CN102974362A - Catalyst for hydrogen production by catalytic reforming with biological oil and preparation method - Google Patents
Catalyst for hydrogen production by catalytic reforming with biological oil and preparation method Download PDFInfo
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- CN102974362A CN102974362A CN2012105049161A CN201210504916A CN102974362A CN 102974362 A CN102974362 A CN 102974362A CN 2012105049161 A CN2012105049161 A CN 2012105049161A CN 201210504916 A CN201210504916 A CN 201210504916A CN 102974362 A CN102974362 A CN 102974362A
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Abstract
The invention relates to a catalyst for hydrogen production by catalytic reforming with biological oil and a preparation method. The catalyst comprises catalyst active components and a catalyst carrier; the catalyst active components refer to the following components in percentage by weight of 10-15 wt% of Ni, 5-13 wt% of Mo, 5-10 wt% of Fe and the balance being attapulgite and sepiolite mixed clay pit catalyst carrier. The catalyst provided by the invention has the advantages of large surface area, strong absorption function and strong promotion function; the cheap and easiest available attapulgite and sepiolite mixed clay pit are used as the catalyst carrier; and the catalyst active components comprise nickel, molybdenum and iron composite components, so that the molecules of the biological oil are subjected to splitting and chain scission to form high-quality synthesis gas of low-molecule hydrocarbon and high-content hydrogen. The catalyst provided by the invention has the advantages of simple catalyst preparation, large strength, strong catalyst activity, and regeneration. Not only can the catalyst be used for hydrogen production by catalytic reforming with the biological oil, but also the catalyst can be applied to direct hydrogen production by catalytic gasification with biomass.
Description
Technical field
The present invention relates to a kind of catalyzing and reforming biologic oil to prepare hydrogen Catalysts and its preparation method, namely prepare the method for the catalyst of high quality gas fuel with the catalyzing and reforming biologic oil to prepare hydrogen of biomass cracking.
Background technology
Utilize living beings to produce hydrogen and not only can effectively utilize abundant renewable resource, and be one of final effective way that solves the huge environmental pollution that global fossil fuel causes, China's fossil fuel resource shortage, biomass resource is very abundant, how cheap cleanly is biomass conversion the core drive-hydrogen fuel of following Hydrogen Energy society, great to China's Significance of Sustainable Development.Living beings high degree of dispersion, lower energy density have determined that the high process of collection cost of transportation is less economical, and biomass flash pyrolysis can make has the higher energy density bio oil, and then it can disperse to produce concentrates processing to process.Fast pyrolysis liquefaction technology is near industrialization at present, and bio oil is because its compositing characteristic can through water vapour catalytic reforming hydrogen making, be the new way that bio oil is utilized.
The research of bio-oil hydrogen making aspect mainly contains at present: development of new cracking hydrogen production reactor, research catalytic reforming condition and reformate, several aspects such as preparation, inactivation and regeneration research of exploration bio oil and model thing hydrogen production reaction rule thereof and reaction mechanism, catalyst.Domestic and international many scholar's research biological oil reforming hydrogen production rule and reformation primary condition, reforming temperature is all higher, generally 700
~800 ℃, too high temperature causes a large amount of generations of carbon distribution, is further raising catalytic effect, suppresses coking and generates, and research catalyzing and reforming biologic oil to prepare hydrogen catalyst is significant to raising hydrogen productive rate, inhibition coking.How to overcome the prior art defective, reduce energy consumption and production cost, remain the difficult problem in present living beings and the bio-oil hydrogen making process.
Attapulgite is that a kind of layer of chain contains Shuifu County's zeopan material, has specialty fibers shape crystal structure, and inner duct is abundant, the large (125～210m of specific area
2/ g), have good absorption, store and help catalysis.Sepiolite not only has high specific surface area, also has the molecular sieve analog characteristic, particularly its microcosmic skeleton is that the nanoscale doughnut forms " cage " structure, and the particularity of its structure has determined that it has sectional area is the tubulose penetrating via of 0.36m x 1.06nm and up to 900m
2The theoretical surface of/g is long-pending.Its 3 D stereo bond structure Si-O-Si key is pulled in thin chain together simultaneously, makes it have one to the special crystalline form that prolongs, and the open type ditch pivot that consists of in the structure is parallel with the crystal major axis, thereby the adsorption capacity of this ditch pivot is extremely strong.The sepiolite surfaces externally and internally is divided into three kinds of suction-operated centers: 1. main suction-operated center is and the hydrone of structural edge magnesium ion coordination that the water that is adsorbed forms with it hydrogen bond; 2. Si-OH ion cluster, it accepts the electricity price of a proton or alkyl compensate for residual, and this ion cluster and absorbate often form covalent bond; 3. the oxygen atom in the tetrahedral si-o film is given body a little less than it is electronics in the isomorphism replacement process.China has abundant attapulgite, sepiolite and rare earth resources, because the micro-pore diameter of attapulgite and sepiolite is different, its compound use can further be improved it to the adsorptive selectivity of gas with various composition.
The biomass flash pyrolysis technology can obtain very high liquid product yield at present, but the bio oil complicated components that produces, the directly easy coking of reformation hydrogen production, the productive rate of hydrogen is not high.In order to suppress coking, the research of biomass hydrogen preparation all is to carry out in two steps at present, be that the first step is carried out quick cracking to living beings, bio oil steam cooled off obtain thick oil, thick oil separated obtain water and oil phase part, the oil phase part can be made industrial chemicals, and aqueous portion can be used to reformation hydrogen production, and development low-cost, efficient, the easily reforming hydrogen-production catalyst of regeneration is with significant.
Summary of the invention
The present invention is the weak point that exists in order to solve existing biological oil reforming hydrogen production technology, provide a kind of expansion bio oil component that in the biological oil reforming process, plays to contact with composition metal, thereby the rate of gasification of the presoma of surperficial carbon deposit or charcoal is accelerated in the absorption that improves the catalyst surface water vapour, improve the catalyst of catalytic performance, the present invention provides the preparation method of this catalyst simultaneously.
Technical solution problem of the present invention adopts following scheme:
A kind of catalyst for the bio oil catalyzing manufacturing of hydrogen comprises catalyst activity composition and catalyst carrier, it is characterized in that, described catalyst activity composition and weight percentage are respectively: Ni is 10-15wt%; Mo is 5-13wt%; Fe is 5-10wt%; More than be divided into attapulgite and sepiolite mixing clay ore deposit catalyst carrier, described attapulgite and sepiolite mixing clay ore deposit mass ratio are 1:1.
As preferably, in the catalyst of the present invention, Ni is 15wt%; Mo is 12wt%; Fe is 15wt%.
A kind of method for preparing catalyst for the bio oil catalyzing manufacturing of hydrogen is characterized in that, carries out as follows:
(1) gets sepiolite and the former clay breeze of attapulgite with mass ratio 1:1, then add distilled water by quality (g)/volume ratio (ml) 100:50-70, stir 10min; The static upper strata suspension that pours out is got the intermediate layer suspension; Vacuum filtration intermediate layer suspension obtains solid filter cake after the filter, solid filter cake grinds 105 ℃ of lower oven dry; Get sepiolite and the former clay mixed-powder of attapulgite;
(2) soluble-salt with nickel, molybdenum and iron is dissolved in the water together, and the total concentration of soluble-salt is 0.05-1.5mol/l, and then the limit heating edge adds attapulgite and sepiolite mixed-powder, and 60 ℃ of constant temperature stir dipping 6h and become emulsion;
(3) to the emulsion of step (2), add simultaneously magnesium nitrate, softex kw, magnesium nitrate is as reinforcing agent, strengthen caking property, the content of magnesium nitrate accounts for the 5-10wt% of total emulsion weight, softex kw is as the surfactant templates compound, to increase active surface and active component decentralization, content accounts for the 0.1-1.0wt% of total emulsion weight, then add alkaline precipitating agent, regulate pH value to 8～12, through precipitation, washing, filtration, drying, moulding, roasting, namely get catalyst n i-Mo-Fe-clay ore;
Described nickel salt consumption is counted the 10-20wt% of catalyst n i-Mo-Fe-clay ore with the weight of nickel in the catalyst, described molybdenum salt consumption is counted the 5-20wt% of catalyst n i-Mo-Fe-clay ore with the weight of molybdenum in the catalyst, and described molysite consumption is counted the 5-15wt% of catalyst n i-Mo-Fe-clay ore with the weight of iron in the catalyst.
Described nickel, molybdenum and iron soluble-salt are selected from respectively following compound: nickel nitrate, ammonium molybdate, ferric nitrate, described alkaline precipitating agent is selected from ammoniacal liquor.
The sepiolite of gained and the former clay mixed-powder of attapulgite are with solid-to-liquid ratio (g/ml) 1:10 in the described step (1), in the salpeter solution of concentration 1.0-2.0 mol/L, soak 24-48h under 20 ℃ of conditions, use the deionized water cyclic washing, filter filter cake at 120 ℃ of temperature heat drying 4h, naturally grind after the cooling; To grind again powder 900 ℃ of lower calcinings 4-6 hour, then be crushed to below 120 orders.
Described roasting time is 2～6 hours, and sintering temperature is 600 ℃～900 ℃.
Compared with the prior art, beneficial effect of the present invention is embodied in:
The invention provides and realize in a kind of catalyzing and reforming biologic oil to prepare hydrogen process that bio oil is converted into the catalyst of high-quality combustible gas, compare with present catalytic reforming technology, be expected to obtain hydrogen content height, high-quality combustible gas that calorific value is high, improving biomass conversion is the economic technology performance of clean energy resource.Sepiolite and attapulgite original ore powder that catalyst carrier adopts, cheap and easy to get, reduce production costs.Add magnesium nitrate in the catalyst and strengthen cohesive force, softex kw increases active surface and active component decentralization, adopts molybdenum, nickel, ferrous metal as the catalyst activity composition, Effective Raise catalytic performance.
Below by being that embodiment is described further technical solution of the present invention.
The specific embodiment:
One, raw material preparation
The sepiolite (commercially available) and attapulgite original ore powder (commercially available) 50g that get mass ratio 1:1 add 120ml distilled water, stir 10min; The static upper strata suspension that pours out is got the intermediate layer suspension.Vacuum filtration intermediate layer suspension, solid filter cake grinds 105 ℃ of lower oven dry.Acid activation: with nitric acid (concentration 1.0-2.0 mol/L) activation, solid-to-liquid ratio (g/ml) 1:10 soaks 24-48h under 20 ℃ of conditions, uses the deionized water cyclic washing, filters filter cake at 120 ℃ of temperature heat drying 4h, naturally grinds after the cooling.
To grind powder 900 ℃ of lower calcinings 4-6 hour, and then be crushed to below 120 orders, the soluble-salt of a certain amount of nickel, molybdenum and iron is dissolved in respectively deionized water, the total concentration of soluble-salt is 0.05-1.5mol/l; Then the limit heating edge adds sepiolite and attapulgite mixing clay breeze end, and 60 ℃ of constant temperature stir dipping 6h and become emulsion.
Two, co-precipitation
Emulsion with above-mentioned acquisition, add again and add simultaneously magnesium nitrate, softex kw, magnesium nitrate is as reinforcing agent, strengthen caking property, the content of magnesium nitrate accounts for the 5-10wt% of total emulsion weight, softex kw is as the surfactant templates compound, and to increase active surface and active component decentralization, content accounts for the 0.1-1.0wt% of total emulsion weight; The nickel salt consumption is counted the 10-20wt% of catalyst n i-Mo-Fe-clay ore in the soluble-salt with the weight of nickel, molybdenum salt consumption is counted the 5-15wt% of catalyst n i-Mo-Fe-clay ore with the weight of molybdenum, and the molysite consumption is counted the 5-15wt% of catalyst n i-Mo-Fe-clay ore with the weight of iron.Then add alkaline precipitating agent ammoniacal liquor in mentioned solution, keeping pH is 8～12, and Precipitation left standstill 6 hours, the precipitation ageing.
Three, moulding, calcining
Behind suction filtration, obtain filter cake through washing, drying, with the shaping of catalyst device filter cake is depressed into 200MP, behind the shaping of catalyst, the general 2-4mm of particle diameter, then roasting is 4～6 hours, and sintering temperature is 600 ℃～900 ℃.The weight percentage of each catalytic active component and carrier is respectively: Ni is 10-20wt%; Mo is 5-15wt%; Fe is 5-15wt%; All the other are sepiolite and attapulgite mixing clay ore deposit catalyst carrier.
Embodiment 1
Take glycerine as bio oil model raw material, in the fixed bed reactors experiment of reforming, and adopt catalyst of the present invention that glycerine steam is carried out catalytic reforming it, feed rate is 1.8g/min, the catalytic reforming time is 30 minutes, collects gaseous product.Contain H in the gaseous product that under not having catalyst action, obtains
231.47%, CO22.52%, CH
410.32%, CO
2Be 35.69%, bio oil conversion ratio 89%.
Contain H in the gaseous product that under adopting catalyst action of the present invention, obtains
261.47%, CO27.52%, CH
43.34%, CO
2Be 17.67%, bio oil conversion ratio 95%.
Embodiment 2
Take acetic acid as bio oil model raw material, in the fixed bed reactors experiment of reforming, and adopt the catalyst of the inventive method preparation that acetic acid steam is carried out catalytic reforming it, feed rate is 1.8g/min, the catalytic reforming time is 30 minutes, collects gaseous product.Contain H in the gaseous product that under not having catalyst action, obtains
236.47%, CO23.52%, CH
46.33%, CO
2Be 33.68%, bio oil conversion ratio 87%.
Contain H in the gaseous product that under the catalyst action that adopts invention, obtains
265.23%, CO
23.12%, CH
41.24%, CO
2Be 10.41%, bio oil conversion ratio 97%.
Embodiment 3
Take the bio-oil phase component of the quick cracking of living beings Wheat Straw as raw material, with it in the fixed bed reactors experiment of reforming, and adopt the catalyst of the inventive method preparation that bio-oil phase component steam is carried out catalytic reforming, feed rate is 2.2g/min, the catalytic reforming time is 30 minutes, collects gaseous product.Contain H in the gaseous product that under not having catalyst action, obtains
221.47%, CO 25.43%, CH
414.32%, CO
2Be 38.78%, bio oil conversion ratio 85%.
Contain H in the gaseous product that under the catalyst action that adopts invention, obtains
267.5%, CO13.5%, CH
41.38%, CO
2Be 17.62%, bio oil conversion ratio 95%.
Claims (6)
1. a catalyst that is used for the bio oil catalyzing manufacturing of hydrogen comprises catalyst activity composition and catalyst carrier, and it is characterized in that described catalyst activity composition and weight percentage are respectively: Ni is 10-15wt%; Mo is 5-13wt%; Fe is 5-10wt%; More than be divided into attapulgite and sepiolite mixing clay ore deposit catalyst carrier, described attapulgite and sepiolite mixing clay ore deposit mass ratio are 1:1.
2. a kind of catalyst for the bio oil catalyzing manufacturing of hydrogen according to claim 1 is characterized in that, described Ni is 15wt%; Mo is 12wt%; Fe is 15wt%.
3. a method for preparing catalyst that is used for the bio oil catalyzing manufacturing of hydrogen is characterized in that, carries out as follows:
(1) gets sepiolite and the former clay breeze of attapulgite with mass ratio 1:1, then add distilled water by quality (g)/volume ratio (ml) 100:50-70, stir 10min; The static upper strata suspension that pours out is got the intermediate layer suspension; Vacuum filtration intermediate layer suspension obtains solid filter cake after the filter, solid filter cake grinds 105 ℃ of lower oven dry; Get sepiolite and the former clay mixed-powder of attapulgite;
(2) soluble-salt with nickel, molybdenum and iron is dissolved in the water together, and the total concentration of soluble-salt is 0.05-1.5mol/l, and then the limit heating edge adds attapulgite and sepiolite mixed-powder, and 60 ℃ of constant temperature stir dipping 6h and become emulsion;
(3) to the emulsion of step (2), add simultaneously magnesium nitrate, softex kw, magnesium nitrate is as reinforcing agent, strengthen caking property, the content of magnesium nitrate accounts for the 5-10wt% of total emulsion weight, softex kw is as the surfactant templates compound, to increase active surface and active component decentralization, content accounts for the 0.1-1.0wt% of total emulsion weight, then add alkaline precipitating agent, regulate pH value to 8～12, through precipitation, washing, filtration, drying, moulding, roasting, namely get catalyst n i-Mo-Fe-clay ore;
Described nickel salt consumption is counted the 10-20wt% of catalyst n i-Mo-Fe-clay ore with the weight of nickel in the catalyst, described molybdenum salt consumption is counted the 5-20wt% of catalyst n i-Mo-Fe-clay ore with the weight of molybdenum in the catalyst, and described molysite consumption is counted the 5-15wt% of catalyst n i-Mo-Fe-clay ore with the weight of iron in the catalyst.
4. a kind of method for preparing catalyst for the bio oil catalyzing manufacturing of hydrogen according to claim 3, it is characterized in that, described nickel, molybdenum and iron soluble-salt are selected from respectively following compound: nickel nitrate, ammonium molybdate, ferric nitrate, described alkaline precipitating agent is selected from ammoniacal liquor.
5. a kind of method for preparing catalyst for the bio oil catalyzing manufacturing of hydrogen according to claim 3, it is characterized in that, the sepiolite of gained and the former clay mixed-powder of attapulgite are with solid-to-liquid ratio (g/ml) 1:10 in the described step (1), in the salpeter solution of concentration 1.0-2.0 mol/L, soak 24-48h under 20 ℃ of conditions, use the deionized water cyclic washing, filter filter cake at 120 ℃ of temperature heat drying 4h, naturally grind after the cooling; To grind again powder 900 ℃ of lower calcinings 4-6 hour, then be crushed to below 120 orders.
6. a kind of method for preparing catalyst for the bio oil catalyzing manufacturing of hydrogen according to claim 3 is characterized in that, described roasting time is 2～6 hours, and sintering temperature is 600 ℃～900 ℃.
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|---|---|---|---|---|
| CN103272604A (en) * | 2013-05-24 | 2013-09-04 | 浙江大学 | Fly ash catalyst for hydrogen production implemented by catalytic reforming of bio-oil and preparation method of fly ash catalyst |
| CN105032421A (en) * | 2015-07-27 | 2015-11-11 | 常州大学 | Preparation method of attapulgite-supported Cu-ZrO2 catalyst and application of attapulgite-supported Cu-ZrO2 catalyst to methanol steam reforming for hydrogen production |
| CN105363450A (en) * | 2014-09-01 | 2016-03-02 | 中科合成油技术有限公司 | Hydro-liquefied iron-based catalyst containing carbon materials and preparation method and application of hydro-liquefied iron-based catalyst |
| CN105396579A (en) * | 2015-12-22 | 2016-03-16 | 盐城工学院 | Fire coal flue gas denitration demercuration catalyst and preparation method and application thereof |
| CN105947979A (en) * | 2016-04-28 | 2016-09-21 | 中国科学院广州能源研究所 | Hydrogen production method by reforming methanol-glycerol in cooperation with water vapor, and catalyst applied to hydrogen production method |
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| CN116371416A (en) * | 2023-04-03 | 2023-07-04 | 安徽理工大学 | Nickel-niobium/attapulgite-based ordered mesoporous catalyst and preparation method and application thereof |
| CN116371416B (en) * | 2023-04-03 | 2024-05-03 | 安徽理工大学 | Nickel-niobium/attapulgite-based ordered mesoporous catalyst and preparation method and application thereof |
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