CN105709749B - Ni-based methanation catalyst of a kind of high intensity integral extruding type and preparation method thereof - Google Patents
Ni-based methanation catalyst of a kind of high intensity integral extruding type and preparation method thereof Download PDFInfo
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Abstract
The present invention provides Ni-based methanation catalysts of a kind of high-intensitive integral extruding type and preparation method thereof.The integral extruding type catalyst is made of active component nickel, co-catalyst lanthanum and catalyst carrier, and wherein carrier is γ-Al2O3With ZrO2、MgO、CaO、SiO2, one or more of ZnO, CuO, MnO mixture, and at least contain a kind of γ-Al2O3Carrier.Above-mentioned catalytic component or its presoma pass through dry-mixed, kneading, pugging, extrusion, drying, roasting and active component supporting procedures and integral extruding type nickel-base catalyst are made.Catalyst provided by the invention has parallel triangle vertical passage, and reaction bed pressure reduction is suitable for full methanation reaction process, is particularly suitable for high-speed methanation reaction process.
Description
Technical field
The present invention relates to a kind of methanation catalyst, more particularly to a kind of high-intensitive integral extruding type nickel-base catalyst and
Preparation method.
Background technique
Methanation reaction refers to CO and CO2Hydrogenation reaction, two reactions are strong exothermal reaction.Exothermic heat of reaction measurement is determined
CO and CO in reactor feed gas2Content, every 1% CO are converted to CH4About 70 DEG C of adiabatic heating, every 1% CO2It is converted to
CH4About 60 DEG C of adiabatic heating.A large amount of heat release not only makes methanation reaction be susceptible to thermodynamical equilibrium limitation, is also methane
The engineering design of change brings difficulty, has also manufactured larger obstacle to the preparation of high activated catalyst.So how to realize reaction bed
One of the problem of effective control of layer temperature is methanation process design overriding concern.Most of synthesis gas full methanation
Technique all uses the gentle body circulation technique of adiabatic reactor, and reactor batch temperature is limited within 700 DEG C and meets methane
That changes catalyst uses temperature requirement, as the methanation process of Davy company of Britain and Denmark Topsoe company is all made of the program
Realize bed temperature control.
It is well known that unstripped gas circulation methanation process is all made of beaded catalyst fixed bed reactors.Beaded catalyst
For stacked filling, the pressure drop of reactor bed is big, this necessarily increases the power consumption of recycle compressor, causes entire circulation technology
Operating cost increases.Therefore, conventional particles catalyst, catalyst pair with abundant longitudinal microchannel are different from using a kind of
Bed resistance drop is reduced to be of great significance with recycle compressor power consumption.For example, foreign countries have is made using cordierite honeycomb ceramic
Occur for the catalyst of carrier impregnation methanation activity component, such as patent US4002658, GB1495127.However, with violet blueness
Stone ceramic honey comb is poorer than conventional particles catalyst with long-time stability as the activity of the coating type methanation catalyst of carrier
It is some, it is unable to satisfy the harsher technical process of reaction condition.So exploitation is suitable for efficiently urging for high-speed methanation
Agent technology greatly improves the intensity of catalyst, to adapt to the methanation demand of high temperature thermal and hydric environment, to full methanation and first
The development of alkanisation gas purification process all has significance.
Summary of the invention
The object of the present invention is to provide Ni-based methanation catalysts of a kind of high-intensitive integral extruding type and preparation method thereof.With
Unlike the Ni-based methanation catalyst of previous granular pattern and coating type catalyst using cordierite honeycomb ceramic as carrier,
Catalyst of the invention is to mix all catalytic components, it is disposably extruded into the entirety with parallel longitudinal direction channel
Modularization catalyst, while catalyst strength and hydrothermal stability are greatly improved by enhanced carrier is added.
The present invention specifically provides a kind of Ni-based methanation catalyst of high-intensitive integral extruding type, and the catalyst includes to live
Property component, co-catalyst and catalyst carrier, wherein
Active component is nickel, and content is the 10-55% of total catalyst weight in terms of metal oxide；
Catalyst aid is the oxide of rare earth lanthanum, and content is the 1- of total catalyst weight in terms of metal oxide
5%；
Surplus in catalyst in addition to active component, catalyst aid and extrusion aid is catalyst load；Catalyst carrier is
γ-Al2O3With ZrO2、MgO、CaO、SiO2, one or more of ZnO, CuO, MnO mixture, and at least containing one kind
γ-Al2O3Carrier；In the catalyst carrier, γ-Al2O3Weight content be not less than total catalyst weight 20%；
MgO、CaO、SiO2, ZnO, CuO, MnO be enhancing carrier, weight content be not higher than total catalyst weight 20%, ZrO2Content
Less than the 20% of total catalyst weight.
Described enhancing carrier MgO, CaO, SiO2, ZnO, CuO and/or MnO content be preferably the 1- of total catalyst weight
8%.
The enhancing carrier is preferably MgO, CaO, SiO2One of or numerous compositions.
A kind of preparation method of the Ni-based methanation catalyst of high intensity integral extruding type, the specific steps are as follows:
(1) by solid material, the oxide of oxide or other predecessors, auxiliary agent lanthanum including catalyst carrier aluminium and zirconium
Or other predecessors, solid extrusion aid, it puts into batch mixer mixing 0.5-1 hours, forms homogeneous solid mixture；Then, will
The soluble predecessor aqueous solution for accounting for solid charged material weight 30-50% water, liquid extrusion aid, nickel and enhancing carrier is added to admittedly
Body mixture is mediated in kneader and forms uniform pug；
(2) by pug pugging 2-3 times in pug mill obtained by step (1), the aging 24- of pug green compact suitable for squeezing out is obtained
48 hours, green compact are extruded into required shape with extruder and are cut into the catalyst green compact of certain size；After drying, horse is moved into
Catalyst intermediate is obtained after not rising to 500-850 DEG C of roasting 4 hours with the heating rate of 0.5-2 DEG C/min in furnace；
(3) catalyst intermediate obtained step (2) is using conventional incipient impregnation or excessive impregnation method, with containing
The catalyst intermediate for having the nitrate aqueous solution impregnation steps (2) of catalyst activity component Ni to obtain, does again using 120 DEG C
It is 2-10 hours dry, it moves into Muffle furnace after being warming up to 500-850 DEG C of roasting 4 hours and obtains catalyst.
The predecessor is water-soluble or sour nitrate, acetate, carbonate, hydroxide, subcarbonate, oxygen
Compound；Wherein enhance support C aO and SiO2Predecessor be preferably diatomite and cement.
The catalyst extrusion aid includes binder, lubricant and moisturizer, and content is that catalyst is total by weight
The 5-15% of weight；The weight ratio of binder and lubricant are as follows: the weight ratio of 3-5:1, lubricant and moisturizer are as follows: 2-5:
1。
The binder includes liquid-containing binder and solid binder, and the liquid-containing binder is preferably nitric acid, acetic acid
Or combinations thereof, dosage is on the basis of aluminium used, molar ratio are as follows: Al/ liquid-containing binder=1-10；The solid binder is preferred
Methylcellulose, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or combinations thereof.
The preferred sesbania powder of solid lubricant in the catalyst extrusion aid, fluid lubricant are tung oil, solid lubrication
Agent and fluid lubricant weight ratio are 0-0.5；Moisturizer preferably glycerine in the catalyst extrusion aid, dosage are right
It is required that in 4 steps (1) solid inventory 0.5-3%.
The additional amount of nickel is the 0-30% of catalyst weight in step (1).
The catalyst green compact of shape needed for described are preferably the structure with parallel longitudinal direction channel, and cross section is triangle
Shape, the thickness of hole wall is between 0.1-1mm.
Used carrier contains MgO, CaO, SiO2, the components such as ZnO, CuO, MnO, main function is that increase catalyst strong
Degree improves catalyst hydrothermal stability.Meanwhile alumina support plays important bonding in this invention and reduces cost work
With being required component.According to the difference of service condition, catalyst activity component fluctuates between 10-55%, with temperature and work
Property require raising, can use high nickel content catalyst, this invention recommend use 15-40% carrying capacity nickel catalyst
Agent.
Ni-based methanation catalyst of a kind of high-intensitive integral extruding type according to the present invention and preparation method thereof, it is main special
Sign is, described enhancing carrier MgO, CaO, SiO2, ZnO, CuO, MnO weight content between 1-8%.It is emphasized that
Catalyst activity and stability are not being reduced, and under the premise of catalyst strength being greatly improved, it is final to determine institute's addition group
Divide dosage, the fewer dosage the better.
One of this invention important feature is exactly to utilize Al3+With Ni2+、Mg2+、Ca2+、Zn2+、Cu2+、Mn2+Ion is easy to shape
At composite oxides or utilize CaO and SiO2It is strong to play enhancing catalyst for crosslinked action fixed solid particle in the catalyst
The effect of degree.The enhancing carrier is preferably MgO, CaO, SiO2One of or numerous compositions.It is emphasized that Ni exists
It is served both functions in the present invention, is active component, and catalyst strength can be enhanced, so high-nickel catalyst is particularly suitable
It is used under high temperature hydrothermal condition.
The another program for enhancing catalyst strength in the present invention is exactly the stability action for utilizing triangle, is guaranteeing to be catalyzed
Under conditions of agent voidage, the structural strength of catalyst is improved.
The invention has the following advantages that
(1) enhancing carrier can be mixed sufficiently with catalyst other components in kneading process, in high-temperature calcination process
Solid solution or composite oxides can be formed with alumina support, improve the intensity and high-temperature hydrothermal stability of catalyst.
(2) integral extruding type catalyst has the structure in parallel longitudinal direction channel, and the cross section of parallel channels is triangle,
It can be further improved the intensity of catalyst.
Specific embodiment
The present invention is described in further details with embodiment below, but this should not be interpreted as to aforesaid right of the present invention and wanted
The range asked is only limitted to following embodiments.Meanwhile embodiment has been merely given as realizing the part Experiment condition of the invention, but not
Mean that must satisfy these conditions can be only achieved the purpose of the present invention.The catalyst provided in specific embodiment is formed, is prepared
Method, reaction condition are the illustration to many possible specific implementations that the present invention applies are represented.
Unless otherwise noted, all numbers occurred in description of the invention and claims, such as dry, roasting
It is absolutely accurate to indicate that the numerical value such as the mass percent of catalyst composition are not construed as temperature, operation temperature and pressure
Value, the numerical value are in that those of ordinary skill in the art is understood, the permitted error range of well-known technique.
Embodiment 1
(1) dry-mixed: to weigh Al (OH)362g intends thin aluminium 195g, γ-Al2O3Powder 387g, hydroxypropyl methyl cellulose
25g, zirconium oxide 70g, kaolin 25g, sesbania powder 5g mix 30 minutes in mixing machine, form uniform solid mixture.
(2) mediate: by lanthanum nitrate hexahydrate 90g, 65% nitric acid 90mL, tung oil 25g, water 300mL, glycerol 7g are added to step
Suddenly it in (1) resulting solid mixture, is mediated 2 hours in kneader, obtains uniform pug.
(3) it pugging and squeezes out: pug room temperature aging 36 hours obtained by step (2) is catalyzed for pugging 2 times in pugging
Agent green compact, room temperature aging 36 hours；Then squeezing out catalyst green compact with extruder and being cut into cross-sectional shape is φ 15mm (straight
Diameter), be highly 60mm, internal for 300 through-holes (300cpsi), through hole section are equilateral triangle, through-hole wall per square inch
Thickness is the catalyst intermediate of 0.2mm.
(4) dry and roast: the catalyst intermediate that step (3) is obtained at room temperature, humidity 80%, it is small to air-dry 48
When；Then it is transferred in baking oven, 120 DEG C of re-dries is warming up to 10 hours with the rate of 0.5 DEG C/min；It moves into Muffle furnace with 0.5
DEG C/rate of min is warming up to 500 DEG C and roasts 4 hours.
(5) active component supports: with Ni (NO3)2.6H2O is predecessor, prepares the Ni (NO that molar concentration is 2M3)2Solution.
Using conventional equi-volume impregnating, support 20% Ni active component, using 120 DEG C re-dry 4 hours, move into Muffle furnace
In with the rate of 2 DEG C/min be warming up to 500 DEG C roasting 4 hours after obtain catalyst 20%NiO-1.8%SiO2- 4%La2O3-
8.2%ZrO2- 66%Al2O3。
Embodiment 2
(1) dry-mixed: to weigh Al (OH)362g intends thin aluminium 195g, γ-Al2O3Powder 387g, hydroxypropyl methyl cellulose
25g, zirconium oxide 70g, cement 30g, sesbania powder 5g mix 30 minutes in mixing machine, form uniform solid mixture.
(2) mediate: by lanthanum nitrate hexahydrate 90g, 65% nitric acid 90mL, tung oil 25g, water 300mL, glycerol 7g are added to step
Suddenly it in (1) resulting solid mixture, is mediated 2 hours in kneader, obtains uniform pug.
(3) pugging and the same embodiment (1) of extrusion.
(4) it dries and roasts same embodiment (1).
(5) active component supports same embodiment (1), obtains catalyst 20%NiO-1%SiO2- 2.2%CaO-3.8%
La2O3- 8%ZrO2- 65%Al2O3。
Embodiment 3
(1) dry-mixed: to weigh Al (OH)362g intends thin aluminium 195g, γ-Al2O3Powder 387g, hydroxypropyl methyl cellulose
25g, zirconium oxide 70g, sesbania powder 5g mix 30 minutes in mixing machine, form uniform solid mixture.
(2) it mediates: by lanthanum nitrate hexahydrate 90g, 150g nickel acetate, 65% nitric acid 90mL, tung oil 25g, water 300mL, glycerol
7g is added in step (1) resulting solid mixture, is mediated 2 hours in kneader, is obtained uniform pug.
(3) pugging and the same embodiment (1) of extrusion.
(4) it dries and roasts same embodiment (1).
(5) active component supports same embodiment (1), obtains catalyst 25.2%NiO--3.8%La2O3- 8%ZrO2-
63%Al2O3。
Embodiment 4
(1) dry-mixed: to weigh Al (OH)362g intends thin aluminium 195g, γ-Al2O3Powder 387g, hydroxypropyl methyl cellulose
25g, zirconium oxide 70g, sesbania powder 5g mix 30 minutes in mixing machine, form uniform solid mixture.
(2) it mediates: by lanthanum nitrate hexahydrate 90g, 130g magnesium acetate, 65% nitric acid 90mL, tung oil 25g, water 300mL, glycerol
7g is added in step (1) resulting solid mixture, is mediated 2 hours in kneader, is obtained uniform pug.
(3) pugging and the same embodiment (1) of extrusion.
(4) dry and roast: the catalyst intermediate that step (3) is obtained at room temperature, humidity 80%, it is small to air-dry 48
When；It is transferred in baking oven, 120 DEG C of re-dries is warming up to 10 hours with the heating rate of 0.5 DEG C/min；It moves into Muffle furnace with 0.5
DEG C/heating rate of min rises to 800 DEG C and roasts 4 hours.
(5) active component supports same embodiment (1), obtains catalyst 20%NiO--4%La2O3- 8%ZrO2- 3%MgO-
65%Al2O3。
Embodiment 5
(1) dry-mixed: to weigh Al (OH)362g intends thin aluminium 195g, γ-Al2O3Powder 260g, hydroxypropyl methyl cellulose
45g, zirconium oxide 30g mix 30 minutes in mixing machine, form uniform solid mixture.
(2) it mediates: by lanthanum nitrate hexahydrate 15g, 320g nickel acetate, 65% nitric acid 80mL, tung oil 45g, water 220mL, glycerol
12g is added in step (1) resulting solid mixture, is mediated 2 hours in kneader, is obtained uniform pug.
(3) it pugging and squeezes out: pug room temperature aging 48 hours obtained by step (2) is catalyzed for pugging 2 times in pugging
Agent green compact, room temperature aging 36 hours；Other same embodiments (1).
(4) it dries and roasts same embodiment (1).
(5) active component supports: with Ni (NO3)2.6H2O is predecessor, prepares the Ni (NO that molar concentration is 2M3)2Solution.
Using conventional equi-volume impregnating, support 20% Ni active component, using 120 DEG C re-dry 4 hours, move into Muffle furnace
In with the rate of 2 DEG C/min be warming up to 500 DEG C roasting 4 hours after, obtain catalyst 33.5%NiO-0.8%La2O3- 4.2%
ZrO2- 61.5%Al2O3。
Embodiment 6
(1) dry-mixed: to weigh Al (OH)362g, intends thin aluminium 195g, MgO powder 100g, nickel oxide 120g, and hydroxypropyl methyl is fine
Element 65g, zirconium oxide 100g, sesbania powder 10g are tieed up, is mixed 30 minutes in mixing machine, forms uniform solid mixture.
(2) it mediates: by lanthanum nitrate hexahydrate 20g, 320g nickel acetate, 65% nitric acid 120mL, tung oil 45g, water 260mL, glycerol
12g is added in step (1) resulting solid mixture, is mediated 2 hours in kneader, is obtained uniform pug.
(3) it pugging and squeezes out: pug room temperature aging 48 hours obtained by step (2) is catalyzed for pugging 2 times in pugging
Agent green compact, room temperature aging 36 hours；Other same embodiments (1).
(4) it dries and roasts same embodiment (1).
(5) active component supports: with Ni (NO3)2.6H2O is predecessor, prepares the Ni (NO that molar concentration is 2M3)2Solution.
Using conventional equi-volume impregnating, support 20% Ni active component, using 120 DEG C re-dry 4 hours, move into Muffle furnace
In with the rate of 2 DEG C/min be warming up to 500 DEG C roasting 4 hours after, obtain catalyst 50.8%NiO-1.1%La2O3- 7.3%
ZrO2- 14.8%MgO-26%Al2O3。
Embodiment 7
(1) dry-mixed: to weigh Al (OH)362g intends thin aluminium 195g, γ-Al2O3Powder 200g, MgO powder 130g, hydroxypropyl
Methylcellulose 45g, zirconium oxide 140g mix 30 minutes in mixing machine, form uniform solid mixture.
(2) mediate: by lanthanum nitrate hexahydrate 100g, 240g magnesium acetate, 65% nitric acid 100mL, tung oil 50g, water 240mL is sweet
Oily 20g is added in step (1) resulting solid mixture, is mediated 2 hours in kneader, is obtained uniform pug.
(3) it pugging and squeezes out: pug room temperature aging 48 hours obtained by step (2) is catalyzed for pugging 2 times in pugging
Agent green compact, room temperature aging 36 hours；Other same embodiments (1).
(4) it dries and roasts same embodiment (1).
(5) active component supports: with Ni (NO3)2.6H2O is predecessor, prepares the Ni (NO that molar concentration is 2M3)2Solution.
Using conventional equi-volume impregnating, support 20% Ni active component, using 120 DEG C re-dry 4 hours, move into Muffle furnace
In with the rate of 2 DEG C/min be warming up to 500 DEG C roasting 4 hours after, obtain catalyst 20%NiO-4.1%La2O3- 15%ZrO2-
19.2%MgO-41.7%Al2O3。
Embodiment 8
(1) dry-mixed: to weigh γ-Al2O3Powder 400g, zirconium oxide 170g, hydroxypropyl methyl cellulose 60g, sesbania powder 5g,
It is mixed 30 minutes in mixing machine, forms uniform solid mixture.
(2) it mediates: by lanthanum nitrate hexahydrate 110g, 240g nickel acetate, 120g magnesium acetate, 65% nitric acid 90mL, tung oil 50g,
Water 260mL, glycerol 15g are added in step (1) resulting solid mixture, are mediated 2 hours in kneader, are obtained uniform
Pug.
(3) it pugging and squeezes out: pug room temperature aging 48 hours obtained by step (2) is catalyzed for pugging 2 times in pugging
Agent green compact, room temperature aging 36 hours；Other same embodiments (1).
(4) it dries and roasts same embodiment (1).
(5) active component supports: with Ni (NO3)2.6H2O is predecessor, prepares the Ni (NO that molar concentration is 2M3)2Solution.
Using conventional equi-volume impregnating, support 20% Ni active component, using 120 DEG C re-dry 4 hours, move into Muffle furnace
In with the rate of 2 DEG C/min be warming up to 500 DEG C roasting 4 hours after, obtain catalyst 28.2%NiO-4.7%La2O3- 19%
ZrO2- 2.6%MgO-45.5%Al2O3。
Comparative example 1:
(1) dry-mixed: to weigh Al (OH)362g intends thin aluminium 195g, γ-Al2O3Powder 387g, hydroxypropyl methyl cellulose
25g, zirconium oxide 70g, sesbania powder 5g mix 30 minutes in mixing machine, form uniform solid mixture.
(2) mediate: by lanthanum nitrate hexahydrate 90g, 65% nitric acid 90mL, tung oil 25g, water 300mL, glycerol 7g are added to step
Suddenly it in (1) resulting solid mixture, is mediated 2 hours in kneader, obtains uniform pug.
(3) it pugging and squeezes out: pug room temperature aging 36 hours obtained by step (2) is urged for pugging 2 times in pug mill
Agent green compact, room temperature aging 36 hours；Then squeezing out catalyst green compact with extruder and being cut into cross-sectional shape is φ 15 (straight
Diameter), be highly 60mm, it is internal be square for 300 through-holes (300cpsi), through-holes per square inch, through-hole wall thickness is
The catalyst intermediate of 0.3mm.
(4) it dries and roasts same embodiment (1).
(5) active component supports same embodiment (1), obtains catalyst 20%NiO--4%La2O3- 8%ZrO2- 68%
Al2O3。
Comparative example 2:
(1) dry-mixed: to weigh Al (OH)362g intends thin aluminium 195g, γ-Al2O3Powder 387g, hydroxypropyl methyl cellulose
25g, zirconium oxide 70g, sesbania powder 5g mix 30 minutes in mixing machine, form uniform solid mixture.
(2) mediate: by lanthanum nitrate hexahydrate 90g, 65% nitric acid 90mL, tung oil 25g, water 300mL, glycerol 7g are added to step
Suddenly it in (1) resulting solid mixture, is mediated 2 hours in kneader, obtains uniform pug.
(3) pugging and the same embodiment (1) of extrusion.
(4) it dries and roasts same embodiment (1).
(5) active component supports same embodiment (1), obtains catalyst 20%NiO--4%La2O3- 8%ZrO2- 68%
Al2O3。
The intensity contrast table of catalyst obtained by the embodiment of the present invention
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Side pressure strength N/cm | 40 | 55 | 75 | 91 | 20 | 33 |
Claims (9)
1. the Ni-based methanation catalyst of a kind of high intensity integral extruding type, it is characterized in that the catalyst includes active component, helps
Catalyst and catalyst carrier；Wherein,
Active component is nickel, and content is the 10-55% of total catalyst weight in terms of metal oxide；
Catalyst aid is the oxide of rare earth lanthanum, and content is the 1-5% of total catalyst weight in terms of metal oxide；
Catalyst carrier is the surplus in catalyst in addition to active component and catalyst aid；Catalyst carrier is γ-Al2O3With
ZrO2And MgO, CaO, SiO2, one or more of ZnO, CuO, MnO mixture；
In the catalyst carrier, γ-Al2O3Weight content be not less than total catalyst weight 20%；MgO,CaO,
SiO2, ZnO, CuO, and/or MnO be enhancing carrier, weight content be not higher than total catalyst weight 20%, ZrO2Content is small
In the 20% of total catalyst weight.
2. according to the Ni-based methanation catalyst of a kind of high intensity integral extruding type described in claim 1, which is characterized in that the increasing
Intense loading body MgO, CaO, SiO2, ZnO, CuO and/or MnO content be total catalyst weight 1-8%.
3. according to the Ni-based methanation catalyst of a kind of high intensity integral extruding type described in claim 1, which is characterized in that the increasing
Intense loading body is MgO, CaO, SiO2One of or numerous compositions.
4. according to a kind of preparation method of the Ni-based methanation catalyst of high intensity integral extruding type described in claim 1, feature
It is to carry out in accordance with the following steps:
(1) according to catalyst composition ratio by solid material, oxide or other predecessors including catalyst carrier aluminium and zirconium,
The oxide of auxiliary agent lanthanum or other predecessors, solid extrusion aid are put into batch mixer mixing 0.5-1 hours, form homogeneous solid
Mixture；Then, by account for solid feed intake the water of object weight 40-50%, liquid extrusion aid, nickel and enhancing carrier oxide or
Soluble predecessor aqueous solution is added to solid mixture, mediates in kneader and forms uniform pug；
(2) it by pug pugging 2-3 times in pug mill obtained by step (1), obtains small suitable for the aging 24-48 of pug green compact of extrusion
When, green compact are extruded into required shape with extruder and are cut into the catalyst green compact of certain size；After drying, Muffle furnace is moved into
In with the heating rate of 0.5-2 DEG C/min rise to 500-850 DEG C roasting 4 hours after obtain catalyst intermediate；
(3) catalyst intermediate for obtaining step (2) is urged using conventional incipient impregnation or excessive impregnation method with containing
The catalyst intermediate that the nitrate aqueous solution impregnation steps (2) of agent active component Ni obtain, using 120 DEG C of re-dry 2-
It 10 hours, moves into Muffle furnace after being warming up to 500-850 DEG C of roasting 4 hours and obtains catalyst.
5. according to a kind of preparation method of the Ni-based methanation catalyst of high intensity integral extruding type described in claim 4, feature
Be, the catalyst solid extrusion aid and liquid extrusion aid include binder, lubricant and moisturizer, content with
Poidometer is the 5-15% of total catalyst weight；The weight ratio of binder and lubricant are as follows: 3-5:1, lubricant and moisturizer
Weight ratio are as follows: 2-5:1.
6. according to a kind of preparation method of the Ni-based methanation catalyst of high intensity integral extruding type described in claim 5, feature
It is, the binder includes liquid-containing binder and solid binder, and the liquid-containing binder is nitric acid, acetic acid or its group
It closes, dosage is on the basis of aluminium used, molar ratio are as follows: Al/ liquid-containing binder=1-10；The solid binder is Methyl cellulose
Element, ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or combinations thereof.
7. according to a kind of preparation method of the Ni-based methanation catalyst of high intensity integral extruding type described in claim 5, feature
It is, the solid lubricant in the catalyst extrusion aid is sesbania powder, and fluid lubricant is tung oil, solid lubricant and liquid
Body lubricant weight is 0-0.5, and does not include zero point；Moisturizer in the catalyst extrusion aid is glycerol, dosage
For the 0.5-3% of solid inventory in step described in claim 4 (1).
8. according to a kind of preparation method of the Ni-based methanation catalyst of high intensity integral extruding type described in claim 4, feature
It is, the additional amount of nickel is the 0-30% of catalyst weight in step (1), and does not include zero point.
9. according to a kind of preparation method of the Ni-based methanation catalyst of high intensity integral extruding type described in claim 4, feature
It is, the catalyst green compact of the required shape are the structure with parallel longitudinal direction channel, and cross section is triangle, hole wall
Thickness is between 0.1-1mm.
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| CN102029162A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Wide-temperature full methanation catalyst and preparation method thereof |
| CN102247861A (en) * | 2011-05-11 | 2011-11-23 | 神华集团有限责任公司 | Coal gas high-temperature methanation catalyst and preparation method thereof |
| US20120063963A1 (en) * | 2009-04-24 | 2012-03-15 | University Of Yamanashi | Selective co methanation catalyst, method of producing the same, and apparatus using the same |
| CN103203237A (en) * | 2013-05-02 | 2013-07-17 | 神华集团有限责任公司 | Aluminum oxide loaded methanation catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120063963A1 (en) * | 2009-04-24 | 2012-03-15 | University Of Yamanashi | Selective co methanation catalyst, method of producing the same, and apparatus using the same |
| CN102029162A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院大连化学物理研究所 | Wide-temperature full methanation catalyst and preparation method thereof |
| CN102247861A (en) * | 2011-05-11 | 2011-11-23 | 神华集团有限责任公司 | Coal gas high-temperature methanation catalyst and preparation method thereof |
| CN103203237A (en) * | 2013-05-02 | 2013-07-17 | 神华集团有限责任公司 | Aluminum oxide loaded methanation catalyst |
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