CN101757919B - Integral catalyst applied to biological oil reforming hydrogen production, preparation and application thereof - Google Patents
Integral catalyst applied to biological oil reforming hydrogen production, preparation and application thereof Download PDFInfo
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Abstract
The invention provides an integral catalyst for biological oil steam reforming hydrogen production, which has high reaction activity, strong carbon deposition resistance and good stability, and further provides a preparation method and application thereof. The catalyst consists of a carrier and an active component and comprises the following components by weight percentage: 5-20wt percent of active component nickel oxide, 0-5wt percent of alkali metal auxiliary agent, 0-5wt percent of metal auxiliary agent and the balance of integral ceramic carrier with the surface coated with 1-5 percent of Gamma-Al2O3. The integral catalyst is applied to biological oil reforming hydrogen production and has the characteristics of simple preparation method, easy control of conditions and good catalyst repeatability. Compared with the common granular type catalyst, the integral catalyst has the characteristics of more even heating, less mass transfer resistance, has higher activity to reaction, strong carbon deposition resistance and good stability, and greatly improves the biological oil conversion rate, hydrogen yield and catalyst service life.
Description
Technical field
The present invention relates to the bio-oil hydrogen making technology, be specifically related to a kind of integral catalyst that is applied to hydrogen production by bio-oil steam reforming.
Technical background
Hydrogen more and more receives people's attention as efficient, clean secondary energy sources, and in many industries, has obtained extensive use.Expand to the use in the civilian industry field, particularly fuel cell of today from the aerospace field in past,, also promoted the extensive attention of people more Hydrogen Energy for the efficient and clean utilization of Hydrogen Energy has brought good economic outlook and environment-friendly advantage.Utilizing regenerative resource such as living beings to produce hydrogen, have special meaning for nervous problem of the energy supply and demand of alleviating growing tension and problem of environmental pollution, is one of approach of very attractive and development prospect.
Utilizing one of relatively more popular technology of biomass hydrogen preparation at present is hydrogen production by bio-oil steam reforming.This comes from recent years people and produces the technical realization of bio oil at biomass flash pyrolysis and break through, and makes the commercialization abroad of having produced of bio oil.Therefore, biological oil reforming hydrogen production is considered to one of most economical route of realizing living beings mass preparation hydrogen, and application prospect is very wide.Yet people still are in the starting stage to the theoretical research and the technological development of biological oil reforming hydrogen production process.Particularly the research to the biological oil reforming hydrogen production catalyst still has a large amount of exploration spaces.
At present, it is main being adapted to the main nickel-base catalyst of biological oil reforming hydrogen production catalyst.The Wang of Chornet seminar just once carried out the biological oil reforming hydrogen production experiment to nine kinds of different commercial nickel-base catalysts.He finds to use commercial nickel-base catalyst, realizes that the productive rate of bio-oil hydrogen making can reach about 70% (Czernik, S; French, R; Feik, C; Chornet; E, Hydrogen by catalytic steam reforming of liquid byproducts from biomass thermoconversion processes, Industrial & engineering chemistry research; 2002,41 (17): 4209-4215).Noble metal catalyst also obtains exploitation in recent years gradually in the research of bio-oil steam reformation, be master (Takanabe, K with Pt, Rh, Ru etc. mainly; Aika, K; Seshan, K; Lefferts; L; Steam reforming of acetic acid as a biomass derived oxygenate:Bifunctionalpathway for hydrogen formation over Pt/ZrO2 catalysts; Journal of catalysis, 2006,243 (2): 263-269).Experiment finds that reaction has good catalytic activity to noble metal catalyst to the bio-oil steam reformation hydrogen production, and follows double-function catalyzing mechanism, and promptly active noble metals and carrier are all participated in reaction.Recently, there is the researcher to find again, these noble metals are loaded on on the integral catalyst; Also can have good catalytic effect (Marcelo Eduardo Dominea, Eduard Emil Iojoiua, Thomas Davidiana to the vapor reforming hydrogen production of bio oil; Nolven Guilhaume; ClaudeMirodatos, Hydrogen production from biomass-derived oil over monolithic Pt-and Rh-basedcatalysts using steam reforming and sequential cracking processes, Catalysis Today; 2008,133-135:565-573).
We can say that the noble metal catalyst activity is good, carbon deposition rate is low, but its cost an arm and a leg, reserves are limited, can't satisfy the requirement of industrial catalyst large-scale production.And non-precious metal catalysts such as existing nickel still exist poor stability, are prone to carbon distribution, are prone to shortcoming such as inactivation, big limitations its actual industrial applications.In view of above situation; The bio oil steam reformation hydrogen production catalyst of the active height of exploitation, good stability, further investigation its preparation method, catalytic mechanism, and Stability Analysis of Structures mechanism etc.; Have important theory and using value, will lay the foundation for the industrial applications of biomass hydrogen preparation.
Summary of the invention
The object of the present invention is to provide that a kind of reactivity is high, carbon accumulation resisting ability is strong, the hydrogen production by bio-oil steam reforming integral catalyst of good stability.This catalyst can be used for fixed bed reactors, and flow resistance is little, good stability, and the active component utilization rate is high.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
A further object of the invention provides the purposes of above-mentioned catalyst applications in biological oil reforming hydrogen production.
For realizing above-mentioned purpose, the technical scheme below the present invention has taked:
A kind of integral catalyst that is applied to hydrogen production by bio-oil steam reforming, calculate by mass percentage by following one-tenth and be grouped into: the precious metal additive of the active component nickel of 5～20wt%, the metal promoter of 0～5wt%, 0～5wt%, all the other are the γ-Al of surface-coated carrier mass percent 1～5%
2O
3The monolithic devices ceramic monolith.
The mass percent of monolithic devices ceramic monolith can be at 70～95wt%.
Said metal promoter is one or more a auxiliary agent of potassium, magnesium, calcium, lanthanum, cerium; Said precious metal additive is one or more a auxiliary agent of ruthenium, rhodium, platinum, palladium, silver.
Preparation method's following steps of integral catalyst of the present invention:
One, the preparation of carrier:
1) specific area is about 0.5～5m
2The ceramic monolith of/g like cylindric porous ceramics of cordierite multichannel or foamed ceramics, puts into that to naturally cool to room temperature after the Muffle furnace roasting subsequent use, obtains carrier A;
2) with average grain diameter be γ-Al of 100～600nm
2O
3, deionized water and surface dispersant mix by 15～60% solid content, batch mixing is prepared into suspension on ball mill, grinds evenly; With above-mentioned suspension carrier A is flooded, applied then, make γ-Al
2O
3Mass percentage content reaches 1～5%, and then oven dry, roasting can be prepared biological oil reforming hydrogen production integral catalyst carrier B.
Two, Preparation of catalysts:
3) alkali metal promoter of selecting for use and precious metal additive are made into corresponding soluble-salt solution C.
4) mix with C by the aqueous solution of aforementioned catalyst proportion of composing the Ni-based salt of solubility; After stirring; Prepared catalyst carrier B is immersed in the mixed solution, after ultrasonic concussion, aging, the oven dry, roasting; In hydrogen atmosphere, reduce again, make the hydrogen production by bio-oil steam reforming integral catalyst.
Raw material bio oil involved in the present invention is the biomass cracked oil by using that various renewable biomass obtain through quick cracking.Said living beings comprise crops production and processing waste, production of forestry and processing waste, rubbish.
Hydrogen production by bio-oil steam reforming of the present invention reaction is under normal pressure, is raw material with the bio-oil solution of water molar equivalent 1～9, and feeding temperature is 180～250 ℃, reacts under the condition that reaction temperature is 300～850 ℃.
Catalyst involved in the present invention should be warming up to 400～600 ℃ under nitrogen atmosphere before reaction, at first heat half an hour; Close nitrogen, feed hydrogen again, in 400～600 ℃; Reductase 12 hour is controlled at 300～850 ℃ with reaction temperature then, close hydrogen after; After being heated to 180～250 ℃, arrive beds.
Main innovation part of the present invention is aforementioned integer catalyzer is applied to biological oil reforming hydrogen production, and this is a prior art an open question still.Compared with prior art, the present invention has following beneficial effect:
1. integral catalyst of the present invention has the network structure of three-dimensional UNICOM, compares with plain particles type catalyst, has characteristics such as more even heating, resistance to mass tranfer be littler.
2. apply one deck γ-Al2O3 at ceramic surface, can effectively increase the specific area of carrier, improve single loading capability of carrier.Catalyst of the present invention adopts direct dipping process to make, and the preparation method is simple, and condition is controlled easily, the good reproducibility of catalyst.
3. catalyst of the present invention is higher to reactive activity, carbon accumulation resisting ability is strong, good stability, improved bio oil conversion ratio, hydrogen manufacturing productive rate and catalyst service life greatly.
The specific embodiment
Below specify the present invention through specific embodiment.
The concrete preparation technology of catalyst is in following examples:
1) specific area is about 0.5～5m
2Cylindric porous ceramics of cordierite multichannel or the foamed ceramics of/g, putting into Muffle furnace, to naturally cool to room temperature after 4～8 hours in 500～600 ℃ of roastings subsequent use, obtains carrier A;
2) with average grain diameter be γ-Al of 100～600nm
2O
3, deionized water and surface dispersant mix by 15～60% solid content, batch mixing is prepared into suspension on ball mill, grinds 40 hours; With above-mentioned suspension carrier A is flooded, applied then, make γ-Al
2O
3Mass percentage content reaches 1～5%, then places baking oven 120 ℃ of oven dry 8～12 hours, again 400～800 ℃ of roastings 6～10 hours, can prepare biological oil reforming hydrogen production integral catalyst carrier B.
Two, Preparation of catalysts:
3) alkali metal promoter of selecting for use and precious metal additive are made into corresponding soluble-salt solution C.
4) mix with C by the aqueous solution of aforementioned catalyst proportion of composing the Ni-based salt of solubility; After stirring, prepared catalyst carrier B is immersed in the mixed solution ultrasonic concussion, aging 24 hours; And through 120 ℃ the oven dry 8～12 hours after; In 500～800 ℃ of roastings 6～10 hours, 400～600 ℃ of following reductase 12～4 hour in hydrogen atmosphere made the hydrogen production by bio-oil steam reforming integral catalyst again.
Embodiment 1 monoblock type Ni Preparation of catalysts
With commercially available cellular ceramic substrate, specification is φ 15 * 30mm, and hole density is 300 hole/square inches, and specific area is 1.0m
2/ g, it is subsequent use in Muffle furnace, to naturally cool to room temperature after 6 hours in 600 ℃ of roastings.γ-Al2O3, deionized water and the polyethylene glycol that average grain diameter is respectively 100nm mixes by 30% solid content, and batch mixing is prepared into suspension on ball mill, grinds 40 hours.Then ready cellular ceramic substrate is repeatedly flooded, make its surface can evenly apply the γ-Al of one deck 5%
2O
3, then being placed in the baking oven 120 ℃, oven dry in 8 hours again 600 ℃ of roastings 6 hours, can be prepared biological oil reforming hydrogen production integral catalyst carrier.With nickel content is that the nickel nitrate of catalyst quality 20% is dissolved in deionized water; The integral catalyst carrier that incipient impregnation makes; Ultrasonic concussion 30 minutes, aging 24 hours, 110 ℃ of dryings, 600 ℃ of roasting 6h; 400 times reduction 4 hours in hydrogen atmosphere again make the monoblock type Ni catalyst that is used for hydrogen production by bio-oil steam reforming reaction.
Embodiment 2 monoblock type Ni-Pt Preparation of catalysts
With commercially available foamed ceramic carrier, specification is φ 15 * 20mm, and hole density is 350 hole/square inches, and specific area is 5.0m
2/ g, it is subsequent use in Muffle furnace, to naturally cool to room temperature after 6 hours in 600 ℃ of roastings.Average grain diameter is respectively γ-Al of 600nm
2O
3, deionized water and polyethylene glycol mix by 15% solid content, batch mixing is prepared into suspension on ball mill, grinds 40 hours.Then ready foamed ceramic carrier is repeatedly flooded, make its surface can evenly apply the γ-Al of one deck 3%
2O
3, then being placed in the baking oven 120 ℃, oven dry in 8 hours again 600 ℃ of roastings 6 hours, can be prepared biological oil reforming hydrogen production integral catalyst carrier.With Ni content is the deionized water that the nickel nitrate of catalyst quality 5% and platinum nitrate that Pt content is catalyst quality 2% are dissolved in metering; The integral catalyst carrier that incipient impregnation makes; Ultrasonic concussion 30 minutes, aging 24 hours, 110 ℃ of dryings, 600 ℃ of roasting 6h; 400 times reduction 4 hours in hydrogen atmosphere again make the monoblock type Ni-Pt catalyst that is used for hydrogen production by bio-oil steam reforming reaction.
Embodiment 3 monoblock type Ni-Mg Preparation of catalysts
With commercially available cordierite ceramic carrier, specification is φ 15 * 20mm, and hole density is 200 hole/square inches, and specific area is 0.5m
2/ g, it is subsequent use in Muffle furnace, to naturally cool to room temperature after 6 hours in 600 ℃ of roastings.Average grain diameter is respectively γ-Al of 300nm
2O
3, deionized water and polyethylene glycol mix by 50% solid content, batch mixing is prepared into suspension on ball mill, grinds 40 hours.Then ready cordierite carrier is repeatedly flooded, make its surface can evenly apply the γ-Al of one deck 3%
2O
3, then being placed in the baking oven 120 ℃, oven dry in 8 hours again 600 ℃ of roastings 6 hours, can be prepared biological oil reforming hydrogen production integral catalyst carrier.With Ni content is the deionized water that the nickel nitrate of catalyst quality 10% and magnesium nitrate that Ce content is catalyst quality 5% are dissolved in metering; The integral catalyst carrier that incipient impregnation makes; Ultrasonic concussion 30 minutes, aging 24 hours, 110 ℃ of dryings, 600 ℃ of roasting 6h; 400 times reduction 4 hours in hydrogen atmosphere again make the monoblock type Ni-Mg catalyst that is used for hydrogen production by bio-oil steam reforming reaction.
Embodiment 4 monoblock type Ni-Pd-Ce Preparation of catalysts
With commercially available cellular ceramic substrate, specification is φ 15 * 10mm, and hole density is 250 hole/square inches, and specific area is 1.5m
2/ g, it is subsequent use in Muffle furnace, to naturally cool to room temperature after 6 hours in 600 ℃ of roastings.Average grain diameter is respectively γ-Al of 300nm
2O
3, deionized water and polyethylene glycol mix by 15% solid content, batch mixing is prepared into suspension on ball mill, grinds 40 hours.Then ready cellular ceramic substrate is repeatedly flooded, make its surface can evenly apply the γ-Al of one deck 1%
2O
3, then being placed in the baking oven 120 ℃, oven dry in 8 hours again 600 ℃ of roastings 6 hours, can be prepared biological oil reforming hydrogen production integral catalyst carrier.The cerous nitrate that Ni content is the nickel nitrate of catalyst quality 10%, palladium nitrate that Pd content is catalyst quality 3%, Ce content is catalyst quality 3% is dissolved in the deionized water of metering; The integral catalyst carrier that incipient impregnation makes; Ultrasonic concussion 30 minutes, aging 24 hours, 110 ℃ of dryings, 600 ℃ of roasting 6h; 400 times reduction 4 hours in hydrogen atmosphere again make the monoblock type Ni-Pd-Ce catalyst that is used for hydrogen production by bio-oil steam reforming reaction.
Embodiment 5 monoblock type Ni-Ag-La Preparation of catalysts
With commercially available cellular ceramic substrate, specification is φ 15 * 30mm, and hole density is 300 hole/square inches, and specific area is 1.0m
2/ g, it is subsequent use in Muffle furnace, to naturally cool to room temperature after 6 hours in 600 ℃ of roastings.γ-Al2O3, deionized water and the polyethylene glycol that average grain diameter is respectively 300nm mixes by 30% solid content, and batch mixing is prepared into suspension on ball mill, grinds 40 hours.Then ready cellular ceramic substrate is repeatedly flooded, make its surface can evenly apply the γ-Al of one deck 2%
2O
3, then being placed in the baking oven 120 ℃, oven dry in 8 hours again 600 ℃ of roastings 6 hours, can be prepared biological oil reforming hydrogen production integral catalyst carrier.With nickel content is that the nickel nitrate of catalyst quality 10%, the silver nitrate that Ag content is catalyst quality 5%, the lanthanum nitrate that La content is catalyst quality 3% are dissolved in deionized water; The integral catalyst carrier that incipient impregnation makes; Ultrasonic concussion 30 minutes, aging 24 hours, 110 ℃ of dryings, 600 ℃ of roasting 6h; 400 times reduction 4 hours in hydrogen atmosphere again make the monoblock type Ni-Ag-La catalyst that is used for hydrogen production by bio-oil steam reforming reaction.
Embodiment 6 monoblock type Ni-Rh-K Preparation of catalysts
With commercially available cellular ceramic substrate, specification is φ 15 * 30mm, and hole density is 300 hole/square inches, and specific area is 1.0m
2/ g, it is subsequent use in Muffle furnace, to naturally cool to room temperature after 6 hours in 600 ℃ of roastings.γ-Al2O3, deionized water and the polyethylene glycol that average grain diameter is respectively 300nm mixes by 30% solid content, and batch mixing is prepared into suspension on ball mill, grinds 40 hours.Then ready cellular ceramic substrate is repeatedly flooded, make its surface can evenly apply the γ-Al of one deck 2%
2O
3, then being placed in the baking oven 120 ℃, oven dry in 8 hours again 600 ℃ of roastings 6 hours, can be prepared biological oil reforming hydrogen production integral catalyst carrier.With nickel content is that the nickel nitrate of catalyst quality 10%, the radium chloride that Rh content is catalyst quality 3%, the potassium nitrate that K content is catalyst quality 5% are dissolved in deionized water; The integral catalyst carrier that incipient impregnation makes; Ultrasonic concussion 30 minutes, aging 24 hours, 110 ℃ of dryings, 600 ℃ of roasting 6h; 400 times reduction 4 hours in hydrogen atmosphere again make the monoblock type Ni-Rh-K catalyst that is used for hydrogen production by bio-oil steam reforming reaction.
Embodiment 7 monoblock type Ni-Ru-Ca Preparation of catalysts
With commercially available cellular ceramic substrate, specification is φ 15 * 30mm, and hole density is 300 hole/square inches, and specific area is 1.0m
2/ g, it is subsequent use in Muffle furnace, to naturally cool to room temperature after 6 hours in 600 ℃ of roastings.γ-Al2O3, deionized water and the polyethylene glycol that average grain diameter is respectively 300nm mixes by 30% solid content, and batch mixing is prepared into suspension on ball mill, grinds 40 hours.Then ready cellular ceramic substrate is repeatedly flooded, make its surface can evenly apply the γ-Al of one deck 2%
2O
3, then being placed in the baking oven 120 ℃, oven dry in 8 hours again 600 ℃ of roastings 6 hours, can be prepared biological oil reforming hydrogen production integral catalyst carrier.With nickel content is that the nickel nitrate of catalyst quality 10%, the ruthenic chloride that Ru content is catalyst quality 5%, the calcium nitrate that Ca content is catalyst quality 5% are dissolved in deionized water; The integral catalyst carrier that incipient impregnation makes; Ultrasonic concussion 30 minutes, aging 24 hours, 110 ℃ of dryings, 600 ℃ of roasting 6h; 400 times reduction 4 hours in hydrogen atmosphere again make the monoblock type Ni-Ru-Ca catalyst that is used for hydrogen production by bio-oil steam reforming reaction.
The evaluating catalyst method for preparing among each embodiment is: gets the 5g catalyst and puts into the quartz ampoule that diameter is 10mm, under N2 atmosphere, be warming up to 400 ℃, at first heat half an hour, close nitrogen, feed hydrogen again, and in 400 ℃, reductase 12 hour.Close hydrogen, the feeding flow is 4.0ml/min, is preheating to the bio-oil solution after 180 ℃, and its water molar equivalent is 4: 1, and the reaction temperature of beds is controlled at 550～850 ℃.Reacted product is through the gas-chromatography sample analysis.The hydrogen manufacturing result is as shown in table 1.
Hydrogen productive rate Y is expressed as formula:
Table 1: catalyst and hydrogen production by bio-oil steam reforming result
Claims (3)
1. integral catalyst that is applied to biological oil reforming hydrogen production; Be made up of carrier and active component, it is characterized in that: said catalyst is calculated by mass percentage by following one-tenth and is grouped into: the precious metal additive of the active component nickel oxide of 5～20wt%, the metal promoter of 0～5wt%, 0～5wt%, all the other are the γ-Al of surface-coated carrier mass percent 1～5%
2O
3The monolithic devices ceramic monolith; Said metal promoter is selected from one or more auxiliary agent of potassium, magnesium, calcium, lanthanum, cerium; Said precious metal additive is selected from one or more auxiliary agent of ruthenium, rhodium, platinum, palladium, silver; Said ceramic monolith is the cylindric porous ceramics of cordierite multichannel.
2. the described preparation method who is applied to the integral catalyst of biological oil reforming hydrogen production of claim 1 is characterized in that may further comprise the steps:
1) be 0.5～5m with specific area
2The ceramic monolith of/g puts into that to naturally cool to room temperature after the Muffle furnace roasting subsequent use, obtains carrier A;
2) with average grain diameter be γ-Al of 100～600nm
2O
3, deionized water and surface dispersant mix by 15～60% solid content, batch mixing is prepared into suspension on ball mill, grinds evenly; With above-mentioned suspension carrier A is flooded, applied then, make γ-Al
2O
3Mass percentage content reaches 1～5%, and then oven dry, roasting can be prepared biological oil reforming hydrogen production integral catalyst carrier B;
3) metal promoter of selecting for use and precious metal additive are made into corresponding soluble-salt solution C;
4) mix with C by the aqueous solution of aforementioned catalyst proportion of composing the Ni-based salt of solubility; After stirring; Prepared catalyst carrier B is immersed in the mixed solution, after ultrasonic concussion, aging, the oven dry, roasting; In hydrogen atmosphere, reduce again, make the hydrogen production by bio-oil steam reforming integral catalyst.
3. the described integral catalyst of claim 1 is applied to the purposes of biological oil reforming hydrogen production.
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| CN102513110A (en) * | 2011-11-18 | 2012-06-27 | 中国科学院宁波材料技术与工程研究所 | Integral type catalyst for reforming reaction of water vapor of natural gas as well as preparation method and use method thereof |
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| CN106422557A (en) * | 2016-11-01 | 2017-02-22 | 大唐环境产业集团股份有限公司 | Filter element for removing biomass gasification tar, filter system and method |
| CN106807387B (en) * | 2017-01-17 | 2019-06-25 | 陕西师范大学 | A kind of bifunctional catalyst and preparation method thereof for absorption enhancement hydrogen production by bio-oil steam reforming |
| 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 |
| CN108554418B (en) * | 2017-12-12 | 2020-10-30 | 宁波大学 | Ni-B-La catalyst for hydrogen production by catalytic reforming of bio-oil and preparation method thereof |
| CN116850988A (en) * | 2019-04-19 | 2023-10-10 | 中国石油化工股份有限公司 | Method for preparing hydrogen by alcohol liquid phase reforming |
| CN113289630B (en) * | 2021-05-19 | 2022-11-22 | 哈尔滨工业大学（深圳） | Catalyst for diesel reforming reaction, preparation method thereof, hydrogen production reformer and system |
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