CN105983427A - Apatite loaded platinum catalyst as well as preparation method and application thereof - Google Patents
Apatite loaded platinum catalyst as well as preparation method and application thereof Download PDFInfo
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a catalyst for a carbon monoxide water gas shift (WGS) reaction, in particular to preparation of hydroxyapatite (HAP) and halogen-substituted apatite (FAP, ClAP and BrAP) by virtue of a co-precipitation method. Platinum is introduced by virtue of a dipping method. The carrying capacity of the platinum in the catalyst is 0.3-5% of the total mass of the catalyst. The regulation and control of the activity of the catalyst can be realized by controlling Ca/P of a carrier. The catalyst prepared by the method is used for performing a water gas shift reaction in a typical reformed gas, has high activity and selectivity and good high-temperature stability, and shows higher activity compared with that of a catalyst in which a noble metal is loaded to a reducible rare earth oxide carrier (CeO2) under the same noble metal carrying capacity.
Description
Technical field
The present invention relates to a kind of water gas shift reation catalyst, specifically a kind of for an oxygen
Change carbon water-gas shift (WGS) the apatite load platinum catalyst that reacts and preparation thereof and application.
Background technology
China's expanding economy causes environmental pollution increasingly severe, and environmental problem has become as limit
The major issue of China processed economic development.Fuel cell (such as PEMFC) is a kind of preferable
Power generation mode, has energy transformation ratio high, product is pollution-free outstanding advantages of Denging.Along with fuel electricity
How the development of pool technology, provide cheap and practical hydrogen source to have become as at present for so connecting battery
One of obstacle limiting its sizable application.Containing H in fuel reformation gas2、CO、CO2On a small quantity
For the fuel converted.The H of low-temperature fuel cell (such as PEMFC)2In unstripped gas, CO concentration
Have to be lower than 100ppm.Water gas shift reation is a kind of to effectively eliminate the side of CO in reformation gas
Method, is reacted by water and CO is converted into CO, and obtain the H of equimolar number2。
By H2Separate the palladium film reactor being coupled together with water gas shift reation and can not only prepare height
Pure H2, moreover it is possible to reduce equipment investment.In order to prevent the hydrogen embrittlement of palladium film, the use of palladium film reactor
Temperature is higher than 350 degree.The main WGS catalysts of current industrial application mainly has
Iron-based high conversion catalyst, cuprio low change catalyzer and cobalt molybdenio resistant to sulfur width temperature catalyst.But by
There is reducing condition harshness in these catalyst, use temperature poisoning narrow, easy, exposure air easy
The shortcomings such as spontaneous combustion, are not therefore suitable for palladium film reactor system.Therefore, work out activity high,
The water-gas shift catalyst that Heat stability is good, stability are high becomes water-gas shift palladium film reactor
One of crucial.In this field, noble metal (Pt, Au, Pd etc.)/reducibility carrier
(CeO2,La2O3Deng) system causes the extensive attention of whole world scientist.But it is many expensive
Metal/reducibility carried catalyst is not sufficiently stable (Zalc, J.M. in reformation gas；
Sokolovskii,D.G.；D.G.J.Catal.2002,209,169.), additionally, due to valency
The noble metal of lattice costliness and rare earth element (CeO2, La2O3) also limit it in practice
Application.Hydroxyapatite is cheap as one, environment friendly material, and it is as catalyst
Application also obtains certain concern.Au loads to hydroxyapatite and simply should for water-gas shift
Use 320 degree, and Ru loads to hydroxyapatite and has serious methanation secondary for water-gas shift
There is (A.Venugopal, M.S.Scurrell, Applied Catalysis A:General in reaction
2003,245,137.)。
Summary of the invention
It is an object of the invention to provide a kind of low cost, the noble metal that catalysis activity is good/phosphorus ash
Stone catalyst and preparation thereof and application, this catalyst when water gas shift reation, activity is high,
Good stability.
To achieve these goals, the technical solution used in the present invention is:
A kind of for carbon monoxide water-gas shift (WGS) catalysts, described catalyst
Consist of platinum/apatite；Platinum load capacity is: mass fraction 0.01%-10%；Carrier apatite is
Hydroxyapatite (HAP, Ca10-Z(HPO4)Z(PO4)6-Z(OH)2-Z), the substituted hydroxyl of fluorion
Base apatite (FAP, Ca10-Z(HPO4)Z(PO4)6-ZF2-Z), the substituted hydroxy-apatite of chloride ion
Stone (ClAP, Ca10-Z(HPO4)Z(PO4)6-ZCl2-Z), or the substituted hydroxy-apatite of bromide ion
Stone (BrAP, Ca10-Z(HPO4)Z(PO4)6-ZBr2-Z), wherein Ca/P molar ratio range is: 1.5
≤Ca/P≤1.93。
In described catalyst, platinum content is preferably 0.3%-5% (mass fraction), described catalysis
The preparation of agent: the hydroxyapatite solid of hydroxyapatite or halogen substiuted is placed in a certain amount of
H2PtCl6Or PdCl2In aqueous solution, at room temperature impregnate 10-24h, be dried,
400-600 DEG C of roasting 2-4 hour, obtains the catalyst that Pt or Pd is carried on apatite.
Prepared by described carrier hydroxyapatite mainly comprises the following steps: by calcium nitrate and diammonium phosphate
It is dissolved in respectively in a certain amount of water, adds the pH value of strong aqua ammonia regulation solution, at the bar of stirring
Under part, ammonium dibasic phosphate solution is added drop-wise in calcium nitrate solution, stirs 2-4h at 80-95 DEG C,
Precipitation aged at room temperature, washing is dried, and 400-600 DEG C of roasting 2-4 hour obtains carrier hydroxyl
Apatite.
Prepared by the hydroxyapatite of described carrier halogen substiuted mainly comprises the following steps: by calcium nitrate and
Diammonium phosphate is dissolved in a certain amount of water respectively, ammonium fluoride, ammonium chloride or ammonium bromide is added
Enter in ammonium dibasic phosphate solution, add the pH value of strong aqua ammonia regulation solution, at the bar of stirring
Under part, the mixed solution of diammonium phosphate and ammonium fluoride, ammonium chloride or ammonium bromide is added drop-wise to nitre
In acid calcium solution, stirring 2-4h at 80-95 DEG C, precipitate aged at room temperature, washing is dried,
400-600 DEG C of roasting 2-4 hour, obtains the hydroxyapatite of carrier halogen substiuted.
The catalyst of the present invention application in water gas shift reation.
The invention have the advantages that
1. the present invention uses the sedimentation method and preparation catalyst.Operating process is simple, bar
The advantages such as part is gentle, reproducible；
Catalyst the most involved in the present invention need not the rare earth elements such as Ce, La, then uses
Cheap Ca and P, reduces the cost of catalyst；
3. the catalyst that prepared by the present invention is for water gas shift reation, even if at high temperature
(450 DEG C) do not have the side reactions such as methanation to occur yet；
4. the catalyst that prepared by the present invention at high temperature shows ratio for water gas shift reation
Pt/CeO2The higher catalysis activity of catalyst；
5. the catalyst that prepared by the present invention need not do any oxidation or reduction before using
Pretreatment；
Catalyst the most involved in the present invention has eco-friendly feature, and (hydroxyapatite is
Typical biomaterial), and catalyst has good stability；
The catalyst that the above advantage makes the present invention prepare becomes one and has commercial Application
The catalyst of prospect.
Accompanying drawing explanation
Fig. 1 is 1%Pt/HAP-X catalysis activity contrast in 5%CO-20%H2O-75%He
Figure.
Fig. 2 is 1%Pt/CeO2, 1%Pt/HAP-1.75,1%Pt/FAP and 1%Pt/ClAP exist
Catalysis activity comparison diagram in 5%CO-20%H2O-75%He.
Fig. 3 is 1%Pt/CeO2Exist with 1%Pt/HAP-1.75
15%CO-5%CO2-30%H2O-40%H2-10N2In stability experiment result figure.
Detailed description of the invention
The technology of the present invention details is by following embodiment and experimental example detailed description in addition.Need explanation
Be lifted embodiment and experimental example, the technology that its effect simply further illustrates the present invention is special
Levy rather than limit the present invention.
Comparative example 1
Preparation 1%Pt/CeO2(numeral before Pt represents the quality hundred of Pt in catalyst to catalyst
Proportion by subtraction).
Take Ce (NO3)3·4H2O is placed in Muffle furnace, 450 DEG C of roastings 4 hours, obtains CeO2
Powder.Take 1g CeO2Powder joins the H of 1.365ml 0.02g/ml2PtCl6In aqueous solution,
60 DEG C of water-baths are evaporated to most of moisture be evaporated, impregnate 24 hours under room temperature, 60 DEG C of bakings
Being dried 12 hours in case, in 450 DEG C of Muffle furnace air, roasting 4 hours, obtains 1%Pt/CeO2
Catalyst.
Embodiment 1
(numeral before Pt represents the percent mass of Pt in catalyst to prepare 1%Pt/HAP-X
Than), Ca/P mol ratio during wherein X is the catalyst obtained according to following preparation method.Such as
HAP-1.76 represents that in catalyst, the mol ratio of Ca/P is 1.76.
Weigh 7.87g Ca (NO3)2·4H2O is dissolved in 100ml distilled water, weighs 2.64g
(NH4)2HPO4Being dissolved in 100ml distilled water, stirring makes it be completely dissolved, with commercially available
It is 10.5 that 25%-28% ammonia regulates the pH value of solution respectively, under conditions of stirring, uses constant current
Pump is by (NH4)2HPO4Solution is slowly dropped to Ca (NO3)2·4H2During O is molten, after completion of dropwise addition,
Mixed solution is transferred in 90 DEG C of water-baths, continue stirring, take out after 2 hours, be placed in room
Aging 6 hours of temperature, washing of precipitate is filtered, and is dried 12 hours, 500 DEG C of Muffles in 60 DEG C of baking ovens
Roasting 4 hours in stove air, obtain carrier HAP-1.76.After 1g HAP-1.76 is ground, add
Enter the H to 1.365ml 0.02g/ml2PtCl6In aqueous solution, dipping 24 hours under room temperature, 60 DEG C
Being dried 12 hours in baking oven, in 500 DEG C of Muffle furnace air, roasting 4 hours, obtains 1%
Pt/HAP-X catalyst.
Embodiment 2
Preparation 1%Pt/FAP and 1%Pt/ClAP, wherein FAP represents fluorion substituted hydroxyl phosphorus
Lime stone, ClAP represents the substituted hydroxyapatite of chloride ion.
Weigh 7.87g Ca (NO3)2·4H2O is dissolved in 100ml distilled water, weighs 2.64g
(NH4)2HPO4With 0.247g NH4F or 0.357g NH4Cl is dissolved in 100ml distilled water, stirs
Mixing and make it be completely dissolved, the pH value regulating solution with commercially available 25%-28% ammonia respectively is 10,
Under conditions of stirring, with constant flow pump by (NH4)2HPO4Solution is slowly dropped to
Ca(NO3)2·4H2During O is molten, after completion of dropwise addition, mixed solution is transferred in 90 DEG C of water-baths,
Continuing stirring, take out, be placed in aged at room temperature 6 hours after 2 hours, washing of precipitate is filtered, 60 DEG C
Being dried 12 hours in baking oven, in 500 DEG C of Muffle furnace air, roasting 4 hours, obtains carrier FAP
Or ClAP.After being ground by 1g FAP or ClAP, join 1.365ml 0.02g/ml's
H2PtCl6In aqueous solution, impregnate 24 hours under room temperature, 60 DEG C of baking ovens be dried 12 hours,
In 500 DEG C of Muffle furnace air, roasting 4 hours, respectively obtains 1%Pt/FAP and 1%Pt/ClAP and urges
Agent.
Embodiment 3
By Ca (NO3)2The modified Ca/P mol ratio changing catalyst.
0.12g Ca(NO3)24H2O is dissolved in 1ml H2In O, add 0.5g HAP-1.58, stir
Mix uniformly, room temperature immersion 24h, 60 DEG C of baking ovens are dried 12 hours, 500 DEG C of Muffle furnace air
Middle roasting 4 hours, obtains HAP-1.74.
Application examples 1
The application 1%Pt/HAP-1.76,1%Pt/HAP-1.75,1% of catalyst
Pt/HAP-1.68,1%Pt/HAP-1.58,1%Pt/HAP-1.74.
Catalyst tabletting, is broken for 40-60 mesh size, takes 75mg catalyst granules and 100mg
The quartz sand dilution of identical mesh number, is placed in the quartz reactor of internal diameter 8mm, N2Or He
Under heat to 250 DEG C, be passed through 5%CO-20%H2O-75%He (V/V) reaction gas,
Gas overall flow rate is 187.5ml/min, mass space velocity GHSV=150,000ml/g/h.Reaction temperature
Degree steps up 450 DEG C, investigates the reactivity of catalyst under different temperatures.Experimental result
As shown in Figure 1.
Along with the increase of Ca/P mol ratio in catalyst, reactivity steps up, and works as
When Ca/P mol ratio increases further, reactivity is not changed in.
Application examples 2
The application 1%Pt/CeO of catalyst2, 1%Pt/HAP-1.75,1%Pt/FAP and 1%
Pt/ClAP
Catalyst tabletting, is broken for 40-60 mesh size, takes 75mg catalyst granules and 100mg
The quartz sand dilution of identical mesh number, is placed in the quartz reactor of internal diameter 8mm, N2Or He
Under heat to 250 DEG C, be passed through 5%CO-20%H2O-75%He reaction gas, gas always flows
Speed is 187.5ml/min, mass space velocity GHSV=150,000ml/g/h.Reaction temperature progressively carries
High to 450 DEG C, investigate the reactivity of catalyst under different temperatures.Experimental result such as Fig. 2 institute
Show.
When 250 DEG C, 1%Pt/CeO2The reactivity of catalyst is the highest, but is as temperature
Raising, the activity of 1%Pt/HAP-1.75 and 1%Pt/ClAP catalyst is more than 1%Pt/CeO2Urge
Agent, and within the scope of whole temperature, 1%Pt/HAP-1.75 and 1%Pt/ClAP is catalyzed
Agent shows identical reactivity.
Application examples 3
The evaluation 1%Pt/CeO of catalyst stability2And 1%Pt/HAP-1.75
Catalyst tabletting, is broken for 40-60 mesh size, takes 100mg catalyst granules, in being placed in
In the quartz reactor of footpath 8mm, N2Under heat to 400 DEG C, be passed through gas of typically reforming,
Consist of: 15%CO-5%CO2-30%H2O-40%H2-10N2, gas overall flow rate is
150ml/min, mass space velocity is: GHSV=90,000ml/g/h.Reaction is carried out 100 hours,
Investigate the stability of catalyst.Experimental result is as shown in Figure 3.
1%Pt/HAP-1.75 and 1%Pt/CeO2Catalyst is reacting the incipient stage, catalysis
Activity slightly reduces, and after about 30 hours, reaches steady statue, whole 100 hours comment
During valency, the activity of 1%Pt/HAP-1.75 is consistently higher than 1%Pt/CeO2, and show
And 1%Pt/CeO2The stability that catalyst is suitable.
By gas chromatogram, on-line analysis, CO conversion ratio following equation are carried out for product
Calculate.
CO in conversion ratio (%)=(concentration of CO in the concentration-product of CO in raw material)/raw material
Concentration
Conclusion: from application examples 1 it can be seen that along with the increase of Ca/P mol ratio, reactivity
Stepping up, being embodied in CO conversion ratio increases.From application examples 2 it can be seen that 1%
The activity of Pt/HAP-1.75,1%Pt/ClAP catalyst is the most close, and above 1%
Pt/CeO2Catalyst.From application examples 3 it can be seen that 1%Pt/HAP-1.75 catalyst is typical case
Reformation gas in show good stability.
Analytic explanation: catalyst prepared by the present invention shows in typical case reforms gas and well urges
Changing activity, its catalysis activity is higher than rare earth oxide (CeO2) catalyst that loads.This is urged
Agent does not use rare earth element, then uses cheap Ca and P so that the cost of catalyst
Relative to Pt/CeO2Catalyst is low.Catalyst shows fine high-temperature stable in the application
Property.
Claims (8)
1. an apatite load platinum catalyst, it is characterised in that: platinum is carried on apatite and carries
On body, in catalyst, the mass loading amount of platinum is 0.01%-10%.
Catalyst the most according to claim 1, it is characterised in that: carrier apatite is hydroxyl
Base apatite (HAP, Ca10-Z(HPO4)Z(PO4)6-Z(OH)2-Z, 0 < z≤1), fluorion takes
Hydroxyapatite (FAP, the Ca in generation10-Z(HPO4)Z(PO4)6-ZF2-Z, 0 ＜ z≤1), chloride ion
Substituted hydroxyapatite (ClAP, Ca10-Z(HPO4)Z(PO4)6-ZCl2-Z, 0 ＜ z≤1) or
Person's bromide ion substituted hydroxyapatite (BrAP, Ca10-Z(HPO4)Z(PO4)6-ZBr2-Z, 0 ＜ z
≤ 1) one or two or more kinds in, in apatite, Ca/P molar ratio range is: 1.5≤Ca/P
≤1.93。
Catalyst the most according to claim 1 or claim 2, it is characterised in that: platinum is at catalyst
Middle load capacity is mass fraction 0.3%-5%, and in apatite, Ca/P molar ratio range is: 1.58≤
Ca/P≤1.8。
4. the preparation method of the arbitrary described catalyst of claim 1-3, it is characterised in that:
By hydroxyapatite, the substituted hydroxyapatite of fluorion, chloride ion substituted hydroxyl phosphorus
One or two or more kinds in lime stone or bromide ion substituted hydroxyapatite solid is placed in
H2PtCl6In aqueous solution, at room temperature dipping 10-24 hour, it is dried, 400-600 DEG C of roasting
Burn 2-4 hour, obtain the catalyst that Pt is carried on apatite.
5. the preparation method of catalyst as claimed in claim 4, it is characterised in that: wherein,
Prepared by carrier hydroxyapatite mainly comprises the following steps: calcium nitrate and diammonium phosphate are dissolved in respectively
In water, it is separately added into the pH value 9-11 of strong aqua ammonia regulation solution, calcium nitrate solution molar concentration
0.05mol/L to 4mol/L (usually 0.33mol/L), ammonium dibasic phosphate solution molar concentration
0.05mol/L to 3mol/L (usually 0.20mol/L), by phosphoric acid under conditions of stirring
Hydrogen two ammonium salt solution is added drop-wise in calcium nitrate solution, controls to rub by needed for calcium nitrate and diammonium phosphate
That ratio 1.5 to 2.0, stirs 2-4 hour at 80-95 DEG C, precipitates aged at room temperature, and washing is dry
Dry, 400-600 DEG C of roasting 2-4 hour, obtain carrier hydroxyapatite.
6. the preparation method of catalyst as claimed in claim 4, it is characterised in that: wherein,
The hydroxyapatite (one or two or more kinds in FAP, ClAP, BrAP) of carrier halogen substiuted
Mainly comprising the following steps of preparation: by the most soluble in water to calcium nitrate and diammonium phosphate, by ammonium fluoride,
One or two or more kinds in ammonium chloride or ammonium bromide joins in ammonium dibasic phosphate solution, point
Not Jia Ru strong aqua ammonia regulation solution pH value=9-11, calcium nitrate solution molar concentration 0.05mol/L
To 4mol/L (usually 0.33mol/L), ammonium dibasic phosphate solution molar concentration 0.05mol/L arrives
3mol/L (usually 0.20mol/L), the one in ammonium fluoride, ammonium chloride or ammonium bromide
Or more than two kinds in solution, molar concentration 0.0167mol/L to 1mol/L is (usually
0.667mol/L), under conditions of stirring by diammonium phosphate and ammonium fluoride, ammonium chloride or
The mixed solution of one or two or more kinds in ammonium bromide is added drop-wise in calcium nitrate solution, controls to press
Molar ratio 1.5 to 2.0 needed for calcium nitrate and diammonium phosphate, stirs 2-4h at 80-95 DEG C,
Precipitation aged at room temperature, washing is dried, and 400-600 DEG C of roasting 2-4 hour obtains carrier halogen
Substituted hydroxyapatite.
7. according to the preparation method of described catalyst arbitrary in claim 5 or 6, its feature
It is: the Ca/P ratio of carrier apatite can be by carrying out modulation with calcium salt modification；Particularly as follows:
The Ca/P mol ratio of target as required, by hydroxyapatite, the substituted hydroxyl of fluorion
The substituted hydroxyapatite of apatite, chloride ion or bromide ion substituted hydroxyapatite solid
Being placed in calcium saline solution, aqueous solution Ca ion molar concentration is 0.5mol/L to 5mol/L
(usually 2mol/L), at room temperature dipping 10-24 hour, be dried, at 400-600 DEG C
Roasting 2-4 hour；Calcium salt is Ca (NO3)2、CaCl2In one or two kinds.
8. the arbitrary described catalyst of the claim 1-3 application in water gas shift reation.
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