CN107252689A - A kind of composite catalyst and its preparation method and application - Google Patents
A kind of composite catalyst and its preparation method and application Download PDFInfo
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- CN107252689A CN107252689A CN201710591775.4A CN201710591775A CN107252689A CN 107252689 A CN107252689 A CN 107252689A CN 201710591775 A CN201710591775 A CN 201710591775A CN 107252689 A CN107252689 A CN 107252689A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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Abstract
The invention discloses a kind of composite catalyst and its preparation method and application.The composite catalyst includes absorbed component CaO, active component Ni, auxiliary agent MgO and inert component Al2O3, absorbed component CaO, active component Ni, auxiliary agent MgO and inert component Al2O3Material amount ratio be 1:0.01~0.5:0.001~0.05:0.05~1.The present invention uses coprecipitation, and precipitating reagent is rapidly added in calcium, nickel, magnesium, the mixed solution of aluminium precursor salt and reacted, and then obtains composite catalyst through suction filtration, washing, drying, calcining.The catalyst solves existing CO2The problem of active low and cyclical stability of composite catalyst is poor used in the process of adsorption forced methane vapor reforming hydrogen production.Preparation technology of the present invention is simple and convenient to operate, synthesis condition is easy to control, it is easy to industrialized, and prepared catalyst has high catalytic activity and CO2Absorption property.
Description
Technical field
The present invention relates to a kind of composite catalyst and its preparation method and application, belong to field of catalyst preparation.
Background technology
CO2Adsorption forced methane vapor reforming hydrogen production is to provide inexpensive high-purity H2With realize CO2Effective way of emission reduction
Footpath.Synthesis has catalysis concurrently, the composite catalyst of absorption property is that the process realizes industrialized key.Compared to catalyst and suction
Attached dose of simple mechanical mixing, Ni/CaO based composite catalysts are adsorbed closer to situ catalytic, and resistance to mass tranfer is small, thus with latent
High catalytic activity and CO2Absorption property.But the composite catalyst is applied to CO2Adsorption forced methane vapor reforming hydrogen production
During reaction, with the increase of reaction cycle number of times, the active component in composite catalyst is easily sintered, and causes Ni's scattered
Degree reduction, and then cause composite catalyst activity decrease；The specific surface area and pore volume of composite catalyst also can significantly drop simultaneously
It is low, cause the CO of composite catalyst2Adsorption capacity declines, and weakens CO2Adsorption forced effect.
Contrast existing literature to find, Chinese invention patent CN200610052788.6 discloses a kind of carbon dioxide that is used for and inhaled
The composite catalyst of attached forced mathane vapor reforming hydrogen production, mainly by micron order and/or nano level calcium carbonate and/or hydrogen-oxygen
It is the CaO of presoma and the active nickel composition by presoma of nickelous carbonate, nickel oxide or nickel nitrate aqueous solution and oxygen to change calcium powder
Change alumina supporter to be composited, but the catalyst is easily inactivated, and is not suitable for the recycling economy requirement of commercial scale.Chinese invention
Patent CN201010155831.8 discloses a kind of composite catalyst for being used to react adsorption forced methane vapor reforming hydrogen production
And its preparation method and application, the composite catalyst is by the CaO using nanometer grade calcium carbonate as presoma, using silver nitrate as presoma
Active nickel composition and nanometer ZrO by presoma of zirconium oxychloride2And alumina support is composited, its hydrogen manufacturing is most highly concentrated
Spend for 97%, methane maximum conversion is 93.4%, be can be recycled 20 times or so.But because catalyst and adsorbent are CO2Inhale
Attached reinforcing CH4/H2Important component in O reforming hydrogen producing process, its activity constrains speed and the production of reaction with selectivity
Rate, its life-span length is related to the height of production cost, therefore, and how to prepare both has high catalytic activity and CO2Absorption is held
The composite catalyst with cyclical stability is still one of research emphasis of whole technology to amount again.
The content of the invention
The present invention is intended to provide a kind of composite catalyst for having catalytic adsorption performance concurrently, solves CO2Adsorption forced CH4/H2O
The problem of active low and cyclical stability of composite catalyst is poor used in the process of reformation hydrogen production.
The invention provides a kind of composite catalyst, the composite catalyst includes absorbed component CaO, active component Ni, helped
Agent MgO and inert component Al2O3, absorbed component CaO, active component Ni, auxiliary agent MgO and inert component Al2O3Material amount ratio
For 1:0.01~0.5:0.001~0.05:0.05~1.
Preferably, the absorbed component CaO, active component Ni, auxiliary agent MgO and inert component Al2O3The amount ratio of material be
1:0.2~0.3:0.01~0.03:0.1~0.2。
The invention provides a kind of described preparation method for having catalytic adsorption performance composite catalyst concurrently, including following step
Suddenly：
Hybrid metal ion salt solution A is made into Step 1: weighing nickel, magnesium, calcium, the precursor salt of aluminium and being dissolved in deionized water,
The concentration of calcium ion is 0.1 ~ 1mol/L in solution A, and the amount ratio of calcium ion and nickel ion, magnesium ion, aluminium ion material is 1:
0.01~0.5.:0.001~0.05:0.1~2；
Solution B is obtained Step 2: weighing precipitating reagent and being dissolved in deionized water, the concentration of precipitating reagent is 0.1 ~ 3mol/L；Wherein,
The amount ratio of precipitating reagent and nickel ion, magnesium ion, aluminium ion, the material of calcium ion sum is 1:0.1~1.5；Solution B and solution A
Volume ratio is 1:0.5~2；
Step 3: hybrid metal ion salt solution A is warming up into 50 ~ 150 DEG C under stirring, solution B is added rapidly mixed
In metal ion salting liquid A, 0.5 ~ 3h is reacted under stirring；
Step 4: the product that step 3 is obtained crystallizes 8 ~ 20h in aging at 60 ~ 120 DEG C, precipitation is collected by centrifugation, and use is gone
Ion water washing, suction filtration, untill filtrate is in neutrality；
Step 5: step 4 gained sediment is obtained in 90 ~ 150 DEG C of dry 6 ~ 24 h in 400 ~ 900 DEG C of 3 ~ 20h of high-temperature roasting
To the composite catalyst for having catalytic adsorption performance concurrently.
In above method step one, the precursor salt of nickel is one kind in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, magnesium
Precursor salt be one kind in magnesium nitrate, magnesium acetate, magnesium sulfate, magnesium chloride, the precursor salt of calcium is calcium nitrate, calcium acetate,
One kind in calcium sulfate, calcium chloride, the precursor salt of aluminium is one kind in aluminum nitrate, aluminium acetate, aluminum sulfate, aluminium chloride.
In above method step 2, described precipitating reagent is in sodium carbonate, urea, potassium carbonate, sodium hydroxide, potassium hydroxide
One or two；Include OH when choosing two kinds-And CO3 2-, and OH-And CO3 2-Mol ratio be 1:2.
A kind of preferred preparation method is provided, comprised the following steps：
Hybrid metal ion salt solution A is made into Step 1: weighing nickel, magnesium, calcium, the precursor salt of aluminium and being dissolved in deionized water,
The concentration of calcium ion is 0.2 ~ 0.4mol/L in solution A, and the amount ratio of calcium ion and nickel ion, magnesium ion, aluminium ion material is 1:
0.2~0.3:0.01~0.03:0.2~0.4；
Solution B is obtained Step 2: weighing precipitating reagent and being dissolved in deionized water, wherein, precipitating reagent and nickel ion, magnesium ion, aluminium
Ion, the amount ratio of the material of calcium ion sum are 1:0.5~0.7；The volume ratio of solution B and solution A is 1:1~1.5；
Step 3: hybrid metal ion salt solution A is warming up into 70 ~ 80 DEG C under stirring, solution B is added mixed rapidly
In metal ion salt solution A, 1 ~ 1.5h is reacted under stirring；
Step 4: the product that step 3 is obtained crystallizes 10h in aging at 96 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality；
Step 5: by step 4 gained sediment in 100 ~ 120 DEG C of dry 10-15h, in 700 ~ 800 DEG C of 8 ~ 10h of high-temperature roasting
Obtain having concurrently the composite catalyst of catalytic adsorption performance.
The invention provides the above-mentioned catalytic adsorption performance composite catalyst that has concurrently in CO2Adsorption forced methane steam reforming
Application in hydrogen production reaction.
In described application, catalyst is before use, need to be at 700 DEG C with 50 mL/min H2Reduce 1h, suitable reaction
Condition is that the volume ratio of unstrpped gas methane and vapor is 1:4, reaction temperature is 600 DEG C, and catalyst regeneration temperature is 700
℃.The composite catalyst is used for CO2Adsorption forced methane steam reforming reaction, methane conversion is up to 95.46%, H2Concentration reaches
98.67%。
Catalyst is reduced using preceding, it is therefore an objective to：Active component Ni is with NiO shapes in the composite catalyst prepared
Formula is present, and needs to be reduced to metallic state before use.
Because of the Activity and stabill and active component Ni decentralization, the close phase of property of absorbed component of composite catalyst
Close.In general, composite catalyst specific surface area is bigger, active component is distributed more uniform, catalyst surface in absorbed component
Active reaction sites are more, and catalytic activity is higher.Hydrotalcite-like compound（Hydrotalcite-like Compounds,
HTlcs）As catalyst precursor, the catalyst obtained after calcining has the spy of bigger serface and high metal decentralization
Point.Therefore, use for reference hydrotalcite-like structuring compound to be had the special feature that, prepared using coprecipitation multiple with hydrotalcite-like compound
Catalyst precursor is closed, then preparing the catalysis that has concurrently with bigger serface and high metal decentralization by roasting, reduction inhales
The composite catalyst of attached performance.
Beneficial effects of the present invention：
（1）The invention provides a kind of composite catalyst for having catalytic adsorption performance concurrently, existing CO is solved2Adsorption forced CH4/
H2The problem of active low and cyclical stability of composite catalyst is poor used in the process of O reformation hydrogen productions.
（2）The preparation technology that the present invention is provided is simple and convenient to operate, synthesis condition is easy to control, it is easy to industrialized,
（3）The characteristics of catalyst being prepared by the method for the present invention out has bigger serface and high metal decentralization, using when
With high catalytic activity and CO2Absorption property.
Brief description of the drawings
The composite catalyst CO that Fig. 1 is prepared for composite catalyst prepared by the present invention with comparative example 1 and comparative example 22Circulation
Absorption property figure.
The composite catalyst CO that Fig. 2 is prepared for the present invention2Adsorption forced methane vapor reforming hydrogen production activity figure.
Fig. 3 is composite catalyst CO prepared by comparative example 12Adsorption forced methane vapor reforming hydrogen production activity figure.
Fig. 4 is the composite catalyst of the invention prepared in CO2H in 50 circular responses of adsorption forced methane steam reforming2
And CO2Concentration.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1：
A kind of composite catalyst for having catalytic adsorption performance concurrently is prepared using the inventive method, comprised the following steps：
（1）Weigh 18.88g calcium nitrate, 6.28g nickel nitrates, 0.41g magnesium nitrates and 6.9g aluminum nitrates and be dissolved in 300mL deionizations
Mixed solution A is made into water；
（2）Weigh 5.51g sodium hydroxides and 7.30g sodium carbonate is dissolved in 200mL deionized waters and obtains solution B；
（3）Mixed solution A is warming up to 70 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
1h is reacted under state.
（4）The product that step 3 is obtained crystallizes 10h in aging at 96 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 120 DEG C of dry 12h, obtain having catalytic adsorption concurrently in 800 DEG C of high-temperature roasting 8h
The composite catalyst of performance.
Embodiment 2：
A kind of composite catalyst for having catalytic adsorption performance concurrently is prepared using the inventive method, comprised the following steps：
（1）Weigh 17.62g calcium acetates, 5.30g nickel acetates, 0.13g magnesium acetates and 6.12g aluminium acetates and be dissolved in 300mL deionizations
Mixed solution A is made into water；
（2）Weigh 4.82g urea and be dissolved in 240mL deionized waters and obtain solution B；
（3）Mixed solution A is warming up to 80 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
1h is reacted under state.
（4）The product that step 3 is obtained crystallizes 20h in aging at 60 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 100 DEG C of dry 15h, obtain having catalytic adsorption concurrently in 900 DEG C of high-temperature roasting 4h
The composite catalyst of performance.
Embodiment 3：
A kind of composite catalyst for having catalytic adsorption performance concurrently is prepared using the inventive method, comprised the following steps：
（1）Weigh 51.66g calcium sulfate, 3.94g nickel sulfates, 0.15g magnesium sulfate and 10.26g aluminum sulfate be dissolved in 500mL go from
Mixed solution A is made into sub- water；
（2）Weigh 12.90g potassium hydroxide and 12.2g sodium carbonate is dissolved in 400mL deionized waters and obtains solution B；
（3）Mixed solution A is warming up to 100 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
0.5h is reacted under state.
（4）The product that step 3 is obtained crystallizes 12h in aging at 80 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 140 DEG C of dry 8h, obtain having catalytic adsorption concurrently in 700 DEG C of high-temperature roasting 10h
The composite catalyst of performance.
Embodiment 4：
A kind of composite catalyst for having catalytic adsorption performance concurrently is prepared using the inventive method, comprised the following steps：
（1）Weigh 17.76g calcium chloride, 3.80g nickel chlorides, 0.33g magnesium chlorides and 8.54g aluminium chloride and be dissolved in 300mL deionizations
Mixed solution A is made into water；
（2）Weigh 11.73g potassium hydroxide and 14.45g potassium carbonate is dissolved in 450mL deionized waters and obtains solution B；
（3）Mixed solution A is warming up to 60 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
2.5h is reacted under state.
（4）The product that step 3 is obtained crystallizes 15h in aging at 90 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 90 DEG C of dry 20h, obtain having catalytic adsorption concurrently in 800 DEG C of high-temperature roasting 10h
The composite catalyst of performance.
Embodiment 5：
A kind of composite catalyst for having catalytic adsorption performance concurrently is prepared using the inventive method, comprised the following steps：
（1）Weigh 23.60g calcium nitrate, 11.63g nickel nitrates, 0.51g magnesium nitrates and 13.35g aluminium chloride be dissolved in 350mL go from
Mixed solution A is made into sub- water；
（2）Weigh 5.16g sodium hydroxides and 8.91g potassium carbonate is dissolved in 450mL deionized waters and obtains solution B；
（3）Mixed solution A is warming up to 90 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
1.5h is reacted under state.
（4）The product that step 3 is obtained crystallizes 8h in aging at 110 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 110 DEG C of dry 18h, obtain having catalysis suction concurrently in 500 DEG C of high-temperature roasting 20h
The composite catalyst of attached performance.
Embodiment 6：
A kind of composite catalyst for having catalytic adsorption performance concurrently is prepared using the inventive method, comprised the following steps：
（1）Weigh 35.40g calcium nitrate, 0.71g nickel chlorides, 0.15g magnesium nitrates and 30.04g aluminium chloride be dissolved in 300mL go from
Mixed solution A is made into sub- water；
（2）Weigh 20.19g sodium hydroxides and 26.75g sodium carbonate is dissolved in 300mL deionized waters and obtains solution B；
（3）Mixed solution A is warming up to 120 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
0.5h is reacted under state.
（4）The product that step 3 is obtained crystallizes 15h in aging at 96 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 130 DEG C of dry 10h, obtain having catalysis suction concurrently in 600 DEG C of high-temperature roasting 18h
The composite catalyst of attached performance.
Embodiment 7：
A kind of composite catalyst for having catalytic adsorption performance concurrently is prepared using the inventive method, comprised the following steps：
（1）Weigh 17.62g calcium acetates, 4.42g nickel acetates, 0.74g magnesium sulfate and 8.16g aluminium acetates and be dissolved in 300mL deionizations
Mixed solution A is made into water；
（2）Weigh 14.11g urea and be dissolved in 330mL deionized waters and obtain solution B；
（3）Mixed solution A is warming up to 70 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
2h is reacted under state.
（4）The product that step 3 is obtained crystallizes 18h in aging at 70 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 110 DEG C of dry 15h, obtain having catalysis suction concurrently in 800 DEG C of high-temperature roasting 12h
The composite catalyst of attached performance.
Comparative example 1
Prepare a kind of composite catalyst（Without magnesium）, comprise the following steps：
（1）Weigh 18.88g calcium nitrate, 6.28g nickel nitrates and 6.90g aluminum nitrates and be dissolved in 300mL deionized waters and be made into mixing
Solution A；
（2）Weigh 5.44g sodium hydroxides and 7.21g sodium carbonate is dissolved in 200mL deionized waters and obtains solution B；
（3）Mixed solution A is warming up to 70 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
1h is reacted under state.
（4）The product that step 3 is obtained crystallizes 10h in aging at 96 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 120 DEG C of dry 12h, obtain having catalytic adsorption concurrently in 800 DEG C of high-temperature roasting 8h
The composite catalyst of performance.
Comparative example 2
Prepare a kind of composite catalyst（Without aluminium and magnesium）, comprise the following steps：
（1）Weigh 18.88g calcium nitrate, 6.28g nickel nitrates and be dissolved in 300mL deionized waters and be made into mixed solution A；
（2）Weigh 4.61g sodium hydroxides and 6.11g sodium carbonate is dissolved in 200mL deionized waters and obtains solution B；
（3）Mixed solution A is warming up to 70 DEG C under stirring, rapidly added solution B in mixed solution A, in stirring shape
1h is reacted under state.
（4）The product that step 3 is obtained crystallizes 10h in aging at 96 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality.
（5）By step 4 gained sediment in 120 DEG C of dry 12h, obtain having catalytic adsorption concurrently in 800 DEG C of high-temperature roasting 8h
The composite catalyst of performance.
Data Detection result：
Table 1 provides composite catalyst and composite catalyst prepared by comparative example 1 and comparative example 2 prepared by the embodiment of the present invention 1
Physical data.It can be seen that, composite catalyst specific surface area and pore volume prepared by the present invention is significantly greater than comparative example 1 and contrast
Example 2, composite catalyst specific surface area is bigger, be more conducive to CO2The raising of adsorption capacity.It can be found that simultaneously：The present invention is made
Standby composite catalyst Ni decentralization is 2.48%, and higher than comparative example 1 and comparative example 2, and its Ni crystallite dimension is minimum, is 13.2
Nm, shows that the composite catalyst has obvious anti-caking power.
The prepared composite catalyst physical data of the present invention of table 1
Ni decentralization and specific surface area active pass through H in table 12Pulse adsorption is measured；Ni crystallite dimensions and CaO crystallite dimensions are by thanking
Happy formula is calculated and obtained；Specific surface area of catalyst and catalyst pore volume pass through N2Physical absorption is measured.
Embodiment 8：CO2Absorption property is evaluated
The composite catalyst that embodiment 1 is prepared carries out CO2Absorption property is evaluated, and by adsorption effect and comparative example 1 and
The adsorption effect of comparative example 2 is compared.
Specific experiment is：30 mg composite catalysts are weighed, in 600 DEG C, 50% CO2-N2（100 mL/min）Inhaled under atmosphere
Attached CO240min；Then 700 DEG C are warming up to 10 DEG C/min, in N2（50 mL/min）40 min are desorbed under atmosphere, then with 50
DEG C/min is cooled to 600 °C, in 50% CO2-N2（100 mL/min）CO is carried out under atmosphere2Adsorption experiment, is and so on circulated
Carry out CO2Adsorption-desorption is tested 100 times.
Embodiment 9：CO2Adsorption forced CH4/H2O reformation hydrogen production activity ratings
The composite catalyst that the present invention is prepared is used for CO2Adsorption forced CH4/H2O reformation hydrogen productions are reacted, and catalysis is imitated
The composite catalyst catalytic activity that fruit prepares with comparative example 1 and comparative example 2 is compared.
Specific experiment is：6.0g particle diameters are loaded in fixed bed reactors for 0.25-0.43 mm composite catalyst,
Before reaction, composite catalyst is at 700 DEG C, using 50 mL/min H21h is reduced, then in N2（50 mL/min）Will under atmosphere
Reaction temperature is down to 600 DEG C, then by N2Switch to CH4（18.7 mL/min）And water vapour（74.8 mL/min）Reacted.Instead
Answer after 1.5h, atmosphere is switched into N again2Atmosphere, and temperature of reactor is risen into 700 DEG C of progress regeneration 1h, then by temperature
It is down to 600 DEG C and switches reaction gas, such iterative cycles reacts 50 times.Reacted aerogenesis composition is by gas chromatograph（Hai Xin
GC-950）Detected.
Fig. 1 shows the composite catalyst CO that composite catalyst prepared by the present invention is prepared with comparative example 1 and comparative example 22
Circulation absorption performance.It can be seen that, the initial CO of composite catalyst prepared by the present invention2Adsorption capacity and cyclical stability are best,
Initial adsorption capacity is 8.1mmol/g, with CO2The increase and decrease of adsorption-desorption cycle reaction times and reduce, it is anti-in 20 circulations
Ying Hou, the CO of composite catalyst2Adsorption capacity basically reaches stabilization（6.1mmol/g）, this specific surface area with catalyst, pore volume
There is direct relation（Table 1）.Specific surface area is bigger, the CO of composite catalyst2Adsorption capacity is bigger.Prepared by comparative example 1 answers
Close catalyst CO2Adsorption capacity initial capacity is 6.7mmol/g, is gradually reduced since first time circular response, to the 30th time
During adsorption reaction, adsorption capacity basically reaches stable state（2.6mmol/g）, this is primarily due in circulation absorption-be desorbed
Cheng Zhong, is present in the Al in CaO skeletons3+Ion can form the Ca-Al-O oxide phases of weak crystallization at high temperature, and it can be prevented
CaO is sintered in roasting process.Composite catalyst CO prepared by comparative example 22Adsorption capacity is minimum（1.76mmol/g）, this
The initial specific surface and pore volume very little of the composite catalyst are primarily due to, is caused substantially without too many hole.
Fig. 2 and Fig. 3 show composite catalyst CO prepared by the composite catalyst of the invention prepared and comparative example 12Absorption
Forced mathane vapor reforming hydrogen production activity.It can be seen that：Reaction can be divided into according to production concentration distribution by 4 stages, point
Area Wei not started, proparea, penetrating region is penetrated and penetrate back zone.Proparea is being penetrated, with the increase in reaction time, H2Concentration and CH4
Conversion ratio gradually raising, and CO, CO2、CH4Concentration is gradually being reduced, and this inlet amount for being primarily due to reactant compares
It is small, entering reactor, then in catalyst surface diffusion, absorption there is certain hysteresis quality to cause in incipient stage H2It is dense
Degree is relatively low.Balance is reached in the reaction density for penetrating proparea stage each product, now H2Concentration and CH4Conversion ratio reach most
Height, and CO2、CO、CH4Concentration is all very low, and the H of high concentration can be obtained with a step in this stage2, composite catalyzing prepared by the present invention
Agent is in CO2Adsorption forced CH4/H2In O reforming reactions, proparea stage, H are being penetrated2Concentration reach 98.67%, and CH4Conversion
Rate is up to 95.46%, the composite catalyst prepared compared to comparative example 1（Fig. 3）, composite catalyst prepared by the present invention is in CO2Absorption
There is more preferable CO in forced mathane steam reforming2Adsorption forced effect, and it can also be seen that prepared by the present invention from Fig. 2
Composite catalyst penetrates the reaction time in proparea in 47 min, and composite catalyst prepared by comparative example 1 penetrates the reaction in proparea
Time about 20min（Fig. 3）, this is primarily due to composite catalyst CO prepared by the present invention2Adsorption capacity is big, and has 80% CO2
Adsorbance is to participate in CO in the fast response stage of composite catalyst2Absorption.
Fig. 4 shows the composite catalyst of the invention prepared in CO250 circulations of adsorption forced methane steam reforming are anti-
Should middle H2And CO2Concentration.It can be seen that with the increase of reaction cycle number of times, penetrating proparea and penetrating the H in back zone2And CO2
Concentration does not change substantially, and after this 50 circular response of explanation, the activity of composite catalyst does not decline substantially, illustrates this
Active component Ni in the prepared composite catalyst of invention is not sintered, and the composite catalyst has good stabilization
Property.
Claims (8)
1. a kind of composite catalyst, it is characterised in that：Including absorbed component CaO, active component Ni, auxiliary agent MgO and inert component
Al2O3, absorbed component CaO, active component Ni, auxiliary agent MgO and inert component Al2O3Material amount ratio be 1:0.01~0.5:
0.001~0.05:0.05~1。
2. composite catalyst according to claim 1, it is characterised in that：The absorbed component CaO, active component Ni, help
Agent MgO and inert component Al2O3Material amount ratio be 1:0.2~0.3:0.01~0.03:0.1~0.2.
3. the preparation method of the composite catalyst described in a kind of claim 1 or 2, it is characterised in that comprise the following steps：
Hybrid metal ion salt solution A is made into Step 1: weighing nickel, magnesium, calcium, the precursor salt of aluminium and being dissolved in deionized water,
The concentration of calcium ion is 0.1 ~ 1mol/L in solution A, and the amount ratio of calcium ion and nickel ion, magnesium ion, aluminium ion material is 1:
0.01~0.5.:0.001~0.05:0.1~2；
Solution B is obtained Step 2: weighing precipitating reagent and being dissolved in deionized water, the concentration of precipitating reagent is 0.1 ~ 3mol/L, wherein,
The amount ratio of precipitating reagent and nickel ion, magnesium ion, aluminium ion, the material of calcium ion sum is 1:0.1~1.5；
Step 3: hybrid metal ion salt solution A is warming up into 50 ~ 150 DEG C under stirring, solution B is added rapidly mixed
In metal ion salting liquid A, 0.5 ~ 3h is reacted under stirring；
Step 4: the product that step 3 is obtained crystallizes 8 ~ 20h in aging at 60 ~ 120 DEG C, precipitation is collected by centrifugation, and use is gone
Ion water washing, suction filtration, untill filtrate is in neutrality；
Step 5: step 4 gained sediment is obtained in 90 ~ 150 DEG C of dry 6 ~ 24 h in 400 ~ 900 DEG C of 3 ~ 20h of high-temperature roasting
To the composite catalyst for having catalytic adsorption performance concurrently.
4. the preparation method of composite catalyst according to claim 3, it is characterised in that：In step one, the presoma of nickel
Salt is one kind in nickel nitrate, nickel acetate, nickel sulfate, nickel chloride, and the precursor salt of magnesium is magnesium nitrate, magnesium acetate, magnesium sulfate, chlorine
Change one kind in magnesium, the precursor salt of calcium is one kind in calcium nitrate, calcium acetate, calcium sulfate, calcium chloride, and the precursor salt of aluminium is
One kind in aluminum nitrate, aluminium acetate, aluminum sulfate, aluminium chloride.
5. the preparation method of composite catalyst according to claim 3, it is characterised in that：In step 2, described precipitation
Agent is one or both of sodium carbonate, urea, potassium carbonate, sodium hydroxide, potassium hydroxide；Include OH when choosing two kinds-With
CO3 2-, and OH-And CO3 2-Mol ratio be 1:2.
6. the preparation method of composite catalyst according to claim 3, it is characterised in that：Comprise the following steps：
Hybrid metal ion salt solution A is made into Step 1: weighing nickel, magnesium, calcium, the precursor salt of aluminium and being dissolved in deionized water,
The concentration of calcium ion is 0.2 ~ 0.4mol/L in solution A, and the amount ratio of calcium ion and nickel ion, magnesium ion, aluminium ion material is 1:
0.2~0.3:0.01~0.03:0.2~0.4；
Solution B is obtained Step 2: weighing precipitating reagent and being dissolved in deionized water, wherein, precipitating reagent and nickel ion, magnesium ion, aluminium
Ion, the amount ratio of the material of calcium ion sum are 1:0.5~0.7；The volume ratio of solution B and solution A is 1:1~1.5；
Step 3: hybrid metal ion salt solution A is warming up into 70 ~ 80 DEG C under stirring, solution B is added mixed rapidly
In metal ion salt solution A, 1 ~ 1.5h is reacted under stirring；
Step 4: the product that step 3 is obtained crystallizes 10h in aging at 96 DEG C, precipitation is collected by centrifugation, and use deionized water
Washing, suction filtration, untill filtrate is in neutrality；
Step 5: by step 4 gained sediment in 100 ~ 120 DEG C of dry 10-15h, in 700 ~ 800 DEG C of 8 ~ 10h of high-temperature roasting
Obtain having concurrently the composite catalyst of catalytic adsorption performance.
7. the composite catalyst described in a kind of claim 1 or 2 is in CO2In the reaction of adsorption forced methane vapor reforming hydrogen production
Using.
8. application according to claim 7, it is characterised in that：The composite catalyst is before use, need to be at 700 DEG C with 50
mL/min H21h is reduced, suitable reaction condition is that the volume ratio of unstrpped gas methane and vapor is 1:4, reaction temperature is
600 DEG C, composite catalyst regeneration temperature is 700 DEG C.
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| CN109529855A (en) * | 2018-12-26 | 2019-03-29 | 济南大学 | A kind of efficient low carrying capacity acetic acid reformation hydrogen production nickel-base catalyst and preparation method thereof that KOH is modified |
| CN110433811A (en) * | 2019-07-31 | 2019-11-12 | 天津大学 | MgO modified Ni/CaO bifunctional catalyst and preparation method and application |
| CN111482181A (en) * | 2020-04-26 | 2020-08-04 | 太原理工大学 | Reforming hydrogen production composite catalyst and preparation method and application thereof |
| CN114160141A (en) * | 2021-12-18 | 2022-03-11 | 太原理工大学 | Adsorption hydrogen production composite catalyst and preparation method thereof |
| CN114260013A (en) * | 2021-12-27 | 2022-04-01 | 太原理工大学 | Hollow core-shell structure composite catalyst and preparation method thereof |
| CN114377679A (en) * | 2022-01-26 | 2022-04-22 | 中国科学院上海高等研究院 | Carbon dioxide capturing and converting integrated bifunctional catalyst, preparation method and application |
| CN114558624A (en) * | 2022-03-24 | 2022-05-31 | 南京工业大学 | Mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst and application thereof |
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| CN109529855A (en) * | 2018-12-26 | 2019-03-29 | 济南大学 | A kind of efficient low carrying capacity acetic acid reformation hydrogen production nickel-base catalyst and preparation method thereof that KOH is modified |
| CN110433811A (en) * | 2019-07-31 | 2019-11-12 | 天津大学 | MgO modified Ni/CaO bifunctional catalyst and preparation method and application |
| CN110433811B (en) * | 2019-07-31 | 2022-04-19 | 天津大学 | MgO modified Ni/CaO bifunctional catalyst, preparation method and application |
| CN111482181A (en) * | 2020-04-26 | 2020-08-04 | 太原理工大学 | Reforming hydrogen production composite catalyst and preparation method and application thereof |
| CN114160141A (en) * | 2021-12-18 | 2022-03-11 | 太原理工大学 | Adsorption hydrogen production composite catalyst and preparation method thereof |
| CN114160141B (en) * | 2021-12-18 | 2024-02-02 | 太原理工大学 | Composite catalyst for adsorption hydrogen production and preparation method thereof |
| CN114260013A (en) * | 2021-12-27 | 2022-04-01 | 太原理工大学 | Hollow core-shell structure composite catalyst and preparation method thereof |
| CN114260013B (en) * | 2021-12-27 | 2024-02-20 | 太原理工大学 | Composite catalyst with hollow core-shell structure and preparation method thereof |
| CN114377679A (en) * | 2022-01-26 | 2022-04-22 | 中国科学院上海高等研究院 | Carbon dioxide capturing and converting integrated bifunctional catalyst, preparation method and application |
| CN114558624A (en) * | 2022-03-24 | 2022-05-31 | 南京工业大学 | Mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst and application thereof |
| CN114558624B (en) * | 2022-03-24 | 2023-12-05 | 南京工业大学 | Mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst and application thereof |
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