CN103846088A - Nickel-based steam reforming catalyst for biomass tar and preparation and application method of catalyst - Google Patents
Nickel-based steam reforming catalyst for biomass tar and preparation and application method of catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of the energy and chemical industry and particularly relates to a nickel-based steam reforming catalyst for biomass tar and a preparation and application method of the catalyst. The catalyst adopts low-cost brown coal as a carrier and comprises the following components by weight percent: 23-25% of Ni, 64.26-66.26% of C, 6.06% of O and 6% of impurity elements. The catalyst is prepared by adopting the cooperation of an ion exchange method and an impregnation method. The catalyst has the good activity and economy, the brown coal is low in cost and large in specific surface area, after being washed by sodium hydroxide, micropores of the brown coal become mesopores and macropores, so that macromolecular compounds of the tar are relatively easy to pass; simultaneously, a relatively large quantity of new through holes are also formed in the brown coal; in the process of catalytic reformation of the tar, a relatively large quantity of effective pore channels are formed, so that the efficiency for reforming the biomass tar is relatively high; the carbon deposited amount of the catalyst and the carbon consumption amount of catalyst carrier carbon can form dynamic balance, so that the service life of the catalyst is prolonged and the catalyst is not easily inactivated.
Description
Technical field
The invention belongs to derived energy chemical technical field, particularly a kind of nickel-base biomass tar steam reforming catalyst and preparation and application method thereof.
Background technology
Along with the day by day exhausted and global environment of fossil energy worsens, living beings are as all replacing the regenerative resource of fossil energy more and more to get more and more people's extensive concerning at solid, liquid, gas three aspects:.Wherein, biomass gasification technology, because technology path is relatively simple, can produce high-grade energy as hydrogen, carbon monoxide etc., and relevant research is carried out early more fully.But, in gasification, there is a bottleneck always, be exactly the generation that is inevitably accompanied by tar in gasification.Tar causes the loss of equipment corrosion, obstruction and energy because of condensation at low temperatures, gathering, how efficiently to remove tar, purifies the gas producing and become the focal issue that is subject to extensive concern in biomass gasification technology.In numerous tar removal technology, the most effective with water vapour catforming.Associated catalysts has obtained broad research as dolomite, alkali metal and nickel-base catalyst etc.Existing alundum (Al2O3) nickel-loaded catalyst has good catalyst effect, and the research of a lot of mechanisms, but its manufacturing cost is higher, is difficult to large-scale application in industrial production.
Up to the present, China is actually rare in biomass gasification process tar decomposition, reforming catalyst patent of invention.Wherein a kind of preparation method of integral biomass gasified tarcracking catalyst (200610122580.7) and biomass gasification tar cracking catalyst and preparation method thereof (200910272415.3), although they start with discussing how to prepare efficient nickel-base catalyst from the preparation method of catalyst, but the real active component of catalyst itself and catalytic cracking of tar mechanism thereof are also lacked to enough understanding, and catalyst raw material cost higher (price of analyzing pure alundum (Al2O3) is 100 yuan/kilogram), be difficult to realize commercial operation.
The present invention selects the carrier of cheap brown coal (the harbour valency of brown coal is 300～350 yuan/ton) as coke tar reforming catalyst, through a large amount of experimental studies and the phenetic analysis to coke tar reforming catalyst XRD and SEM thereof, find the activation method of coke tar reforming catalyst carrier, and nickel-base catalyst preparation method taking brown coal as carrier.
Summary of the invention
The technical problem to be solved in the present invention is: make up weak point in prior art, increase the effective duct of catalyst quantity by certain density NaOH modification, a kind of nickel-base biomass tar steam reforming catalyst and preparation and application method thereof are provided.
A kind of nickel-base biomass tar steam reforming catalyst, described catalyst is taking brown coal as carrier, and described catalyst composition and mass percent are as follows:
Ni is that 23%～25%, C is that 64.26%～66.26%, O is 6.06%, and impurity element is 6%.
A preparation method for nickel-base biomass tar steam reforming catalyst, its concrete steps are as follows:
(1) metal salt solution preparation: analytically pure nickel salt is dissolved and makes the aqueous solution with pure water, wherein dissolve every gram of nickel salt pure water 20mL～40mL; Add a small amount of ammonium carbonate pH is adjusted to 6～7, and stir concussion, make local complex compound or the sediment producing of solution in the process of adding ammonium carbonate disappear molten;
(2) preparation of brown coal carrier: brown coal are dipped in sodium hydrate aqueous solution, and boil 0.5～1 hour, brown coal are pulled out by extremely neutrality of purified rinse water, finally brown coal are carried out to oxidation drying;
(3) ion-exchange is collaborative with dipping: by the aqueous solution that adds step (1) to configure through the brown coal carrier of step (2) processing, the mass ratio of described brown coal carrier and nickel salt is that (1:1)～(2:1), stirring at normal temperature is more than 12 hours;
(4) filtration drying: step (3) gained is impregnated with to the solution of brown coal, filters after static 1～2 hour, gained filter residue and drying is removed to moisture;
(5) shaping of catalyst: by the dried filter residue of step (4), under the environment of nitrogen, be heated to 300 DEG C from room temperature, and keep 1～2 hour, make catalyst surface stable crystal form, continue to be heated to 600 DEG C from 300 DEG C, and keep 30min, take off the volatile ingredient in brown coal carrier, increase specific surface area of catalyst, after moulding, obtain nickel-base biomass tar steam reforming catalyst.
Nickel salt described in step (1) is six water nickel nitrates.
Described in step (2), in the aqueous solution of NaOH, the concentration of NaOH is 1g/100ml～5g/100ml.
The drying means of oxidation drying described in step (2) is for being put in 120 DEG C of air dry ovens oxidation drying 24 hours by brown coal.
Dry baking temperature described in step (4) is 90 DEG C～110 DEG C.
Described in step (5), being heated to the heating rate of 300 DEG C from room temperature is 10 DEG C/min.
Described in step (5), be 10 DEG C/min from 300 DEG C of heating rates that are heated to 600 DEG C.
An application process for nickel-base biomass tar steam reforming catalyst, described nickel-base biomass tar steam reforming catalyst is for temperature reaction, and its reaction temperature is 550 DEG C～700 DEG C.
The impurity elements such as the Ca, the Fe that contain in described brown coal, Al, Na, Ti are natural promoter.
The invention has the beneficial effects as follows:
1, the carrier of catalyst of the present invention select brown coal, it have cheap, specific area is high and active good performance.In catalyst, for active component provides large carrier surface, and can prevent the sintering of active component, the stability of catalyst is guaranteed;
2, in steam reforming tar process, tar can produce carbon distribution in reforming process, and the carbon distribution reaction that the carbon in steam meeting and brown coal carrier and catalyst surface produce, makes catalyst reach the dynamic equilibrium of carbon, not only anti-carbon but also balance the consumption of carrier, the service life of extending catalyst;
3, brown coal carrier is through the washing of NaOH, and most apertures form mesoporous, and through hole road does not become through hole, contributes to the macromolecular organic compound of tar to pass through;
4, in brown coal carrier, contain a large amount of humic acid, humic acid is good ion-exchange raw material, can increase the load capacity of nickel, also can from the nickel solution of low concentration, obtain the catalyst of high capacity amount simultaneously.Catalyst of the present invention boils oxidation processes by certain density NaOH to brown coal, makes a lot of new active groups of the oxidized formation of brown coal, has greatly improved the ion-exchange capacity of original brown coal, has improved the load capacity of catalyst;
5, by the adjusting of pH value of solution and the modification to carrier, the obvious Zeng Qiang of ability of catalyst cupport nickel, in catalytic reforming process, tar conversion ratio is high, and total gas production is large, and hydrogen proportion is high;
6, brown coal are as the one of natural crystal, including the multiple element (Ca, Fe, Al, Na, Ti etc.) with catalytic action is all main auxiliary agents of biogasification pyrolysis fuel oil catalyst, therefore can improve the catalytic effect of nickel-base catalyst, and use brown coal as carrier, compare the biomass tar cracking catalyst that other add auxiliary agent, not only simplify operation, the pollution to environment while having reduced preparation, and saved cost;
7, in metal salt solution process for preparation, add ammonium carbonate for regulating pH value, pH is raise, because brown coal carrier contains a large amount of humic acid, the active group (hydroxyl, carboxyl) on it has the characteristic of ion-exchange, and pH rising can promote the forward of ion-exchange to carry out;
8, existing biomass tar cracking catalyst, the present invention is because of taking brown coal as carrier, carbon have reproducibility and with nickel formation nickel carbon bond, the nickel of firing catalyst back loading can oxidation by air, activate without hydrogen before use, and the preparation method of catalyst is simple, preparation cost is cheap;
9, brown coal are compared with other coal, phosphorus content is low, high being not suitable for of ash burnt, wasted with the form of burning but actual conditions are a large amount of brown coal, for rationally efficiently utilize brown coal, to descendants be responsible for, this catalyst proposed a kind of method of efficiently utilizing brown coal.
Brief description of the drawings
Fig. 1 is the SEM figure of the nickel-base biomass tar steam reforming catalyst of preparation in the embodiment of the present invention 1;
Fig. 2 is the EDX figure of the nickel-base biomass tar steam reforming catalyst of preparation in the embodiment of the present invention 1;
Fig. 3 is the SEM figure of the nickel-base biomass tar steam reforming catalyst of preparation in the embodiment of the present invention 2;
Fig. 4 is the EDX figure of the nickel-base biomass tar steam reforming catalyst of preparation in the embodiment of the present invention 2;
Fig. 5 is the XRD figure of the nickel-base biomass tar steam reforming catalyst of preparation in the embodiment of the present invention 1.
Detailed description of the invention
The invention provides a kind of nickel-base biomass tar steam reforming catalyst and preparation and application method thereof, below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment 1
By analytically pure 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 3g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 630 DEG C, through experiment in 2 hours, toluene conversion reached more than 95%.
Table 1 is the XRF scanning result that the brown coal of preparation in embodiment 1 carry nickel-base biomass tar reforming catalyst.
Table 1 embodiment 1 brown coal carry nickel-base biomass tar reforming catalyst XRF scan-data table
Embodiment 2
By analytically pure 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 1g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 630 DEG C, through experiment in 2 hours, toluene conversion reached more than 95%.
Embodiment 3
By analytically pure 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 3g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution,
Stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 680 DEG C, through experiment in 2 hours, toluene conversion reached more than 95%.
Embodiment 4
By analytically pure 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 1g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 680 DEG C, through experiment in 2 hours, toluene conversion reached more than 95%.
Embodiment 5
By analytically pure 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 1g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 630 DEG C, through experiment in 2 hours, toluene conversion reached more than 95%.
Embodiment 6
By analytically pure 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 3g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 630 DEG C, through experiment in 2 hours, toluene conversion reached more than 95%.
Embodiment 7
By analytically pure 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 1g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 680 DEG C, through experiment in 2 hours, toluene conversion reached more than 95%.
Embodiment 8
By analytically pure 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 3g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 680 DEG C, through experiment in 2 hours, toluene conversion reached more than 95%.
Embodiment 9
By analytically pure 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: As-received brown coal be dipped in pure water and boil 1 hour, brown coal are pulled out and caused neutrality with purified rinse water, finally brown coal being put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, tests toluene conversion less than 35% in the time of 680 DEG C through 2 hours.
Embodiment 10
By analytically pure 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: As-received brown coal be dipped in pure water and boil 1 hour, brown coal are pulled out and caused neutrality with purified rinse water, finally brown coal being put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, tests toluene conversion less than 35% in the time of 680 DEG C through 2 hours.
Embodiment 11
By analytically pure 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 6g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 680 DEG C, through experiment in 2 hours, toluene conversion reached less than 70%.
Embodiment 12
By analytically pure 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjusting pH value is 6～7, and stirs concussion, makes complex compound or the sediment of the local generation of solution in the process of adding ammonium carbonate disappear molten.
The preparation of brown coal carrier: to be dipped in concentration be in 9g/100ml sodium hydrate aqueous solution and boil 1 hour by As-received brown coal, pulls brown coal to cause neutrality with purified rinse water out, finally brown coal is put in 120 DEG C of air dry ovens to oxidation drying 24 hours.
Ion-exchange and dipping: get the brown coal carrier that 10g handles well and be added in configured nickel nitrate solution, stirring at normal temperature 12 hours.
Filtration drying: by above-mentioned solution, filter after static 1 hour, the filter residue obtaining is placed in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: the programming rate with 10 DEG C/min under the environment of nitrogen is heated to 300 DEG C from room temperature, and keeping 1 hour, continues to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keeps 30min.After moulding, obtain nickel-base biomass tar steam reforming catalyst.
Take 1g catalyst, taking toluene as tar model, nitrogen is carrier gas, and in the time of 680 DEG C, through experiment in 2 hours, toluene conversion reached less than 55%.
Claims (9)
1. a nickel-base biomass tar steam reforming catalyst, is characterized in that: described catalyst is taking brown coal as carrier, and described catalyst composition and mass percent are as follows:
Ni is that 23%～25%, C is that 64.26%～66.26%, O is 6.06%, and impurity element is 6%.
2. the preparation method of a kind of nickel-base biomass tar steam reforming catalyst as claimed in claim 1, is characterized in that, concrete steps are as follows:
(1) metal salt solution preparation: analytically pure nickel salt is dissolved and makes the aqueous solution with pure water, wherein dissolve every gram of nickel salt pure water 20mL～40mL; Add a small amount of ammonium carbonate pH is adjusted to 6～7, and stir concussion, make local complex compound or the sediment producing of solution in the process of adding ammonium carbonate disappear molten;
(2) preparation of brown coal carrier: brown coal are dipped in sodium hydrate aqueous solution, and boil 0.5～1 hour, brown coal are pulled out by extremely neutrality of purified rinse water, finally brown coal are carried out to oxidation drying;
(3) ion-exchange is collaborative with dipping: by the aqueous solution that adds step (1) to configure through the brown coal carrier of step (2) processing, the mass ratio of described brown coal carrier and nickel salt is that (1:1)～(2:1), stirring at normal temperature is more than 12 hours;
(4) filtration drying: step (3) gained is impregnated with to the solution of brown coal, filters after static 1～2 hour, gained filter residue and drying is removed to moisture;
(5) shaping of catalyst: by the dried filter residue of step (4), under the environment of nitrogen, be heated to 300 DEG C from room temperature, and keep 1～2 hour, make catalyst surface stable crystal form, continue to be heated to 600 DEG C from 300 DEG C, and keep 30min, take off the volatile ingredient in brown coal carrier, increase specific surface area of catalyst, after moulding, obtain nickel-base biomass tar steam reforming catalyst.
3. the preparation method of a kind of nickel-base biomass tar steam reforming catalyst according to claim 2, is characterized in that: nickel salt described in step (1) is six water nickel nitrates.
4. the preparation method of a kind of nickel-base biomass tar steam reforming catalyst according to claim 2, is characterized in that: described in step (2), in the aqueous solution of NaOH, the concentration of NaOH is 1g/100ml～5g/100ml.
5. the preparation method of a kind of nickel-base biomass tar steam reforming catalyst according to claim 2, is characterized in that: the drying means of oxidation drying described in step (2) is for being put in 120 DEG C of air dry ovens oxidation drying 24 hours by brown coal.
6. the preparation method of a kind of nickel-base biomass tar steam reforming catalyst according to claim 2, is characterized in that: dry baking temperature described in step (4) is 90 DEG C～110 DEG C.
7. the preparation method of a kind of nickel-base biomass tar steam reforming catalyst according to claim 2, is characterized in that: described in step (5), being heated to the heating rate of 300 DEG C from room temperature is 10 DEG C/min.
8. the preparation method of a kind of nickel-base biomass tar steam reforming catalyst according to claim 2, is characterized in that: described in step (5), be 10 DEG C/min from 300 DEG C of heating rates that are heated to 600 DEG C.
9. the application process of a kind of nickel-base biomass tar steam reforming catalyst as claimed in claim 1, is characterized in that: described nickel-base biomass tar steam reforming catalyst is for temperature reaction, and its reaction temperature is 550 DEG C～700 DEG C.
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Cited By (7)
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| CN106807382A (en) * | 2017-03-29 | 2017-06-09 | 中国矿业大学 | A kind of preparation method of high dispersive Ni/C catalyst |
| CN109126799A (en) * | 2018-08-07 | 2019-01-04 | 淮阴工学院 | A kind of red brick powder supported nickel catalyst and preparation method for biomass char oil-breaking reformation |
| CN110639527A (en) * | 2019-10-15 | 2020-01-03 | 嘉兴学院 | Integral catalyst for hydrogen production by reforming biological oil steam and preparation method thereof |
| CN110711584A (en) * | 2019-10-08 | 2020-01-21 | 宁夏大学 | Semicoke-loaded coke oil steam reforming catalyst and preparation method and application thereof |
| CN113181920A (en) * | 2021-04-28 | 2021-07-30 | 中国矿业大学 | Application of high-dispersion Co/C catalyst in low-temperature catalytic tar steam reforming |
| CN113600198A (en) * | 2021-07-06 | 2021-11-05 | 同济大学 | Biomass tar reforming catalyst and preparation method thereof |
| CN115888720A (en) * | 2022-11-22 | 2023-04-04 | 安徽工业大学 | Ni/C catalyst with lignite as carrier and preparation method and application thereof |
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| CN106807382A (en) * | 2017-03-29 | 2017-06-09 | 中国矿业大学 | A kind of preparation method of high dispersive Ni/C catalyst |
| CN109126799A (en) * | 2018-08-07 | 2019-01-04 | 淮阴工学院 | A kind of red brick powder supported nickel catalyst and preparation method for biomass char oil-breaking reformation |
| CN109126799B (en) * | 2018-08-07 | 2021-04-23 | 淮阴工学院 | Red brick powder loaded nickel catalyst for biomass tar cracking and reforming and preparation method thereof |
| CN110711584A (en) * | 2019-10-08 | 2020-01-21 | 宁夏大学 | Semicoke-loaded coke oil steam reforming catalyst and preparation method and application thereof |
| CN110711584B (en) * | 2019-10-08 | 2022-03-25 | 宁夏大学 | Semicoke-loaded coke oil steam reforming catalyst and preparation method and application thereof |
| CN110639527A (en) * | 2019-10-15 | 2020-01-03 | 嘉兴学院 | Integral catalyst for hydrogen production by reforming biological oil steam and preparation method thereof |
| CN110639527B (en) * | 2019-10-15 | 2021-05-18 | 嘉兴学院 | Integral catalyst for hydrogen production by reforming biological oil steam and preparation method thereof |
| CN113181920A (en) * | 2021-04-28 | 2021-07-30 | 中国矿业大学 | Application of high-dispersion Co/C catalyst in low-temperature catalytic tar steam reforming |
| CN113600198A (en) * | 2021-07-06 | 2021-11-05 | 同济大学 | Biomass tar reforming catalyst and preparation method thereof |
| CN115888720A (en) * | 2022-11-22 | 2023-04-04 | 安徽工业大学 | Ni/C catalyst with lignite as carrier and preparation method and application thereof |
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