CN109908903A - A kind of high-specific surface area Lignin-Based Activated Carbon is nickel-base catalyst and its preparation and application of carrier - Google Patents
A kind of high-specific surface area Lignin-Based Activated Carbon is nickel-base catalyst and its preparation and application of carrier Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysis material, nickel-base catalyst and its preparation and application that a kind of high-specific surface area Lignin-Based Activated Carbon is carrier are disclosed.Method: 1) mixing lignin with the aqueous solution of additive, heating stirring, dry, obtains lignin-additive；2) lignin-additive is subjected to vacuum pyrolysis, obtains pyrolytic carbon；3) the unreacted additive in pyrolytic carbon is removed, washing to neutrality is dry, obtains active carbon with high specific surface area；4) active carbon with high specific surface area is impregnated in nickel source solution, dry, vacuum calcining obtains nickel-base catalyst.Method of the invention is simple, and prepared specific surface area of catalyst is big, and nickel particle is uniformly dispersed, catalytic efficiency with higher and lower reduction temperature.Catalyst of the invention is used for carbon dioxide hydrogenation reaction and/or carbon monoxide hydrogenation.
Description
Technical field
The invention belongs to the technical fields of catalysis material, and in particular to a kind of high-specific surface area Lignin-Based Activated Carbon is to carry
Nickel-base catalyst of body and the preparation method and application thereof.
Background technique
With the development of industry with a large amount of uses of fossil fuel, the discharge amount of carbon dioxide is growing, this is exacerbated
The trend of greenhouse effects and global warming.In order to solve or slow down this great environmental problem, scientists are dedicated to studying
The technology of exploitation storage and fixed carbon dioxide.Currently, the pressuring method of carbon dioxide physics is thrown into underground to be acknowledged as
Be it is a kind of effectively and feasible method reduces the greenhouse gases discharged in atmosphere.However, this handled carbon dioxide
There are some apparent challenges and disadvantages for storage and fixed mode: the carbon dioxide collection in the whole world is got up the skill of centralized processing
Efficiency and carbon dioxide leakage after art, the high cost problem because studying technology generation, storage and fixed carbon dioxide
The problems such as be all a problem to be solved.Therefore, these problems promote people to have to find other feasible methods, such as will
The discharge amount that carbon dioxide conversion is the chemicals of other available fuel either high added value to reduce carbon dioxide.
Currently, carbon dioxide hydrogenation reaction by being produced methanol, carbon by people in order to reduce the discharge amount of carbon dioxide
The chemicals such as hydrogen compound (such as methane) and carbon monoxide.But the carbon dioxide conversion of these reactions is all very low, and at
This is higher.Therefore, improving carbon dioxide conversion becomes the hot spot of researcher's concern.For synthesizing methanol, current research
Copper based catalyst systems are usually used, the catalyst carrier of this kind of catalyst usually has zinc oxide, titanium oxide, zirconium oxide and oxygen
Change aluminium etc..But this kind of catalyst is the problem is that the framework of copper-based catalysts is very sensitive to the induction of temperature, and synthesizes
This reaction of methanol is exothermic reaction, thus the production rate of methanol theoretically and experiment in be all very low, even reaction item
Part is 300 DEG C, the methanol yield under 0.1MPa only 0.06%.As for hydrocarbon (mainly alkanes and alkene
Class), it can be synthesized by Fischer-Tropsch reaction (Fischer-Tropsh), this reaction is exothermic reaction, so temperature is unsuitable excessively high.
Although Fischer-Tropsch reaction is that a kind of very promising method carrys out Synthin compound, designs synthesizing hydrophobic and alkanes produce
The highly selective catalyst of object has very big challenge.However, it is that one kind can be with that hydrogenation of carbon dioxide, which generates carbon monoxide,
Reduce the feasible path of CO2 emission.The reaction by anti-water gas reaction generate carbon monoxide, and carbon monoxide be can
With by Fischer-Tropsch reaction and other chemical reactive synthesis various chemicals and fuel, therefore carbon dioxide hydrogenation reaction generates one
Carbonoxide it is significant！
Both at home and abroad at present in the research papers about the catalyst of preparation synthesis carbon dioxide hydrogenation reaction, researcher
The active metal generally selected have: noble metal (platinum, palladium, rhodium), transition metal (iron, cobalt, nickel), there are also some other metals such as
Copper and molybdenum are also commonly used active metal.In addition, researchers generally use cerium oxide, aluminium oxide, silica, oxidation
Titanium, molybdenum carbide and molecular sieve etc. make catalyst carrier.However, there is also many problems for these catalyst, such as: treating capacity compared with
Small, conversion ratio is lower or high cost disadvantage.
The present invention is pyrolyzed under vacuum after selecting lignin to mix with additive, and it is living to obtain high specific area later through overactivation
Property charcoal, then by dipping and vacuum calcining after, prepare active carbon with high specific surface area supported nickel based catalysts.This Gao Bibiao
The catalyst of area can promote active metal nickel to be distributed uniformly in carrier active carbon, and then improve hydrogenation of carbon dioxide
Reaction conversion ratio.Certainly, the application of the catalyst is far above in carbon dioxide hydrogenation reaction, is also applied to other plus hydrogen
Reaction such as carbon monoxide hydrogenation either some other pyroreactions.
Summary of the invention
For the deficiency for preparing hydrogenation of carbon dioxide catalyst material at present, the purpose of the present invention is to provide one kind can be big
The active carbon with high specific surface area of amount production makees nickel-base catalyst of carrier and preparation method thereof.Catalyst of the invention has high
Specific surface area and there is lower reduction temperature (to show to need less heat to supply before reduction using the catalyst, therefore
It can be reduced energy consumption).In addition the active metal nickel of catalyst EDS maps on carrier active carbon are relatively uniform, so that reaction gas
It can be come into full contact with nickel, and then promote the conversion ratio of hydrogenation of carbon dioxide generation reaction of carbon monoxide.Carbon monoxide is in formic acid
The preparation (as raw material) of sodium, metallurgy, which restore the fields such as (reducing agent), gaseous fuel, good application prospect.In addition, should
The preparation method of catalyst is possible to be applied to the catalyst system that design synthesizes relevant high temperature resistant and high-specific surface area.
Another object of the present invention is to provide the nickel catalysts that above-mentioned high-specific surface area Lignin-Based Activated Carbon is carrier
The application of agent.The high-specific surface area Lignin-Based Activated Carbon is the nickel-base catalyst of carrier in carbon dioxide hydrogenation reaction or one
Application in carbonoxide hydrogenation reaction.
The purpose of the present invention is achieved through the following technical solutions:
A kind of high-specific surface area Lignin-Based Activated Carbon is the preparation method of the nickel-base catalyst of carrier, including following step
It is rapid:
1) lignin is mixed with the aqueous solution of additive, heating stirring, it is dry, obtain lignin-additive；
2) lignin-additive is subjected to vacuum pyrolysis, obtains pyrolytic carbon；
3) the unreacted additive in pyrolytic carbon is removed, washing to neutrality is dry, obtains active carbon with high specific surface area；
4) active carbon with high specific surface area is impregnated in nickel source solution, dry, vacuum calcining obtains nickel-base catalyst.
In the aqueous solution of additive described in step 1) mass volume ratio of additive and water be (1~10) g:(100~
200)mL；The temperature of the heating stirring is 50~90 DEG C, heating stirring to muddy, and the temperature of the drying is 60~105
℃；
The lignin is broadleaf lignin, needle lignin or vegetation class lignin.
The lignin is preferably alkali lignin.
Additive described in step 1) is one in potassium hydroxide, sodium hydroxide, phosphoric acid, zinc chloride, sodium carbonate or potassium carbonate
Kind or more, promote the pyrolysis of lignin and the generation of the pore structure of active carbon to construct.
The mass ratio of additive described in step 1) and lignin is (0.5~3): 1.
The temperature of vacuum pyrolysis described in step 2) is 600~900 DEG C, and the time of vacuum pyrolysis is 1~5h.
The rate of the heating of vacuum pyrolysis is 1 DEG C/min~10 DEG C/min.
Unreacted additive in removal pyrolytic carbon described in step 3), which refers to, grinds pyrolytic carbon, and cleaning solution impregnates,
It boils, cleaning solution cleans after cooling.
The cleaning solution is dilute hydrochloric acid or ammonium hydroxide, for neutralizing extra additive；The boiling time and use cleaning solution
The number washed is respectively 15~30min, 2~5 times.
Nickel source described in step 4) is more than one in Nickelous nitrate hexahydrate, Nickel dichloride hexahydrate or nickel acetate.
The concentration of nickel source solution described in step 4) is 0.1~0.5mol/L；Nickel element is active carbonaceous in the nickel source
The 1%~5% of amount.
The dipping, which refers to, mixes active carbon with nickel source solution, heating stirring to muddy.The temperature of the heating is
50~90 DEG C.The temperature of the drying is 80~120 DEG C.
The temperature of vacuum calcining described in step 4) is 400~700 DEG C, and the time of the vacuum calcining is 3~5h.
The high-specific surface area Lignin-Based Activated Carbon is that the nickel-base catalyst of carrier is prepared by the above method.
The specific surface area of the catalyst is 700~1 800cm2/ g, total pore volume is up to 0.4~1.0cm3/ g, including
Micropore has 0.2~0.5cm3/g。
Catalyst of the invention has up to 700~1 800m2The specific surface area of/g, this shows that catalyst of the invention carries
Body active carbon is capable of providing enough active site load nickel particles, so that nickel particle dispersion is relatively uniform, and then improves catalysis
Efficiency；And the reduction temperature of the nickel particle in the catalyst reduces, it is meant that need when hydrogenation catalyst reaction lower
Temperature can restore the nickel oxide in catalyst, it is possible to reduce energy consumption needed for certain reduction.Meanwhile the catalyst has
Have it is compressible at blocky, lightweight and convenient transport, preparation method is simple and convenient, short preparation period, is easy to the features such as largely preparing, because
This is easy to implement industrialized production, and then has great prospects for commercial application.
Compared with prior art, present invention has the advantage that
1. method of the invention is simple, prepared nickel-base catalyst has high specific surface area, and can largely prepare,
It is easy to industrialized production.
2. catalyst of the invention has lower reduction temperature, show to need before reduction using the catalyst less
Heat supply, therefore can be reduced energy consumption.
3. active metal nickel is evenly distributed on carrier active carbon in catalyst of the invention, so that reaction gas and nickel
It can come into full contact with, and then hydrogenation of carbon dioxide is promoted to generate the conversion ratio of reaction of carbon monoxide, two discharged can be reduced
The amount of carbonoxide is of great significance to the speed for delaying global warming and sea level rise.
4. catalyst hydrogenation of carbon dioxide of the invention generates carbon monoxide in raw material, the metallurgy for preparing sodium formate
In make the fields such as reducing agent, gaseous fuel and will have good application prospect.
Detailed description of the invention
Fig. 1 is the TEM figure of nickel-base catalyst prepared by embodiment 1,2,5 and 6；A is embodiment 1, and b is embodiment 2, and c is
Embodiment 6, d are embodiment 5；
Fig. 2 is nickel particle size-frequency distribution of the nickel-base catalyst of Examples 1 and 2 preparation；A is embodiment 1, and b is
Embodiment 2；
Fig. 3 is the XRD diagram of nickel-base catalyst prepared by embodiment 1；
Fig. 4 is the hydrogen temperature programmed reduction (H of nickel-base catalyst prepared by embodiment 32- TPR) figure.
Specific embodiment
Further detailed description is done to the present invention below with reference to embodiment, embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of high-specific surface area Lignin-Based Activated Carbon is that the nickel-base catalyst of carrier is prepared by the following method to obtain:
4g potassium hydroxide is taken to be dissolved in 150mL deionized water, mechanical stirring obtains potassium hydroxide solution to abundant dissolution；It will
4g alkali lignin is dissolved in potassium hydroxide solution, using magnetic stirring apparatus heating (70 DEG C) and is stirred to muddy, is placed air blast
105 DEG C of dry 12h in baking oven obtain potassium hydroxide-alkali lignin；Dried potassium hydroxide-alkali lignin is put into tubular type
In furnace, under vacuum with 5 DEG C/min temperature programming to 800 DEG C, and kept for 5 hours, then cooling obtains pyrolytic carbon under vacuum；It will
Pyrolytic carbon is ground to powder, then impregnates 12h with 0.1mol/L dilute hydrochloric acid, later boils soak 20 minutes, liquid cooling to be boiled
But, it is first washed 2 times with dilute hydrochloric acid, then is washed till neutrality with a large amount of deionized waters, then 105 DEG C of freeze-day with constant temperature into air dry oven, obtained
To active carbon with high specific surface area；8.5mL0.1mol/L Nickelous nitrate hexahydrate is impregnated into 1g active carbon, magnetic stirring apparatus is utilized
Heating stirring is to muddy at 85 DEG C, then by its in air dry oven 105 DEG C it is dried after, in tube furnace 550 DEG C it is true
Sky calcining 4 hours obtains the nickel-base catalyst that high-specific surface area Lignin-Based Activated Carbon is carrier.
The transmission electron microscope picture (TEM figure) of the nickel-base catalyst of the present embodiment is such as shown in Fig. 1 (a), it can be seen that nickel particle point
It dissipates relatively uniform.Further, Fig. 2 (a) is nickel particle size-frequency distribution of the present embodiment nickel-base catalyst, can be seen
Nickel particle size is concentrated mainly on 10~12nm out.Fig. 3 is the XRD diagram of the nickel-base catalyst of the present embodiment, is not seen very
Sharp strong peak illustrates that the lattice arrangement of nickel particle is irregular, that is, that disperses is relatively uniform.Because nickel particle is uniformly dispersed, institute
To improve the conversion ratio of carbon dioxide hydrogenation reaction.The catalytic performance of nickel-base catalyst manufactured in the present embodiment: carbon dioxide
Conversion ratio is 58.5%, and carbon monoxide selective is then 98% or more.
Embodiment 2
1g potassium hydroxide is taken to be dissolved in 100mL deionized water, mechanical stirring obtains potassium hydroxide solution to abundant dissolution；It will
1g alkali lignin is dissolved in potassium hydroxide solution, using magnetic stirring apparatus heating (70 DEG C) and is stirred to muddy, is placed air blast
105 DEG C of dry 12h in baking oven obtain potassium hydroxide-alkali lignin；Dried potassium hydroxide-alkali lignin is put into tubular type
In furnace, under normal pressure with 5 DEG C/min temperature programming to 700 DEG C, and kept for 3 hours, then cooling obtains pyrolytic carbon under normal pressure；It will
Pyrolytic carbon is ground to powder, then impregnates 12h with 0.1mol/L dilute hydrochloric acid, later boils soak 30 minutes, liquid cooling to be boiled
But, it is first washed 3 times with dilute hydrochloric acid, then is washed till neutrality with a large amount of deionized waters, then 105 DEG C of freeze-day with constant temperature into air dry oven, obtained
To active carbon with high specific surface area；2.6mL0.1mol/L Nickelous nitrate hexahydrate is impregnated into 0.5g active carbon, magnetic agitation is utilized
Device at 85 DEG C heating stirring to muddy, then by its in air dry oven 105 DEG C it is dried after, 450 DEG C in tube furnace
Vacuum calcining 5 hours, just obtain the nickel-base catalyst that the high-specific surface area Lignin-Based Activated Carbon is carrier.
Shown in the transmission electron microscope picture of nickel-base catalyst manufactured in the present embodiment such as Fig. 1 (b), it can be seen that nickel particle at this time compared with
Greatly.Fig. 2 (b) is nickel particle size-frequency distribution of nickel-base catalyst manufactured in the present embodiment, it can be seen that nickel particle size
It is concentrated mainly on 15~40nm, illustrates the sintering that is easy to happen of the catalyst prepared under normal pressure, thus is prepared under the normal pressure
Catalyst the good dispersion degree that does not prepare under vacuum of active metal.
Embodiment 3
6g potassium hydroxide is taken to be dissolved in 200mL deionized water, mechanical stirring obtains potassium hydroxide solution to abundant dissolution；It will
2g alkali lignin is dissolved in potassium hydroxide solution, using magnetic stirring apparatus heating (70 DEG C) and is stirred to muddy, is placed air blast
105 DEG C of dry 12h in baking oven obtain potassium hydroxide-alkali lignin；Dried potassium hydroxide-alkali lignin is put into tubular type
In furnace, under vacuum with 5 DEG C/min temperature programming to 900 DEG C, and kept for 1 hour, then cooling obtains pyrolytic carbon under vacuum；It will
Pyrolytic carbon is ground to powder, then uses 0.1mol/L dilute hydrochloric acid soaked overnight, later boils soak 15 minutes, liquid cooling to be boiled
But, it is first washed 4 times with dilute hydrochloric acid, then is washed till neutrality with a large amount of deionized waters, then 105 DEG C of freeze-day with constant temperature into air dry oven, obtained
To active carbon with high specific surface area；1.7mL0.1mol/L Nickelous nitrate hexahydrate is impregnated into 1g active carbon, magnetic stirring apparatus is utilized
Heating stirring is to muddy at 85 DEG C, then by its in air dry oven 105 DEG C it is dried after, in tube furnace 650 DEG C it is true
Sky calcining 3 hours just obtains the nickel-base catalyst that high-specific surface area Lignin-Based Activated Carbon is carrier.
The specific surface area of catalyst manufactured in the present embodiment is 1790cm2/ g, huge specific surface area are active metal nickel
Sufficient load site is provided, so that EDS maps are more uniform on the activated carbon for nickel particle, and then carbon dioxide is promoted to add
The efficiency of hydrogen.Fig. 4 is the H of nickel-base catalyst manufactured in the present embodiment2- TPR figure, illustrate the reduction temperature of nickel oxide particle compared with
It is low, energy consumption needed for hydrogenation of carbon dioxide pre reduction catalyst can be reduced.
Embodiment 4
4g zinc chloride is taken to be dissolved in 150mL deionized water, mechanical stirring obtains liquor zinci chloridi to abundant dissolution；By 4g alkali
Lignin is dissolved in liquor zinci chloridi, using magnetic stirring apparatus heating (70 DEG C) and is stirred to muddy, is placed in convection oven
105 DEG C of dry 12h obtain zinc chloride-alkali lignin；Dried zinc chloride-alkali lignin is put into tube furnace, in vacuum
Under with 5 DEG C/min temperature programming to 800 DEG C, and keep 3 hours, then under vacuum cooling obtain pyrolytic carbon；Pyrolytic carbon is ground
To powder, then use 0.1mol/L dilute hydrochloric acid soaked overnight, later boil soak 20 minutes, liquid cooling to be boiled but, first with dilute
Salt pickling 4 times, then it is washed till neutrality with a large amount of deionized waters, then 105 DEG C of freeze-day with constant temperature into air dry oven, obtain high-ratio surface
Product active carbon；8.5mL0.1mol/L Nickelous nitrate hexahydrate is impregnated into 1g active carbon, is added at 85 DEG C using magnetic stirring apparatus
Thermal agitation to muddy, then by its in air dry oven 105 DEG C it is dried after, 550 DEG C of vacuum calcinings 4 are small in tube furnace
When, obtain the nickel-base catalyst that high-specific surface area Lignin-Based Activated Carbon is carrier.Nickel-base catalyst manufactured in the present embodiment
Specific surface area is 860cm2/ g, in carbon dioxide hydrogenation reaction, titanium dioxide charcoal percent conversion is 32%, the reduction of catalyst
Temperature is 283 DEG C.
Embodiment 5
3g zinc chloride is taken to be dissolved in 120mL deionized water, mechanical stirring obtains liquor zinci chloridi to abundant dissolution；By 5g alkali
Lignin is dissolved in liquor zinci chloridi, using magnetic stirring apparatus heating (70 DEG C) and is stirred to muddy, is placed in convection oven
105 DEG C of dry 12h obtain zinc chloride-alkali lignin；Dried zinc chloride-alkali lignin is put into tube furnace, in normal pressure
Under with 5 DEG C/min temperature programming to 700 DEG C, and keep 5 hours, then under vacuum cooling obtain pyrolytic carbon；Pyrolytic carbon is ground
To powder, then use 0.1mol/L dilute hydrochloric acid soaked overnight, later boil soak 30 minutes, liquid cooling to be boiled but, first with dilute
Salt pickling 4 times, then it is washed till neutrality with a large amount of deionized waters, then 105 DEG C of freeze-day with constant temperature into air dry oven, obtain high-ratio surface
Product active carbon；2.6mL 0.1mol/L Nickelous nitrate hexahydrate is impregnated into 0.5g active carbon, using magnetic stirring apparatus at 85 DEG C
Lower heating stirring to muddy, then by its in air dry oven 105 DEG C it is dried after, 450 DEG C of vacuum calcinings 5 in tube furnace
Hour, obtain the nickel-base catalyst that high-specific surface area Lignin-Based Activated Carbon is carrier.Nickel-base catalyst manufactured in the present embodiment
Transmission electron microscope picture such as Fig. 1 (d) shown in, the specific surface area of catalyst manufactured in the present embodiment is 700cm2/ g, in titanium dioxide
In carbon hydrogenation reaction, titanium dioxide charcoal percent conversion is 29%, and the reduction temperature of catalyst is 287 DEG C.
Embodiment 6
6g zinc chloride is taken to be dissolved in 200mL deionized water, mechanical stirring obtains liquor zinci chloridi to abundant dissolution；By 2g alkali
Lignin is dissolved in liquor zinci chloridi, using magnetic stirring apparatus heating (70 DEG C) and is stirred to muddy, is placed in convection oven
105 DEG C of dry 12h obtain zinc chloride-alkali lignin；Dried zinc chloride-alkali lignin is put into tube furnace, in vacuum
Under with 5 DEG C/min temperature programming to 900 DEG C, and keep 1 hour, then under vacuum cooling obtain pyrolytic carbon；Pyrolytic carbon is ground
To powder, then impregnate 12h with 0.1mol/L dilute hydrochloric acid, later boil soak 15 minutes, liquid cooling to be boiled but, first with dilute salt
Pickling 4 times, then it is washed till neutrality with a large amount of deionized waters, then 105 DEG C of freeze-day with constant temperature into air dry oven, obtain high-specific surface area
Active carbon；1.7mL 0.1mol/L Nickelous nitrate hexahydrate will be taken to be impregnated into 1g active carbon, using magnetic stirring apparatus at 85 DEG C
Heating stirring to muddy, then by its in air dry oven 105 DEG C it is dried after, 650 DEG C of vacuum calcinings 3 are small in tube furnace
When, just obtain the nickel-base catalyst that high-specific surface area Lignin-Based Activated Carbon is carrier.
Shown in the transmission electron microscope picture of nickel-base catalyst manufactured in the present embodiment such as Fig. 1 (c), it can be seen that nickel particle dispersed phase
To uniform, the present embodiment is more slightly bigger than the nickel particle size of embodiment 1, illustrates additive potassium hydroxide more than zinc chloride
It can promote to form the lesser nickel particle of size.
Fig. 1 is the TEM figure of nickel-base catalyst prepared by embodiment 1,2,5 and 6；A is embodiment 1, and b is embodiment 2, and c is
Embodiment 6, d are embodiment 5；
Fig. 2 is nickel particle size-frequency distribution of the nickel-base catalyst of Examples 1 and 2 preparation；A is embodiment 1, and b is
Embodiment 2；
Fig. 3 is the XRD diagram of nickel-base catalyst prepared by embodiment 1；
Fig. 4 is the hydrogen temperature programmed reduction (H of nickel-base catalyst prepared by embodiment 32- TPR) figure.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (9)
1. the preparation method that a kind of high-specific surface area Lignin-Based Activated Carbon is the nickel-base catalyst of carrier, it is characterised in that: packet
Include following steps:
1) lignin is mixed with the aqueous solution of additive, heating stirring, it is dry, obtain lignin-additive；
2) lignin-additive is subjected to vacuum pyrolysis, obtains pyrolytic carbon；
3) the unreacted additive in pyrolytic carbon is removed, washing to neutrality is dry, obtains active carbon with high specific surface area；
4) active carbon with high specific surface area is impregnated in nickel source solution, dry, vacuum calcining obtains nickel-base catalyst；
The additive is more than one in potassium hydroxide, sodium hydroxide, phosphoric acid, zinc chloride, sodium carbonate or potassium carbonate；
The temperature of the vacuum pyrolysis is 600~900 DEG C；The temperature of the vacuum calcining is 400~700 DEG C.
2. high-specific surface area Lignin-Based Activated Carbon is the preparation method of the nickel-base catalyst of carrier according to claim 1,
It is characterized by: the mass ratio of additive described in step 1) and lignin is (0.5~3): 1；
Nickel source described in step 4) is more than one in Nickelous nitrate hexahydrate, Nickel dichloride hexahydrate or nickel acetate.
3. high-specific surface area Lignin-Based Activated Carbon is the preparation method of the nickel-base catalyst of carrier according to claim 1,
It is characterized by: the concentration of nickel source solution described in step 4) is 0.1~0.5mol/L；Nickel element is active carbon in the nickel source
The 1%~5% of quality.
4. high-specific surface area Lignin-Based Activated Carbon is the preparation method of the nickel-base catalyst of carrier according to claim 1,
It is characterized by: the time of vacuum pyrolysis described in step 2) is 1~5h, time of vacuum calcining described in step 4) is 3~
5h。
5. high-specific surface area Lignin-Based Activated Carbon is the preparation method of the nickel-base catalyst of carrier according to claim 1,
It is characterized by:
The mass volume ratio of additive and water is (1~10) g:(100~200 in the aqueous solution of additive described in step 1))
mL；The temperature of the heating stirring is 50~90 DEG C, heating stirring to muddy；
The lignin is alkali lignin.
6. high-specific surface area Lignin-Based Activated Carbon is the preparation method of the nickel-base catalyst of carrier according to claim 1,
Active carbon is mixed with nickel source solution it is characterized by: dipping described in step 4) refers to, heating stirring to muddy；In dipping
The temperature of heating is 50~90 DEG C；
The rate of the heating of vacuum pyrolysis is 1 DEG C/min~10 DEG C/min in step 2).
7. high-specific surface area Lignin-Based Activated Carbon is the preparation method of the nickel-base catalyst of carrier according to claim 1,
Pyrolytic carbon is ground it is characterized by: the unreacted additive in removal pyrolytic carbon described in step 3) refers to, cleaning solution leaching
Bubble, boils, and cleaning solution cleans after cooling；
The cleaning solution is dilute hydrochloric acid or ammonium hydroxide, for neutralizing extra additive.
8. a kind of high-specific surface area Lignin-Based Activated Carbon obtained by the described in any item preparation methods of claim 1~7 is
The nickel-base catalyst of carrier.
9. high-specific surface area Lignin-Based Activated Carbon is that the nickel-base catalyst of carrier adds in carbon dioxide according to claim 8
Application in hydrogen reaction and/or carbon monoxide hydrogenation.
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| CN114588910A (en) * | 2022-03-15 | 2022-06-07 | 福州大学 | Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization |
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| RU2741006C1 (en) * | 2020-06-17 | 2021-01-22 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of producing carbon monoxide from hydrolysed lignin under action of co2 |
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| CN114272932A (en) * | 2021-12-31 | 2022-04-05 | 安徽理工大学 | Nickel-cerium biochar catalyst and preparation method and application thereof |
| CN114272932B (en) * | 2021-12-31 | 2023-11-07 | 安徽理工大学 | Nickel-cerium biochar catalyst and preparation method and application thereof |
| CN114602524A (en) * | 2022-03-02 | 2022-06-10 | 武汉科技大学 | Preparation of nitrogen modified catalyst and application thereof in preparation of cyclohexanone by phenol hydrogenation |
| CN114588910A (en) * | 2022-03-15 | 2022-06-07 | 福州大学 | Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization |
| CN114931953A (en) * | 2022-06-02 | 2022-08-23 | 南昌大学 | Preparation method of catalyst for converting biomass into hydrocarbon compound |
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