CN106902837B - A kind of load-type nickel tungsten bimetal composite oxide and its preparation method and application - Google Patents
A kind of load-type nickel tungsten bimetal composite oxide and its preparation method and application Download PDFInfo
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- 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
- C01B3/34—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
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C01B2203/1041—Composition of the catalyst
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Abstract
The invention belongs to hydrogen production of chemical chain technical field, a kind of load-type nickel tungsten bimetal composite oxide and its preparation method and application, molecular formula Ni are disclosedyW1O3+y/Al2O3, y 0.3-1；Preparation method is that Nickelous nitrate hexahydrate, tungsten hexachloride and ANN aluminium nitrate nonahydrate are first thoroughly mixed dissolution in ethanol in proportion；Then it mixes with the dropwise addition of NaOH aqueous solution, washs flocky precipitate centrifugal filtration after standing；Up to product after dry, roasting；The load-type nickel tungsten bimetal composite oxide can be used for low-carbon alkanes three from it is thermal evaporation, reform direct hydrogen production and carbon dioxide.The present invention has coupled the advantages of burning chemistry chains, catalytic reforming and pyrolysis water high-purity hydrogen and gas-solid counter-current operation three reactor self-heating recapitalizations of formula, using simple and easy, low-cost co-precipitation preparation method, realize fuel be converted into carbon dioxide and high-purity hydrogen produce and nearly zero energy consumption of product separates in situ.
Description
Technical field
The invention belongs to the hydrogen production of chemical chain technical fields using metal oxide, in particular to a kind of double gold
Belong to oxide and preparation method thereof and the application for self-heating direct hydrogen production and separation carbon dioxide.
Background technique
With global energy requirements steeply rise and the continuous aggravation of greenhouse gas emission problem, the deployment of Hydrogen Energy industry
Have become one of solution society, economy and grand strategy of environment sustainable development.Hydrogen it is widely used, can be used for liquid combustion
The synthesis and upgrading of material produce gasoline, diesel oil to substitute conventional petroleum；Meanwhile using hydrogen as the pem fuel of fuel electricity
Pond efficient energy conversion is high, and by-product is only water, is expected to become the power core of the vehicles of new generation.
Hydrogen needs to extract from the hydrogenous materials such as hydrocarbon and water by energy conversion process as secondary energy sources,
Major technique path includes [Sherif SA, the Goswami DY, Stefanakos such as heat chemistry, electrolysis water, photolysis water hydrogen
EK,Steinfeld A.Handbook of Hydrogen Energy[M].2014,Boca Raton,USA:CRC
Press.].It mainly include that methane steams currently, being industrially most widely used by the thermochemical process of raw material of fossil energy
The techniques such as vapour reformation, ethanol steam reforming, naphtha reforming, coal gasification, carbon emission problem are serious.Since reforming reaction is strong inhales
Thermal response proposes higher requirement to structure of reactor and material, and manages CO caused by outer burn2It is mixed with residual air
It closes, needs just to can be carried out carbon capture by additional separation process.There is provided steam reformation institute calorific requirement another way be
Pure oxygen is introduced in reaction system, carries out strongly exothermic partial oxidation reaction, such as coal gasification and self-heating recapitalization process, but needs
Air-separating plant with high energy consumption, equipment investment are very high with operating cost.In order to improve H in product2Purity is usually adopted
With higher steam/hydrocarbons ratio, the operating cost of great number is thus brought.To sum up, Conventional thermal process for making hydrogen carries out hydrocarbon in process end
Separation, it is low that energy conversion separates integrated level with product, gas separating energy consumption height.
Product may be implemented while fuel conversion as a kind of advanced efficient thermochemical techniques in chemical chain technology
Nearly zero energy consumption separates in situ, has received extensive attention [Fan L-S, Zeng L, Wang W, Luo S.Chemical
looping processes for CO2capture and carbonaceous fuel conversion-prospect
and opportunity[J].Energy&Environmental Science,2012,5(6),7254-7280.].Chemical chain
Technology is using water vapour or pure oxygen needed for the reformation of solid metal oxide replacement tradition, gasification or combustion process, by fuel
It is converted into synthesis gas or carbon dioxide and water, the metal oxide being reduced can be regenerated with air reaction releases heat
Power generation, or hydrogen can be generated with steam regeneration and directly, nearly zero energy consumption for realizing hydrogen separates in situ.
Metal oxide is in the solid material being constantly circulated between each reactor in chemical chain process, in fuel and water
Or oxygen atom and reaction heat are transmitted between air, it is the key that the development of chemical chain technology, is mainly with single metal oxide at present
Active component.Calculation of thermodynamics shows some metal oxides such as Fe3O4/ FeO/Fe, CeO2/Ce2O3, WO3/WO2.96/WO2.72/
W, V2O5/V2O3/ VO, MoO3/MoO2/ Mo, Nb2O5/NbO2, SnO2Chemistry may be implemented in the metal oxides such as/Sn, ZnO/Zn
Chain hydrogen manufacturing, and main problem existing for these single metal oxides is that thermodynamic temperature is high, reactivity is low, leads to hydrogen manufacturing
Efficiency is lower, and oxidability is limited, and process can not self-heating realization.And other metal oxides, such as NiO/Ni, CuO/
Cu2O/Cu、Co3O4/CoO/Co、Fe2O3/Fe3O4、MnO2/Mn2O3/Mn3O4/ MnO etc. is because its oxidability is strong, reactivity is high
The advantages that, burning chemistry chains are applied to, chemical chain oxygen decoupling process is produced and separate carbon dioxide in situ, while its reduction-state
W metal, Cu, Co, Fe are also excellent reforming catalyst, but because thermodynamics limitation is not directly applicable pyrolysis water hydrogen manufacturing.
Therefore research of the single metal oxide oxygen for hydrogen production of chemical chain at present is concentrated mainly on iron oxide, due to
Fe2O3-Fe3O4It is only used for burning chemistry chains and generates carbon dioxide, subsequent Fe3O4Reducing degree is by Material Thermodynamics and moves
The limitation of mechanical property and the limitation of reactor types, the Lattice Oxygen for hydrogen production of chemical chain are limited, the chemical energy in fuel
It is more discharged for heat, hydrogen gas production efficiency is generally lower than 65%, and also there is a big difference with theoretical optimal hydrogen generation efficiency.And
Metal composite oxide with specific crystal formation is taken seriously in iron based oxygen carrier exploitation, wherein being prepared by sol-gel method
Perovskite type metal oxide (perovskite, ABO3) it is conducive to Lattice Oxygen transmitting, it is a kind of comparatively ideal composite oxygen carrier
Structure, but since the disadvantages of oxygen carrying content is limited, preparation method is complicated, cost is high limits it in hydrogen production of chemical chain
Using.And another common ferronickel bimetal composite oxide, improved using lead oxygen property of the nickel to iron oxide, hydrogen manufacturing
Efficiency can be improved to 70%, but there is serious high temperature sintering, and hydrogen purity is lower.
On reactor and operating process implementation, chemical chain reaction device can enter the mode point of system according to gas
Two classes are operated continuously for single reactor intermittently operated and multiple reactor circulation, and according to the carrier of oxygen in each reactor
Geldart particle classifying and forms of motion can be divided into fixed bed, moving bed and fluidized bed three classes again.Wherein fixed bed reactors
Not high to the mechanical property requirements of the carrier of oxygen due to its simple structure, more application is in laboratory test.But the process is only suitable for
The conversion of gaseous fuel, and require constantly to switch fuel gas, inert purge gas, vapor under conditions of high temperature and pressure,
It industrially temporarily cannot achieve large-scale continuous production.Heat transfer effect is poor between fixed-bed design has another disadvantage that gas-solid,
The hot spot or temperature runaway phenomenon be easy to causeing in bed.In design of Fluidized bed, fuel gas (coal based synthetic gas) and the carrier of oxygen are two
Reverse flow between grade, not only substantially increases the conversion ratio of fuel and the carrier of oxygen, but also enhance the heat transfer between gas-solid, but
The whole utilization of heat is inefficient, needs extraneous additional heat, causes hydrogen production efficiency limited.
Summary of the invention
The present invention is to solve single reactive metal oxide temperature height, reactivity in existing hydrogen production of chemical chain technology
The technical problem that low low with hydrogen production efficiency and metal composite oxide oxygen carrying content is low, preparation method is complicated and cost is high,
Provide a kind of load-type nickel tungsten bimetal composite oxide and preparation method thereof and in fuel such as low-carbon alkanes three from thermogravimetric
Straightening connects the application in hydrogen and carbon dioxide, has coupled the Ni catalysis weight of the burning of NiO Metal Oxide Chemical chain, reduction-state
Whole and reduction-state WOx(0≤x < 3) metal oxide is pyrolyzed three reactors of water high-purity hydrogen and gas-solid counter-current operation formula
The advantages of self-heating recapitalization, utilization is simple and easy, low-cost co-precipitation preparation method, realizes fuel and is converted into dioxy
Change carbon and producing for high-purity hydrogen separates in situ with nearly zero energy consumption of product.
In order to solve the above-mentioned technical problem, the present invention is achieved by technical solution below:
The molecular formula of a kind of load-type nickel tungsten bimetal composite oxide, the load-type nickel tungsten bimetal composite oxide is
NiyW1O3+y/Al2O3, wherein y indicates amount of the Ni relative to the substance of 1mol W, y 0.3-1；The load-type nickel tungsten bimetallic
Composite oxides are using aluminium oxide as carrier, using tungsten and its oxide as the active component of hydrogen production by water decomposition, with metallic nickel and
Its oxide is the active component for aoxidizing low-carbon alkanes trapping carbon dioxide.
Preferably, 0.5 y.
A kind of preparation method of load-type nickel tungsten bimetal composite oxide, this method follow the steps below:
Step 1, by the Nickelous nitrate hexahydrate (Ni (NO of 0.4867-1.4540 mass parts3)2·6H2O), 1.9828 mass parts
Tungsten hexachloride (WCl6) and 12.7903 mass parts ANN aluminium nitrate nonahydrate (Al (NO3)3·9H2O) in ethyl alcohol ultrasound to complete
Fully dissolved；
It step 2, is 0.5-1M in volumetric flask constant volume with ultrapure water by NaOH particle；
Step 3, under conditions of magnetic agitation, the solution that step 1 and step 2 configuration are completed is slowly added dropwise simultaneously mixed
It closes, until pH is 9-10, and resulting flocky precipitate is stood into 1-2h at room temperature；
Step 4, the flocky precipitate after step 3 being stood successively is centrifuged with ethyl alcohol and distilled water, is filtered, washed 5-6 times,
Until pH is 7-8；
Step 5, step 4 obtained material is dried at room temperature for 8-12h, then the dry 8-12h at 70-90 DEG C, finally existed
4-6h is roasted under 600-800 DEG C of air atmosphere, obtains being carried on the nickel tungsten bimetal composite oxide on aluminium oxide, molecule
Formula is NiyW1O3+y/Al2O3, wherein y indicates amount of the Ni relative to the substance of 1mol W, y 0.3-1.
Preferably, 0.5 y.
The nickel tungsten bimetal composite oxide of support type, can be the metal composite oxide being supported on same particle,
Either two kinds of metals prepare the metal mixture being supported on variable grain respectively.Al can be considered in carrier2O3、TiO2、SiO2
Deng.When being supported on same particle, the mass percent of tungsten oxide can be in 10-60%, the quality percentage of nickel oxide
Than can be in 1-30%.When being optimal product and when using hydrogen manufacturing as optimal objective with hydrogen, the ratio of metallic nickel tungsten is by chemical chain
Burning is enough to provide reaction heat and other units of the process operation institute's calorific requirement of following overall reaction to determine.
CxHyOz+aH2O+bO2=cCO2+dH2
In fuel reactor, it will be fired using the strong oxidizing property and gas-solid counter-current operation reactor types of metal nickel oxide
Material is (with CH4For) complete oxidation be CO2And H2O obtains high-purity CO after water vapour condenses2, metal oxide nickel and tungsten quilt
It is reduced to lower valency, wherein the metallic nickel of reduction-state plays the role of hydrocarbon catalytic reformation, fuel reaction in fuel reactor
The overall heat absorption of reaction (reaction 1) in device.The nickel and tungsten of lower valency, which enter in vapor reactor, produces height with steam reaction
Pure H2, tungsten obtains partial regeneration (reaction 2) simultaneously in oxide.It is anti-that the oxide not being clearly regenerated then continues into air
Device is answered to realize complete oxidation regeneration, the heat of release then supplies fuel reactor (reaction 3), realizes self-heating hydrogen manufacturing and carbon dioxide
Separation.
React 1:CH4+NiO/WO3--CO2+H2O+Ni/WOm(3>m)
React 2:WOm+H2O--H2+WOn(n>m)
React 3:Ni/WOn+O2=NiO/WO3(3>n)
The fuel reactor design of gas-solid counter-current modes of operation can utilize the strong of W metal oxide in reactor head
Oxidability, it is ensured that the complete oxidation of fuel, and in reactor bottom, fresh fuel avoids and CO2And H2The mixing of O,
Strong reducing power is conducive to the generation of as-reduced metal Ni and W.Nickel tungsten bimetallic oxide is direct for three bed chemical chain self-heatings
Hydrogen manufacturing, system overall reaction are equivalent to fuel and react generation CO with oxygen2And H2O is strong exothermal reaction, and the heat released can be with
For heat needed for fuel vapour reformation hydrogen production.So by adjusting the charge proportion and double gold of air in system and vapor
The coproduction of self-heating hydrogen making or hydrogen and hot (electricity) may be implemented in the ratio for belonging to oxide nickel tungsten, while nearly zero energy consumption is produced
H2With separation CO2。
Load-type nickel tungsten bimetal composite oxide of the invention, three bed chemical chain self-heating direct hydrogen production gas being applied to and
Separate carbon dioxide, reactor and operating process can be according to being implemented as follows:
Step 1, the load-type nickel tungsten bimetal composite oxide of above-mentioned preparation is subjected to compression molding processing, to obtain
The solid oxide particles of 20-40 mesh carry out using；
Step 2, the solid oxide particles after forming processes are packed into three reactors, solid oxide particles are from fuel
Reactor top enters, and maintains and react under the conditions of 700-1000 DEG C of temperature；Low-carbon alkanes and oxide counter current contacting, fuel
The gas of reactor head outlet obtains pure carbon dioxide gas after condensation and separation of moisture；Fuel reactor bottom
Obtain the WO of reduction-statexAnd W metal；
Step 3, the WO of reduction-statexVapor reactor head, temperature are entered in fuel reactor bottom compartment with W metal
Control is at 500-900 DEG C；Vapor is passed through by vapor reactor lower end, the WO of reduction-statexIt is WO by steam oxidation3/
WO2.96And it is raw with hydrogen generation；WO3/WO2.96The W metal not reacted with vapor is from vapor reactor bottom
It leaves；Gaseous product leaves after condensing and separating from vapor reactor head, obtains pure hydrogen；
Step 4, the solid particle after separation enters air reactor bottom, and reaction temperature is 700-900 DEG C；Ni and
WO3/WO2.96NiO and WO are regenerated as by air is reoxidized3, while heat is released, it is run for system self-heating；
In above-mentioned steps, the WO of the reduction-statex, 0≤x < 3；
Regenerated bimetallic oxide can participate in reaction realization again and recycle.
Preferably, the WO of the reduction-statexFor W, WO2、WO2.72And WO2.92。
Preferably, the fuel reactor and the steam reaction device select moving-burden bed reactor or multistage fluidized bed
Reactor.
Fuel reactor, can using gas-solid is counter-flow moving bed, multistage fluidized bed design, fuel can be considered natural gas,
The richness carbon fuel such as heavy oil.
In fuel reactor maintain 700-1000 DEG C of thermotonus, oxide from fuel reactor top enter, fuel by
Reactor bottom enters, the oxide counter current contacting of generated reducibility gas uplink and downlink.At the top of fuel reactor
NiO ensures that the complete oxidation of fuel obtains pure after the gas of fuel reactor top exit is condensation and separation of water therein
Carbon dioxide.W metal after reduction can be reformed with catalytic fuel, accelerate gas phase reaction and solid phase WO3Reduction, reactor bottom
Fuel reproducibility it is strong, it is ensured that WOxThe reducing degree of (0≤x < 3) is high, is conducive to improve in next step steam reaction device and steam with water
The conversion ratio and yield of vapour reaction hydrogen manufacturing.
Steam reaction device, the WO of reduction-statexIt is anti-that (0≤x < 3) and W metal in fuel reactor bottom compartment enter vapor
It answers at the top of device, temperature is controlled at 500-900 DEG C；It is passed through vapor in vapor reactor lower end, gas-solid contact mode can be
Countercurrently, cocurrent and cross-flow, optimal is gas-solid counter current contacting, is realized by moving bed or multistage fluidized bed form, is conducive to mention
Conversion ratio of the high water vapour to hydrogen, the WO of reduction-statexIt is reacted with vapor and generates hydrogen, solid product WO3/WO2.96Not with
The Ni that vapor reacts, gaseous product obtain pure hydrogen after condensation and separation of water therein.
Air reactor, solid Ni and WO after separation3/WO2.96Into air reactor, by the reoxidized regeneration of air
Realization recycles, while releasing heat, runs for system self-heating.
The beneficial effects of the present invention are:
(1) oxide of the invention is support type (with Al2O3For), with WO3Bimetal composite oxide is formed with NiO；
NiO is completely reduced with stronger reactivity and fuel is fully converted to CO for metallic state (Ni) and strong oxidation performance2
And H2O；The metal (Ni) of reduction-state has the function of catalytic reforming；And WO3It is reduced to low-oxidation-state (WOx) or metallic state (W)
High purity hydrogen is reacted with vapor.Compared to single metal oxide, bimetallic is compound or mixed oxide oxygen carrier exists
Burning chemistry chains, catalytic reforming and pyrolysis water hydrogen production process are coupled in cyclic process, the ratio by adjusting nickel and tungsten is realized
The optimization of energy, conducive to the operation of self-heating hydrogen generating system, hydrogen production efficiency is higher；Compared to existing bimetal composite oxide,
The anti-caking power of high temperature is stronger, and hydrogen purity is higher.
(2) co-precipitation preparation method that the present invention uses is simple and easy, compared to existing metal composite oxide and preparation
Method is cheap, is convenient for large-scale use.
(3) the time required to the faster Ni/NiO of reaction rate can shorten reaction in the hydrogen production process, and thermodynamically water
The higher WO of vapor equalization conversion ratiox(0≤x < 3) can further increase product on the reduction result of the first W metal
Density of hydrogen, and then improve hydrogen production efficiency；And it is lower that Ni/NiO reacts equilibrium concentration with hydrogen, therefore major part Ni is in sky
Gas oxidation stage becomes NiO again, and what it mainly underwent is burning chemistry chains reaction；And the mainly chemical chain system of W experience
Hydrogen process.By adjusting the energy way of output of the adjustable chemical chain process of proportion of both metals, system is increased
Flexibility ratio.
(4) present invention can use three bed chemical chain direct hydrogen production techniques, couple fuel reactor, vapor reactor
And air reactor, the overall reaction of three bed systems are the self-heating recapitalization of fuel；Wherein fuel reactor and steam reaction device are equal
It is preferred that moving-burden bed reactor or multistage fluidized bed reactor with gas-solid counter-current operation, be conducive to gas and solids conversion and
The raising of hydrogen yield；Charge proportion by adjusting air in system and vapor (it is multiple to adjust load-type nickel tungsten bimetallic
Close the value of y in oxide), self-heating hydrogen making may be implemented, while nearly zero energy consumption separates H2With trapping CO2。
Detailed description of the invention
Fig. 1 is fuel reactor WO3/Al2O3And Ni0.3W1Ox/Al2O3, Ni0.5W1Ox/Al2O3, Ni1W1Ox/Al2O3Work
Property test chart；
Fig. 2 is vapor reactor WO3/Al2O3And Ni0.5W1Ox/Al2O3Production hydrogen activity test chart；
Fig. 3 is Ni0.5W1Ox/Al2O310 circulation stability test figures；
Fig. 4 is that three reactor assembly schematic diagrames (are used for CH with nickel tungsten bimetal composite oxide4Three bed chemical chains are reformed
For direct hydrogen production).
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, and following embodiment can make this profession
The present invention, but do not limit the invention in any way is more completely understood in technical staff.
Embodiment 1
(1) 1.9828g tungsten hexachloride (WCl is weighed6), the ANN aluminium nitrate nonahydrate (Al (NO of 12.7903g3)3·9H2O) and
Nickelous nitrate hexahydrate (Ni (the NO of 0.7270g3)2·6H2O it) is dissolved in 50mL ethyl alcohol, ultrasonic 0.5h；
(2) weighing the NaOH of 20g with 500mL volumetric flask constant volume is 1M；
(3) under conditions of magnetic agitation, mixing is slowly added dropwise simultaneously in the solution that step 1 and step 2 configuration are completed, directly
It is 9-10 to pH, and resulting flocky precipitate is stood into 1h at room temperature；
(4) flocky precipitate after standing (3) is successively centrifuged with ethyl alcohol and distilled water, is filtered, washed 5-6 times, until
PH is 7-8；
(5) (4) obtained material is dried at room temperature for 12h, then the dry 12h at 70-90 DEG C, finally in 800 DEG C of sky
4h is roasted under gas atmosphere, obtains being carried on the nickel tungsten bimetal composite oxide on aluminium oxide, molecular formula Ni0.5W1Ox/
Al2O3。
Embodiment 2
(1) 1.9828g tungsten hexachloride (WCl is weighed6) and 12.7903g ANN aluminium nitrate nonahydrate (Al (NO3)3·9H2O) molten
In 50mL ethyl alcohol, ultrasonic 0.5h；
(2) weighing the NaOH of 20g with 500mL volumetric flask constant volume is 1M；
(3) under conditions of magnetic agitation, mixing is slowly added dropwise simultaneously in the solution that step 1 and step 2 configuration are completed, directly
It is 9-10 to pH, and resulting flocky precipitate is stood into 1h at room temperature；
(4) flocky precipitate after standing (3) is successively centrifuged with ethyl alcohol and distilled water, is filtered, washed 5-6 times, until
PH is 7-8；
(5) (4) obtained material is dried at room temperature for 12h, then the dry 12h at 70-90 DEG C, finally in 800 DEG C of sky
4h is roasted under gas atmosphere, obtains being carried on the tungsten oxide on aluminium oxide, molecular formula WO3/Al2O3。
Embodiment 3
(1) 1.9828g tungsten hexachloride (WCl is weighed6), the ANN aluminium nitrate nonahydrate (Al (NO of 12.7903g3)3·9H2O) and
0.4847 Nickelous nitrate hexahydrate (Ni (NO3)2·6H2O it) is dissolved in 50mL ethyl alcohol, ultrasonic 0.5h；
(2) weighing the NaOH of 20g with 500mL volumetric flask constant volume is 0.5M；
(3) under conditions of magnetic agitation, mixing is slowly added dropwise simultaneously in the solution that step 1 and step 2 configuration are completed, directly
It is 9-10 to pH, and resulting flocky precipitate is stood into 2h at room temperature；
(4) flocky precipitate after standing (3) is successively centrifuged with ethyl alcohol and distilled water, is filtered, washed 5-6 times, until
PH is 7-8；
(5) (4) obtained material is dried at room temperature for 8h, then the dry 8h at 70-90 DEG C, finally in 600 DEG C of air
5h is roasted under atmosphere, obtains being carried on the nickel tungsten bimetal composite oxide on aluminium oxide, molecular formula Ni0.3W1Ox/
Al2O3。
Embodiment 4
(1) 1.9828g tungsten hexachloride (WCl is weighed6), the ANN aluminium nitrate nonahydrate (Al (NO of 12.7903g3)3·9H2O) and
Nickelous nitrate hexahydrate (Ni (the NO of 1.4540g3)2·6H2O it) is dissolved in 50mL ethyl alcohol, ultrasonic 0.5h；
(2) weighing the NaOH of 20g with 500mL volumetric flask constant volume is 0.8M；
(3) under conditions of magnetic agitation, mixing is slowly added dropwise simultaneously in the solution that step 1 and step 2 configuration are completed, directly
It is 9-10 to pH, and resulting flocky precipitate is stood into 2h at room temperature；
(4) flocky precipitate after standing (3) is successively centrifuged with ethyl alcohol and distilled water, is filtered, washed 5-6 times, until
PH is 7-8；
(5) (4) obtained material is dried at room temperature for 10h, then the dry 10h at 70-90 DEG C, finally in 700 DEG C of sky
6h is roasted under gas atmosphere, obtains being carried on the nickel tungsten bimetal composite oxide on aluminium oxide, molecular formula Ni1W1Ox/
Al2O3。
Embodiment 5:
WO obtained in embodiment 1-43/Al2O3、Ni0.3W1Ox/Al2O3、Ni0.5W1Ox/Al2O3、Ni1W1Ox/Al2O3It is firing
Expect that each gas composition of fuel reactor changes over time such as Fig. 1 with methane reaction in reactor.With WO3/Al2O3Catalyst phase
Than on the one hand part enters WO for the addition of NiO3Lattice, formation is bulk phase-doped, to improve mobility of lattice oxygen ability, reduces also
Former temperature and raising oxide reduction degree；The NiO on another aspect surface is reduced to metallic state Ni, plays catalytic activation methane
Effect improves methane reaction activity.Fig. 1 clearly shows the addition of NiO to raising oxide reduction degree and methane reaction activity
It plays an important role.
Table 1, steam transforming rate, hydrogen and carbon monoxide composition
| Sample | Steam transforming rate (%) | Hydrogen forms (%) | Carbon monoxide forms (%) |
| WO3/Al2O3 | 21 | 61 | 39 |
| Ni0.5W1Ox/Al2O3 | 58 | 97 | 3 |
Seen from table 1, with the addition of NiO, in vapor reactor, the conversion ratio of vapor is gradually increased, and
H2Composition gets a promotion.As a result illustrate simultaneously, the WO in fuel reactor3/Al2O3Carbon distribution is more after reduction, reacts in vapor
Cause CO concentration higher in device, and adds Ni after appropriate NiO0.5W1Ox/Al2O3The carbon distribution of association is seldom when reduction, is conducive to mention
The concentration that hydrogen is produced in high vapour reactor.
Fig. 2 is vapor consumption and the activity figure that hydrogen, carbon monoxide composition change over time, it can be seen that Ni0.5W1O3/
Al2O3Compared to WO3/Al2O3Hydrogen composition significantly improves, and illustrates that the addition of NiO promotes WO in fuel reactor3Reduction,
WO3It is reduced to more lower valency, so that steam transforming rate is promoted.
Fig. 3 is Ni0.5W1Ox/Al2O310 circulation fixed bed reactors stability test figures.Loop tester:
Loop tester: 800 DEG C of reaction 10min, air speed 5mL CH of fuel reactor4/ (min.g), 800 DEG C of vapor reactor anti-
Answer 20min, air speed 5mL H2O/ (min.g), 800 DEG C of reaction 20min, air speed 30mL air/ (min.g) of air reactor.With
For methane portion oxidation, from figure 3, it can be seen that CO is selectively slightly improved, H after 10 regeneration cycles of experience2/ CO
It slightly improves, there is relatively good stability.
Embodiment 6:
(1) the resulting load-type nickel tungsten bimetal composite oxide material of embodiment 1-4 is according to reactor types selection
Particle size molding, obtains the solid oxide particles of 20-40 mesh size, and the solid oxide particles after forming processes are packed into three
Bed reactor.
(2) in fuel reactor, oxide is fallen by fuel bed reactor head, and fuel is entered by reactor bottom,
Temperature is controlled at 700-1000 DEG C, the oxide counter current contacting of generated reducibility gas uplink and downlink, in top NiO
Ensure that the complete oxidation of fuel obtains pure two after the gas of fuel reactor top exit is condensation and separation of water therein
Carbon oxide gas；Fuel reactor bottom obtains the WO of reduction-statex(0≤x < 3) and W metal；
(3) in steam reaction device, the WO of reduction-statex(0≤x < 3) and Ni enter vapor in fuel reactor bottom compartment
Reactor head, temperature are controlled at 500-900 DEG C；Vapor, the WO of reduction-state are passed through in vapor reactor lower endxIt is steamed by water
Gas is oxidized to WO3/WO2.96And it is raw with hydrogen generation, solid product WO3/WO2.96The Ni not reacted with vapor,
It is left from vapor reactor bottom；Gaseous product leaves after condensation and separation of water therein from vapor reactor head,
Obtain pure hydrogen.
(4) in air reactor, reaction temperature is 700-900 DEG C, solid particle Ni and WO after separation3/WO2.96Into
Enter air reactor, is regenerated as NiO and WO by air is reoxidized3, while heat is released, and it is run for system self-heating, it is extra
Heat can be used for generating steam or power generation.
Regenerated bimetallic oxide can participate in reaction realization again and recycle.
Fuel reactor be averaged methane conversion, hydrogen selective, by dividing rate and vapor reactor with each gas molar
Vapor average conversion and hydrogen composition various are calculated by following:
Methane conversion:
Hydrogen selective:
Each gas molar divides rate:
Steam transforming rate:
Hydrogen composition:
Reaction product uses mass spectrum on-line analysis, and fuel reactor test methane conversion, hydrogen selective, each gas rub
You divide the relationship of rate and time as shown in table 2.
Table 2, methane conversion, hydrogen selective and corresponding system hydrogen production efficiency
As can be seen from Table 2, with the addition of NiO, the conversion ratio of methane is gradually increased, wherein being improved the most with Ni:W=1:2
Significantly, when NiO is excessive, oxide can gradually be inactivated because of methane cracking carbon distribution.System hydrogen production efficiency and Ni:W ratio are related,
Wherein Ni:W=1:2 oxide reduction degree highest, hydrogen production efficiency is also maximum, up to 80%.
Although the preferred embodiment of the present invention is described above in conjunction with attached drawing, the invention is not limited to upper
The specific embodiment stated, the above mentioned embodiment is only schematical, be not it is restrictive, this field it is common
Technical staff under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, may be used also
By make it is many in the form of specific transformation, within these are all belonged to the scope of protection of the present invention.
Claims (7)
1. a kind of load-type nickel tungsten bimetal composite oxide, which is characterized in that the load-type nickel tungsten bimetal composite oxide
Molecular formula be Niy W1 O 3+y /Al2 O3 , wherein y indicates amount of the Ni relative to the substance of 1 mol W, y 0.3-1；This is negative
Load type nickel tungsten bimetal composite oxide is using aluminium oxide as carrier, using tungsten and its oxide as the active group of hydrogen production by water decomposition
Point, it is the active component for aoxidizing low-carbon alkanes trapping carbon dioxide with metallic nickel and its oxide；And by following preparation method
It obtains:
Step 1, by the Nickelous nitrate hexahydrate of 0.4867-1.4540 mass parts, the tungsten hexachloride of 1.9828 mass parts and 12.7903
The ANN aluminium nitrate nonahydrate of mass parts in ethyl alcohol ultrasound to being completely dissolved；
It step 2, is 0.5-1 M in volumetric flask constant volume with ultrapure water by NaOH particle；
Step 3, under conditions of magnetic agitation, mixing is slowly added dropwise simultaneously in the solution that step 1 and step 2 configuration are completed, directly
It is 9-10 to pH, and resulting flocky precipitate is stood into 1-2 h at room temperature；
Step 4, the flocky precipitate after step 3 being stood successively is centrifuged with ethyl alcohol and distilled water, is filtered, washed 5-6 times, until
PH is 7-8；
Step 5, step 4 obtained material is dried at room temperature for 8-12 h, then the dry 8-12 h at 70-90 DEG C, finally existed
4-6 h is roasted under 600-800 DEG C of air atmosphere, obtains being carried on the nickel tungsten bimetal composite oxide on aluminium oxide.
2. a kind of load-type nickel tungsten bimetal composite oxide according to claim 1, which is characterized in that y 0.5.
3. a kind of preparation method of load-type nickel tungsten bimetal composite oxide as described in claim 1, which is characterized in that should
Method follows the steps below:
Step 1, by the Nickelous nitrate hexahydrate of 0.4867-1.4540 mass parts, the tungsten hexachloride of 1.9828 mass parts and 12.7903
The ANN aluminium nitrate nonahydrate of mass parts in ethyl alcohol ultrasound to being completely dissolved；
It step 2, is 0.5-1 M in volumetric flask constant volume with ultrapure water by NaOH particle；
Step 3, under conditions of magnetic agitation, mixing is slowly added dropwise simultaneously in the solution that step 1 and step 2 configuration are completed, directly
It is 9-10 to pH, and resulting flocky precipitate is stood into 1-2 h at room temperature；
Step 4, the flocky precipitate after step 3 being stood successively is centrifuged with ethyl alcohol and distilled water, is filtered, washed 5-6 times, until
PH is 7-8；
Step 5, step 4 obtained material is dried at room temperature for 8-12 h, then the dry 8-12 h at 70-90 DEG C, finally existed
4-6 h is roasted under 600-800 DEG C of air atmosphere, obtains being carried on the nickel tungsten bimetal composite oxide on aluminium oxide, point
Minor is Niy W1 O3+y /Al2 O3 , wherein y indicates amount of the Ni relative to the substance of 1 mol W, y 0.3-1.
4. a kind of preparation method of load-type nickel tungsten bimetal composite oxide according to claim 3, which is characterized in that
Y is 0.5.
5. a kind of load-type nickel tungsten bimetal composite oxide as described in claim 1 is for low-carbon alkanes three from hot gas
The method changed, reform direct hydrogen production and carbon dioxide, which is characterized in that this method follows the steps below:
Step 1, load-type nickel tungsten bimetal composite oxide is subjected to compression molding processing, to obtain the solid oxygen of 20-40 mesh
Compound particle carry out using；
Step 2, the solid oxide particles after forming processes are packed into three reactors, solid oxide particles are from fuel reaction
Device top enters, and maintains and react under the conditions of 700-1000 DEG C of temperature；Low-carbon alkanes and oxide counter current contacting, fuel reaction
The gas of device top exit obtains pure carbon dioxide gas after condensation and separation of moisture；Fuel reactor bottom obtains
The WO of reduction-statexAnd W metal；
Step 3, the WO of reduction-statexVapor reactor head is entered in fuel reactor bottom compartment with W metal, temperature control exists
500-900 ℃；Vapor is passed through by vapor reactor lower end, the WO of reduction-statex It is WO by steam oxidation3 /WO2.96 And
It is generated with hydrogen；WO3 /WO2.96 The W metal not reacted with vapor leaves from vapor reactor bottom；Gas
Body product leaves after condensing and separating from vapor reactor head, obtains pure hydrogen；
Step 4, the solid particle after separation enters air reactor bottom, and reaction temperature is 700-900 DEG C；Ni and WO3 /
WO2.96 NiO and WO are regenerated as by air is reoxidized3, while heat is released, it is run for system self-heating；
In above-mentioned steps, the WO of the reduction-statex, 0≤x < 3；
Regenerated bimetallic oxide can participate in reaction realization again and recycle.
6. load-type nickel tungsten bimetal composite oxide according to claim 5 for low-carbon alkanes three from it is thermal evaporation,
The method for reforming direct hydrogen production and carbon dioxide, which is characterized in that the WO of the reduction-statexFor W, WO2 、WO2.72 And WO2.92 。
7. load-type nickel tungsten bimetal composite oxide according to claim 5 for low-carbon alkanes three from it is thermal evaporation,
The method for reforming direct hydrogen production and carbon dioxide, which is characterized in that the fuel reactor and the steam reaction device select
With moving-burden bed reactor or multistage fluidized bed reactor.
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| MY192817A (en) * | 2019-04-22 | 2022-09-12 | Univ Kebangsaan Malaysia | A catalyst composition and method of making thereof for pure hydrogen production |
| CN110553275B (en) * | 2019-07-29 | 2022-01-11 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Hydrogen elimination device and method for closed system |
| CN110876941B (en) * | 2019-11-05 | 2022-11-18 | 天津大学 | Load type iron-tungsten bimetal composite oxide and preparation method and application thereof |
| CN111111684B (en) * | 2020-01-17 | 2020-09-15 | 成都理工大学 | Mesoporous silica-loaded tungsten-promoted nickel-based catalyst for autothermal reforming of acetic acid |
| US11628426B2 (en) * | 2020-04-29 | 2023-04-18 | Uti Limited Partnership | Catalyst for chemical looping combustion |
| CN112811476B (en) * | 2020-12-31 | 2022-05-17 | 华中科技大学 | Nickel-doped brownmillerite type oxygen carrier and preparation method and application thereof |
| CN112978815B (en) * | 2021-03-14 | 2022-11-15 | 北京工业大学 | Preparation method of nickel-tungsten phosphide-nickel-tungsten oxide with heterostructure |
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