CN103272604A - Fly ash catalyst for hydrogen production implemented by catalytic reforming of bio-oil and preparation method of fly ash catalyst - Google Patents
Fly ash catalyst for hydrogen production implemented by catalytic reforming of bio-oil and preparation method of fly ash catalyst Download PDFInfo
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Abstract
The invention discloses a fly ash catalyst for hydrogen production implemented by the catalytic reforming of bio-oil. The fly ash catalyst comprises a catalyst active component and a catalyst carrier, wherein the catalyst carrier refers to fly ash; and the catalyst active component refers to Ni or Co, and the content of the catalyst active component accounts for 5-30% of the weight of the catalyst carrier. The invention also discloses a preparation method of the catalyst, which is implemented through impregnating cobalt or nickel on fly ash through an impregnation method. The preparation method is simple, and mild in reaction conditions. The catalyst disclosed by the invention takes the fly ash as the catalyst carrier, therefore, the catalyst has the characteristics of high stability, wide sources and low price, and the application of the catalyst provides an efficient and economic way for the comprehensive utilization of the fly ash produced by coal-fired power plants; and the catalyst has the advantages of high catalytic activity, long catalytic life, and high yield of prepared hydrogen.
Description
Technical field
The present invention relates to the synthetic field of chemical industry, relate in particular to a kind of flyash Catalysts and its preparation method for catalyzing and reforming biologic oil to prepare hydrogen.
Background technology
China is that a coal mining utilizes big country, and shared ratio is up to more than 70% in China's energy-consuming for coal, and its energy supply mainly is to pass through coal-fired station.Along with fast development of national economy, China's thermal power generation in recent years development is very fast, and flyash output increases fast, " 12 " end, flyash year generation will reach 5.7 hundred million tons, the situation that comprehensive utilization faces is very severe.Just new revision issue " total utilization of PCA management method " expression of National Development and Reform Committee encourages flyash is carried out high added value and big addition content utilization.
Flyash is a kind of pozzolanic materials, is to produce under high-temperature fluidizedization state in coal-fired process, through Fast Heating, cooling fast, forms the particle of compact structure, and is very stable to water under the normal temperature, can not be dissolved.Chemical composition is with SiO
2And Al
2O
3Be main, other composition is Fe
2O
3, CaO, MgO, K
2O, TiO
2, Na
2O, SO
3And unburnt carbon etc.At present, flyash is mainly for the production of building materials (cement, concrete, mortar, brick and tile and haydite etc.), build the road (embankment, roadbed, road surface) and backfill (structure backfill, building backfill, filling mine, tidal land).Yet present application makes that the added value effect of flyash is also not obvious, if can take full advantage of the Al that is rich in the flyash
2O
3, SiO
2, alkali metal and alkaline earth oxide, and the high-specific surface area of flyash and high-temperature stability, with it as catalyst carrier, pass through infusion process again, with active constituent loading on this catalyst carrier, make highly active flyash catalyst, will greatly promote the using value of flyash, the new situation of developing utilization of fly ash.
Hydrogen Energy is considered to the most potential new forms of energy of 21st century, is not only a kind of very important industrial chemicals, for the synthesis of ammonia, participation hydrogenation reaction etc., and is a kind of very energy carrier of cleaning, as can be used for internal combustion engine and fuel cell.Catalyzing and reforming biologic oil to prepare hydrogen is a kind of low cost, high efficiency hydrogen production technology, is in the presence of catalyst, at high temperature reacts by bio oil and water vapour to obtain hydrogen, and is attended by side reactions such as water gas reaction and carbon monodixe conversion reaction.Total reaction equation is as follows:
Wherein, the raw material bio oil is to adopt the abundant living beings (stalk, wood chip etc.) of stock number for raw material, and heat scission reaction takes place under anaerobic, medium temperature condition, collects the liquid that obtains after the rapid condensation, and preparation process is simply efficient, and is with low cost.The technology core of catalyzing and reforming biologic oil to prepare hydrogen is catalyst, and this catalyst is had the requirement of two aspects, the one, can efficiently reactant be decomposed, and the 2nd, can adsorb efficiently and decomposition water.Metal Ni and Co can impel carbon-carbon bond and carbon-oxygen bond to rupture, and can be used for the decomposition that catalysis contains the oxygen bio oil; Alkali metal and alkali earth metal K, Ca, Mg and Na can promote catalyst that the absorption of water is decomposed effectively.Therefore, preparation is active component with Ni or Co, is rich in the catalyst of alkalies and alkaline earth elements such as K, Ca, Mg, Na simultaneously, has very important significance for the catalyzing and reforming biologic oil to prepare hydrogen tool.
In addition, because bio oil is formed complexity, oxygen content is high, in catalytic reforming process, catalyst is very easy to inactivation.There are some researches show that when bio oil was carried out catalytically reforming hydrogen producing at fixed bed reactors, one way service life of catalyst is the longest only to be 9 hours, therefore, the catalyst that obtains longer one way service life also is the current problem that presses for solution.
Summary of the invention
The invention provides a kind of flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen, this catalyst is carrier with discarded object-flyash that coal-fired station produces, realized the high value added utilization of flyash, and the catalyst of preparation have catalytic activity height, long catalytic life and advantage with low cost.
A kind of flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen comprises catalyst activity component and catalyst carrier, and described catalyst carrier is flyash; Described catalyst activity component is Ni or Co, and the catalyst activity components contents is 5～30% of catalyst carrier weight.
As preferably, described catalyst carrier is the flyash that coal-fired station produces.Flyash is the topmost discarded object that coal-fired station produces, be the porous type alveolate texture, through after the high-temperature calcination, specific area is bigger, has higher adsorption activity, above-mentioned design feature is used its carrier that can be used as catalyst, and is not only with low cost, and realized the high value added utilization of flyash.
As preferably, described flyash consist of Al
2O
310～35%, SiO
230～60%, Fe
2O
32～15%, CaO2～20%, MgO1～10%, K
2O0.5～5%, Na
2O0.1～2%, TiO
20.5～3%, ZnO0.3～1%, CuO0.2～1%; More preferably: Al
2O
315～25%, SiO
230～45%, Fe
2O
38～15%, CaO10～20%, MgO1～5%, K
2O1～2%, Na
2O0.1～0.5%, TiO
21～2%, ZnO0.4～0.8%, CuO0.3～0.7%.Al
2O
3And SiO
2For the main component of flyash, after high-temperature calcination, have splendid heat endurance and bigger specific area, can become good catalyst carrier.The alkalies and alkaline earth oxide CaO, MgO, the K that contain in the flyash
2O and Na
2O can suppress the catalyst surface carbon distribution on the one hand, prolongs life of catalyst; Can promote the dispersion of active component on the other hand, improve catalytic activity,
The auxiliary agent that can be used as catalyst uses.Therefore, the compositing characteristic of flyash itself makes it both can be used as catalyst carrier, also plays the effect of catalyst promoter simultaneously.
The present invention also provides a kind of flyash Preparation of catalysts method for catalyzing and reforming biologic oil to prepare hydrogen, comprises the steps:
(1) flyash was calcined 2～6 hours under 700～900 ° of C, obtained catalyst carrier (Ash);
(2) soluble-salt with nickel or cobalt is dissolved in the solvent, obtains nickel or cobalt salt solution; Described solvent is one or both of water or alcohols; The concentration of described nickel or cobalt salt solution is 0.05～1.5mol/L;
(3) add the catalyst carrier of step (1) gained in above-mentioned nickel or the cobalt salt solution, flooded 2～12 hours, stir evaporate to dryness and dry the processing again, obtain catalyst precursor A; Described stirring evaporate to dryness temperature is 70～100 ° of C; Described baking temperature is that 100～130 ° of C, drying time are 6～12 hours;
(4) with the catalyst precursor A of step (3) gained, under 700～900 ° of C, roasting obtained described flyash catalyst after 2～6 hours.
Flyash is carried out calcination processing, removing the impurity of surface absorption, and obtain the stable catalyst carrier.Calcining heat is 700～900 ° of C, and activation effect is good, and calcining heat interval and the actual serviceability temperature of catalyst are that the interval of reforming reaction temperature is complementary.When calcining heat surpassed 900 ℃, activation effect was not obvious, even can weaken, and may be because the transformation of crystal formation at high temperature takes place flyash.
As preferably, the soluble-salt of the described nickel of step (2) or cobalt is halide, nitrate, oxalates or acetate, more preferably nickel nitrate or cobalt nitrate.Nickel nitrate or cobalt nitrate have that raw material is easy to get, relative low price and the good characteristics of dissolubility in water or ethanolic solution.
As preferably, the described alcohols of step (2) is one or more in ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, the isobutanol, more preferably ethanol.Ethanol is the most frequently used organic solvent, and nickel or the solubility of cobalt salt in ethanol are big, and it is therefore as preferred.
The concentration of the described nickel of step (2) or cobalt salt solution is 0.05～1.5mol/L, and the concentration of nickel or cobalt salt solution is in above-mentioned scope, and the activity of such catalysts of preparation reaches selective best.Nickel or cobalt salt solution concentration are proportional to the load capacity of active component nickel or cobalt, if nickel or cobalt salt solution concentration are excessive, activity component load quantity is too high, and then active component is difficult for disperseing, and the problem that sintering runs off occurs, and causes reactivity and selective decline; If nickel or cobalt salt solution concentration are too small, activity component load quantity is low excessively, and then the activated centre number deficiency does not reach best catalytic effect.
The described dip time of step (3) is 2～12 hours, and dip time is too short, and then nickel or cobalt salt are difficult to dipping fully on the flyash surface; Dip time is long, influences migration and the distribution of nickel or cobalt salt, and then influences its catalytic performance.
As preferably, the described sintering temperature of step (4) is 750～900 ° of C, in this scope, and dispersion degree of active components height after the roasting, then catalytic activity height.When sintering temperature is higher than 900 ℃, active component can be gathered and grows up, and reduces decentralization, causes catalytic activity to descend.If sintering temperature is lower than the actual serviceability temperature of catalyst, may cause the catalyst structure instability, make catalyst in use crystal formation new variation takes place.
The described roasting time of step (4) is 2～6 hours, in this scope, and dispersion degree of active components height after the roasting, then catalytic activity height.Long when roasting time, then sintering can take place in active component, causes catalytic activity to descend; If roasting time is too short, then metallic salt decomposes not exclusively, and catalytic effect descends.
Described catalyst needed to use H before using
2Reduction activation, reduction temperature are 750～900 ℃, and reduction temperature is 2～6 hours.Select this temperature range based on following two aspect reasons: the first, this temperature range is higher than the actual serviceability temperature of catalyst, avoids catalyst in use owing to the temperature reason causes crystal transfer, is conducive to obtain the high catalyst of stability; The second, reduction rear catalyst good dispersion is active high.The too high active component generation sintering that easily makes of reduction temperature causes catalytic activity to descend; Reduction temperature is low excessively, and then catalyst reduction is incomplete, activates not thoroughly, and catalytic activity also can descend.
A kind of flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen of the present invention, with discarded object-flyash of producing in the coal-fired station as catalyst carrier, this carrier has stability height, wide material sources, cheap characteristics, and this comprehensive utilization that is applied as the flyash of coal-fired station's generation provides the approach of a high-efficiency and economic.
A kind of flyash Preparation of catalysts method for catalyzing and reforming biologic oil to prepare hydrogen, be carrier with flyash, flyash itself is rich in alkali metal and alkali earth metals such as Ca, Mg, K and Na, can be used as catalyst promoter, therefore, in this Preparation of catalysts, do not need additionally to add catalyst promoter, make that preparation technology simplifies, cost descends.
Through the catalytic activity height, the long catalytic life that experiment showed, this catalyst of catalysis biological oil reforming hydrogen production, the conversion ratio of reactant bio oil is greater than 90%, and the hydrogen yield for preparing is greater than 85%.
Description of drawings
Fig. 1 is the XRD figure of the catalyst n i/Ash-15 of embodiment 1 preparation.
The specific embodiment
Embodiment 1
Get fine coal ash sample 1, it consists of: Al
2O
319.9%, SiO
244.5%, Fe
2O
39.9%, CaO18.1%, MgO3.3%, K
2O1.2%, Na
2O0.2%, TiO
21.3%, ZnO0.6%, CuO0.6%.Place Muffle furnace, rise to 815 ° of C with the heating rate of 10 ° of C/min, calcined 4 hours, the cooling back is taken out and is placed drying basin standby naturally.Get commercial nickel nitrate 7.5g, join in the 100mL deionized water, be stirred to nickel nitrate and all dissolve.Get the flyash after 10g calcines then, add in this nickel nitrate aqueous solution, continue to stir 6 hours, then suspension is stirred evaporate to dryness under 90 ° of C; The product of evaporate to dryness is put into drying box, dry 8 hours of 110 ° of C, last in Muffle furnace the heating rate with 10 ° of C/min rise to 815 ° of C, roasting 4 hours, cooling back taking-up naturally, the gained catalyst places drying basin standby.
This catalyst is designated as Ni/Ash-15, and its XRD figure sees Fig. 1, and wherein, the content of Ni is 15% of catalyst carrier quality.
Embodiment 2
Get fine coal ash sample 2, it consists of: Al
2O
325.1%, SiO
250.4%, Fe
2O
313.5%, CaO4.6%, MgO1.7%, K
2O1.6%, Na
2O0.4%, TiO
21.1%, ZnO0.8%, CuO0.8%.Place Muffle furnace, rise to 900 ° of C with the heating rate of 10 ° of C/min, calcined 2 hours, the cooling back is taken out and is placed drying basin standby naturally.Get commercial nickel nitrate 15g, join in the 200mL ethanol, be stirred to nickel nitrate and all dissolve.Get the flyash after 10g calcines then, add in the nickel nitrate ethanolic solution, continue to stir 12 hours, then suspension is stirred evaporate to dryness under 80 ° of C; The product of evaporate to dryness is put into drying box, dry 6 hours of 120 ° of C, last in Muffle furnace the heating rate with 15 ° of C/min rise to 900 ° of C, roasting 2 hours, cooling back taking-up naturally, the gained catalyst places drying basin standby.
This catalyst is designated as Ni/Ash-30, and wherein, the content of Ni is 30% of catalyst carrier quality.
Embodiment 3
Get fine coal ash sample 3, it consists of: Al
2O
316.3%, SiO
258.7%, Fe
2O
312.4%, CaO2.3%, MgO1.1%, K
2O4.8%, Na
2O0.6%, TiO
22.6%, ZnO0.2%, CuO1.0%.Place Muffle furnace to rise to 700 ° of C with the heating rate of 10 ° of C/min, calcined 6 hours, the cooling back is taken out and is placed drying basin standby naturally.Get commercial nickel nitrate 2.5g, join in the 50mL ethanol, be stirred to nickel nitrate and all dissolve.Get the flyash after 10g calcines then, add in the nickel nitrate ethanolic solution, continue to stir 2 hours, then suspension is stirred evaporate to dryness under 70 ° of C; The product of evaporate to dryness is put into drying box, dry 12 hours of 100 ° of C, last in Muffle furnace the heating rate with 5 ° of C/min rise to 700 ° of C, roasting 6 hours, cooling back taking-up naturally, the gained catalyst places drying basin standby.
This catalyst is designated as Ni/Ash-5, and wherein, the content of Ni is 5% of catalyst carrier quality.
Embodiment 4
Get fine coal ash sample 4, it consists of: Al
2O
311.2%, SiO
252.4%, Fe
2O
38.6%, CaO19.6%, MgO2.1%, K
2O3.5%, Na
2O0.7%, TiO
20.8%, ZnO0.5%, CuO0.6%.Place Muffle furnace to rise to 815 ° of C with the heating rate of 5 ° of C/min, calcined 5 hours, the cooling back is taken out and is placed drying basin standby naturally.Get commercial cobalt nitrate 7.4g, join in the 100mL deionized water, be stirred to cobalt nitrate and all dissolve.Get the flyash after 10g calcines then, add in the cobalt nitrate aqueous solution, continue to stir 10 hours, then suspension is stirred evaporate to dryness under 90 ° of C; The product of evaporate to dryness is put into drying box, dry 8 hours of 120 ° of C, last in Muffle furnace the heating rate with 10 ° of C/min rise to 815 ° of C, roasting 5 hours, cooling back taking-up naturally, the gained catalyst places drying basin standby.
This catalyst is designated as Co/Ash-15, and wherein, the content of Co is 15% of catalyst carrier quality.
Embodiment 5
Get fine coal ash sample 5, it consists of: Al
2O
328.4%, SiO
238.2%, Fe
2O
313.2%, CaO8.5%, MgO3.4%, K
2O4.3%, Na
2O0.5%, TiO
22.3%, ZnO0.4%, CuO0.8%.Place Muffle furnace to rise to 750 ° of C with the heating rate of 5 ° of C/min, calcined 3 hours, the cooling back is taken out and is placed drying basin standby naturally.Get commercial cobalt nitrate 14.8g, join in the 200mL deionized water, be stirred to cobalt nitrate and all dissolve.Get the flyash after 10g calcines then, add in the cobalt nitrate aqueous solution, continue to stir 8 hours, then suspension is stirred evaporate to dryness under 80 ° of C; The product of evaporate to dryness is put into drying box, dry 10 hours of 110 ° of C, last in Muffle furnace the heating rate with 5 ° of C/min rise to 750 ° of C, roasting 3 hours, cooling back taking-up naturally, the gained catalyst places drying basin standby.
This catalyst is designated as Co/Ash-30, and wherein, the content of Co is 30% of catalyst carrier quality.
Embodiment 6
Get fine coal ash sample 6, it consists of: Al
2O
316.5%, SiO
254.3%, Fe
2O
310.8%, CaO2.6%, MgO8.7%, K
2O3.9%, Na
2O0.4%, TiO
21.5%, ZnO0.3%, CuO1.0%.Place Muffle furnace to rise to 900 ° of C with the heating rate of 15 ° of C/min, calcined 2 hours, the cooling back is taken out and is placed drying basin standby naturally.Get commercial cobalt nitrate 2.5g, join in the 50mL ethanol, be stirred to cobalt nitrate and all dissolve.Get the flyash after 10g calcines then, add in the cobalt nitrate ethanolic solution, continue to stir 2 hours, then suspension is stirred evaporate to dryness under 75 ° of C; The product of evaporate to dryness is put into drying box, dry 8 hours of 120 ° of C, last in Muffle furnace the heating rate with 15 ° of C/min rise to 900 ° of C, roasting 2 hours, cooling back taking-up naturally, the gained catalyst places drying basin standby.
This catalyst is designated as Co/Ash-5, and wherein, the content of Co is 5% of catalyst carrier gross mass.
Performance test
The catalyst that embodiment 1～6 is prepared reduces in fixed bed reactors after (reduction temperature is 800 ℃, and the time is 3h), carries out the test of catalyzing and reforming biologic oil to prepare hydrogen reactive activity.Test process is as follows: be in the stainless steel fixed bed reactors of 8mm at internal diameter, the catalyst of 1g embodiment 1～6 preparation is fixed on the constant temperature zone of reactor with quartz sand, the reaction raw materials bio oil in the vaporizer of 300 ° of C, vaporize and with feed after water vapour mixes in the reactor, behind the successive reaction 5h, utilize gas chromatograph analytical gas product to form under the normal pressure.Reaction temperature, reaction raw materials mole when the charging air speed of raw material bio oil see Table 1, the conversion ratio of raw material bio oil, product H
2Productive rate and data such as catalyst one way life-span be shown in table 1.
Table 1
From last table result as can be known, catalyst provided by the invention is active high, and hydrogen yield is all greater than 85%, and the conversion ratio of feedstock oil is all greater than 90%, and the catalyst one way life-span all was longer than 24 hours.
Claims (6)
1. a flyash catalyst that is used for catalyzing and reforming biologic oil to prepare hydrogen comprises catalyst activity component and catalyst carrier, it is characterized in that described catalyst carrier is flyash; Described catalyst activity component is Ni or Co, and the catalyst activity components contents is 5～30% of catalyst carrier weight.
2. the flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen according to claim 1 is characterized in that, described catalyst carrier is the flyash that coal-fired station produces.
3. the flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen according to claim 2 is characterized in that, described flyash consist of Al
2O
310～35%, SiO
230～60%, Fe
2O
32～15%, CaO2～20%, MgO1～10%, K
2O0.5～5%, Na
2O0.1～2%, TiO
20.5～3%, ZnO0.3～1%, CuO0.2～1%.
4. the flyash Preparation of catalysts method for catalyzing and reforming biologic oil to prepare hydrogen according to claim 1 is characterized in that, comprises the steps:
(1) flyash was calcined 2～6 hours under 700～900 ° of C, obtained catalyst carrier;
(2) soluble-salt with nickel or cobalt is dissolved in the solvent, obtains nickel or cobalt salt solution; Described solvent is one or both of water or alcohols; The concentration of described nickel or cobalt salt solution is 0.05～1.5mol/L;
(3) add the catalyst carrier of step (1) gained in above-mentioned nickel or the cobalt salt solution, flood after 2～12 hours, stir evaporate to dryness and dry the processing again, obtain catalyst precursor A; Described stirring evaporate to dryness temperature is 70～100 ° of C; Described baking temperature is that 100～130 ° of C, drying time are 6～12 hours;
(4) with the catalyst precursor A of step (3) gained, under 700～900 ° of C, roasting obtained described flyash catalyst after 2～6 hours.
5. the flyash Preparation of catalysts method for catalyzing and reforming biologic oil to prepare hydrogen according to claim 4 is characterized in that the soluble-salt of the described nickel of step (2) or cobalt is halide, nitrate, oxalates or acetate.
6. the flyash Preparation of catalysts method for catalyzing and reforming biologic oil to prepare hydrogen according to claim 4 is characterized in that, the described alcohols of step (2) is one or more in ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, the isobutanol.
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