CN104475098B - A kind of catalyst of methane portion oxidation synthesis gas and preparation method thereof - Google Patents
A kind of catalyst of methane portion oxidation synthesis gas and preparation method thereof Download PDFInfo
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- CN104475098B CN104475098B CN201410763312.8A CN201410763312A CN104475098B CN 104475098 B CN104475098 B CN 104475098B CN 201410763312 A CN201410763312 A CN 201410763312A CN 104475098 B CN104475098 B CN 104475098B
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Abstract
A kind of catalyst of methane portion oxidation synthesis gas and preparation method thereof, is related to the nanocatalyst of preparing synthetic gas.The catalyst of the methane portion oxidation synthesis gas is with SiO2For carrier, CeO2For auxiliary agent, by mass percentage, the content of active component Rh is 0.005%～1%, auxiliary agent CeO2For 5% 30%, remaining is SiO2.The particle diameter of Rh is 1～2nm, and specific surface area is 350～450m2/g.1) by carrier S iO2It is immersed in salpeter solution, washs to pH=6.5～7.0, it is standby after being dried；2) prepare the salting liquid of the salting liquid and cerium of rhodium by catalyst components content proportioning respectively, and mixed impregnant liquor is merged into according to catalyst components ratio；3) by step 1) SiO that obtains2With step 2) maceration extract that obtains mixes, impregnates, and drying is obtained the catalyst of methane portion oxidation synthesis gas after roasting.
Description
Technical field
The present invention relates to the nanocatalyst of preparing synthetic gas, more particularly, to a kind of urging for methane portion oxidation synthesis gas
Agent and preparation method thereof.
Background technology
The main component of natural gas and shale gas is methane, as the large scale mining of natural gas and shale gas is utilized, first
The effectively utilizes of alkane are increasingly paid close attention to by people.One of effective way of high added value product is converted into using methane is exactly
Synthesis gas is translated into, and then methyl alcohol, liquid fuel and other chemical products is prepared using synthesis gas.With traditional methane water
Steam reforming preparing synthetic gas are compared, methane portion oxidation synthesis gas have that reactor volume is little, reaction rate is fast, energy consumption is low and
The advantages of C/Hratio of product is adapted to follow-up methyl alcohol and Fiscber-Tropscb synthesis.Thus methane portion oxidation synthesis gas react in recent years
To receive much concern.
Methane portion oxidation synthesis gas catalyst is mainly load type metal catalyst, wherein two classes can be divided into：One
Class is load-type nickel, Co catalysts, the easy carbon distribution of Raney nickel, and active component is easy to run off, and Co catalysts activity is relatively low, living
Property is mutually easily oxidized；Another kind of is loaded noble metal catalyst, and the type catalyst has reliable stability and excellent
It is active and selective, but its price is relatively expensive.
Rhodium catalyst has the features such as stability is high, oxidation resistance is strong, thus shows excellent reactivity worth.
1wt%Rh/SiO2Catalyst can show at 450 DEG C good catalysis activity (J.Catal.2004,226,247-
259).As rhodium is expensive, prepare that load capacity is low and the catalyst of stable in catalytic performance be the reaction is pushed to it is industrialized
Essential step.Document (ChemCatChem 2012,4,1368-1375) synthesizes particle diameter by reduction of ethylene glycol method and there was only 1.3nm
The Rh nano-particles of left and right are simultaneously supported on γ-Al2O3On prepare catalyst for the reaction, due to Rh decentralization very
Height, as the load capacity as little as 0.005wt% of Rh, remains to show good catalysis activity and stability.But the catalyst system
Preparation Method is complicated and is only applicable to the relatively low reaction condition of air speed.Therefore by adding suitable auxiliary agent, further improve catalysis
The active of agent, selectivity and stability, are the effective ways of the consumption for reducing rhodium.CeO2With unique redox property,
Oxygen can be stored and discharge, while CeO2Soluble solids can be formed between Rh, is prevented Rh in the migration of catalyst surface, is carried
The stability of high catalyst.
The content of the invention
It is an object of the invention to provide a kind of catalyst of methane portion oxidation synthesis gas and preparation method thereof.
The catalyst of the methane portion oxidation synthesis gas is with SiO2For carrier, CeO2For auxiliary agent, by mass percentage,
The content of active component Rh is 0.005%～1%, auxiliary agent CeO2For 5%-30%, remaining is SiO2；It is preferred that active component Rh
Content is 0.01%～1%, auxiliary agent CeO2For 5%-30%, remaining is SiO2.The particle diameter of Rh is 1～2nm, and specific surface area is 350
～450m2/g。
The preparation method of the catalyst of the methane portion oxidation synthesis gas, comprises the following steps：
1) by carrier S iO2It is immersed in salpeter solution, washs to pH=6.5～7.0, it is standby after being dried；
2) prepare the salting liquid of the salting liquid and cerium of rhodium by catalyst components content proportioning respectively, and it is each according to catalyst
Component ratio is merged into mixed impregnant liquor；
3) by step 1) SiO that obtains2With step 2) maceration extract that obtains mixes, impregnates, and drying is obtained methane after roasting
Catalyst (the Rh-CeO of portion oxidation synthesis gas2/SiO2Catalyst).
In step 1) in, the condition of the immersion can be to be immersed in 12～24h in the salpeter solution that mass concentration is 20%；
The washing can be using distillation water washing；The condition of the drying can be to be dried 12h at 110～120 DEG C；
In step 2) in, precursor salt used by the salting liquid of the rhodium and cerium is acetylacetone,2,4-pentanedione rhodium and acetylacetone,2,4-pentanedione cerium, solvent
For acetylacetone,2,4-pentanedione or toluene.
In step 3) in, the time at least 12h of the immersion；The condition of the drying can be 110～120 DEG C of air atmospheres
Middle drying 2h；The condition of the roasting can be：Temperature is 800 DEG C, and heating rate is 1～10 DEG C/min, and atmosphere is air, roasting
Time is 2～4h.
Catalyst of the present invention is used for the performance evaluation of methane portion oxidation synthesis gas reaction in miniature fixed bed stream
Carry out on dynamic reaction unit, adopt internal diameter for 6mm quartz reactor, K-type (chromel-alumel) thermocouple for temperature control fixes
In quartzy pipe outer wall, its thermometric end is close to the reaction pipe outer wall of beds first half.Catalyst in a hydrogen atmosphere 700
Reacted after DEG C prereduction 1h.In molar ratio, the composition CH of unstripped gas4/O2=2 (whetheing there is carrier gas), unstripped gas air speed
100000h-1, reaction pressure 0.1MPa, 700～800 DEG C of reaction temperature.Catalyst continuously uses 400h, and activity is without significant change.
The catalyst is applied to the methane of wide proportioning and oxygen feed gas system, is applicable to inert free gas diluted system.
The present invention is a kind of anti-sintering support type rhodium base of high dispersive for being carrier with ceria as auxiliary agent with silica
Catalyst and preparation method thereof, and it is used for methane portion oxidation synthesis gas.The present invention is carrier from silica, by nitre
Acid solution cleans surface residues and promotes surface hydroxyl to expose, and promotes rhodium precursor salt to disperse in surface of silica support, together
When add ceria prevent rhodium the processes such as roasting, reduction agglomeration, so as to prepare with high dispersive high stability
Rh-CeO2/SiO2Catalyst, and the catalyst is used for into methane portion oxidation synthesis gas, study its catalytic performance.
The advantage of catalyst that the present invention is provided is：Ceria stratiform spreads in silica surface, active phase rhodium
Soluble solids is formed with stratiform ceria, rhodium and the weak shortcoming of silica surface active force is overcome；Ceria has simultaneously
There is the redox property of uniqueness, can store and discharge oxygen, so as to significantly improve catalyst performance.Preparation technology letter of the present invention
Single, required bullion content is extremely low, and with cost advantage, and catalysis activity is high, at a temperature of methane conversion is close to respective reaction
Thermodynamic equilibrium value, to H2Selection with CO is high, with excellent anti-carbon performance and stability, continuous anti-under high-speed
Answer in the test period of 400h, catalyst activity keeps stable, and post catalyst reaction surface is generated without carbon distribution.
Description of the drawings
Fig. 1 is 0.5%Rh-10%CeO2/SiO2800 DEG C of roasting 2h of catalyst, the transmission electron microscope picture after 700 DEG C of reduction 1h.
Specific embodiment
Embodiment 1
Catalyst preparation：Choose 10g SiO2As carrier, 24h in 20% salpeter solution is immersed in, with distillation
Water washing is to pH=6.5～7.0, standby after being dried；Weigh acetylacetone,2,4-pentanedione rhodium 0.0098g and be dissolved in 20ml acetylacetone,2,4-pentanedione solution
In, then weigh acetylacetone,2,4-pentanedione cerium 0.0763g and be dissolved in 60ml acetylacetone,2,4-pentanediones, two solvents are mixed into into mixed impregnant liquor, are weighed
Processed good SiO20.5g impregnates 24h in adding mixed impregnant liquor, period stirs for several times, then at 110 DEG C steams solution
Do, in atmosphere 800 DEG C of roasting 2h, heating rate is 1 DEG C/min, obtains catalyst 0.5%Rh-5%CeO2/SiO2。
Appreciation condition：Reaction procatalyst uses hydrogen reducing 1h at 700 DEG C.In continuous sample introduction fixed-bed quartz reactor
Middle reaction, reaction temperature are 700 DEG C, unstripped gas composition CH4∶O2: Ar=2: 1: 4 (mol ratios), air speed 1 × 105h-1, product Jing
Gas-chromatography on-line analysis is used after condensation eliminating water.Evaluation result is shown in Table 1.
0.5%Rh-10%CeO2/SiO2800 DEG C of roasting 2h of catalyst, the transmission electron microscope picture after 700 DEG C of reduction 1h is referring to figure
1。
Embodiment 2
Solvent is changed to toluene by acetylacetone,2,4-pentanedione with reference to embodiment 1 by catalyst preparation, and remaining condition is identical, is catalyzed
Agent 0.5%Rh-10%CeO2/SiO2With embodiment 1, evaluation result is shown in Table 1 to appreciation condition.
Table 1
Embodiment 3～5：Catalyst preparation with reference to embodiment 1, by the quality of acetylacetone,2,4-pentanedione cerium be changed to respectively 0.1525g,
Remaining condition of 0.3050g, 0.4575g is identical, obtains catalyst 0.5%Rh-10%CeO2/SiO2, 0.5%Rh-20%CeO2/
SiO2, 0.5%Rh-30%CeO2/SiO2.With embodiment 1, evaluation result is shown in Table 2 to appreciation condition.
Table 2
Reference examples 1
Catalyst preparation weighs acetylacetone,2,4-pentanedione rhodium 0.0098 and is dissolved in 20ml acetylacetone,2,4-pentanedione solution with reference to embodiment 1, claims
Take processed good SiO20.5g impregnates 24h in adding mixed impregnant liquor, period is stirred for several times, then by solution at 110 DEG C
It is evaporated, in atmosphere 800 DEG C of roasting 2h, heating rate is 1 DEG C/min, obtains 0.5%Rh/SiO2-Catalyst.Appreciation condition is same
Embodiment 1, evaluation result is shown in Table 3.
Table 3
Embodiment 6～7
The quality of acetylacetone,2,4-pentanedione rhodium is changed to 0.0050g and 0.0020g, by second with reference to embodiment 1 by catalyst preparation respectively
The quality of acyl acetone cerium is changed to 0.1525g and catalyst 0.25%Rh-10%CeO is obtained2/SiO2And 0.1%Rh-10%CeO2/
SiO2Remaining condition is identical.With embodiment 1, evaluation result is shown in Table 4 to appreciation condition.
Table 4
Reference examples 2～3
The quality of acetylacetone,2,4-pentanedione rhodium is changed to 0.0050g and 0.0020g with reference to reference examples 1 by catalyst preparation respectively, is obtained
0.25%Rh/SiO2And 0.1%Rh/SiO2, remaining condition is identical.With embodiment 1, evaluation result is shown in Table 5 to appreciation condition.
Table 5
Embodiment 8～9
The quality of acetylacetone,2,4-pentanedione rhodium is changed to 0.0005g and 0.0002g, by second with reference to embodiment 1 by catalyst preparation respectively
The quality of acyl acetone cerium is changed to 0.1525g, and catalyst 0.025%Rh-10%CeO is obtained2/SiO2And 0.01%Rh-10%
CeO2/SiO2Remaining condition is identical.Reaction temperature is risen to into 800 DEG C by 700 DEG C, as a result other appreciation conditions are shown in embodiment 1
Table 6.
Table 6
Embodiment 10
The quality of acetylacetone,2,4-pentanedione rhodium is changed to 0.0050g with embodiment 1 by catalyst preparation respectively, by acetylacetone,2,4-pentanedione cerium
Quality is changed to 0.1525g, and catalyst 0.25%Rh-10%CeO is obtained2/SiO2, reactor feed gas are constituted by CH4∶O2: Ar=
2: 1: 4 (mol ratios) are changed to CH4∶O2=2: 1 (without diluent gas), with embodiment 1, evaluation result is shown in Table 6 to other appreciation conditions.
Embodiment 11
The quality of acetylacetone,2,4-pentanedione rhodium is changed to 0.0050g with embodiment 1 by catalyst preparation respectively, by acetylacetone,2,4-pentanedione cerium
Quality is changed to 0.1525g, and catalyst 0.25%Rh-10%CeO is obtained2/SiO2, reactor feed gas are constituted by CH4∶O2: Ar=
2: 1: 4 (mol ratios) are changed to CH4∶O2=2: 1 (without diluent gas), and reaction temperature is risen to into 800 DEG C by 700 DEG C, other evaluations
With embodiment 1, evaluation result is shown in Table 7 to condition.
Table 7
Embodiment 12
The quality of acetylacetone,2,4-pentanedione rhodium is changed to 0.005g, by acetylacetone,2,4-pentanedione cerium with reference to embodiment 1 by catalyst preparation respectively
Quality is changed to 0.1525g, and remaining condition is identical, and catalyst 0.25%Rh-10%CeO is obtained2/SiO2.Reactor feed gas are consisted of
CH4∶O2: Ar=2: 1: 4 (mol ratios), appreciation condition are evaluated to catalyst life with embodiment 1, the results are shown in Table 8.
Table 8
Preparation process is simple of the present invention, required bullion content are extremely low, and with cost advantage, and catalysis activity is high, methane
Conversion ratio is close to the thermodynamic equilibrium value at a temperature of respective reaction, to H2Selection with CO is high, with excellent anti-carbon performance
And stability.
Claims (8)
1. a kind of catalyst of methane portion oxidation synthesis gas, it is characterised in that with SiO2For carrier, CeO2For auxiliary agent, by matter
Amount percentage, the content of active component Rh is 0.005%～1%, auxiliary agent CeO2For 5%～30%, remaining is SiO2；
The catalyst of the methane portion oxidation synthesis gas is prepared by following methods：
1) by carrier S iO2It is immersed in salpeter solution, washs to pH=6.5～7.0, it is standby after being dried；
2) prepare the salting liquid of the salting liquid and cerium of rhodium by catalyst components content proportioning respectively, and according to catalyst components
Ratio is merged into mixed impregnant liquor；Precursor salt used by the salting liquid of the rhodium and cerium is acetylacetone,2,4-pentanedione rhodium and acetylacetone,2,4-pentanedione cerium；
3) by step 1) SiO that obtains2With step 2) maceration extract that obtains mixes, impregnates, and drying is obtained methane moiety after roasting
The catalyst of oxidation preparing synthetic gas；The condition of the roasting is：Temperature be 800 DEG C, heating rate be 1～10 DEG C/min, atmosphere
For air, roasting time is 2～4h.
2. as claimed in claim 1 a kind of catalyst of methane portion oxidation synthesis gas, it is characterised in that by mass percentage,
The content of active component Rh is 0.01%～1%, auxiliary agent CeO2For 5%-30%, remaining is SiO2。
3. the preparation method of the catalyst of methane portion oxidation synthesis gas as claimed in claim 1, it is characterised in that include with
Lower step：
1) by carrier S iO2It is immersed in salpeter solution, washs to pH=6.5～7.0, it is standby after being dried；
2) prepare the salting liquid of the salting liquid and cerium of rhodium by catalyst components content proportioning respectively, and according to catalyst components
Ratio is merged into mixed impregnant liquor；Precursor salt used by the salting liquid of the rhodium and cerium is acetylacetone,2,4-pentanedione rhodium and acetylacetone,2,4-pentanedione cerium；
3) by step 1) SiO that obtains2With step 2) maceration extract that obtains mixes, impregnates, and drying is obtained methane moiety after roasting
The catalyst of oxidation preparing synthetic gas；The condition of the roasting is：Temperature be 800 DEG C, heating rate be 1～10 DEG C/min, atmosphere
For air, roasting time is 2～4h.
4. the preparation method of the catalyst of methane portion oxidation synthesis gas as claimed in claim 3, its feature is in step 1)
In, the condition of the immersion is to be immersed in 12～24h in the salpeter solution that mass concentration is 20%.
5. the preparation method of the catalyst of methane portion oxidation synthesis gas as claimed in claim 3, its feature is in step 1)
In, the washing is using distillation water washing.
6. the preparation method of the catalyst of methane portion oxidation synthesis gas as claimed in claim 3, its feature is in step 1)
In, the condition of the drying is to be dried 12h at 110～120 DEG C.
7. the preparation method of the catalyst of methane portion oxidation synthesis gas as claimed in claim 3, its feature is in step 3)
In, the time at least 12h of the dipping.
8. the preparation method of the catalyst of methane portion oxidation synthesis gas as claimed in claim 3, its feature is in step 3)
In, the condition of the drying is to dry 2h in 110～120 DEG C of air atmospheres.
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Non-Patent Citations (3)
| Title |
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| Pt/Al2O3和Pt/CeO2/Al2O3催化甲烷部分氧化制合成气反应;严前古等;《高等学校化学学报》;19980831;第19卷(第8期);摘要及第2.1节 * |
| Rh/SiO2和Rh/NaY催化剂上合成气反应的高压原位红外光谱研究;孙科强等;《化学学报》;20010131;第59卷(第1期);第22-27页 * |
| 负载型Rh, Ru催化剂上甲烷部分氧化制合成气反应机理的原位时间分辨红外光谱研究;翁维正等;《科学通报》;20000831;第45卷(第16期);摘要及第1节 * |
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