CN110252362A - A kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification - Google Patents

A kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification Download PDF

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CN110252362A
CN110252362A CN201910475865.6A CN201910475865A CN110252362A CN 110252362 A CN110252362 A CN 110252362A CN 201910475865 A CN201910475865 A CN 201910475865A CN 110252362 A CN110252362 A CN 110252362A
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catalyst
nickel
tungsten carbide
biological oil
surface modification
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刘庆
杨洪远
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Shandong University of Science and Technology
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
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    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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Abstract

The present invention relates to energy catalytic fields, in particular it relates to a kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification.The catalyst is using tungsten carbide as carrier, nickel oxide is as active component, using porous inorganic oxide as modification agent, active component is supported on carrier using excessive infusion process, modification agent is then deposited on by catalyst surface using deposition-precipitation method and is modified.The mass percent of the catalyst components are as follows: nickel oxide is 5-50%, and inorganic oxide modification agent is 5-40%, and surplus is tungsten carbide carrier.The catalyst that the present invention obtains is simple with catalyst preparation, high mechanical strength, catalytic activity are high, the advantage that anti-carbon, anti-sintering property are strong, low in cost, the high-temperature biological oil reforming reaction system being particularly suitable for.

Description

A kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification
Technical field
The present invention relates to energy catalytic fields, in particular it relates to which a kind of Tungsten Carbides nickel of surface modification is raw Object oil reforming catalyst.
Background technique
Hydrogen is ideal energy carrier, only generates water in burning and does not generate any pollutant, with traditional energy substance It is high-efficient compared to thermal transition, convey many outstanding advantages such as at low cost, be for fuel cell and internal combustion engine ideal it is clear Clean fuel.However, environmental pollution can not only be brought by extracting hydrogen from fossil fuel, but also the deposit of fossil fuel is consuming nearly To the greatest extent.Renewable and clean energy resource-biomass energy is developed, to Chinese Energy restructuring, reduces greenhouse gas emission, protecting ecology Environment will play a great role.However, the high dispersion of biomass and lower energy density determine its high transport at Sheet and economic feasibility, and the bio oil as made from biomass flash pyrolysis is a kind of raw material with higher energy density, It can be easier to dispersion and produce, and then concentrate hydrogen making, and be waste hydrogen using bio oil mentions as the utilization of bio oil A new approach is supplied.
Bio-oil hydrogen making technology have the hydrogen manufacturing of bio oil thermal cracking, bio oil water phase reformation hydrogen production, bio oil hydrogen preparation under a supercritical condition, Several approach of bio oil steam reformation hydrogen production.The hydrogen manufacturing of bio oil thermal cracking generally carries out at high temperature, and energy consumption is high, and catalyst is easily tied Coke, hydrogen yield and purity is not high；Bio oil water phase reformation hydrogen production and bio oil hydrogen preparation under a supercritical condition are mainly for cellulose, half fiber Dimension element carbohydrate as made from hydrolysis converts hydrogen manufacturing, and the bad control of reaction condition, operating cost is higher, and energy transformation ratio is lower； Hydrogen-enriched fuel gas can be made in the case where gasifying medium water vapour, air, oxygen participate in bio oil, reformed, separation can hydrogen making. Bio oil steam reformation hydrogen production has scale, stable, control simplicity, heats easy feature, is biomass system of realizing The preferred method of hydrogen.
Research in terms of bio oil steam reformation hydrogen production is concentrated mainly on exploitation new hydrogen production reactor, studies catalytic reforming Bio oil and its model object hydrogen production reaction rule and reaction mechanism, the preparation of catalyst, mistake are explored in condition and reformate distribution Living and regeneration research etc..Wherein, the exploitation of reforming catalyst is its crucial and core component.The reaction is highly endothermic anti- It answers, high temperature is conducive to going on smoothly for reaction, but high temperature can make reforming catalyst be sintered and lose activity.Further, since raw Object oil reforming reaction itself is easy to make catalyst because carbon distribution inactivates, and the anti-carbon performance and high temperature resistance of catalyst will be direct Influence the service life of catalyst.Therefore, it develops that a kind of catalytic activity is high, and is capable of the catalysis of long-term stable work at high temperature Agent is one of the key factor of bio oil steam reformation hydrogen production technique.
Although having compared both at home and abroad about the research of reforming catalyst more, some problems are still remained.Noble metal Good catalyst activity, carbon deposition rate are low, but it is expensive, reserves are limited, are unable to satisfy wanting for industrial catalyst large-scale production It asks.And the non-precious metal catalysts such as existing nickel, however it remains the disadvantages of stability is poor, easy carbon distribution, easy in inactivation, limit significantly Its actual industrial applications.In view of the above circumstances, the bio oil steam reformation hydrogen production catalysis that exploitation activity is high, stability is good Agent, further investigation preparation method, catalytic mechanism and stable structure mechanism etc., has important theory and application value, will It lays the foundation for the industrial applications of biomass hydrogen preparation.
In tungsten carbide, carbon atom is embedded in the gap of tungsten metal lattice, does not destroy the lattice of original metal, forms calking Solid solution, the i.e. carbon atom of small volume occupy a kind of compound that the gap of tungsten atom closs packing layer is formed.This material tool There are unique physics and chemical property, i.e., with the high rigidity of covalent compound, and the high-melting-point with ionic compound, also have There is the electric conductivity of transition metal.Tungsten carbide is the important source material for preparing hard alloy, while its characteristic electron with eka-platinium, is A kind of potential anode of fuel cell cathode material catalyst, but there has been no the application reports for being applied to biological oil reforming field It leads.It is obvious as catalyst carrier defect since the specific surface area of tungsten carbide is smaller, it is weaker with the active force of active specy.With Porous oxide such as Al2O3、SiO2、ZrO2、TiO2After modification, its drawbacks described above can be made up, better catalysis is obtained Active and higher stability.These features provide possibility for the application of high-temperature biological oil vapour reforming catalyst.
Summary of the invention
The present invention uses high mechanical strength, thermal stability are good, pyroconductivity is high tungsten carbide for carrier, in conjunction with porous, inorganic The surface modification technology of oxide prepares a kind of high reactivity, anti-sintering, anti-carbon biological oil reforming catalyst.Not only mention The high activity and stability of catalyst, and tungsten carbide has been widened in the application of catalytic field.
Based on this, one of the objects of the present invention is to provide a kind of Tungsten Carbides nickel biological oil reformings of surface modification to urge Agent.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification, the catalyst include active component, carrier and Modification agent, wherein the active component is nickel oxide；Carrier is tungsten carbide；Modification agent is porous inorganic oxide.
Preferably, with the content meter of oxide, the gross mass of catalyst is 100%, and each component accounts for the hundred of total catalyst weight Divide ratio are as follows: active component nickel oxide is 5-50%, and modification agent is 5-40%, and surplus is carrier tungsten carbide.
The Tungsten Carbides nickel biological oil reforming catalyst of a kind of surface modification of the invention, using with excellent machinery Intensive properties and the tungsten carbide of pyroconductivity are carrier, can be improved the heating conduction of catalyst, to improve catalyst in high temperature Tolerance when reaction.Modification agent is scattered between active component Ni particle or is covered on Ni particle, can play pair The physical barrier of active specy acts on, the generation of carbon distribution when inhibiting metallic particles reunion at high temperature and sintering and reaction.
The second object of the present invention is to provide the preparation method of above-mentioned catalyst.
A kind of preparation method of the Tungsten Carbides nickel biological oil reforming catalyst of surface modification of the present invention, including with Lower step:
(1) pretreatment of tungsten carbide carrier:
Tungsten carbide particle is crushed using ball mill, is ground to nanoscale by (1-1), and range scale is 200-500 nm；
Tungsten carbide after grinding is carried out pickling by (1-2), then filters, is dry.
Preferably, the acid is HCl, HNO3Or in acetic acid any one or at least two mixture.
Preferably, the concentration of the acid is 0.5-2.0 mol/L.
Preferably, the number of the pickling is at least once.
Preferably, the pickling time is 6-24 h.
(2) preparation of catalyst:
The soluble nickel salt of calculation amount is dissolved in a certain amount of ethyl alcohol by (2-1), until completely dissolved, is added in step (1-2) Obtained nanometer tungsten carbide, is stirred overnight at room temperature.Then the solvent in water bath method said mixture, sufficiently after drying, In inert atmosphere, 400-600oNiO/WC sample is made after roasting 2-6 h under C, it is spare after grinding.
Preferably, the soluble nickel salt is appointing in nickel acetate, nickel acetylacetonate, nickel sulfate, nickel nitrate or nickel chloride It anticipates a kind of or at least two mixtures.
Preferably, the concentration of the soluble nickel salt ethanol solution is 0.1-2.0 mol/L.
Preferably, the load capacity of the soluble nickel salt is 5-50%.
Preferably, the maturing temperature is 400-600oC, calcining time are 2-6 h.
Preferably, the inertia calcination atmosphere is nitrogen or argon gas.
(2-2) disperses the resulting NiO/WC sample of step (2-1) in high purity water, and ultrasound 10-30 minutes is heated to 30–80 oC uses the pH value of precipitating reagent regulation system to obtain the dispersion liquid of NiO/WC for 6-11.
Presoma needed for modification agent is configured to solution according to the practical composition of catalyst by (2-3), with precipitating Agent solution cocurrent is added in the resulting NiO/WC dispersion liquid of step (2-2), precipitating reagent is added dropwise, and adjustment and control system pH value is 7- 11,2-6 h are aged, catalyst precarsor suspension is obtained.
Preferably, raw material needed for modification agent be selected from containing silicon, aluminium, the ester of zirconium, nitrate, chloride, acetate, Silicate or sulfate, concentration are 0.1-2.0 mol/L.
Preferably, the precipitating reagent is NH3·H2O、(NH4)2CO3、K2CO3, NaOH and urea aqueous solution in it is any It is a kind of or at least two combination, concentration be 0.1-2.0 mol/L.
Catalyst precarsor suspension obtained by step (2-3) is filtered, washed, is dried, gained powder is 350-650 by (2-4)o2-6 h are roasted under C in inert atmosphere, obtain the Tungsten Carbides nickel biological oil reforming catalyst of surface modification.
Preferably, the inertia calcination atmosphere is nitrogen or argon gas.
Compared with prior art, the invention has the following advantages:
The present invention is used as biological oil reforming hydrogen production catalyst carrier using tungsten carbide, and carries out sequent surface modification, prepares Catalyst has that high mechanical strength, thermal conductivity be good, pore-size distribution concentrates that adjustable, catalytic activity is high, stability is good, anti-sintering and The features such as anti-carbon performance is strong is evenly distributed especially in high temperature reformation catalysis reaction with bed temperature, is not easy temperature runaway, produces The advantages that object is selectively high.
Detailed description of the invention
Fig. 1 is a kind of nanometer tungsten carbide of the Tungsten Carbides nickel biological oil reforming catalyst of surface modification in embodiment 1 A kind of Tungsten Carbides nickel biological oil reforming catalyst 10N/WC@SiO of surface modification in WC, 10N/WC-1 and embodiment 22 XRD spectra；
Fig. 2 is a kind of Tungsten Carbides nickel biological oil reforming catalyst 10N/WC@SiO of surface modification in embodiment 22Times magnification Number is schemed for 6000 TEM；
Fig. 3 is a kind of Tungsten Carbides nickel biological oil reforming catalyst 10N/WC@Al of surface modification in embodiment 42O3XRD Spectrogram.
Specific embodiment
Technical solution of the present invention is described further below by way of being embodiment, but the present invention is not limited to following implementation Example.
Embodiment 1
The pretreatment of tungsten carbide carrier:
1) that tungsten carbide particle is ground to 500 nm is spare；
2) the above-mentioned nanometer tungsten carbide of 10 g is placed in beaker, the HNO of 20 mL 2mol/L is added3Aqueous solution is stirred at room temperature 24 h, supernatant pour into waste liquid bottle；Adding ion water washing to cleaning solution is neutrality, then by gained sample in 80oC baking oven Dry 24 h or more, storage are good spare.
The preparation of catalyst:
By 2.91 g Ni (NO3)2·6H2O is dissolved in 5 mL ethyl alcohol, until completely dissolved, the above-mentioned nano-sized carbon of 6.72 g is added Change tungsten, is stirred overnight at room temperature, heating water bath to 70oC solvent evaporated, 100oAfter C drying, gained sample is 600 in nitrogen atmosphereo6 h are roasted under C, and 10NiO/WC catalyst is made.This sample is in H2600 in atmosphereoC reductase 12 h, obtained catalyst label For 10N/WC-1.
Embodiment 2
The preparation of 10NiO/WC-1 is the same as embodiment 1.
The preparation of catalyst:
10NiO/WC-1 is fully ground in the round-bottomed flask for being placed on 50 mL deionized waters, heating water bath to 80oC, and prepare The ethanol solution of 0.1 mol/L ethyl orthosilicate and the ammonium carbonate solution of 0.1 mol/L, then above two solution cocurrent It is added drop-wise in round-bottomed flask, uses pH meter real-time detection pH value during being added dropwise, by its pH control 11 or so, after being aged 6 h, take out Filter washing to pH be neutrality, by obtained sample in 100oC dries 24 h.Gained sample is 650 in nitrogen atmosphereoIt is roasted under C 5 h, heating rate 2oC/min, then in H2600 in atmosphereoC reductase 12 h, obtained catalyst are labeled as 10N/WC@SiO2。
Above-mentioned sample is subjected to XRD survey on Dutch Panalytical company X ' Pert PRO MPD type X-ray diffractometer Examination.
Fig. 1 give in embodiment 1 pretreated tungsten carbide carrier and preparation 10N/WC sample and embodiment 2 Middle 10N/WC@SiO2The XRD spectra of sample.In three samples, the characteristic diffraction peak of tungsten carbide illustrates urging there is no variation Tungsten carbide keeps stablizing in agent preparation and reduction process.10N/WC@SiO2Gold Samples belong to Ni diffraction maximum significantly less than 10N/WC sample, facilitate to reduce Ni crystallite dimension after explanation silica modification, improves its dispersibility.
Fig. 2 is 10N/WC@SiO in embodiment 22The TEM image of sample, it is seen that the Ni particle size of this method preparation is small And it is uniform, modification agent is also uniformly dispersed in around carrier.
Embodiment 3
The pretreatment of tungsten carbide carrier:
1) that tungsten carbide particle is ground to 200 nm is spare；
2) the above-mentioned nanometer tungsten carbide of 10 g is placed in beaker, the HCL aqueous solution of 20 mL0.2mol/L is added, is stirred at room temperature 24 h, supernatant pour into waste liquid bottle；Adding ion water washing to cleaning solution is neutrality, then by gained sample in 80oC baking oven Dry 24 h or more, storage are good spare.
The preparation of catalyst:
By 2.91 g Ni (NO3)2·6H2O is dissolved in 100 mL ethyl alcohol, until completely dissolved, the above-mentioned nanometer of 0.75 g is added Tungsten carbide is stirred overnight at room temperature, heating water bath to 70oC solvent evaporated, 100oAfter C drying, gained sample is in nitrogen atmosphere 400 o2 h are roasted under C, and 50NiO/WC catalyst is made.
50NiO/WC is fully ground in the round-bottomed flask for being placed on 50 mL deionized waters, heating water bath to 30oC, and match The ethanol solution of 2.0 mol/L zirconium-n-butylates and the ammonium carbonate solution of 2.0 mol/L are made, then above-mentioned three kinds of solution cocurrents It is added drop-wise in round-bottomed flask, uses pH meter real-time detection pH value during being added dropwise, by its pH control 7 or so, after being aged 2 h, take out Filter washing to pH be neutrality, by obtained sample in 100oC dries 24 h.Gained sample is 350 in argon atmosphereoIt is roasted under C 2 h, heating rate 2oC/min, then in H2600 in atmosphereoC reductase 12 h, obtained catalyst are labeled as 50N/WC@ZrO2。
Embodiment 4
The pretreatment of tungsten carbide carrier:
1) that tungsten carbide particle is ground to 300 nm is spare；
2) the above-mentioned nanometer tungsten carbide of 10 g is placed in beaker, the acetic acid aqueous solution of 20 mL1.0 mol/L is added, room temperature is stirred 24 h are mixed, supernatant pours into waste liquid bottle；Adding ion water washing to cleaning solution is neutrality, then by gained sample in 80oC dries Case dries 24 h or more, and storage is good spare.
The preparation of catalyst:
By 2.91 g Ni (NO3)2·6H2O is dissolved in 5 mL ethyl alcohol, until completely dissolved, the above-mentioned nano-sized carbon of 6.72 g is added Change tungsten, is stirred overnight at room temperature, heating water bath to 70oC solvent evaporated, 100oAfter C drying, gained sample is 500 in nitrogen atmosphereo4 h are roasted under C, and 10NiO/WC-2 catalyst is made.
10NiO/WC-2 is fully ground in the round-bottomed flask for being placed on 50 mL deionized waters, heating water bath to 60oC, and Prepare 1.0 mol/L aluminum nitrate aqueous solutions and the K of 0.1 mol/L2CO3Aqueous solution, then above two solution cocurrent is added drop-wise to In round-bottomed flask, pH meter real-time detection pH value is used during being added dropwise, by its pH control in 8 or so, after being aged 4 h, filtering and washing It is neutrality to pH, by obtained sample in 100oC dries 24 h.Gained sample is 500 in nitrogen atmosphereo4 h are roasted under C, are risen Warm rate 2oC/min, then in H2600 in atmosphereoC reductase 12 h, obtained catalyst are labeled as 10N/WC@Al2O3。
Fig. 3 is 4 gained catalyst 10N/WC@Al of embodiment2O3The XRD spectra of sample, it is seen that after aluminium oxide modification, Ni crystallite dimension is equally smaller, dispersibility with higher.
Catalytic performance test
Catalytic performance test is carried out to embodiment 1,2,3,4.Analogies of the acetic acid as biomass cracked oil are chosen, second is had studied Steam reformation behavior of the acid on above-mentioned catalyst.Using fixed bed reactors, the charging of acetic acid and water is injected by two respectively Pump control, waterfront economy is first passed through steam generator and enters back into reactor after penetrating pump, so that acetic acid is sufficiently reacted with water, reaction temperature It is fixed as 600oC。
Table 1 is the conversion ratio for catalyst CO in methanation reaction that embodiment 1,2,3,4 obtains.
Serial number Acetic acid conversion (%) H2Yield (%)
Embodiment 1 80 40
Embodiment 2 98 50
Embodiment 3 100 55
Embodiment 4 95 51
Seen from table 1, the Ni-based reforming catalyst activity of the load of pure WC prepared by embodiment 1 is poor.
Seen from table 1, using silica as the 10N/WC@SiO of modifying agent prepared by embodiment 22Reforming catalyst activity It is significantly higher than unmodified catalyst, acetic acid conversion 98%, hydrogen yield is 50%.
Seen from table 1, using zirconium oxide as the 10N/WC@ZrO of modifying agent prepared by embodiment 32Reforming catalyst activity Higher, acetic acid conversion is up to 100%, and hydrogen yield is 55%.
Seen from table 1, using aluminium oxide as the 10N/WC@Al of modifying agent prepared by embodiment 32O3Reforming catalyst activity Equally higher than unmodified catalyst, for acetic acid conversion up to 95%, hydrogen yield is 51%.
As described above, the Ni-based biological oil reforming catalyst of the Tungsten Carbides of surface modification proposed by the present invention is with higher Activity, have a good application prospect in industrial application.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent defines.

Claims (5)

1. a kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification, including catalyst active component, catalyst carry Body and modification agent.
2. a kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification according to claim 1, feature exist In the catalyst active component is nickel oxide；The catalyst carrier is tungsten carbide；The modification agent is porous, inorganic Oxide；Wherein, the weight percentage of catalyst active component nickel oxide is respectively 5-50%, inorganic oxide modification Agent is 5-40%, remaining to be divided into tungsten carbide carrier.
3. a kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification, which is characterized in that carry out as follows:
(1) pretreatment of tungsten carbide carrier:
Tungsten carbide is crushed using ball mill, is ground to nanoscale by (1-1), and range scale is 200-500 nm；
Tungsten carbide after grinding is carried out pickling by (1-2), is then filtered, washed, is dried；
(2) preparation of catalyst:
The soluble nickel salt of calculation amount is dissolved in a certain amount of ethyl alcohol by (2-1), until completely dissolved, is added in step (1-2) Obtained nanometer tungsten carbide, is stirred overnight at room temperature, then the solvent in water bath method said mixture, sufficiently after drying, In inert atmosphere, 400-600oNiO/WC sample is made after roasting 2-6 h under C, it is spare after grinding；
(2-2) disperses the resulting NiO/WC sample of step (2-1) in high purity water, and ultrasound 10-30 minutes is heated to 30-80oC uses the pH value of precipitating reagent regulation system to obtain the dispersion liquid of NiO/WC for 6-11；
Presoma needed for modification agent is configured to solution according to the practical composition of catalyst by (2-3), molten with precipitating reagent Liquid cocurrent is added in the resulting NiO/WC dispersion liquid of step (2-2), precipitating reagent is added dropwise, and adjustment and control system pH value is 7-11, old Change 2-6 h, obtains catalyst precarsor suspension；
Catalyst precarsor suspension obtained by step (2-3) is filtered, washed, is dried, gained powder is 350-650 by (2-4)oUnder C 2-6 h are roasted in inert atmosphere, obtain the Tungsten Carbides nickel biological oil reforming catalyst of surface modification.
4. a kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification according to claim 3, feature exist In in the step (2-1), soluble nickel salt is nickel acetate, nickel acetylacetonate, nickel sulfate, nickel nitrate or nickel chloride.
5. a kind of Tungsten Carbides nickel biological oil reforming catalyst of surface modification according to claim 3, feature exist In in the step (2-3), modification agent is one in porous inorganic oxide, such as silica, aluminium oxide, zirconium oxide Kind is several；Its presoma is silicon, aluminium, the ester of zirconium, nitrate, chloride, acetate, silicate or sulfate, such as positive silicon Sour methyl esters, ethyl orthosilicate, aluminum nitrate, aluminium isopropoxide, aluminium secondary butylate, zirconium nitrate, zirconyl nitrate or zirconium-n-butylate.
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