is characterized in that comprising the steps:
(1) pretreatment: nickel powder is soaked to 5-60min with dilute acid soln, then use soaked in absolute ethyl alcohol 5-10min, with deionized water washing 2-4 time, standby at 50-110 ℃ of dry 1-8 hour afterwards;
Aluminium powder is soaked to 5-30 minute with organic solvent, then with deionized water washing 2-4 time, standby at 50-110 ℃ of dry 1-8 hour;
(2) Nickel Aluminium Alloy Powder preparation: nickel powder and aluminium powder are mixed, fuse in the high temperature furnace of externally-applied magnetic field, cool to room temperature under inert gas shielding, grinds to form 40-100 object particle by Nickel Aluminium Alloy Powder standby;
(3) Raney's nickel catalyst preparation: in advance the rustless steel container that NaOH solution is housed is placed in ultrasonic thermostatic water bath groove, regulate constant temperature water bath temperature and ultrasonic intensity, the Nickel Aluminium Alloy Powder preparing is joined to above-mentioned NaOH solution while stirring, then at 0-70 ℃ of constant temperature, stir 3-12h, after reaction finishes, remove upper strata alkali lye, by deionized water, repeatedly rinse to neutrality, with absolute ethyl alcohol, rinse 2-4 time again, obtain Raney's nickel catalyst.
2. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that the described pretreated nickel powder of step (1) is technical grade nickel powder.
3. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that the described pretreated aluminium powder of step (1) is technical grade aluminium powder.
4. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that the described dilute acid soln of step (1) is a kind of in watery hydrochloric acid, dilute sulfuric acid, rare nitric acid.
5. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that described step (1) organic solvent is a kind of in benzene, toluene, ether or acetone.
6. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that being dried as vacuum drying of the described nickel powder of step (1), aluminium powder.
7. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that the percentage that nickel powder in the nickel powder, aluminium powder of the described mixing of step (2) accounts for gross mass is between 15-90%.
8. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 1, while it is characterized in that prepared by the described Nickel Aluminium Alloy Powder of step (2), externally-applied magnetic field intensity is 1-40T.
9. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 8, while it is characterized in that prepared by the described Nickel Aluminium Alloy Powder of step (2), externally-applied magnetic field intensity is 5-30T.
10. a kind of preparation method who is applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that it is 900-1600 ℃ that the described Nickel Aluminium Alloy Powder of step (2) is prepared high temperature furnace temperature while fusing.
11. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 10, is characterized in that it is 1250-1400 ℃ that the described Nickel Aluminium Alloy Powder of step (2) is prepared high temperature furnace temperature while fusing.
12. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that described Nickel Aluminium Alloy Powder preparation fusion time under fusion temperature of step (2) is 1-5h.
13. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 12, is characterized in that described Nickel Aluminium Alloy Powder preparation fusion time under fusion temperature of step (2) is 2-3h.
14. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that it is N that the described Nickel Aluminium Alloy Powder of step (2) passes into inert gas while preparing
2, a kind of in Ar.
15. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that the described NaOH solution molar concentration of step (3) is between 3-10mol/L.
16. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 15, is characterized in that the described NaOH solution molar concentration of step (3) is between 4-6mol/L.
17. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that it is 0-70 ℃ that the described Water Tank with Temp.-controlled of step (3) is controlled temperature.
18. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that the described hyperacoustic power of step (3) is 100-2000W.
19. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 18, is characterized in that the described hyperacoustic power of step (3) is 400-1300W.
20. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that NaOH solution that step (3) is described and the ratio of nickel alumin(i)um alloy are: 3-10ml:1g.
21. a kind of preparation methods that are applicable to fixed bed methanation catalyst as claimed in claim 1, is characterized in that the described stir speed (S.S.) of step (3) is 100-900r/min.
22. a kind of prepared fixed bed methanation catalysts of preparation method that are applicable to fixed bed methanation catalyst as described in claim 1-21 any one, is characterized in that the nickel content of catalyst is 85-97wt%, and specific area is at 100-230m
2between/g.
The application of 23. fixed bed methanation catalysts as claimed in claim 22, is characterized in that comprising the steps:
Raney's nickel catalyst is evenly added in fixed bed bed reactor, and synthesis gas is at H
2/ CO mol ratio is 3.0-3.5, and pressure is 1.0-4.0MPa, and temperature is 400-650 ℃, and volume space velocity is under 7000-9000L/hkg condition, to carry out methanation reaction.
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| CN106497619A (en) * | 2015-09-06 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of method that Raney alloy catalyst is applied to synthesis gas preparing natural gas by methanation |
| CN112871180A (en) * | 2021-01-15 | 2021-06-01 | 万华化学集团股份有限公司 | Structural catalyst and preparation method and application thereof |
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