CN106732622A - A kind of preparation method of resistance to sintering methanation catalyst - Google Patents

A kind of preparation method of resistance to sintering methanation catalyst Download PDF

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CN106732622A
CN106732622A CN201611034558.7A CN201611034558A CN106732622A CN 106732622 A CN106732622 A CN 106732622A CN 201611034558 A CN201611034558 A CN 201611034558A CN 106732622 A CN106732622 A CN 106732622A
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catalyst
sintering
resistance
composite oxide
metal composite
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CN106732622B (en
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任军
韩亚红
刘树森
朱继宇
靳永勇
李忠
李海霞
程铭
王娟
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Taiyuan University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field that coke-stove gas and coal produce synthetic natural gas catalyst preparation and application, specifically a kind of preparation method of resistance to sintering methanation catalyst, particularly a kind of order mesoporous La2O3‑SiO2The preparation method of metal composite oxide supported ni catalyst.By La2O3‑SiO2Metal composite oxide make it is order mesoporous, using dipping by the way of load active component nickel, quickly obtain nickel-containing catalyst by high-temperature roasting, due to CTAB have it is nontoxic, easily remove（Cleaned with ethanol）The advantages of, and as template；Each component is uniformly dispersed in catalyst, and be limited in active component nickel in duct by ordered mesopore structure, plays " protection " effect, effectively prevents its high temperature sintering；In SiO2Middle addition La2O3Catalyst activity is increased, changes La2O3Content cause that the activity of catalyst reaches most preferably.

Description

A kind of preparation method of resistance to sintering methanation catalyst
Technical field
The invention belongs to the technical field that coke-stove gas and coal produce synthetic natural gas catalyst preparation and application, specifically A kind of preparation method of resistance to sintering methanation catalyst, particularly a kind of order mesoporous La2O3-SiO2Metal composite oxide is born Carry the preparation method of Ni catalyst.
Background technology
Natural gas is a kind of cleaning, efficient new energy.But the energy resource structure of China is " rich coal, oil-poor, few gas ", day Right gas yield wretched insufficiency, and consumption figure rapid development, the inlet natural gas since 2006, natural gas dependence on external supply degree Deepen year by year, natural gas imbalance between supply and demand is protruded.Therefore, it is necessary to developing new approach solves this problem.With oven gas or coal system It is an effective behave to take synthetic natural gas, optimizes energy consumption structure；Reduce use of the coal as primary energy Ratio；Reduce environmental pollution.
Due to SiO2The features such as thermal conductivity that has is high, hardness is high and be widely used as catalyst carrier.Patent CN105396592A specific surface areas of catalyst are smaller, and agglomeration easily occurs.Patent CN105498781A is with SiO2And other two Kind of oxide adds rare earth metal as auxiliary agent, then load active component nickel as catalyst carrier, and preparation technology is cumbersome, Cost is increased, is not suitable for large-scale use.Metal oxide supported nickel is usually used in methanation reaction, nickel have it is cheap, The advantage of high activity and high selectivity.But methanation reaction is strong exothermal reaction, in course of reaction, temperature is too high is easily caused nickel Sintering, reunites, and specific surface area active declines, and then causes catalyst to inactivate.
The content of the invention
The present invention is in order to solve the problems, such as existing methanation catalyst easy in inactivation, there is provided a kind of methanation catalyst of resistance to sintering The preparation method of agent.
The present invention is achieved by the following technical solutions：A kind of preparation method of resistance to sintering methanation catalyst, including Following steps：
(1) order mesoporous La is prepared3O2-SiO2Metal composite oxide carrier：
Weigh during ammoniacal liquor, lanthanum nitrate, tetraethyl orthosilicate add to CTAB solution, stirred 6 hours in the environment of being sealed in 40 DEG C, Adjust the amount of each component so that lanthanum nitrate：TEOS=(0-0.4):(0.6-1), TEOS：Ammoniacal liquor：CTAB=6：1：2；
Template agent removing CTAB is gone using ethanol, second alcohol and water is then removed using dried process；By the product after dried process Thing is placed under 550 DEG C of environment, constant temperature calcining 4 hours, obtains metal composite oxide carrier；
(2) order mesoporous La is prepared2O3-SiO2Metal composite oxide supported ni catalyst：
Nickel nitrate is weighed, it is 1 it is dissolved completely in volume ratio:In 1 ethanol and the mixed solvent of water；Then by step (1) metal composite oxide carrier impregnation in nickel nitrate solution, ultrasonic disperse 30min under 65 DEG C of environment, then in this temperature It is upper to continue to stir until solvent volatilizees to form paste product；Then paste product is placed in drying in 90 DEG C of baking ovens and forms solid powder End, removes the second alcohol and water of residual；Then solid powder is placed under 500 DEG C of environment, constant temperature calcining 3 hours is naturally cooled to After room temperature, resistance to sintering methanation catalyst Ni/L is obtainedxSy, the load capacity of Ni is 5%-30% (w/w) wherein on catalyst.
Resistance to sintering methanation catalyst Ni/L of the present inventionxSyMiddle L refers to La (lanthanum), the Si (silicon) that S refers to.The present invention Preparing order mesoporous La3O2-SiO2During metal composite oxide carrier, the amount of each component is adjusted so that lanthanum nitrate：TEOS= (0-0.4):(0.6-1), TEOS：Ammoniacal liquor：CTAB=6：1：2；Aforementioned molar ratio lanthanum nitrate from scratch, is added by amount, and then Help to analyze the effect of auxiliary agent, the addition of control ammoniacal liquor and CTAB amounts so that TEOS is decomposed and then formed completely regular to be had Sequence duct；The load capacity of Ni is required on the catalyst for preparing for 5%-30%, if being more than 30%, can the too high appearance of nickel content Agglomeration, while the effect that can be just reached using as far as possible few raw material from from the point of view of economy；If being less than 5%, nickel Content is too low, and then catalysis activity is low, without practical significance.
During concrete application, (2) middle nickel nitrate and mixed solvent are the constant temperature stirring and dissolvings under 65 DEG C of environment to step.
Further, step (1) and (2) in constant temperature calcining be to implement in Muffle furnace.
Preferably, step (1) in product be placed in Muffle furnace after be heated to 550 to be not higher than the thermograde of 5 DEG C/min ℃.Step (2) in solid powder be placed in Muffle furnace after be heated to 500 DEG C not to be not higher than the thermograde of 5 DEG C/min.If Thermograde is excessive, it is most likely that cause structure collapses.
In order to further study the test effect of the methanation catalyst of resistance to sintering that the present invention is prepared, inventor uses Catalyst in embodiment 1 is in hydrogen and carbon monoxide (volume ratio 3:1) activity rating is carried out in mixed reaction gas, is commented Valency result such as following table：
Reaction temperature (DEG C) CO conversion ratios (%) CH4Selectivity (%)
280 97.65 92.78
300 98.32 92.49
320 98.85 93.21
340 99.12 93.83
360 99.14 93.69
380 99.15 93.43
400 99.14 93.46
420 99.19 93.65
440 99.20 93.49
460 99.14 93.46
The present invention has obvious advantage compared with background technology, by La2O3-SiO2Metal composite oxide is made in order Mesoporous, the load active component nickel by the way of dipping, quickly obtains nickel-containing catalyst, because CTAB has by high-temperature roasting It is nontoxic, easily except (being cleaned with ethanol) the advantages of, and as template；Each component is uniformly dispersed in catalyst, in order Be limited in active component nickel in duct by meso-hole structure, plays " protection " effect, effectively prevents its high temperature sintering；In SiO2In Add La2O3Catalyst activity is increased, changes La2O3Content cause that the activity of catalyst reaches most preferably.Prepared by the method Catalyst not only has catalysis activity at low temperature, and anti-caking power is strong in catalytic reaction, and technological process simple and fast, original Material reasonable mixture ratio, the data for obtaining are true and reliable, are method of the very effective quick preparation containing nickel methenyl catalyst.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of the methanation catalyst of resistance to sintering that embodiment 1 is prepared.In figure：Ordinate is Diffracted intensity, abscissa is the θ of the angle of diffraction 2, and 44.370 °, 51.890 ° and 76.410 ° is the diffraction maximum of elemental nickel in figure, can by figure Find out, diffraction peak width, show that simple substance nickel dispersity is high；Only one of which SiO2Peak position and there is not La2O3Peak position, explanation Lanthanum atom is evenly dispersed in SiO2In lattice.
Fig. 2 is Muffle stove heat roasting bed temperature and time coordinate graph of a relation in embodiment 1.Heating-up temperature is opened by 25 DEG C Begin to heat up, i.e. A points, with the speed of 3 DEG C/min, rise to 500 ± 2 DEG C, i.e. B points in this thermostatic, are incubated 180 ± 2min, i.e., B-C sections, then stop heat temperature raising, it is naturally cooled to 25 DEG C with stove, i.e. D points, and heat temperature raising temperature and time is into just Than.
Specific embodiment
The chemical substance material that the present invention is used is：Lanthanum nitrate, tetraethyl orthosilicate, cetyl trimethyl ammonia bromide (CTAB), nickel nitrate, ammoniacal liquor, ethanol, deionized water, it is as follows that it prepares consumption：It is measurement unit with gram, milliliter.
Preparation method is as follows：
(1), selected chemical substance material
Chemical substance material needed for preparation to be carried out selected, and carry out quality purity control：
Embodiment 1
(2) order mesoporous La, is prepared3O2-SiO2Metal composite oxide carrier
1. the CTAB aqueous solution is prepared
Quality is weighed for 0.87 ± 0.01g CTAB (0.002mol), 30.00 ± 0.01g deionized waters, in addition beaker, It is stirred until homogeneous, obtains solution A.
2. mixed solution is prepared
Weigh the ammoniacal liquor (28%, 0.001mol) of 0.13 ± 0.01g, the lanthanum nitrate (0.004mol) of 1.73 ± 0.01g, 1.25 ± 0.01g tetraethyl orthosilicates (TEOS, 0.006mol) form mixed system B in adding to solution A, are wrapped up B with preservative film To get up stirred 6 hours under conditions of 40 DEG C of constant temperature.
3. dried process
Three times removing templates are washed with ethanol, is hereafter placed at room temperature one week and is removed second alcohol and water.The colloidal sol that will be obtained is put In 80 DEG C of baking ovens, dry 3 days.
4. roasting shaping
Sample is put into quartzy product boat to be placed in Muffle furnace, 550 DEG C, perseverance are heated to the thermograde of 0.5 DEG C/min Temperature 4 hours.
(3), order mesoporous La2O3-SiO2Metal composite oxide supported ni catalyst
1. nickel nitrate solution is prepared
Appropriate nickel nitrate is weighed, is dissolved separately in and is filled 60mL ethanol/waters (V (EtOH)/V (H2O)=1:1) beaker In, beaker is placed in 65 DEG C of thermostat water baths, stir 20min.
2. impregnation process
During the catalyst carrier of preparation added into nickel nitrate solution, uniform mixing is placed in ultrasound point in 65 DEG C of ultrasonic instruments 30min is dissipated, and continues to stir untill solvent is almost evaporated completely in this temperature, form paste product.
3. dried process
Sample is placed in the baking oven that temperature is 90 DEG C and is dried 8 hours, remove the second alcohol and water of residual.
4. sample roasting
Dried solid powder is placed in quartzy product boat and is put into Muffle furnace, with the heating rate liter of 3 DEG C/min To 500 DEG C and keep 3 hours.
5. after naturally cooling to room temperature, obtain catalyst sample and be designated as Ni/L respectivelyxSy(x:Y=0.4:0.6, Ni load Measure as 15%).
(4), detect, chemically examine, analyze, characterize
1. the color and luster of catalyst fines for preparing, pattern, composition, Chemical Physics performance detected, is chemically examined, analyzed, Characterize.
2. crystal phase analysis are carried out with X-ray powder diffraction instrument.
3. morphology analysis are carried out with SEM.
Conclusion：Catalyst is black solid；Particle diameters≤100nm.
(5), product storage
Black powder to preparing is stored in the glass container of water white transparency, and sealed storage is placed in dry, shady and cool, clean Net environment, waterproof, sun-proof, anti-acid-alkali salt to corrode, 20 ± 2 DEG C of storage temperature, relative humidity≤10%.
Embodiment 2
(2) order mesoporous La, is prepared3O2-SiO2Metal composite oxide carrier
1. the CTAB aqueous solution is prepared
Quality is weighed for 0.97 ± 0.01g CTAB (0.0027mol), 30.00 ± 0.01g deionized waters add beaker In, it is stirred until homogeneous, obtain solution A.
2. mixed solution is prepared
Weigh the ammoniacal liquor (28%, 0.0013mol) of 0.17 ± 0.01g, 1.66 ± 0.01g tetraethyl orthosilicates (TEOS, 0.008mol) add to and mixed system B is formed in solution A, B is wrapped up with preservative film stirs 6 under conditions of 40 DEG C of constant temperature Hour.
3. dried process
Three times removing templates are washed with ethanol, is hereafter placed at room temperature one week and is removed second alcohol and water.The colloidal sol that will be obtained is put In 80 DEG C of baking ovens, dry 3 days.
4. roasting shaping
Sample is put into quartzy product boat to be placed in Muffle furnace, 550 DEG C, perseverance are heated to the thermograde of 0.8 DEG C/min Temperature 4 hours.
(3), order mesoporous La2O3-SiO2Metal composite oxide supported ni catalyst
1. nickel nitrate solution is prepared
Appropriate nickel nitrate is weighed, is dissolved separately in and is filled 60mL ethanol/waters (V (EtOH)/V (H2O)=1:1) beaker In, beaker is placed in 65 DEG C of thermostat water baths, stir 20min.
2. impregnation process
During the catalyst carrier of preparation added into nickel nitrate solution, uniform mixing is placed in ultrasound point in 65 DEG C of ultrasonic instruments 30min is dissipated, and continues to stir untill solvent is almost evaporated completely in this temperature, form paste product.
3. dried process
Sample is placed in the baking oven that temperature is 90 DEG C and is dried 8 hours, remove the second alcohol and water of residual.
4. sample roasting
Dried solid powder is placed in quartzy product boat and is put into Muffle furnace, with the heating rate liter of 4 DEG C/min To 500 DEG C and keep 3 hours.
5. after naturally cooling to room temperature, obtain catalyst sample and be designated as Ni/L respectivelyxSy(x:Y=(0:0.8, Ni load Measure as 5%).
(4), detect, chemically examine, analyze, characterize
1. the color and luster of catalyst fines for preparing, pattern, composition, Chemical Physics performance detected, is chemically examined, analyzed, Characterize.
2. crystal phase analysis are carried out with X-ray powder diffraction instrument.
3. morphology analysis are carried out with SEM.
Conclusion：Catalyst is black solid；Particle diameters≤100nm.
(5), product storage
Black powder to preparing is stored in the glass container of water white transparency, and sealed storage is placed in dry, shady and cool, clean Net environment, waterproof, sun-proof, anti-acid-alkali salt to corrode, 20 ± 2 DEG C of storage temperature, relative humidity≤10%.
Embodiment 3
(2) order mesoporous La, is prepared3O2-SiO2Metal composite oxide carrier
1. the CTAB aqueous solution is prepared
Quality is weighed for 1.21 ± 0.01g CTAB (0.003mol), 30.00 ± 0.01g deionized waters, in addition beaker, It is stirred until homogeneous, obtains solution A.
2. mixed solution is prepared
Weigh the ammoniacal liquor (28%, 0.0017mol) of 0.21 ± 0.01g, the lanthanum nitrate (0.002mol) of 0.87 ± 0.01g, 2.08 ± 0.01g tetraethyl orthosilicates (TEOS, 0.01mol) form mixed system B in adding to solution A, are wrapped up B with preservative film Come under conditions of 40 DEG C of constant temperature to stir 6 hours.
3. dried process
Three times removing templates are washed with ethanol, is hereafter placed at room temperature one week and is removed second alcohol and water.The colloidal sol that will be obtained is put In 80 DEG C of baking ovens, dry 3 days.
4. roasting shaping
Sample is put into quartzy product boat to be placed in Muffle furnace, 550 DEG C, constant temperature 4 are heated to the thermograde of 2 DEG C/min Hour.
(3), order mesoporous La2O3-SiO2Metal composite oxide supported ni catalyst
1. nickel nitrate solution is prepared
Appropriate nickel nitrate is weighed, is dissolved separately in and is filled 60mL ethanol/waters (V (EtOH)/V (H2O)=1:1) beaker In, beaker is placed in 65 DEG C of thermostat water baths, stir 20min.
2. impregnation process
During the catalyst carrier of preparation added into nickel nitrate solution, uniform mixing is placed in ultrasound point in 65 DEG C of ultrasonic instruments 30min is dissipated, and continues to stir untill solvent is almost evaporated completely in this temperature, form paste product.
3. dried process
Sample is placed in the baking oven that temperature is 90 DEG C and is dried 8 hours, remove the second alcohol and water of residual.
4. sample roasting
Dried solid powder is placed in quartzy product boat and is put into Muffle furnace, with the heating rate liter of 2 DEG C/min To 500 DEG C and keep 3 hours.
5. after naturally cooling to room temperature, obtain catalyst sample and be designated as Ni/L respectivelyxSy(x:Y=0.2:1, Ni load capacity For 30%).
(4), detect, chemically examine, analyze, characterize
1. the color and luster of catalyst fines for preparing, pattern, composition, Chemical Physics performance detected, is chemically examined, analyzed, Characterize.
2. crystal phase analysis are carried out with X-ray powder diffraction instrument.
3. morphology analysis are carried out with SEM.
Conclusion：Catalyst is black solid；Particle diameters≤100nm.
(5), product storage
Black powder to preparing is stored in the glass container of water white transparency, and sealed storage is placed in dry, shady and cool, clean Net environment, waterproof, sun-proof, anti-acid-alkali salt to corrode, 20 ± 2 DEG C of storage temperature, relative humidity≤10%.

Claims (5)

1. it is a kind of it is resistance to sintering methanation catalyst preparation method, it is characterised in that comprise the following steps：
(1) order mesoporous La is prepared3O2-SiO2Metal composite oxide carrier：
Weigh during ammoniacal liquor, lanthanum nitrate, tetraethyl orthosilicate add to CTAB solution, stirred 6 hours in the environment of being sealed in 40 DEG C, regulation The amount of each component so that lanthanum nitrate：TEOS = (0-0.4):(0.6-1), TEOS：Ammoniacal liquor：CTAB = 6：1：2；
Template agent removing CTAB is gone using ethanol, second alcohol and water is then removed using dried process；Product after dried process is put In under 550 DEG C of environment, constant temperature calcining 4 hours obtains metal composite oxide carrier；
(2) order mesoporous La is prepared2O3-SiO2Metal composite oxide supported ni catalyst：
Nickel nitrate is weighed, it is 1 it is dissolved completely in volume ratio:In 1 ethanol and the mixed solvent of water；Then by step (1) Metal composite oxide carrier impregnation in nickel nitrate solution, ultrasonic disperse 30min under 65 DEG C of environment, then in this temperature after Continuous stirring is until solvent volatilizees to form paste product；Then paste product is placed in drying in 90 DEG C of baking ovens and forms solid powder, Remove the second alcohol and water of residual；Then solid powder is placed under 500 DEG C of environment, constant temperature calcining 3 hours naturally cools to room Wen Hou, obtains resistance to sintering methanation catalyst Ni/LxSy, the load capacity of Ni is 5%-30% wherein on catalyst.
2. it is according to claim 1 it is a kind of it is resistance to sintering methanation catalyst preparation method, it is characterised in that step (2) in Nickel nitrate and mixed solvent are the constant temperature stirring and dissolvings under 65 DEG C of environment.
3. it is according to claim 1 and 2 it is a kind of it is resistance to sintering methanation catalyst preparation method, it is characterised in that step (1) the constant temperature calcining in and (2) is implemented in Muffle furnace.
4. it is according to claim 3 it is a kind of it is resistance to sintering methanation catalyst preparation method, it is characterised in that step (1) in Product be placed in Muffle furnace after be heated to 550 DEG C to be not higher than the thermograde of 5 DEG C/min.
5. it is according to claim 3 it is a kind of it is resistance to sintering methanation catalyst preparation method, it is characterised in that step (2) in Solid powder be placed in Muffle furnace after be heated to 500 DEG C not to be not higher than the thermograde of 5 DEG C/min.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113413908A (en) * 2021-06-10 2021-09-21 武汉大学 Methane carbon dioxide reforming nickel-based catalyst and preparation method and application thereof

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CN105084372A (en) * 2014-05-21 2015-11-25 中国科学院化学研究所 Method for loading nano-particles of metal or metallic oxide in mesoporous silica channel

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CN105084372A (en) * 2014-05-21 2015-11-25 中国科学院化学研究所 Method for loading nano-particles of metal or metallic oxide in mesoporous silica channel

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FEI HUANG ET AL.,: "Catalytic performances of Ni/mesoporous SiO2 catalysts for dry reforming of methane to hydrogen", 《JOURNAL OF ENERGY CHEMISTRY》 *
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113413908A (en) * 2021-06-10 2021-09-21 武汉大学 Methane carbon dioxide reforming nickel-based catalyst and preparation method and application thereof

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