CN106111144A - A kind of complex function reforming hydrogen-production catalyst and its preparation method and application - Google Patents

A kind of complex function reforming hydrogen-production catalyst and its preparation method and application Download PDF

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CN106111144A
CN106111144A CN201610430940.3A CN201610430940A CN106111144A CN 106111144 A CN106111144 A CN 106111144A CN 201610430940 A CN201610430940 A CN 201610430940A CN 106111144 A CN106111144 A CN 106111144A
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catalyst
preparation
complex function
hydrogen
product
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王超
陈颖
成正东
蔡小燕
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Guangdong University of Technology
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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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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • 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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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The present invention relates to catalyst preparation technical field, disclose a kind of complex function reforming hydrogen-production catalyst and its preparation method and application, catalyst disclosed by the invention has good catalyzing manufacturing of hydrogen performance and CO2Absorption property, preparation process is simple and low cost, beneficially popularization and application.The chemical formula of complex function reforming hydrogen-production catalyst disclosed by the invention is NiO CaO NiAl2O4/Al2O3, described Al2O3For carrier, described NiAl2O4There is spinel structure.The raw material of described catalyst includes NiO 23～42 parts, γ Al by weight2O325～35 parts and Ca (NO3)2·6H2O 23～52 parts.The invention also discloses preparation method and the application in glycerol reformation hydrogen production of the described catalyst of described catalyst.

Description

A kind of complex function reforming hydrogen-production catalyst and its preparation method and application
Technical field
The present invention relates to catalyst preparation technical field, particularly to a kind of complex function reforming hydrogen-production catalyst and system thereof Preparation Method and application.
Background technology
Vapour reforming hydrogen producing technology is ripe and with low cost, has overwhelming superiority in industrial hydrogen production.General steam Reforming hydrogen producing process includes some unit: feed material preparation units, steam reformer unit, high temperature low temperature aqueous vapor conversion unit, go Except CO2Clean unit and waste heat recovery unit etc..But, owing to steam reformation hydrogen production reaction is highly endothermic reversible reaction, Its severe reaction conditions, is the production process of high energy consumption, and overall reaction is inefficient, it is the highest to prepare hydrogen purity.Follow-up hydrogen Purification & isolation process is complicated, and technical price is expensive, and overall hydrogen manufacturing cost is the highest.Commonly use during steam reformation hydrogen production Catalyst the most easily sinters, carbon distribution causes inactivation.
Based on Le Chatelier's principle (Le Chatelier's principle), adsorption forced is while hydrogen produces To remove CO in situ continuously by adsorbent2, thus make the molecular balance of this reversible reaction produce hydrogen towards being conducive to Trend move.The benefit of this method is, is allowed to be fixed except adsorbing in situ, and product can be significantly increased Hydrogen purity in thing, thus reduce the cost that gaseous product separates again.And this method also provide enhanced steam Transformationreation and then the concentration of reduction carbonaceous gas by-product, it is suppressed that methanation side reaction.On the other hand, CO2Chemistry suction Attached usually exothermic reaction, thus part compensate for heat required when reforming reaction is carried out, and makes the energy profit of whole system With highly efficient.
Owing to CaO base adsorbent has CO2The advantages such as good adsorption dynamics adsorption kinetics performance and bigger adsorption capacity, greatly The CO that the most adsorption forced technique is used2The effective ingredient of high-temperature adsorbing agent is CaO.Traditional handicraft is by catalyst and adsorbent Mixing loads reactor, this not only adds complex process degree, it is also difficult to ensure uniformity and the stability of the two of mixing Unanimously, the operation of regenerative process it is unfavorable for.
Therefore, invent a kind of Cheap highly effective, there is CO in situ2The catalyst of absorption and hydrogen manufacturing complex function is the most urgent The technical issues that need to address.In order to improve process efficiency, it is stable that this complex function catalyst must possess preferable high-temperature catalytic Property and good CO2Absorption property.
Summary of the invention
In view of this, the invention discloses a kind of complex function reforming hydrogen-production catalyst and its preparation method and application, this The catalyst of disclosure of the invention has good catalyzing manufacturing of hydrogen performance and CO2Absorption property, preparation process is simple and low cost, is beneficial to Popularization and application.
The invention discloses a kind of complex function reforming hydrogen-production catalyst, the chemical formula of described catalyst is NiO-CaO- NiAl2O4/Al2O3, described Al2O3For carrier, described NiAl2O4There is spinel structure.Described NiAl2O4By NiO and Al2O4Forge Burn and generate.Described Al2O3For γ-Al2O3, γ-Al2O3Being porous material, the internal surface area of every gram is up to hundreds of square metres, institute State NiO, CaO and NiAl2O4It is deposited on γ-Al2O3Surface or hole in.
Preferably, the raw material of described catalyst includes by weight: NiO 23～42 parts, γ-Al2O325～35 parts and Ca(NO3)2·6H2O 23～52 parts.
The invention discloses the preparation method of described complex function reforming hydrogen-production catalyst, comprise the following steps:
Step one, preparation (NO Han Ca3)2·6H2The impregnation liquid of O, impregnates γ-Al2O3, 45-65 DEG C of stirring mixing 3～4h； With alkaline solution, the pH of mixed liquor being adjusted to 8.5～9.5, continue stirring reaction 3-5h, standing 1～2h is aging obtains product one；
Step 2, product one is stirred continuously under conditions of 1 atmospheric pressure and 90～95 DEG C, until moisture is evaporated；To steam Powder body after Gan is dried, grinds, and crosses 60-70 mesh sieve, obtains product two, i.e. catalyst precursor；
Step 3, preparation impregnation liquid Han NiO, two, 10～30 DEG C of uniform stirring mixing 3～4h of impregnation product；Molten by alkalescence The pH of mixed liquor is adjusted to 8.5 by liquid, continues stirring and be extremely dried under the conditions of 90～95 DEG C, is dried 10 under 120 DEG C of air atmospheres ～24h, obtain product three；
Step 4, product three is carried out high-temperature roasting, product of lowering the temperature to obtain, the most described complex function reforming hydrogen-production catalyst.
Preferably, described in step one containing Ca (NO3)2·6H2The impregnation liquid of O is the mass concentration 30～Ca of 50% (NO3)2·6H2O aqueous solution.
Preferably, the γ-Al described in step one2O3For crossing the γ-Al of 60-70 mesh sieve2O3。
Preferably, step one and the ammonia that alkaline solution is 1mol/L described in step 3.
Preferably, the method being dried described in step 2 is to be dried 10～24h under 120 DEG C of air atmospheres.
Preferably, the compound method of the impregnation liquid containing NiO described in step 3 is that the dust technology with 2～3mol/L is NiO It is made into the impregnation liquid containing NiO that mass concentration is 30-50%.
Preferably, step 4 is at 850～900 DEG C and N by product three2With Muffle furnace roasting 3～4h under atmosphere, at N2Gas Stream is down to 10～30 DEG C, prepares product, the most described complex function reforming hydrogen-production catalyst.
The invention also discloses the complex function that described complex function reforming hydrogen-production catalyst and described preparation method prepare Reforming hydrogen-production catalyst application in reformation hydrogen production.
Catalyst disclosed by the invention can remove dominant response by-product in steam reformation hydrogen production course of reaction in situ CO2, it is possible not only to improve feed stock conversion and hydrogen purity, and spinel structure has high-temperature stability, can increase catalyst Service life in pyroreaction and regenerative process.Can original position efficient absorption by the CaO based component in described catalyst Reaction Main By product CO2, and rapid adsorption after the area carbon oxidation of catalytic active site can be become at the CaO of composite catalyst Dividing position, spinel structure has heat stability, can be avoided catalyst and seriously sinters.Complex function weight disclosed by the invention Whole catalyst for preparing hydrogen can be by catalytic reforming, CO2Absorption and water-gas shift height couple in situ, only use a kind of catalyst the most permissible Being directly produced High Purity Hydrogen, off normal parsing CO2, regenerative process produces high-purity CO2, reach the purpose reclaimed.
A kind of complex function reforming hydrogen-production catalyst disclosed by the invention has the advantages that
1, complex function reforming hydrogen-production catalyst is based on NiO/ (CaO/NiAl2O4), have good catalyzing manufacturing of hydrogen performance and CO2Absorption property, the carbon distribution of catalytic active site is oxidized easily as CO in steam ambient2, it is fixed on the adsorption activity position of CaO, Thus avoid the rapid deactivation that catalyst causes because of a large amount of carbon distributions；
2, main prepared composition can generate spinel structure through high-temperature roasting, and this structure has high-temperature stability, Catalyst is made to have good heat stability during reaction and high temperature regeneration.
3, by by catalyst and CO2Adsorbent is prepared as the method for composite catalyst and enormously simplify Hydrogen making technological process, Achieve the process of high-purity hydrogen under the working condition of atmospheric low-temperature, be that a kind of realization can urging with high efficiency, low cost hydrogen manufacturing Agent.The raw material of effect of the present invention is cheap and abundant compound, and preparation process is the most controlled, is not related to the equipment of complexity And operation, cost is relatively low and has environmental friendliness feature.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to The accompanying drawing provided obtains other accompanying drawing.
Fig. 1 shows the X ray diffracting spectrum of complex function reforming hydrogen-production catalyst prepared by the embodiment of the present invention；
Fig. 2 shows scanning electron microscope and the X-ray energy color of complex function reforming hydrogen-production catalyst prepared by the embodiment of the present invention Dispersive spectrometer combination result figure；
Fig. 3 shows that the alternating temperature thermogravimetric determining heating rate of complex function reforming hydrogen-production catalyst prepared by the embodiment of the present invention is divided Analysis figure；
Fig. 4 shows the CO of complex function reforming hydrogen-production catalyst prepared by the embodiment of the present invention2Constant temperature adsorption curve figure；
Fig. 5 shows that the purity figure of complex function reforming hydrogen-production catalyst reformation hydrogen production product gas prepared by the embodiment of the present invention divides Analysis figure.
Detailed description of the invention
The invention discloses a kind of complex function reforming hydrogen-production catalyst and its preparation method and application, disclosed by the invention Catalyst has good catalyzing manufacturing of hydrogen performance and CO2Absorption property, preparation process is simple and low cost, beneficially popularization and application. Those skilled in the art can use for reference present disclosure, is suitably modified technological parameter and realizes.Special needs to be pointed out is, all similar Replacement and change apparent to those skilled in the art, they are considered as being included in the present invention.The present invention Method and application be described by preferred embodiment, related personnel substantially can be without departing from present invention, essence In god and scope, method described herein and application it is modified or suitably changes and combine, realize and apply skill of the present invention Art.
Below in conjunction with embodiment, the present invention is expanded on further.
Embodiment 1
Weigh 3.5g analytically pure Ca (NO3)2·6H2O, with the calcium nitrate water that deionized water preparation mass concentration is 40% Solution, weighs 3g and crosses the γ-Al of 70 mesh sieves2O3With calcium nitrate aqueous solution at 53 DEG C of uniform stirring mixing 3.5h；It is added dropwise over The pH of mixed liquor is adjusted to 8.5 by the ammonia of 1mol/L, continues stirring reaction 4h, stand 1.5 hours aging.
Mixed liquor is stirred continuously under conditions of 1 atmospheric pressure and 95 DEG C, until moisture is evaporated.Powder body after being evaporated exists It is dried 24h under 120 DEG C of air atmospheres, grinds, cross 70 mesh sieves, obtain catalyst precursor.
Weighing the analytically pure NiO of 4g, preparing mass concentration with the dust technology of 2.5mol/L is the nickel nitrate solution of 40%, will Catalyst precursor nickel impregnation, 25 DEG C of uniform stirring mixing 3.5h, it is added dropwise over the ammonia of 1mol/L by mixed liquor PH is adjusted to 8.5, continues stirring at 90 DEG C and is extremely dried, and gained is evaporated powder and is dried 24h under 120 DEG C of air atmospheres.
By gained xeraphium at 900 DEG C and N2Muffle furnace roasting is used, with the heating rate of 15 DEG C/min by Muffle under atmosphere Furnace cavity is warming up to 900 DEG C, and control air-flow velocity is 55ml/min, is maintained at roasting 3.5h at 900 DEG C, finally at N2In air-flow It is down to 25 DEG C, prepares product, the most described spinel structure complex function reforming hydrogen-production catalyst.
Embodiment 2
Weigh 2.3g analytically pure Ca (NO3)2·6H2O, with the calcium nitrate water that deionized water preparation mass concentration is 30% Solution, weighs 2.5g and crosses the γ-Al of 60 mesh sieves2O3With calcium nitrate aqueous solution at 45 DEG C of uniform stirring mixing 3h；It is added dropwise over The pH of mixed liquor is adjusted to 9.0 by the ammonia of 1mol/L, continues stirring reaction 3h, stands 1h aging.
Mixed liquor is stirred continuously under conditions of 1 atmospheric pressure and 90 DEG C, until moisture is evaporated.Powder body after being evaporated exists It is dried 10h under 120 DEG C of air atmospheres, grinds, cross 60 mesh sieves, obtain catalyst precursor.
Weighing the analytically pure NiO of 4.2g, preparing mass concentration with the dust technology of 2.5mol/L is the nickel nitrate solution of 30%, By catalyst precursor nickel impregnation, 10 DEG C of uniform stirring mixing 3h, it is added dropwise over the ammonia of 1mol/L by mixed liquor PH is adjusted to 8.5, continues stirring at 90 DEG C and is extremely dried, and gained is evaporated powder and is dried 10h under 120 DEG C of air atmospheres.
By gained xeraphium at 850 DEG C and N2Muffle furnace roasting is used, with the heating rate of 15 DEG C/min by Muffle under atmosphere Furnace cavity is warming up to 900 DEG C, and control air-flow velocity is 50ml/min, is maintained at roasting 3h at 900 DEG C, finally at N2Air-flow drops To 10 DEG C, prepare product, the most described spinel structure complex function reforming hydrogen-production catalyst.
Embodiment 3
Weigh 5.2g analytically pure Ca (NO3)2·6H2O, with the calcium nitrate water that deionized water preparation mass concentration is 50% Solution, weighs 3.5g and crosses the γ-Al of 60 mesh sieves2O3With calcium nitrate aqueous solution at 65 DEG C of uniform stirring mixing 4h；It is added dropwise over The pH of mixed liquor is adjusted to 9.5 by the ammonia of 1mol/L, continues stirring reaction 5h, stands 2h aging.
Mixed liquor is stirred continuously under conditions of 1 atmospheric pressure and 93 DEG C, until moisture is evaporated.Powder body after being evaporated exists It is dried 10h under 120 DEG C of air atmospheres, grinds, cross 60 mesh sieves, obtain catalyst precursor.
Weighing the analytically pure NiO of 2.3g, preparing mass concentration with the dust technology of 2.5mol/L is the nickel nitrate solution of 50%, By catalyst precursor nickel impregnation, 30 DEG C of uniform stirring mixing 3h, it is added dropwise over the ammonia of 1mol/L by mixed liquor PH is adjusted to 8.5, continues stirring at 95 DEG C and is extremely dried, and gained is evaporated powder and is dried 10h under 120 DEG C of air atmospheres.
By gained xeraphium at 850 DEG C and N2Muffle furnace roasting is used, with the heating rate of 15 DEG C/min by Muffle under atmosphere Furnace cavity is warming up to 900 DEG C, and control air-flow velocity is 60ml/min, is maintained at roasting 4h at 900 DEG C, finally at N2Air-flow drops To 30 DEG C, prepare product, the most described spinel structure complex function reforming hydrogen-production catalyst.
The sign of embodiment 4 catalyst
The catalyst of embodiment 1 preparation is carried out X-ray diffraction analysis, and the X-ray diffractometer of use is Shimadzu XRD-6000, analysis result is as it is shown in figure 1, the abscissa of Fig. 1 is scanning angle (2-Theta (°)), and the vertical coordinate of Fig. 1 is for spreading out Penetrating peak (Intensity), compare XRD standard card, the product that roasting prepares under the conditions of 900 DEG C as can be seen from Figure 1 occurs NiO, CaO and NiAl2O4The characteristic peak of spinelle, illustrates have the existence of above-mentioned 3 kinds of materials and content more in product.Do not send out Existing Al2O3Characteristic peak, show that it is uniformly distributed or is capped with the form of core.
To embodiment 1 preparation catalyst carry out SEM-EDX (LEO 1530) characterize, the catalyst microstructure of gained and Element is as in figure 2 it is shown, the rightest figure represents the element kind in the range of delineation.It can be seen for preparing in raw material is each Element is evenly distributed on the surface of catalyst.
Repeat same analysis with the catalyst of embodiment 2 or 3 preparation, obtain similar result.
Embodiment 5 alternating temperature thermogravimetric analysis
The catalyst prepared embodiment 1 by thermogravimetric analysis system is used for CO2The adsorption curve absorbed is measured.First take 15～the 35mg catalyst samples prepared are placed in the microbalance of thermogravimetric analysis system, then are passed through pure nitrogen gas at room temperature condition Lower purging 30min.Then, the CO that volume fraction is 15% it is passed through2Gas, after air-flow and microbalance are stable, starts with 15 DEG C/heating rate of min gradually heats up, and now observes the mass change of microbalance, until example weight is constant.Such as Fig. 3 institute Showing, the abscissa of Fig. 3 is temperature, and the vertical coordinate of top subgraph is CO2Adsorbance, wherein the left side, summit is absorbed portion, summit The right is desorption part；The vertical coordinate of lower section subgraph is the rate of adsorption.By observing the change of composite catalyst quality, show In 300～800 DEG C of temperature ranges, it is to CO2All there is obvious adsorption, calculate it on 536 DEG C of left sides by the rate of adsorption The right side reaches maximum adsorption speed.Repeat same analysis with the catalyst of embodiment 2 or 3 preparation, obtain similar conclusion.
Embodiment 6 fixed temperature thermogravimetric analysis
Temperature CO with embodiment 52Adsorption assessment is different, and the present embodiment is that the catalyst to embodiment 1 preparation is setting In the fixed bed reactors of fixed some temperature (450 DEG C, 500 DEG C, 550 DEG C and 600 DEG C), carry out CO2The fixing temperature of absorption property Degree is evaluated.Under fixed temperature, the CO of 15% volume fraction2With the nitrogen of 85% volume fraction with total volumetric flow rate 350mL min-1Speed be passed through in reactor, use infrared C O2Concentration measuring apparatus detects CO at reactor outlet2Concentration.Result of the test As shown in Figure 4, the abscissa of Fig. 4 is CO2Adsorption time, the vertical coordinate of Fig. 4 is the CO of reactor outlet2Concentration.Embodiment 1 is made Standby catalyst has preferable CO in 450-650 DEG C of temperature range2Absorption property, and reach time of saturated extent of adsorption with The increase of temperature and increase successively, substantially reach to adsorb saturated 5～10min.Repeat with the catalyst of embodiment 2 or 3 preparation Above-mentioned test, obtains similar conclusion.
Embodiment 7 biological glycerol reformation hydrogen production is tested
Particle size range embodiment 1 prepared loads in fixed bed reactors at the catalyst of (0.5～0.9) mm, bed journey Control 50～55mm, be then 3/1 by water and biological glycerol according to steam and carbon ratio S/C, be passed through cumulative volume stream in reactor Amount is 150mL min-1(STP), wherein the carrier gas nitrogen volume flow of reactor inlet is 300mL min-1(STP), reform Temperature of reactor controls at 550 DEG C, plant running 60 minutes, within every 10 minutes, becomes with the product gas of GC analysis reactor outlet Point, product gas each compositional purity result is as shown in Figure 5.The abscissa of Fig. 5 is response time (time), and the vertical coordinate of Fig. 5 is for producing The purity (Gaseous Products) of product gas, the dotted line in figure is the thermodynamics of the hydrogen purity using simple function catalyst The upper limit (H2purity limitation of Reforming).From the result of Fig. 5 it can be seen that this test prepare hydrogen pure Degree is greatly improved than simple reformation hydrogen production upper purity, and calculating hydrogen average purity in 1 hour reactor product gas is 93.45%, the adsorption forced reformation hydrogen production purity of the catalyst of embodiment 1 preparation improves about than simple reformation hydrogen production upper purity 38.4%.Repeat above-mentioned test with the catalyst of embodiment 2 or 3 preparation, obtain similar conclusion.
Embodiment 8 biological glycerol reformation hydrogen production is tested
Being placed at 550 DEG C by catalyst prepared by embodiment 1 in fixed bed reactors as described in Example 7, bed is program control System, 50～55mm, carries out the biological glycerol many secondary response-regeneration cycle of adsorption forced reformation hydrogen production in situ, and wherein water and biology are sweet Oil is 3/1 according to steam and carbon ratio S/C, and being passed through total volumetric flow rate in reactor is 150mL min-1(STP).Use infrared C O2 Concentration measuring apparatus records outlet CO2Concentration, and calculate the conversion ratio of adsorption component CaO accordingly, through 5 circulations, adsorption component turns Rate is maintained at about 50%, and average conversion is 51.32%.Above-mentioned test is repeated with the catalyst of embodiment 2 or 3 preparation, Obtain same conclusion.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a complex function reforming hydrogen-production catalyst, it is characterised in that the chemical formula of described catalyst is NiO-CaO- NiAl2O4/Al2O3, described Al2O3For carrier, described NiAl2O4There is spinel structure.
Catalyst the most according to claim 1, it is characterised in that its raw material includes by weight: NiO 23～42 parts, γ-Al2O325～35 parts and Ca (NO3)2·6H2O 23～52 parts.
3. the preparation method of the catalyst described in a claim 1 or 2, it is characterised in that comprise the following steps:
Step one, preparation (NO Han Ca3)2·6H2The impregnation liquid of O, impregnates γ-Al2O3, 45-65 DEG C of stirring mixing 3～4h；Use alkali Property solution the pH of mixed liquor is adjusted to 8.5～9.5, continue stirring reaction 3-5h, stand 1～2h aging product one；
Step 2, product one is stirred continuously under conditions of 1 atmospheric pressure and 90～95 DEG C, until moisture is evaporated；To be evaporated After powder body be dried, grind, cross 60-70 mesh sieve, obtain catalyst precursor；
Step 3, the preparation impregnation liquid containing NiO, impregnate described catalyst precursor, 10～30 DEG C of uniform stirring mixing 3～4h； With alkaline solution, the pH of mixed liquor is adjusted to 8.5, under the conditions of 90～95 DEG C, continues stirring be extremely dried, at 120 DEG C of air atmospheres Under be dried 10～24h, obtain product three；
Step 4, product three is carried out high-temperature roasting, product of lowering the temperature to obtain, the most described complex function reforming hydrogen-production catalyst.
Preparation method the most according to claim 3, it is characterised in that described in step one containing Ca (NO3)2·6H2The leaching of O Stain liquid is 30～50% Ca (NO of mass concentration3)2·6H2O aqueous solution.
Preparation method the most according to claim 3, it is characterised in that the γ-Al described in step one2O3For crossing 60-70 mesh sieve γ-Al2O3。
Preparation method the most according to claim 3, it is characterised in that the alkaline solution described in step one and step 3 is The ammonia of 1mol/L.
Preparation method the most according to claim 3, it is characterised in that being dried as at 120 DEG C of air gas described in step 2 10～24h it are dried under atmosphere.
Preparation method the most according to claim 3, it is characterised in that the preparation of the impregnation liquid containing NiO described in step 3 Method is that the dust technology with 2～3mol/L is made into, NiO, the NiO solution that mass concentration is 30-50%.
Preparation method the most according to claim 3, it is characterised in that described step 4 is at 850～900 DEG C by product three And N2Roasting 3～4h under atmosphere, at N2Being down to 10～30 DEG C in air-flow, prepare product, the most described complex function reformation hydrogen production is catalyzed Agent.
10. in complex function reforming hydrogen-production catalyst described in claim 1 or 2 or claim 3 to 9 described in any one Complex function reforming hydrogen-production catalyst prepared by the preparation method application in glycerol reformation hydrogen production.
CN201610430940.3A 2016-06-15 2016-06-15 A kind of complex function reforming hydrogen-production catalyst and its preparation method and application Pending CN106111144A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110548519A (en) * 2019-08-07 2019-12-10 广东工业大学 porous nano cobalt-doped zinc manganate spinel catalyst and preparation method and application thereof
WO2021012737A1 (en) * 2019-07-23 2021-01-28 南京杰科丰环保技术装备研究院有限公司 Reforming hydrogen production catalyst using waste vanadium-titanium denitration catalyst as raw material and preparation method therefor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021012737A1 (en) * 2019-07-23 2021-01-28 南京杰科丰环保技术装备研究院有限公司 Reforming hydrogen production catalyst using waste vanadium-titanium denitration catalyst as raw material and preparation method therefor
CN110548519A (en) * 2019-08-07 2019-12-10 广东工业大学 porous nano cobalt-doped zinc manganate spinel catalyst and preparation method and application thereof
CN110548519B (en) * 2019-08-07 2022-07-12 广东工业大学 Porous nano cobalt-doped zinc manganate spinel catalyst and preparation method and application thereof

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Application publication date: 20161116