CN103272604B - 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 chemical industry synthesis field, particularly relate 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 the ratio of coal shared by China's energy-consuming is up to more than 70%, and its energy supply mainly passes through coal-fired station.Along with the fast development of national economy, the development of China's thermal power generation is in recent years 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.National Development and Reform Committee just newly revises issue " total utilization of PCA management method " and represents, encourages to carry out high added value and the utilization of large addition content to flyash.
Flyash is a kind of pozzolanic materials, is to produce under high-temperature fluidizedization state in coal-fired process, through Fast Heating, cools fast, forms the particle of compact structure, very stable to water under 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 mainly for the production of building materials (cement, concrete, mortar, brick and tile and haydite etc.), build the road on (embankment, roadbed, road surface) and backfill (structure backfill, building backfill, fill mine, tidal land).But current application makes the added value effect of flyash and not obvious, if can make full use of the Al be rich in flyash
2o
3, SiO
2, alkali and alkaline earth metal ions oxide, and the high-ratio surface sum high-temperature stability of flyash, it can be used as catalyst carrier, pass through infusion process again, by active constituent loading in this catalyst carrier, make highly active flyash catalyst, greatly will promote the using value of flyash, the new situation of developing utilization of fly ash.
Hydrogen Energy is considered to 21st century the most potential new forms of energy, is not only a kind of very important industrial chemicals, for the synthesis of ammonia, participates in hydrogenation reaction etc., and is a kind of very clean energy carrier, 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 a catalyst, is at high temperature obtained by reacting hydrogen by bio oil and water vapour, and is attended by the side reaction such as water gas reaction and CO shift reaction.Total reaction equation is as follows:
Wherein, raw material bio oil is the living beings (stalk, wood chip etc.) adopting stock number abundant is raw material, issues heat-dissipating cracking reaction, collect the liquid obtained after rapid condensation at anaerobic, medium temperature condition, and preparation process is simply efficient, with low cost.The technique core of catalyzing and reforming biologic oil to prepare hydrogen is catalyst, this catalyst is had to the requirement of two aspects, and one is to be decomposed by reactant efficiently, and two is can adsorb efficiently and decomposition water.W metal and Co can impel carbon-carbon bond and carbon-oxygen bond to rupture, and can be used for the decomposition of catalysis containing oxygen bio oil; Alkali and alkaline earth metal ions element K, Ca, Mg and Na can effectively promoting catalyst to the adsorption-decomposition function of water.Therefore, to prepare with Ni or Co for active component, be rich in the catalyst of the alkali metal and alkaline earth metals such as K, Ca, Mg, Na simultaneously, catalyzing and reforming biologic oil to prepare hydrogen tool is had very important significance.
In addition, because bio oil composition is complicated, oxygen content is high, in catalytic reforming process, catalyst is very easy to inactivation.There are some researches show, when bio oil carries out catalytically reforming hydrogen producing on fixed bed reactors, one way service life of catalyst is the longest is only 9 hours, and therefore, the catalyst obtaining longer one way service life is also current problem in the urgent need to address.
Summary of the invention
The invention provides a kind of flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen, discarded object-flyash that this catalyst produces with coal-fired station is for carrier, achieve the high value added utilization of flyash, and the catalyst of preparation has that catalytic activity is high, long catalytic life and advantage with low cost.
For a flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen, comprise catalyst activity component and catalyst carrier, described catalyst carrier is flyash; Described catalyst activity component is Ni or Co, and the content of catalyst activity component 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, for porous type alveolate texture, after high-temperature calcination, specific area is larger, there is higher adsorption activity, above-mentioned design feature makes it can use as the carrier of catalyst, not only with low cost, and achieves 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, there is splendid heat endurance and larger specific area, good catalyst carrier can be become.Alkalies and alkaline earth oxide CaO, MgO, K of containing in flyash
2o and Na
2o, can suppress catalyst surface carbon distribution, the life-span of extending catalyst on the one hand; The dispersion of active component can be promoted on the other hand, improve catalytic activity,
Can use as the auxiliary agent of catalyst.Therefore, the compositing characteristic of flyash itself, makes it both as catalyst carrier, can also play the effect of catalyst promoter simultaneously.
Present invention also offers a kind of preparation method of the flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen, comprise the steps:
(1) flyash is calcined 2 ~ 6 hours under 700 ~ 900 ° of C, obtain catalyst carrier (Ash);
(2) soluble-salt of nickel or cobalt is dissolved in 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) in above-mentioned nickel or cobalt salt solution, add the catalyst carrier of step (1) gained, flood 2 ~ 12 hours, then carry out stirring evaporate to dryness and dry process, obtain catalyst precursor A; Described stirring evaporate to dryness temperature is 70 ~ 100 ° of C; Described baking temperature is 100 ~ 130 ° of C, drying time is 6 ~ 12 hours;
(4) by the catalyst precursor A of step (3) gained, under 700 ~ 900 ° of C, roasting, after 2 ~ 6 hours, obtains described flyash catalyst.
Calcination processing is carried out to flyash, to remove the impurity of adsorption, and obtains stable catalyst carrier.Calcining heat is 700 ~ 900 ° of C, and activation effect is good, and calcining heat is interval to match with the interval of the actual serviceability temperature of catalyst and reforming reaction temperature.When calcining heat is more than 900 DEG C, activation effect is not obvious, even can weaken, and may be because the transformation of crystal formation at high temperature occurs flyash.
As preferably, the nickel described in step (2) or the soluble-salt of cobalt are 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 feature that dissolubility is good in water or ethanolic solution.
As preferably, the alcohols described in step (2) is one or more in ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, more preferably ethanol.Ethanol is the most frequently used organic solvent, and nickel or cobalt salt solubility is in ethanol large, and it is therefore as preferred.
Nickel described in step (2) or the concentration of cobalt salt solution are 0.05 ~ 1.5mol/L, the concentration of nickel or cobalt salt solution in above-mentioned scope, the activity of the catalyst of preparation and selective the 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 excessive, activity component load quantity is too high, then active component is not easily disperseed, and occur sinter run off problem, cause reactivity and selective decline; If nickel or cobalt salt solution concentration too small, activity component load quantity is too low, then activated centre number is not enough, does not reach best catalytic effect.
Dip time described in step (3) is 2 ~ 12 hours, and dip time is too short, then nickel or cobalt salt are difficult to dipping completely on flyash surface; Dip time is long, affects migration and the distribution of nickel or cobalt salt, and then affects its catalytic performance.
As preferably, the sintering temperature described in step (4) is 750 ~ 900 ° of C, and within the scope of this, after roasting, the decentralization of active component is high, then catalytic activity is high.When sintering temperature is higher than 900 DEG C, active component can be gathered and grows up, and reduces decentralization, causes catalytic activity to decline.If sintering temperature is lower than the actual serviceability temperature of catalyst, catalyst structure may be caused unstable, make catalyst in use crystal formation there is new change.
Roasting time described in step (4) is 2 ~ 6 hours, within the scope of this, and after roasting, the decentralization of active component is high, then catalytic activity is high.Long upon firing, then active component can sinter, and causes catalytic activity to decline; If roasting time is too short, then metallic salt decomposes not exclusively, and catalytic effect declines.
Described catalyst needs to use H before the use
2reduction activation, reduction temperature is 750 ~ 900 DEG C, and reduction temperature is 2 ~ 6 hours.Select this temperature range based on following two reasons: the first, this temperature range, higher than the actual serviceability temperature of catalyst, avoids catalyst in use because temperature reason causes crystal transfer, is conducive to obtaining the high catalyst of stability; The second, reduction rear catalyst good dispersion is active high.The too high active component that easily makes of reduction temperature sinters, and causes catalytic activity to decline; Reduction temperature is too low, then catalyst reduction is incomplete, and activation is not thorough, and catalytic activity also can decline.
A kind of flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen of the present invention, discarded object-the flyash produced in coal-fired station is as catalyst carrier, this carrier has that stability is high, wide material sources, cheap feature, and this comprehensive utilization being applied as the flyash that coal-fired station produces provides the approach of a high-efficiency and economic.
A kind of preparation method of the flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen, take flyash as carrier, flyash itself is rich in the alkali and alkaline earth metal ions elements such as Ca, Mg, K and Na, can as catalyst promoter, therefore, do not need additionally to add catalyst promoter in the preparation of this catalyst, preparation technology simplified, cost decline.
Experiment through catalysis biological oil reforming hydrogen production proves, the catalytic activity of this catalyst is high, long catalytic life, and the conversion ratio of reactant bio oil is greater than 90%, and the hydrogen yield prepared is greater than 85%.
Accompanying drawing explanation
Fig. 1 is the XRD figure of catalyst n i/Ash-15 prepared by embodiment 1.
Detailed description of the invention
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%.Be placed in Muffle furnace, rise to 815 ° of C with the heating rate of 10 ° of C/min, calcine 4 hours, naturally after cooling, take out that to be placed in drying basin for subsequent use.Get commercial nickel nitrate 7.5g, join in 100mL deionized water, be stirred to nickel nitrate and all dissolve.Then get the flyash after 10g calcining, add in this nickel nitrate aqueous solution, Keep agitation 6 hours, then stirs evaporate to dryness by suspension under 90 ° of C; The product of evaporate to dryness is put into drying box, and dry 8 hours of 110 ° of C, finally rise to 815 ° of C with the heating rate of 10 ° of C/min, roasting 4 hours in Muffle furnace, and taking-up after cooling naturally, it is for subsequent use that gained catalyst is placed in drying basin.
This catalyst is designated as Ni/Ash-15, and its XRD figure is shown in 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%.Be placed in Muffle furnace, rise to 900 ° of C with the heating rate of 10 ° of C/min, calcine 2 hours, naturally after cooling, take out that to be placed in drying basin for subsequent use.Get commercial nickel nitrate 15g, join in 200mL ethanol, be stirred to nickel nitrate and all dissolve.Then get the flyash after 10g calcining, add in nickel nitrate ethanolic solution, Keep agitation 12 hours, then stirs evaporate to dryness by suspension under 80 ° of C; The product of evaporate to dryness is put into drying box, and dry 6 hours of 120 ° of C, finally rise to 900 ° of C with the heating rate of 15 ° of C/min, roasting 2 hours in Muffle furnace, and taking-up after cooling naturally, it is for subsequent use that gained catalyst is placed in drying basin.
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%.Be placed in Muffle furnace and rise to 700 ° of C with the heating rate of 10 ° of C/min, calcine 6 hours, naturally after cooling, take out that to be placed in drying basin for subsequent use.Get commercial nickel nitrate 2.5g, join in 50mL ethanol, be stirred to nickel nitrate and all dissolve.Then get the flyash after 10g calcining, add in nickel nitrate ethanolic solution, Keep agitation 2 hours, then stirs evaporate to dryness by suspension under 70 ° of C; The product of evaporate to dryness is put into drying box, and dry 12 hours of 100 ° of C, finally rise to 700 ° of C with the heating rate of 5 ° of C/min, roasting 6 hours in Muffle furnace, and taking-up after cooling naturally, it is for subsequent use that gained catalyst is placed in drying basin.
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%.Be placed in Muffle furnace and rise to 815 ° of C with the heating rate of 5 ° of C/min, calcine 5 hours, naturally after cooling, take out that to be placed in drying basin for subsequent use.Get commercial cobalt nitrate 7.4g, join in 100mL deionized water, be stirred to cobalt nitrate and all dissolve.Then get the flyash after 10g calcining, add in cobalt nitrate aqueous solution, Keep agitation 10 hours, then stirs evaporate to dryness by suspension under 90 ° of C; The product of evaporate to dryness is put into drying box, and dry 8 hours of 120 ° of C, finally rise to 815 ° of C with the heating rate of 10 ° of C/min, roasting 5 hours in Muffle furnace, and taking-up after cooling naturally, it is for subsequent use that gained catalyst is placed in drying basin.
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%.Be placed in Muffle furnace and rise to 750 ° of C with the heating rate of 5 ° of C/min, calcine 3 hours, naturally after cooling, take out that to be placed in drying basin for subsequent use.Get commercial cobalt nitrate 14.8g, join in 200mL deionized water, be stirred to cobalt nitrate and all dissolve.Then get the flyash after 10g calcining, add in cobalt nitrate aqueous solution, Keep agitation 8 hours, then stirs evaporate to dryness by suspension under 80 ° of C; The product of evaporate to dryness is put into drying box, and dry 10 hours of 110 ° of C, finally rise to 750 ° of C with the heating rate of 5 ° of C/min, roasting 3 hours in Muffle furnace, and taking-up after cooling naturally, it is for subsequent use that gained catalyst is placed in drying basin.
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%.Be placed in Muffle furnace and rise to 900 ° of C with the heating rate of 15 ° of C/min, calcine 2 hours, naturally after cooling, take out that to be placed in drying basin for subsequent use.Get commercial cobalt nitrate 2.5g, join in 50mL ethanol, be stirred to cobalt nitrate and all dissolve.Then get the flyash after 10g calcining, add in cobalt nitrate ethanolic solution, Keep agitation 2 hours, then stirs evaporate to dryness by suspension under 75 ° of C; The product of evaporate to dryness is put into drying box, and dry 8 hours of 120 ° of C, finally rise to 900 ° of C with the heating rate of 15 ° of C/min, roasting 2 hours in Muffle furnace, and taking-up after cooling naturally, it is for subsequent use that gained catalyst is placed in drying basin.
This catalyst is designated as Co/Ash-5, and wherein, the content of Co is 5% of catalyst carrier gross mass.
Performance test
After catalyst embodiment 1 ~ 6 prepared reduces in fixed bed reactors (reduction temperature is 800 DEG C, and the time is 3h), carry out the active testing of catalyzing and reforming biologic oil to prepare hydrogen reaction.Test process is as follows: be in the stainless steel fixed bed reactors of 8mm at internal diameter, with quartz sand, catalyst prepared by 1g embodiment 1 ~ 6 is fixed on the constant temperature zone of reactor, reaction raw materials bio oil is vaporized and is passed into after mixing with water vapour in reactor in the vaporizer of 300 ° of C, under normal pressure after successive reaction 5h, chromatographic gaseous product is utilized to form.The Feed space velocities of reaction temperature, reaction raw materials mole when raw material bio oil in table 1, the conversion ratio of raw material bio oil, product H
2the data such as productive rate and catalyst single pass life be shown in table 1.
Table 1
From upper table result, catalyst activity provided by the invention is high, and hydrogen yield is all greater than 85%, and the conversion ratio of feedstock oil is all greater than 90%, and catalyst single pass life is all longer than 24 hours.
Claims (4)
1. for a flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen, comprise 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 content of catalyst activity component is 5 ~ 30% of catalyst carrier weight;
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%.
2. a preparation method for the flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen according to claim 1, is characterized in that, comprise the steps:
(1) flyash is calcined 2 ~ 6 hours at 700 ~ 900 DEG C, obtain catalyst carrier;
(2) soluble-salt of nickel or cobalt is dissolved in 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) in above-mentioned nickel or cobalt salt solution, add the catalyst carrier of step (1) gained, flood after 2 ~ 12 hours, then carry out stirring evaporate to dryness and dry process, obtain catalyst precursor A; Described stirring evaporate to dryness temperature is 70 ~ 100 DEG C; Described baking temperature is 100 ~ 130 DEG C, drying time is 6 ~ 12 hours;
(4) by the catalyst precursor A of step (3) gained, at 700 ~ 900 DEG C, roasting, after 2 ~ 6 hours, obtains described flyash catalyst.
3. the preparation method of the flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen according to claim 2, is characterized in that, the nickel described in step (2) or the soluble-salt of cobalt are halide, nitrate, oxalates or acetate.
4. the preparation method of the flyash catalyst for catalyzing and reforming biologic oil to prepare hydrogen according to claim 2, is characterized in that, the alcohols described in step (2) is one or more in ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol.
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| CN112427042B (en) * | 2020-11-20 | 2023-08-18 | 江苏海洋大学 | Modified fly ash biodiesel catalyst and preparation method and application thereof |
| CN113649005B (en) * | 2021-08-19 | 2022-07-22 | 华中科技大学 | Magnetic iron-rich component-supported nickel efficient catalyst and preparation method and application thereof |
| CN114797819B (en) * | 2022-03-29 | 2024-04-26 | 浙江科技学院 | Biomass-based Ni/SiO2-La2O3Catalyst, preparation method and application thereof |
| CN115709074A (en) * | 2022-11-07 | 2023-02-24 | 中国科学院山西煤炭化学研究所 | Preparation method of low-cost hydrogenation and olefin removal catalyst |
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