CN103846088B - Nickel-base biomass tar steam reforming catalyst and preparation and application method thereof - Google Patents
Nickel-base biomass tar steam reforming catalyst and preparation and application method thereof Download PDFInfo
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Abstract
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.Catalyst of the present invention is with the brown coal of cheapness for carrier, and catalyst of the present invention composition and mass percent are: Ni is 23% ~ 25%, C be 64.26% ~ 66.26%, O is 6.06%, and impurity element is 6%.Catalyst of the present invention adopt ion-exchange and infusion process coordinate system standby.Catalyst of the present invention has good activity and economy.Brown coal are not only cheap but also specific area large, and after caustic washing, the micropore of brown coal self becomes the mesoporous and macropore macromolecular compound more easily by tar, and brown coal also form much new through hole simultaneously.In tar catalytic reforming process, be just provided with more effectively duct, reforming biomass tar efficiency is higher, and the carbon consumption of catalyzer coke content and catalyst carrier carbon can balance by formative dynamics, extending catalyst service life, makes catalyst not easy in inactivation.
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 of fossil energy and global environment worsen, living beings more and more get more and more people's extensive concerning as all replacing the regenerative resource of fossil energy in solid, liquid, gas three.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 comparatively early more abundant.But in gasification, there is a bottleneck, is exactly the generation inevitably along with tar in gasification always.How tar, because of condensation at low temperatures, gathering and cause the loss of equipment corrosion, blocking and energy, is efficiently removed tar, gas that purification produces is become in biomass gasification technology the focal issue being subject to extensive concern.In numerous tar removal technology, the most effective with water vapour catforming.Associated catalysts such as dolomite, alkali metal and nickel-base catalyst etc. are extensively studied.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 (200610122580.7) and biomass gasification tar cracking catalyst and preparation method thereof (200910272415.3) of integral biomass gasified tarcracking catalyst, although they start with to discuss how to prepare efficient nickel-base catalyst from the preparation method of catalyst, but the active component real to catalyst itself and catalytic cracking of tar mechanism thereof also lack enough understanding, and catalyst cost of material higher (price analyzing pure alundum (Al2O3) is 100 yuan/kilogram), be difficult to realize commercial operation.
The present invention selects cheap brown coal (the harbour valency of brown coal is 300 ~ 350 yuan/ton) as the carrier of 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 be the nickel-base catalyst preparation method of carrier with brown coal.
Summary of the invention
The technical problem to be solved in the present invention is: make up weak point in prior art, increases catalyst effective duct quantity, provide a kind of nickel-base biomass tar steam reforming catalyst and preparation and application method thereof by certain density NaOH modification.
A kind of nickel-base biomass tar steam reforming catalyst, described catalyst take brown coal as carrier, described catalyst composition and mass percent as follows:
Ni is 23% ~ 25%, C be 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 pure water is dissolved and makes the aqueous solution, wherein dissolve every gram of nickel salt pure water 20mL ~ 40mL; Add a small amount of ammonium carbonate and solution ph is adjusted to 6 ~ 7, and stir concussion, make the complex compound of solution local generation in the process of adding ammonium carbonate or sediment 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 with purified rinse water extremely neutral, finally brown coal are carried out oxidation drying;
(3) ion-exchange is collaborative with dipping: added by the brown coal carrier processed through step (2) in the aqueous solution that step (1) configures, the mass ratio of described brown coal carrier and nickel salt is (1:1) ~ (2:1), stirring at normal temperature more than 12 hours;
(4) filtration drying: solution step (3) gained being impregnated with brown coal, filters after static 1 ~ 2 hour, by gained filter residue and drying removing moisture;
(5) shaping of catalyst: by step (4) dried filter residue, 300 DEG C are heated to from room temperature under the environment of nitrogen, 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 shaping, namely obtain nickel-base biomass tar steam reforming catalyst.
Nickel salt described in step (1) is six water nickel nitrates.
In the aqueous solution of NaOH described in step (2), 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 oven internal oxidition dry 24 hours by brown coal.
Baking temperature dry described in step (4) is 90 DEG C ~ 110 DEG C.
The heating rate being heated to 300 DEG C from room temperature described in step (5) is 10 DEG C/min.
The heating rate being heated to 600 DEG C from 300 DEG C described in step (5) is 10 DEG C/min.
An application process for nickel-base biomass tar steam reforming catalyst, described nickel-base biomass tar steam reforming catalyst is used for the reaction of middle temperature, and its reaction temperature is 550 DEG C ~ 700 DEG C.
The impurity elements such as Ca, Fe, Al, Na, Ti of containing in described brown coal are natural promoter.
The invention has the beneficial effects as follows:
1, the carrier of catalyst of the present invention selects brown coal, and it has cheap, that specific area is high and activity is good performance.In the catalyst, for active component provides large carrier surface, and the sintering of active component can be prevented, the stability of catalyst is guaranteed;
2, in steam reforming tar process, tar can produce carbon distribution in reforming process, steam can and brown coal carrier in carbon and catalyst surface produce carbon distribution react, make 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 keyhole formation is mesoporous, and non-through hole road becomes through hole, and the macromolecular organic compound contributing to tar passes through;
4, contain a large amount of humic acid in brown coal carrier, humic acid is good ion-exchange raw material, can increase the load capacity of nickel, also can obtain the catalyst of high capacity amount from the nickel solution of low concentration simultaneously.Catalyst of the present invention boils oxidation processes by certain density NaOH to brown coal, makes the active group that the oxidized formation of brown coal is much new, substantially increases the ion-exchange capacity of original brown coal, improve the load capacity of catalyst;
5, by the adjustment 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 is high, and total gas production is large, and hydrogen proportion is high;
6, brown coal are as the one of natural crystal, include the main auxiliary agent that the multiple element (Ca, Fe, Al, Na, Ti etc.) with catalytic action is all biogasification pyrolysis fuel oil catalyst, therefore the catalytic effect of nickel-base catalyst can be improved, 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 when reducing preparation, and save cost;
7, in metal salt solution process for preparation, ammonium carbonate is added for adjust ph, solution ph is raised, 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 that the forward of ion-exchange carries out;
8, comparatively existing biomass tar cracking catalyst, the present invention is because taking brown coal as carrier, and carbon has reproducibility and forms nickel carbon bond with nickel, the nickel firing catalyst back loading can not oxidation by air, before use without the need to Hydrogen activation, and the preparation method of catalyst is simple, and preparation cost is cheap;
9, brown coal are compared with other coal, phosphorus content is low, ash is high is not suitable for burning, but actual conditions are a large amount of brown coal is wasted by with the form of burning, for reasonable efficiency utilization brown coal, descendants is responsible for, a kind of method that this catalyst proposes efficiency utilization brown coal.
Accompanying drawing explanation
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 for 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 3g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 630 DEG C time, toluene conversion reaches more than 95%.
The brown coal that table 1 is preparation in embodiment 1 carry the XRF scanning result of 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 for 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 1g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 630 DEG C time, toluene conversion reaches more than 95%.
Embodiment 3
By analytically pure for 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 3g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 680 DEG C time, toluene conversion reaches more than 95%.
Embodiment 4
By analytically pure for 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 1g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 680 DEG C time, toluene conversion reaches more than 95%.
Embodiment 5
By analytically pure for 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 1g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 630 DEG C time, toluene conversion reaches more than 95%.
Embodiment 6
By analytically pure for 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 3g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 630 DEG C time, toluene conversion reaches more than 95%.
Embodiment 7
By analytically pure for 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 1g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 680 DEG C time, toluene conversion reaches more than 95%.
Embodiment 8
By analytically pure for 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 3g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 680 DEG C time, toluene conversion reaches more than 95%.
Embodiment 9
By analytically pure for 5g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are finally put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: to be dipped in by As-received brown coal in pure water and to boil 1 hour, being pulled out by brown coal and cause neutrality with purified rinse water.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 680 DEG C time, toluene conversion is less than 35%.
Embodiment 10
By analytically pure for 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are finally put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: to be dipped in by As-received brown coal in pure water and to boil 1 hour, being pulled out by brown coal and cause neutrality with purified rinse water.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 680 DEG C time, toluene conversion is less than 35%.
Embodiment 11
By analytically pure for 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 6g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 680 DEG C time, toluene conversion reaches less than 70%.
Embodiment 12
By analytically pure for 10g six water nickel nitrates, add 200ml deionized water, dissolve and make the aqueous solution; Adding a small amount of ammonium carbonate adjust ph is 6 ~ 7, and stirs concussion, makes the complex compound of solution local generation in the process of adding ammonium carbonate or sediment disappear molten.
Brown coal are pulled out and are caused neutrality with purified rinse water, finally brown coal are put in 120 DEG C of air dry oven internal oxidition dry 24 hours by the preparation of brown coal carrier: As-received brown coal to be dipped in concentration be in 9g/100ml sodium hydrate aqueous solution and boil 1 hour.
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, filters after static 1 hour, is placed on by the filter residue obtained in the drying box of 110 DEG C and removes moisture.
Shaping of catalyst: be heated to 300 DEG C with the programming rate of 10 DEG C/min from room temperature under the environment of nitrogen, and keep 1 hour, continue to be heated to 600 with the programming rate of 10 DEG C/min from 300 DEG C, and keep 30min.Namely nickel-base biomass tar steam reforming catalyst is obtained after shaping.
Taking 1g catalyst, take toluene as tar model, and nitrogen is carrier gas, and through experiment in 2 hours 680 DEG C time, toluene conversion reaches less than 55%.
Claims (9)
1. a nickel-base biomass tar steam reforming catalyst, is characterized in that: described catalyst take brown coal as carrier, described catalyst composition and mass percent as follows:
Ni is 23% ~ 25%, C be 64.26% ~ 66.26%, O is 6.06%, and impurity element is 6%;
Described impurity element comprises Ca, Mg, K, Fe, Al, Na, Si, Ti, S, Cr and Mn.
2. the preparation method of a kind of nickel-base biomass tar steam reforming catalyst as claimed in claim 1, it is characterized in that, concrete steps are as follows:
(1) metal salt solution preparation: analytically pure nickel salt pure water is dissolved and makes the aqueous solution, wherein dissolve every gram of nickel salt pure water 20mL ~ 40mL; Add a small amount of ammonium carbonate and solution ph is adjusted to 6 ~ 7, and stir concussion, make the complex compound of solution local generation in the process of adding ammonium carbonate or sediment 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 with purified rinse water extremely neutral, finally brown coal are carried out oxidation drying;
(3) ion-exchange is collaborative with dipping: added by the brown coal carrier processed through step (2) in the solution that step (1) configures, mass ratio (1:1) ~ (2:1) of described brown coal carrier and nickel salt is stirring at normal temperature more than 12 hours;
(4) filtration drying: solution step (3) gained being impregnated with brown coal, filters after static 1 ~ 2 hour, by gained filter residue and drying removing moisture;
(5) shaping of catalyst: by step (4) dried filter residue, 300 DEG C are heated to from room temperature under the environment of nitrogen, 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 shaping, namely 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: in the aqueous solution of NaOH described in step (2), and 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 oven internal oxidition dry 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: baking temperature dry 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: the heating rate being heated to 300 DEG C from room temperature described in step (5) 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: the heating rate being heated to 600 DEG C from 300 DEG C described in step (5) is 10 DEG C/min.
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 used for the reaction of middle temperature, and its reaction temperature is 550 DEG C ~ 700 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410114626.5A CN103846088B (en) | 2014-03-25 | 2014-03-25 | Nickel-base biomass tar steam reforming catalyst and preparation and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410114626.5A CN103846088B (en) | 2014-03-25 | 2014-03-25 | Nickel-base biomass tar steam reforming catalyst and preparation and application method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103846088A CN103846088A (en) | 2014-06-11 |
| CN103846088B true CN103846088B (en) | 2016-04-20 |
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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 |
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| 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 |
| 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 |
| 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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| CN103566937A (en) * | 2012-08-07 | 2014-02-12 | 中国石油化工股份有限公司 | Catalytic coal gasification catalyst and preparation method thereof |
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| CN103566937A (en) * | 2012-08-07 | 2014-02-12 | 中国石油化工股份有限公司 | Catalytic coal gasification catalyst and preparation method 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 |
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