CN102974362B - 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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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, with the catalyzing and reforming biologic oil to prepare hydrogen of biomass cracking, prepare the method for the catalyst of high quality gas fuel.
Background technology
Utilize living beings to produce hydrogen and not only can effectively utilize abundant renewable resource, and be one of effective way of the huge environmental pollution that finally the global fossil fuel of solution causes, China's fossil fuel resource shortage, biomass resource is very abundant, how cheap is cleanly the core drive-hydrogen fuel of following Hydrogen Energy society biomass conversion, 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 higher energy density bio oil, and then it can disperse to produce concentrates processing to process.Fast pyrolysis liquefaction technology has approached 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 prior art defect, reduce energy consumption and production cost, remain the difficult problem in current living beings and 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), there is good absorption, store and help catalysis.Sepiolite not only has high specific surface area, also there is molecular sieve analog characteristic, particularly its microcosmic skeleton is that 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 extending, and the open type ditch pivot forming in structure is parallel with crystal major axis, thereby the adsorption capacity of this ditch pivot is extremely strong.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 being 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 tetrahedral si-o film, gives body a little less than it is electronics in 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 to its adsorptive selectivity to gas with various composition.
Biomass flash pyrolysis technology can obtain very high liquid product yield at present, but the bio oil complicated components producing, 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 is all to carry out in two steps at present, be that the first step is carried out quick cracking to living beings, bio oil steam is carried out to the cooling thick oil that obtains, thick oil is carried out to separation and obtain water and oil phase part, 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 by significant.
Summary of the invention
The present invention is the weak point existing in order to solve existing biological oil reforming hydrogen production technology, provide a kind of expansion bio oil component that plays in biological oil reforming process 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 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:
For a catalyst for bio oil catalyzing manufacturing of hydrogen, comprise 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 catalyst of the present invention, Ni is 15wt%; Mo is 12wt%; Fe is 15wt%.
A method for preparing catalyst for bio oil catalyzing manufacturing of hydrogen, is characterized in that, carries out as follows:
(1) with mass ratio 1:1, get sepiolite and the former clay breeze of attapulgite, then by quality (g)/volume ratio (ml) 100:50-70, add distilled water, stir 10min; The static upper strata suspension that pours out, gets intermediate layer suspension; Vacuum filtration intermediate layer suspension, obtains solid filter cake after filter, solid filter cake is dried grinding at 105 ℃; Obtain sepiolite and the former clay mixed-powder of attapulgite;
(2) together with the soluble-salt of nickel, molybdenum and iron, be dissolved in the water, the total concentration of soluble-salt is 0.05-1.5mol/l, and then 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 magnesium nitrate, softex kw simultaneously, 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 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, filter, be dried, moulding, roasting, obtain 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 catalyst, described molybdenum salt consumption is counted the 5-20wt% of catalyst n i-Mo-Fe-clay ore with the weight of molybdenum in catalyst, described molysite consumption is counted the 5-15wt% of catalyst n i-Mo-Fe-clay ore with the weight of iron in 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.
In described step (1), the sepiolite of gained and the former clay mixed-powder of attapulgite are with solid-to-liquid ratio (g/ml) 1:10, under 20 ℃ of conditions, in the salpeter solution of concentration 1.0-2.0 mol/L, soak 24-48h, use deionized water cyclic washing, filter filter cake in 120 ℃ of temperature heat drying 4h, naturally cooling rear grinding; To grind again powder and calcine 4-6 hour at 900 ℃, 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 in a kind of catalyzing and reforming biologic oil to prepare hydrogen process and realize the catalyst that bio oil is converted into high-quality combustible gas, compare with current catalytic reforming technology, be expected to obtain the high-quality combustible gas that hydrogen content is high, calorific value is high, the economic technology performance that raising biomass conversion is clean energy resource.Sepiolite and attapulgite original ore powder that catalyst carrier adopts, cheap and easy to get, reduce production costs.In catalyst, add magnesium nitrate to strengthen cohesive force, softex kw increases active surface and active component decentralization, adopts molybdenum, nickel, ferrous metal as catalyst activity composition, has effectively improved 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, gets intermediate layer suspension.Vacuum filtration intermediate layer suspension, solid filter cake is dried grinding at 105 ℃.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 deionized water cyclic washing, filters filter cake in 120 ℃ of temperature heat drying 4h, naturally cooling rear grinding.
To grind powder and calcine 4-6 hour at 900 ℃, and then be crushed to below 120 orders, the soluble-salt of a certain amount of nickel, molybdenum and iron is dissolved in respectively to deionized water, the total concentration of soluble-salt is 0.05-1.5mol/l; Then 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
By the emulsion of above-mentioned acquisition, add again and add magnesium nitrate, softex kw simultaneously, 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 surfactant templates compound, and to increase active surface and active component decentralization, content accounts for the 0.1-1.0wt% of total emulsion weight; In soluble-salt, nickel salt consumption is counted the 10-20wt% of catalyst n i-Mo-Fe-clay ore 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, molysite consumption is counted the 5-15wt% of catalyst n i-Mo-Fe-clay ore with the weight of iron.Then in above-mentioned solution, add alkaline precipitating agent ammoniacal liquor, keeping pH is 8～12, Precipitation, standing 6 hours, precipitation ageing.
Three, moulding, calcining
After suction filtration, obtain filter cake through washing, dry, with shaping of catalyst device, filter cake is depressed into 200MP, after 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 to carry out catalytic reforming to glycerine steam it, feed rate is 1.8g/min, and the catalytic reforming time is 30 minutes, collects gaseous product.In the gaseous product obtaining, contain H under there is no catalyst action
231.47%, CO22.52%, CH
410.32%, CO
2be 35.69%, bio oil conversion ratio 89%.
In the gaseous product obtaining, contain H under adopting catalyst action of the present invention
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 catalyst prepared by the inventive method to carry out catalytic reforming to acetic acid steam it, feed rate is 1.8g/min, the catalytic reforming time is 30 minutes, collects gaseous product.In the gaseous product obtaining, contain H under there is no catalyst action
236.47%, CO23.52%, CH
46.33%, CO
2be 33.68%, bio oil conversion ratio 87%.
In the gaseous product obtaining, contain H under adopting the catalyst action of invention
265.23%, CO
23.12%, CH
41.24%, CO
2be 10.41%, bio oil conversion ratio 97%.
Embodiment 3
The bio-oil phase component of the quick cracking of living beings Wheat Straw of take is raw material, by it in the fixed bed reactors experiment of reforming, and adopt catalyst prepared by the inventive method to carry out catalytic reforming to bio-oil phase component steam, feed rate is 2.2g/min, the catalytic reforming time is 30 minutes, collects gaseous product.In the gaseous product obtaining, contain H under there is no catalyst action
221.47%, CO 25.43%, CH
414.32%, CO
2be 38.78%, bio oil conversion ratio 85%.
In the gaseous product obtaining, contain H under adopting the catalyst action of invention
267.5%, CO13.5%, CH
41.38%, CO
2be 17.62%, bio oil conversion ratio 95%.
Claims (5)
1. for a catalyst for bio oil catalyzing manufacturing of hydrogen, comprise 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.
2. for a method for preparing catalyst for bio oil catalyzing manufacturing of hydrogen, it is characterized in that, carry out as follows:
(1) with mass ratio 1:1, get sepiolite and the former clay breeze of attapulgite, then by mass/volume ratio=100g:50-70ml, add distilled water, stir 10min; Standing, pour out upper strata suspension, get intermediate layer suspension; Vacuum filtration intermediate layer suspension, obtains solid filter cake after filter, solid filter cake is dried grinding at 105 ℃; Obtain sepiolite and the former clay mixed-powder of attapulgite;
(2) together with the soluble-salt of nickel, molybdenum and iron, be dissolved in the water, the total concentration of soluble-salt is 0.05-1.5mol/l, and then 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 magnesium nitrate, softex kw simultaneously, 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 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, filter, be dried, moulding, roasting, obtain 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 catalyst, described molybdenum salt consumption is counted the 5-20wt% of catalyst n i-Mo-Fe-clay ore with the weight of molybdenum in catalyst, described molysite consumption is counted the 5-15wt% of catalyst n i-Mo-Fe-clay ore with the weight of iron in catalyst.
3. a kind of method for preparing catalyst for bio oil catalyzing manufacturing of hydrogen according to claim 2, 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.
4. a kind of method for preparing catalyst for bio oil catalyzing manufacturing of hydrogen according to claim 2, it is characterized in that, in described step (1), the sepiolite of gained and the former clay mixed-powder of attapulgite are with solid-to-liquid ratio=1g:10ml, under 20 ℃ of conditions, in the salpeter solution of concentration 1.0-2.0mol/L, soak 24-48h, use deionized water cyclic washing, filter filter cake in 120 ℃ of temperature heat drying 4h, naturally cooling rear grinding; To grind again powder and calcine 4-6 hour at 900 ℃, then be crushed to below 120 orders.
5. a kind of method for preparing catalyst for bio oil catalyzing manufacturing of hydrogen according to claim 2, is characterized in that, in described step (3) calcination steps, roasting time is 2～6 hours, and sintering temperature is 600 ℃～900 ℃.
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| CN103272604B (en) * | 2013-05-24 | 2015-06-17 | 浙江大学 | Fly ash catalyst for hydrogen production implemented by catalytic reforming of bio-oil and preparation method of fly ash catalyst |
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| CN106853372A (en) * | 2015-12-16 | 2017-06-16 | 中国科学技术大学 | A kind of nickel-base catalyst and the method that hydrogen is prepared using bio oil |
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| CN105947979B (en) * | 2016-04-28 | 2017-10-27 | 中国科学院广州能源研究所 | A kind of methanol glycerol collaboration vapor reforming hydrogen production method and the catalyst for the hydrogen production process |
| CN106064089B (en) * | 2016-06-02 | 2018-12-25 | 安徽理工大学 | A kind of Regenrable catalyzed and preparation method thereof for catalyzing and reforming biologic oil hydrogen manufacturing |
| CN109513443A (en) * | 2017-09-19 | 2019-03-26 | 侯飞燕 | A kind of support type bio-oil reforming hydrogen-production catalyst and preparation method thereof |
| CN108187683A (en) * | 2018-01-12 | 2018-06-22 | 安徽理工大学 | Nickel-copper catalyst of attapulgite load that a kind of calcium oxide is modified and its preparation method and application |
| CN111054364B (en) * | 2018-10-16 | 2023-04-18 | 中国石油化工股份有限公司 | Nickel series alkylation raw material selective hydrogenation catalyst and preparation method thereof |
| CN109847759B (en) * | 2019-01-16 | 2022-03-29 | 安徽理工大学 | Cobalt-cerium/sepiolite catalyst and preparation method and application thereof |
| CN114100616B (en) * | 2020-08-31 | 2023-10-20 | 中国石油化工股份有限公司 | Hydrocarbon steam conversion catalyst and its preparation method |
| CN114308042B (en) * | 2022-01-04 | 2023-11-21 | 安徽理工大学 | Attapulgite-based ordered microporous zeolite catalyst and preparation method and application thereof |
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