CN1203919C - Catalyst for producing hydrogen by partial oxidation of propane and preparation and use thereof - Google Patents
Catalyst for producing hydrogen by partial oxidation of propane and preparation and use thereof Download PDFInfo
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- CN1203919C CN1203919C CN 02159871 CN02159871A CN1203919C CN 1203919 C CN1203919 C CN 1203919C CN 02159871 CN02159871 CN 02159871 CN 02159871 A CN02159871 A CN 02159871A CN 1203919 C CN1203919 C CN 1203919C
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Abstract
The present invention relates to a catalyst for preparing hydrogen through the partial oxidation of propane, a preparation method thereof and application thereof. The catalyst is composite oxide of Ni-Ce-Zr without carriers. The general formula of the catalyst is Ni (x) Ce (y) Zr (z) O (a), wherein x is from 5% to 50%, y is from 5% to 60%, z is from 10% to 90%, and a is the balance (weight percentage content). The catalyst carries out preparation in a coprecipitation method. In the method for preparing hydrogen through the partial oxidation of propane, the reaction is carried out under normal pressure, mixed gas of propane and oxygen with the molar ratio of 0.5 to 3 of the oxygen and the propane is used as raw materials, and the reaction is carried out under the condition of 200 to 700 DEG C. The conversion rate of the propane can reach 93% maximally in the reaction for preparing the hydrogen through the partial oxidation of the propane, and the selectivity of the hydrogen can reach 88%.
Description
Technical field
The present invention relates to a kind of catalyst of propane partial oxidation hydrogen-preparation, be used for producing hydrogen through partial oxidation process from propane.
Background technology
Hydrogen is as one of regenerative resource of a kind of high-efficiency cleaning, and its purposes is the fastest-rising industrial gasses of demand more and more widely.Hydrogen is expected to become the preferred fuels of power-fuel cell of new generation, efficient, is lowly polluting, is starting in the fast power-supply system and play a significant role.
Present plant-scale hydrogen production process has steam reformation, Water gas shift/WGS, methanol decomposition method of water electrolysis, methane or hydro carbons etc.Compare with these methods, the method for partical oxidation reaction raw materials is single, reacts to be exothermic process, thereby has that energy consumption is low, the simple advantage of equipment.
Propane also can pass through vapor reforming hydrogen production, and propane and steam reaction obtain hydrogen when higher relatively temperature has catalyst to participate in.The catalyst that current such reaction is used mostly is with supported catalyst or the solid supported noble metal catalyst (Chinese patent 85102194) of metallic nickel as main active component.The hydrogen manufacturing of partial oxidation propane has bibliographical information.In general, noble metal catalyst has reasonable activity to the propane partial oxidation, such as PtRh/CeO
2/ Al
2O
3Catalyst (Applied Catalysis A:General, 85 (1992) 89-100).But noble metal catalyst involves great expense, and stability is still existing not enough.With Al
2O
3, MgO, SiO
2For the supported carrier Raney nickel also is the catalyst (Applied Catalysis A:General 211 (2001) 145-152) of propane partial oxidation hydrogen-preparation.Chinese patent (99115478.9) also relates to the partial oxidation hydrogen-preparation of hydro carbons, utilizes aluminium oxide to support nickel and copper catalyst is the major catalyst of propane partial oxidation hydrogen-preparation.But this patent does not relate to the content of propane partial oxidation hydrogen-preparation.
Summary of the invention
The object of the present invention is to provide a kind of propane partial oxidation hydrogen-preparation Catalysts and its preparation method and application.
The catalyst that with propane is raw material hydrogen manufacturing is the composite oxides of Ni-Ce-Zr, carrier-free.
The general formula of catalyst of the present invention is Ni (x) Ce (y) Zr (z) O (a), and wherein wt is than x: y: z=10-45: 15-45: 40-80, and a depends on the oxidation state with other element.
Preparation of catalysts method of the present invention, the preparation of employing coprecipitation, it is characterized in that according to catalyst general formula Ni (x) Ce (y) Zr (z) O (a), wherein wt is than x: y: z=10-45: 15-45: 40-80, a depends on the oxidation state with other element, after taking by weighing each component, nitrate, oxalates or the carbonate of Ni, Ce, Zr is soluble in water, at room temperature, drip the solution of precipitating reagent ammoniacal liquor or NaOH, and strong agitation, then leave standstill aging.Aging good catalyst pulp is washed with distilled water to pH value 6-8,100-130 ℃ of drying, 300-700 ℃ roasting 3-8 hour, cool off naturally, be crushed to the 30-70 order.
Propane partial oxidation hydrogen methods, it is the Ni-Ce-Zr composite oxides that catalyst adopts active component, carrier-free; The catalyst general formula is Ni (x) Ce (y) Zr (z) O (a), and wherein wt is than x: y: z=10-45: 15-45: 40-80, and a depends on the oxidation state with other element.Under the normal pressure with O
2With the propane molar ratio range be that the propane oxygen gas mixture of 0.5-3 is a raw material, 200-700 ℃ of reaction.
Propane air speed in the propane partial oxidation hydrogen methods is 200-900h
-1The internal diameter 4mm of laboratory reaction device, the useful load of catalyst is 200ml, O
2With the propane molar ratio range be 0.5-3, reaction temperature is 200-700 ℃, product gas chromatography on-line analysis.The evaluation of catalyst is carried out on atmospheric fixed bed continuous flow reactor, adopts straight type quartz reactor, and internal diameter is 4mm.The loading amount of catalyst is 200mg.Utilize air saturation method to bring propane into reactor, O
2With the propane molar ratio range be 0.5-3, range of reaction temperature is 200 ℃-700 ℃, product gas chromatography on-line analysis.
The present invention has advantages such as hydrogen feedstock propane is inexpensive, nontoxic, and this catalyst prepares with coprecipitation, and cost is low, and active high, selectivity is feasible, the advantage of good stability.
Propane partial oxidation of the present invention H-H reaction, conversion of propane is the highest can to reach 93%, and the selectivity of hydrogen can reach 88%.
The specific embodiment
For further setting forth the present invention, the spy provides following example, and embodiments of the present invention are not limited to following example.
Embodiment 1
By weight Ni: Ce: Zr=10: 30: 80 ratio takes by weighing each component and is dissolved in 100ml distilled water wiring solution-forming, ammoniacal liquor with excessive 10% or sodium hydroxide solution precipitation, and strong agitation, after precipitation finishes, continue aging 3h, the catalyst pulp that above-mentioned precipitation is good, being washed with distilled water to the pH value is 7,110 ℃ of dryings 12 hours, 400 ℃ of roastings 3 hours, with after the stove cooling, compressing tablet smashes that to be screened to the 40-70 order standby.Make catalyst a, get 200 milligrams of catalyst and put into reactor, make O
2With the propane mol ratio be 1.5, reaction temperature is controlled at 300 ℃, the propane air speed is 200h
-1Reaction, conversion of propane is 88%, the selectivity of hydrogen is 60.4%.
Embodiment 2
By weight Ni: Ce: Zr=25: 45: 60 ratio takes by weighing each component and is dissolved in 100ml distilled water wiring solution-forming, ammoniacal liquor with excessive 10% or sodium hydroxide solution precipitation, and strong agitation, after precipitation finishes, continue aging 3h, the catalyst pulp that above-mentioned precipitation is good, being washed with distilled water to pH is 6.6,110 ℃ of dryings 12 hours, 400 ℃ of roastings 3 hours, with after the stove cooling, compressing tablet smashes that to be screened to the 40-70 order standby.Make catalyst b, get 200 milligrams of catalyst and put into reactor, make O
2With the propane mol ratio be 2.0, reaction temperature is controlled at 500 ℃, the propane air speed is 600h
-1Reaction, conversion of propane is 82.0%, the selectivity of hydrogen is 80%.
Embodiment 3
By weight Ni: Ce: Zr=45: 15: 40 ratio takes by weighing each component and is dissolved in 100ml distilled water wiring solution-forming, ammoniacal liquor with excessive 10% or sodium hydroxide solution precipitation, and strong agitation, after precipitation finishes, continue aging 3h, the catalyst pulp that above-mentioned precipitation is good, being washed with distilled water to the pH value is 7.3,110 ℃ of dryings 12 hours, 400 ℃ of roastings 3 hours, with after the stove cooling, compressing tablet smashes that to be screened to the 40-70 order standby.Make catalyst b, get 200 milligrams of catalyst and put into reactor, make O
2With the propane mol ratio be 1.0, reaction temperature is controlled at 700 ℃, the propane air speed is 600h
-1Reaction, conversion of propane is 65.0%, the selectivity of hydrogen is 92%.
Embodiment 4
By weight Ni: Ce: Zr=25: 45: 60 ratio takes by weighing each component and is dissolved in 100ml distilled water wiring solution-forming, ammoniacal liquor with excessive 10% or sodium hydroxide solution precipitation, and strong agitation, after precipitation finishes, continue aging 3h, the catalyst pulp that above-mentioned precipitation is good, being washed with distilled water to the pH value is 7,110 ℃ of dryings 12 hours, 400 ℃ of roastings 3 hours, with after the stove cooling, compressing tablet smashes that to be screened to the 40-70 order standby.Make catalyst b, get 200 milligrams of catalyst and put into reactor, make O
2With the propane mol ratio be 1.5, reaction temperature is controlled at 500 ℃, the propane air speed is 400h
-1Reaction, conversion of propane is 48.0%, the selectivity of hydrogen is 85%.
Embodiment 5
Except that reaction temperature is controlled at 500 ℃, other conditions are made life experiment with embodiment 4, survey once every two hours, experience 100 hours altogether.The conversion ratio of propane increasing progressively in time is basicly stable, the selectivity of hydrogen increasing progressively and slightly reduce in time, by reaction just 85% will be to 72% through 70 hours reaction, and in subsequent reaction, remain unchanged basically.
Claims (4)
1, a kind of catalyst of propane partial oxidation hydrogen-preparation is characterized in that catalyst is the composite oxides of Ni-Ce-Zr, carrier-free; The catalyst general formula is Ni (x) Ce (y) Zr (z) O (a), and wherein wt is than x: y: z=10-45: 15-45: 40-80, and a depends on the oxidation state with other element.
2, according to the described Preparation of catalysts method of claim 1, the preparation of employing coprecipitation method, it is characterized in that according to catalyst general formula Ni (x) Ce (y) Zr (z) O (a), wherein wt is than x: y: z=10-45: 15-45: 40-80, a depends on the oxidation state with other element, after taking by weighing each component, with Ni, Ce, the nitrate of Zr, oxalates or carbonate are dissolved in the distilled water, and strong agitation, after precipitation finishes, continue aging, it is 6-8 that the catalyst pulp that above-mentioned precipitation is good is washed with distilled water to pH, 100-130 ℃ of drying, 300-700 ℃ roasting 3-8 hour, naturally cooling is crushed to the 30-70 order.
3, a kind of propane partial oxidation hydrogen methods is characterized in that it is the composite oxides of Ni-Ce-Zr that catalyst adopts active component, carrier-free; Catalyst general formula Ni (x) Ce (y) Zr (z) O (a), wherein wt are than x: y: z=10-45: 15-45: 40-80, and a depends on the oxidation state with other element; Be reflected under the normal pressure, with O
2With the propane molar ratio range be that the propane oxygen gas mixture of 0.5-3 is a raw material, react under 200-700 ℃ the condition.
4, in accordance with the method for claim 3, the air speed that it is characterized in that propane is 200-900h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02159871 CN1203919C (en) | 2002-12-24 | 2002-12-24 | Catalyst for producing hydrogen by partial oxidation of propane and preparation and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02159871 CN1203919C (en) | 2002-12-24 | 2002-12-24 | Catalyst for producing hydrogen by partial oxidation of propane and preparation and use thereof |
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| CN1424146A CN1424146A (en) | 2003-06-18 |
| CN1203919C true CN1203919C (en) | 2005-06-01 |
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| CN1317074C (en) * | 2003-03-14 | 2007-05-23 | 中国科学院大连化学物理研究所 | Zirconium-base composite oxide catalyst, preparing method and use thereof |
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