CN109529847A - A kind of method and application preparing carbon base catalyst using waste residue of Chinese herbs - Google Patents
A kind of method and application preparing carbon base catalyst using waste residue of Chinese herbs Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The present invention provides a kind of methods for preparing charcoal based metal catalysts using waste residue of Chinese herbs, High water cut waste residue of Chinese herbs after directly being produced using traditional Chinese medicine enterprise is raw material, charcoal base carrier is obtained by the direct Pintsch process waste residue of Chinese herbs of one-step method, by co-impregnation carried metal Ni, charcoal based metal catalysts are prepared.Further, the application the present invention also provides above-mentioned charcoal based metal catalysts in catalytic pyrolysis biomass.Preparation method of the invention is simple, equipment requirement is low, and catalytic activity is higher, and the catalytic pyrolysis that can be used in tar in biomass pyrolytic or gasification prepares hydrogen-rich gas, to realize the resource utilization of waste residue of Chinese herbs.
Description
Technical field
The invention belongs to carbon base catalyst preparation technical fields, and in particular to a kind of to prepare the catalysis of charcoal base using waste residue of Chinese herbs
The method and application of agent.
Background technique
There is charcoal pore structure abundant, biggish specific surface area and surface to contain more oxygen-content active group,
It is a kind of multifunctional material.In recent years, it is widely used in catalysis, refinery practice by the various functional materials of substrate of charcoal
(synthesis gas conversion and purification), production of biodiesel and kitchen air contaminant control etc..Charcoal based metal catalysts are one kind with life
Material pyrolysis product charcoal is as presoma, in the product of high-temperature activation after carried metal or its oxide.With conventional catalyst
Agent is compared, and charcoal based metal catalysts are cheap, have higher catalytic activity, thus can greatly improve yield and economic effect
Benefit[1]。
The shared traditional Chinese medicine enterprise 1636 in China at present, the 32% of Zhan Quanguo pharmaceuticals industry enterprise, the Chinese medicine slag discharged every year
Up to 12,000,000 tons.Most of Chinese medicine factories are to stack and landfill to the major way of Chinese medicine Solid state fermentation, and enterprise is not only thus
Certain charges for disposing pollutants are paid every year, and certain pollution is caused to water quality, air, soil.Therefore, Chinese medicine slag is researched and developed
High-efficiency comprehensive utilization method, not only can bring economic benefit for pharmacy corporation, but also environmental protection may be implemented.Waste residue of Chinese herbs warp
Generally wet stock is crossed after boiling, there are the disadvantages such as water content high (up to 70%), energy density be low, can not directly burn
Or gasification, which has limited the scale of Chinese medicine dreg utilizations.Traditional is all to first pass through drying later again using thermochemical method
Later use is carried out, which increase the costs of technique.
Has related patents technology under above-mentioned technical background, for example, a kind of carbon base catalyst of patent CN104645993-
Preparation method and application, the disclosure of the invention is a kind of using active carbon as the method for preparing catalyst of carbon based material and application.It is living
After property charcoal is boiled in certain density KOH solution first, distilled, washing, being dried, it is placed in Fe2(CO3)3In colloidal solution
Dipping, filtering, dry, roasting, obtain the carbon base catalyst of load Fe.Then the above catalyst is put into certain density KOH
It is dry after ultrasonic immersing in solution.Next above-mentioned catalyst is placed in reaction of low temperature plasma device, using nitrogen, oxygen
Gas or ammonia are modified, and obtain modified carbon base catalyst.Modified catalyst is used to remove industrial production tail at 40-70 DEG C
The carbonyl sulfur discharged in gas and use process.But active carbon itself as a kind of with the carbon material more extensively applied, be used as original
Material prepares carbon base catalyst, higher cost.The carbon base catalyst of invention preparation, with being impregnated twice using KOH in preparation process
And using plasma reactor is modified, technique is cumbersome and more demanding.And preparation is Fe metallic catalyst, is used for carbonyl
The removing of sulphur not can apply to high-temperature catalytic field.
A kind of patent CN106853371- preparation method and application of charcoal base Fe-series catalyst, the disclosure of the invention one
The preparation method and application of kind charcoal base Fe-series catalyst.Using papermaking wastewater lignin as raw material, by lignin and inorganic iron
Salt is added in collagen aqueous solution, and ageing, drying are simultaneously ground.The above grinding product is under 400-1000 DEG C, inert atmosphere
Calcining, obtains biomass carbon Fe-series catalyst.The catalyst is applied to catalytic wet hydrogen peroxide oxidation degradation high concentration
Learn nickel-plating waste liquid.But biomass carbon Fe-series catalyst is mainly used for chemical method degradation high concentration nickel-plating waste liquid, and being not used for
It learns high-temperature catalytic and cracks field.
A kind of charcoal based composite catalyst of patent CN106799230- and its preparation method and application, disclosure of the invention one kind
Charcoal based composite catalyst and its preparation method and application.Using coconut activated powdered carbon as raw material, after active carbon is crushed, gradually carry out
Cleaning-drying-alkali cleaning-pickling-cleaning-drying.After Fe type or the grinding of TiO2 type catalyst, it is configured to supersaturated suspension.
Active carbon is added in suspension and is adsorbed, is mixed slowly, filters, dry, it is compound that charcoal base is obtained after high-temperature roasting
Catalyst.The above composite catalyst is used for O3 catalytic oxidation processing paper waste, dyeing waste water.But cocoanut active charcoal
Inherently have certain adsorption capacity, prepares carbon base catalyst, the higher cost of technique as raw material, and the compound of preparation is urged
Agent is mainly used for field of waste water treatment.
A kind of Chinese medicine slag biomass carbon base urea of patent CN104829326- and preparation method thereof, disclosure of the invention one kind
Chinese medicine slag biomass carbon base urea and preparation method thereof.Using Chinese medicine slag as raw material, it is cracked at high temperature first, obtains Chinese medicine slag
Biomass carbon.It melts after urea is mixed according to a certain percentage with Chinese medicine slag biomass carbon, be granulated, collect, obtain
Dregs of a decoction biomass carbon base urea.Chinese medicine slag charcoal base urea in the invention is mainly used for improvement and fertilizing soil, improves fertilizer
Utilization rate increases soil organic matter content, improves soil water-reataining fertilizer-keeping ability, promotes plant growth.But the patent is mainly applied
In terms of agricultural.
Bibliography: the synthesis of [1] Wang Haiyan mesoporous carbon based metal catalysts and application [D] Shanghai Normal University,
2009.
Summary of the invention
In view of this, for current waste residue of Chinese herbs resource utilization and biomass carbon base catalysis preparation process technique and
Process challenge, the present invention provides a kind of methods and application that charcoal based metal catalysts are prepared using waste residue of Chinese herbs, directly
High water cut waste residue of Chinese herbs after being produced using traditional Chinese medicine enterprise obtains charcoal base as raw material, by the direct Pintsch process waste residue of Chinese herbs of one-step method
Carrier prepares charcoal based metal catalysts by co-impregnation carried metal Ni.Preparation method of the invention is simple, equipment requirement
Low, catalytic activity is higher, and the catalytic pyrolysis that can be used in tar in biomass pyrolytic or gasification prepares hydrogen-rich gas, thus
Realize the resource utilization of waste residue of Chinese herbs.
First aspect present invention provides a kind of method for preparing charcoal based metal catalysts using waste residue of Chinese herbs, step packet
It includes:
S1, waste residue of Chinese herbs is obtained, the moisture content of the waste residue of Chinese herbs is 50-80%, grain diameter < 2cm；
S2, waste residue of Chinese herbs is placed in Muffle furnace, is warming up under limited oxygen condition with the heating rate of at least 30 DEG C/min
Carbonization temperature is carbonized, and the carbonization temperature is 700-900 DEG C, carbonization time 1-3h, obtains carbonized material carrier after cooling；
S3, by carbonized material carrier obtained by step S2 and Ni (NO3)2·6H2O mixing is added deionized water and stirs, later
Mixed solution is dry, obtain the catalyst that Ni load capacity is 5-20%；
S4, catalyst obtained by step S3 being activated under inert gas protection, activation temperature is 600-800 DEG C, it is cooling, i.e.,
Obtain carbon base catalyst.
The above-mentioned method flow schematic diagram for preparing charcoal based metal catalysts using waste residue of Chinese herbs is as shown in Fig. 1.
Waste residue of Chinese herbs in above-mentioned preparation method is not limited to the single dregs of a decoction, is also possible to the compound dregs of a decoction.
Waste residue of Chinese herbs belongs to biomass resource, produces biomass carbon by Pintsch process under anaerobic or anoxia condition.
The waste residue of Chinese herbs of high-moisture percentage can prepare Chinese medicine slag charcoal by high-temperature cracking method.At the same time, what is generated in cracking process is big
Amount vapor can also catalysis biological charcoal obtain more preferable gap structure and bigger surface area.It is prepared relative to biomass such as stalks
Charcoal, waste residue of Chinese herbs compare concentration, eliminate manpower and cost issues caused by biomass collection, and raw materials for production are at low cost
It is honest and clean, price advantage is obvious.
Ni be a kind of inexpensive catalytic metal and Raney nickel can efficiently catalytic pyrolysis hydrogen-oxygen key and charcoal charcoal key, and
The resistance to deactivation of Raney nickel is higher.Therefore carbon base catalyst is prepared using waste residue of Chinese herbs, is a kind of feasible utilization approaches,
By waste residue of Chinese herbs charcoal, by infusion process, carried metal Ni prepares charcoal based metal catalysts, and process is simple, catalyst applications compared with
Extensively.Carbon base catalyst preparation process provided by the invention based on waste residue of Chinese herbs, by the direct pyrocarbon of the waste residue of Chinese herbs of High water cut
Change, saves intermediate baking step.Charcoal after waste residue of Chinese herbs charing is that carrier prepares catalyst, can not only dissolve Chinese medicine enterprise
The a large amount of waste residue of Chinese herbs generated in industry pharmacy procedure, reduce the production cost of enterprise；Still further aspect can also realize waste residue of Chinese herbs
Resource recycles.
Preferably, in step S2, the heating rate: 40-100 DEG C/min.Heating rate influences waste residue of Chinese herbs pyrocarbon
Change effect, influences the formation of charcoal pore structure.
Preferably, in step S3, the carbonized material carrier and Ni (NO3)2·6H2The weight ratio of O is 10-20:1.
More preferred, in step S3, the mixing time is 5-7h.
Preferably, in step S3, the drying temperature is 100-110 DEG C, drying time 10-14h.
Second aspect of the present invention provides the charcoal that the above-mentioned method for preparing carbon base catalyst using waste residue of Chinese herbs is prepared
Base catalyst.
Third aspect present invention provides application of the above-mentioned carbon base catalyst in catalytic pyrolysis biomass.
Preferably, it is former as pyrolysis less than the biological particles of 0.25mm (60 mesh) that partial size is chosen after the biomass crushes
Material, with carbon base catalyst at 600-900 DEG C catalytic pyrolysis.
More preferred, the pyrolysis feed is cracked at 500 DEG C in a nitrogen atmosphere, then again with the charcoal base
Catalyst carries out catalytic pyrolysis.
More preferred, the pyrolysis feed and the carbon base catalyst catalytic pyrolysis at 600-800 DEG C.
Compared with the prior art, the beneficial effects of the present invention are:
(1) the waste residue of Chinese herbs charcoal that the present invention is prepared by one-step method, specific surface area and pore volume are aobvious to be apparently higher than on an equal basis
Under the conditions of biomass carbon specific surface area and pore volume；
(2) carbon base catalyst preparation process of the invention and process are simple, easy to promote and utilize, equipment requirement and cost
It is low；
(3) charcoal based metal catalysts prepared by the present invention can be used in catalytic pyrolysis, prepare hydrogen-rich gas；
(4) present invention provides a feasible approach for the resource utilization of waste residue of Chinese herbs.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram provided by the invention that charcoal based metal catalysts are prepared using waste residue of Chinese herbs.
Fig. 2 is the X ray diffracting spectrum of different catalysts, wherein a is Chinese medicine slag charcoal；B is load 5%Ni catalyst；c
To load 10%Ni catalyst；D is load 20%Ni catalyst.
Specific embodiment
To facilitate the understanding of the present invention, below in conjunction with Figure of description and embodiment to the present invention make more comprehensively, it is careful
Ground description, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment one
A kind of method for preparing charcoal based metal catalysts using waste residue of Chinese herbs is present embodiments provided, step includes:
Step 1: the waste residue of Chinese herbs that will be obtained from the pharmaceutical factory of traditional Chinese medicine, the moisture content of measurement are 70%, dregs of a decoction grain diameter < 2cm；
Step 2: waste residue of Chinese herbs is placed in Muffle furnace, under limited oxygen condition, 45 DEG C/min of heating rate, carbonization temperature
800 DEG C, carbonization time 2h, waste residue of Chinese herbs carbonized material is obtained after cooling；
Step 3: by carbonized material carrier and Ni (NO3)2·6H2O is mixed according to the weight ratio of 10:1,15:1,20:1 respectively
Close, be added deionized water simultaneously stir 6h, later by mixed solution in thermostatic drying chamber in 105 DEG C of dry 12h, respectively obtain Ni
The carbon base catalyst that load capacity is 5%, 10%, 20%.
Step 4: the carbon base catalyst after dry is in N2It is activated under atmosphere protection, activation temperature is 700 DEG C, is cooled to room temperature
Obtain the charcoal base Ni catalyst that Ni load capacity is respectively 5%, 10%, 20%.
In the present embodiment, using specific surface area analysis instrument (U.S.'s Mike's instrument, ASAP2020) to the waste residue of Chinese herbs of preparation
The specific surface area and pore volume of carbonized material measure.The specific surface area 204.4m of the waste residue of Chinese herbs carbonized material measured2/ g, aperture
For 2.5nm, Kong Rongwei 0.13cm3/g.Consulting literatures are it is found that biomass obtains charcoal under conventional anaerobic cracking conditions
Specific surface area is usually less than 50m2/ g, therefore one-step method of the present invention cracking waste residue of Chinese herbs prepares charcoal and has obviously
Later use advantage.
Embodiment two
The present embodiment has investigated the crystal form knot of the Chinese medicine slag charcoal and supported ni catalyst that are prepared in embodiment one respectively
Structure obtains the X-ray diffractogram of different samples using the X'Pert PRO type X-ray diffractometer that Dutch Panaco company produces
Spectrum.X-ray emitter be the Cu target in K α excitation state, working voltage 40kV, electric current 40mA, as a result as shown in Figure 2.
Fig. 2 describes the XRD that Chinese medicine slag charcoal carried metal Ni catalyst is obtained in different quality ratio, using wet impregnation
Map, wherein curve a, b, c, d respectively represent the XRD diagram of pure charcoal, Ni-5%, Ni-10% and Ni-20%.It can be with from figure
Find out: with pure carbon phase ratio, by the charcoal (b, c, d) of carried metal Ni in 2 θ=37.2 °, 44.7 °, 52.1 ° and 76.8 ° have very
Apparent NiO diffraction maximum, and the increase of the load capacity with W metal, the oxide or compound of Ni is at the peak of XRD analysis
Area is also bigger, illustrates that the load effect of the load metallic Ni catalyst of Chinese medicine slag charcoal made from this experiment is fine, while in catalyst
Surface has preferable dispersion degree.
Embodiment three
The charcoal base Ni catalyst that embodiment one is prepared is used for catalytic pyrolysis biomass, catalytic pyrolysis mistake by the present embodiment
Journey is as follows:
The charcoal base Ni catalyst that the Ni load capacity being prepared is 15% is used for catalytic pyrolysis peanut shell, peanut shell passes through
After crushing, screening partial size is less than the sample of 0.25mm range as pyrolysis feed.Experimental system is two-part reaction furnace, peanut shell
N is carried out in first segment2Cracking under atmosphere, reaction temperature are 500 DEG C, and carbon base catalyst carries out catalytic pyrolysis in second segment, urges
Changing temperature is 600 DEG C.After catalyst layer catalytic pyrolysis occurs for fugitive constituent.
As control, pyrolysis feed is subjected to N in first segment2Cracking under atmosphere, reaction temperature are 500 DEG C, second segment
Cracking process does not add carbon base catalyst, and catalytic temperature is 600 DEG C.
In above-mentioned catalytic pyrolysis process, it is made up of gas chromatograph (Wuhan Tai Te instrument, GC2030) detection gas
And content.The results show that being mainly H in gas-phase product after peanut shell Pintsch process in control2、CH4、CO、CO2, content (volume
Concentration, ppm) it is respectively as follows: 555,1429,27493,7859.Under the same terms, 10% metal of load is added in reactor second segment
After the carbon base catalyst of Ni, H in gas-phase product2、CH4、CO、CO2Content (ppm) be respectively as follows: 27852,2335,105954,
18315.It can be seen that Chinese medicine slag carbon base catalyst can significantly improve H in exit gas2With the content of the combustible gases component such as CO,
It can be applied to catalytic pyrolysis biomass and prepare hydrogen-rich combustion gas.
Example IV
A kind of method for preparing charcoal based metal catalysts using waste residue of Chinese herbs is present embodiments provided, step includes:
Step 1: the waste residue of Chinese herbs that will be obtained from the pharmaceutical factory of traditional Chinese medicine, the waste residue of Chinese herbs are the compound dregs of a decoction, and the moisture content of measurement is
60%, dregs of a decoction grain diameter < 2cm；
Step 2: waste residue of Chinese herbs is placed in Muffle furnace, under limited oxygen condition, 50 DEG C/min of heating rate, carbonization temperature
850 DEG C, carbonization time 3h, waste residue of Chinese herbs carbonized material is obtained after cooling；
Step 3: by carbonized material carrier and Ni (NO3)2·6H2O is mixed according to the weight ratio of 18:1 respectively, and addition is gone
Ionized water simultaneously stirs 7h, later by mixed solution in thermostatic drying chamber in 105 DEG C of dry 12h, obtain carbon base catalyst.
Step 4: the carbon base catalyst after dry is in N2It is activated under atmosphere protection, activation temperature is 750 DEG C, is cooled to room temperature
Obtain charcoal base Ni catalyst.
The above-mentioned charcoal base Ni catalyst that obtains is used for catalytic pyrolysis biomass, catalytic pyrolysis process is as follows:
The charcoal base Ni catalyst being prepared is used for catalytic pyrolysis peanut shell, peanut shell screens partial size after crushing
Less than 0.25mm range sample as pyrolysis feed.Experimental system is two-part reaction furnace, and peanut shell carries out N in first segment2
Cracking under atmosphere, reaction temperature are 500 DEG C, and carbon base catalyst carries out catalytic pyrolysis in second segment, and catalytic temperature is 800 DEG C.
After catalyst layer catalytic pyrolysis occurs for fugitive constituent.
The catalytic effect and embodiment three for the charcoal base Ni catalyst that the present embodiment obtains are almost the same.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although ginseng
It is described the invention in detail according to preferred embodiment, those skilled in the art should understand that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit and scope of the technical solution of the present invention, should all cover
In the scope of the claims of the present invention.
Claims (10)
1. a kind of method for preparing carbon base catalyst using waste residue of Chinese herbs, step include:
S1, waste residue of Chinese herbs is obtained, the moisture content of the waste residue of Chinese herbs is 50-80%, grain diameter < 2cm；
S2, waste residue of Chinese herbs is placed in Muffle furnace, charing is warming up to the heating rate of at least 30 DEG C/min under limited oxygen condition
Temperature is carbonized, and the carbonization temperature is 700-900 DEG C, carbonization time 1-3h, obtains carbonized material carrier after cooling；
S3, by carbonized material carrier obtained by step S2 and Ni (NO3)2·6H2O mixing is added deionized water and stirs, will mix later
Solution drying is closed, the catalyst that Ni load capacity is 5-20% is obtained；
S4, catalyst obtained by step S3 is activated under inert gas protection, activation temperature is 600-800 DEG C, cooling to get arriving
Carbon base catalyst.
2. the method for preparing carbon base catalyst using waste residue of Chinese herbs as described in claim 1, it is characterised in that: in step S2,
The heating rate is 40-100 DEG C/min.
3. the method for preparing carbon base catalyst using waste residue of Chinese herbs as described in claim 1, it is characterised in that: in step S3,
The carbonized material carrier and Ni (NO3)2·6H2The weight ratio of O is 10-20:1.
4. the method for preparing carbon base catalyst using waste residue of Chinese herbs as claimed in claim 3, it is characterised in that: in step S3,
The mixing time is 5-7h.
5. the method for preparing carbon base catalyst using waste residue of Chinese herbs as described in claim 1, it is characterised in that: in step S3,
The drying temperature is 100-110 DEG C, drying time 10-14h.
6. being prepared described in any one of claim 1-5 claim using the method that waste residue of Chinese herbs prepares carbon base catalyst
Carbon base catalyst.
7. application of the carbon base catalyst as claimed in claim 6 in catalytic pyrolysis biomass.
8. the use as claimed in claim 7, it is characterised in that: the biomass chooses the life that partial size is less than 0.25mm after crushing
Material grains as pyrolysis feed, with carbon base catalyst at 600-900 DEG C catalytic pyrolysis.
9. application as claimed in claim 8, it is characterised in that: the pyrolysis feed carries out at 500 DEG C in a nitrogen atmosphere
Then cracking carries out catalytic pyrolysis with the carbon base catalyst again.
10. application as claimed in claim 8, it is characterised in that: the pyrolysis feed and carbon base catalyst are at 600-800 DEG C
Catalytic pyrolysis.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721686A (en) * | 2019-09-27 | 2020-01-24 | 中国科学院广州能源研究所 | Catalytic cracking catalyst using peat carbon base as carrier |
| CN115212911A (en) * | 2022-09-21 | 2022-10-21 | 中国农业科学院农业环境与可持续发展研究所 | Nickel-loaded nitrogen-doped hierarchical pore biochar material and preparation method and application thereof |
| CN117142471A (en) * | 2023-11-01 | 2023-12-01 | 陕西天谷药业有限公司 | Modified activated carbon based on traditional Chinese medicine waste residues and preparation method thereof |
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| CN110721686A (en) * | 2019-09-27 | 2020-01-24 | 中国科学院广州能源研究所 | Catalytic cracking catalyst using peat carbon base as carrier |
| CN110721686B (en) * | 2019-09-27 | 2022-10-14 | 中国科学院广州能源研究所 | Catalytic cracking catalyst using peat carbon as carrier |
| CN115212911A (en) * | 2022-09-21 | 2022-10-21 | 中国农业科学院农业环境与可持续发展研究所 | Nickel-loaded nitrogen-doped hierarchical pore biochar material and preparation method and application thereof |
| CN117142471A (en) * | 2023-11-01 | 2023-12-01 | 陕西天谷药业有限公司 | Modified activated carbon based on traditional Chinese medicine waste residues and preparation method thereof |
| CN117142471B (en) * | 2023-11-01 | 2023-12-22 | 陕西天谷药业有限公司 | Modified activated carbon based on traditional Chinese medicine waste residues and preparation method thereof |
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