CN110124613A - It is a kind of using discarded shrimp shell as nitrogenous biomass carbon adsorbent of raw material and preparation method thereof - Google Patents
It is a kind of using discarded shrimp shell as nitrogenous biomass carbon adsorbent of raw material and preparation method thereof Download PDFInfo
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- CN110124613A CN110124613A CN201910376751.6A CN201910376751A CN110124613A CN 110124613 A CN110124613 A CN 110124613A CN 201910376751 A CN201910376751 A CN 201910376751A CN 110124613 A CN110124613 A CN 110124613A
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- shrimp shell
- biomass carbon
- raw material
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- carbon adsorbent
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4881—Residues from shells, e.g. eggshells, mollusk shells
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The present invention relates to a kind of using discarded shrimp shell as nitrogenous biomass carbon adsorbent of raw material and preparation method thereof.Its technical solution is: discarded shrimp shell clear water being rinsed 5~8 times, 4~8 hours dry under the conditions of 60~80 DEG C, being crushed to partial size is 0.15~2.0mm, obtains shrimp shell broken material.The shrimp shell broken material is placed in electric tube furnace, is warming up to 400~1000 DEG C in nitrogen atmosphere with the rate of 5~10 DEG C/min, 2~3 hours is kept the temperature, is cooled to room temperature, obtains nitrogenous biomass carbon material.It is rinsed 5~8 times by the nitrogenous biomass carbon material dilute acid wash, then with deionized water, it is 8~10 hours dry under the conditions of 90~110 DEG C, it obtains using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material.The present invention has the characteristics that production cost is low and simple process, prepared to discard shrimp shell as the nitrogenous biomass carbon adsorbent porosity of raw material is high and large specific surface area, good to the absorption property of heavy metal.
Description
Technical field
The invention belongs to nitrogenous biomass carbon technical field of absorbent.More particularly to it is a kind of to discard shrimp shell containing as raw material
Nitrogen biomass carbon adsorbent and preparation method thereof.
Background technique
Vertical distribution mainly includes the significant element of the bio-toxicities such as mercury, cadmium, lead, copper.Heavy metal easily passes through food
Object chain and biological concentration, finally enter human body, and in human body and the strong interaction of the generations such as protein and enzyme and make it
Lose activity, it is also possible to certain organs accumulation in human body causes slow poisoning, causes to seriously endanger to human health.Than
Such as, the toxicity of lead is very big, can cause harm to the human body, especially to the lung of human body, cardiovascular system, kidney and reproductive system
It will cause big injury.Therefore, the Treatment process for seeking heavy metal pollution in recent years have become the difficult point studied both at home and abroad and
Hot fields, and biomass carbon is because having good suction-operated to be increasingly interested by researchers in heavy metal.
A kind of " preparation method of the activated carbon from activated sludge rich in nitrogen and oxygen " (CN105692611A) patented technology, being will be wooden
The biological materials such as edge corner material, sawdust with it is nitrogenous and mix containing alkaline matter, heated charing obtains nitrogenous, oxygen biomass
Charcoal.The shortcomings that above method is biological materials such as sawdust used not Nitrogen element itself, need on the basis of raw material into
One step is added compound and introduces nitrogen-atoms, and step is relatively complicated and higher cost, is unfavorable for industrialized production." rich N active carbon electricity
The preparation method of pole " (CN102360959A) patented technology, be using the Waste particleboard rich in Lauxite as raw material,
It carbonizes after being blended under inert atmosphere with potassium hydroxide, is then activated with phosphoric acid, the active carbon rich in nitrogen is made.It is above-mentioned
The shortcomings that method, is: 1, the raw material sources rich in Lauxite are not wide and yield is small, and price is also relatively expensive；2, it is needed before preparation
It is added after alkaline matter is blended with raw material and heats, phosphoric acid is then also added and is activated, complex steps are unfavorable for industry
Metaplasia produces.
In addition, annual in the world can all generate largely discarded shrimp shell due to consumption shrimps, discard in shrimp shell
Rich in the nitrogen substances such as chitin, protein and CaCO3.It is recorded according to " global science " original text, 2016, these discarded shrimp shells
Total amount has just reached 600~8,000,000 tons.Only in Southeast Asia, about 1,400,000 tons of discarded shrimp shells can be generated every year.Most of
Developing country, discarded shrimp shell be generally only simply as rubbish fill up or be poured directly into it is marine.In China, shrimp shell is discarded
Only only a few is made into animal feed, and most shrimp shells are taken as a kind of discarded agricultural and sideline product and are disposed off.
Summary of the invention
The present invention is directed to overcome prior art defect, and it is an object of the present invention to provide a kind of production cost is low and simple process with useless
The preparation method for abandoning the nitrogenous biomass carbon adsorbent that shrimp shell is raw material, with this method preparation to discard shrimp shell containing as raw material
Nitrogen biomass carbon adsorbent porosity height and large specific surface area are good to the absorption property of heavy metal.
To achieve the above object, the technical solution adopted by the present invention comprises the concrete steps that:
Step 1: discarded shrimp shell clear water is rinsed 5~8 times, it is 4~8 hours dry under the conditions of 60~80 DEG C, it is crushed
It is 0.15~2.0mm to partial size, obtains shrimp shell broken material.
Step 2: the shrimp shell broken material is placed in electric tube furnace, with the rate of 5~10 DEG C/min in nitrogen atmosphere
400~1000 DEG C are warming up to, 2~3 hours is kept the temperature, is cooled to room temperature, obtains nitrogenous biomass carbon material.
Step 3: by the nitrogenous biomass carbon material dilute acid wash, then rinsed 5~8 times with deionized water, 90~
It is 8~10 hours dry under the conditions of 110 DEG C, it obtains using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material.
The discarded shrimp shell is the discarded outer of the red shrimp in the South Pole, freshwater shrimp, river prawn, Procambius clarkii, prawn, prawn and lobster
Shell；In the discarded shrimp shell: the content of chitin is 20~30wt%, and the content of protein is 20~30wt%, CaCO3Contain
Amount is 40~50wt%.
The diluted acid is dilute hydrochloric acid or is spirit of vinegar, and the concentration of the diluted acid is 1~5vol%.
Due to using the technical solution, the present invention has following technical effect that compared with prior art
The present invention is prepared as a raw material with the high discarded shrimp shell of nitrogen content, due to have in discarded shrimp shell chitin,
The presence of the nitrogen substances such as protein, so that exempting from during the preparation process using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material
It has gone substep to introduce the troublesome operation of nitrogen-atoms, has simplified technical process.
The present invention uses discarded shrimp shell for raw material, is discarded in ring due to there is a large amount of discarded shrimp shell to be taken as rubbish every year
In border, therefore carrying out source electrode extensively and measuring greatly for shrimp shell is discarded, becomes a kind of nitrogenous biology being easy to get and do not directly affect food chain
Matter source, it is at low cost.The present invention has height texture, high table to discard the nitrogenous biomass carbon adsorbent that shrimp shell is prepared as raw material
The features such as area, high high pore volume and nitrogen content, because it is rich in nitrogen-atoms, relatively unazotized biomass carbon has better
Hydrophily and adsorption capacity.
Nitrogenous biomass carbon material is carried out pickling by the present invention, removes the CaCO in nitrogenous biomass carbon3, thus in situ
Porous structure is formed, having the prepared nitrogenous biomass carbon adsorbent to discard shrimp shell raw material, porosity is high, compares table
The features such as area is big and absorption property is good, can Pb in efficient absorption water2+And Cu2+。
Prepared by the present invention using discarded shrimp shell is the nitrogenous biomass carbon adsorbent of raw material through detecting: being inhaled to lead (II) ion
Attached amount is 58.739~120.27mg/g；It is 46.735~94.394mg/g to cupric ion adsorption.
Therefore, the present invention has the characteristics that production cost is low and simple process, prepared using discarded shrimp shell as raw material
Nitrogenous biomass carbon adsorbent porosity height and large specific surface area are good to the absorption property of heavy metal.
Detailed description of the invention
Fig. 1 is prepared by the present invention a kind of to discard shrimp shell as the SEM of the nitrogenous biomass carbon adsorbent of raw material figure；
Fig. 2 is prepared by the present invention another to discard shrimp shell as the SEM of the nitrogenous biomass carbon adsorbent of raw material figure；
Fig. 3 be it is prepared by the present invention another using discard shrimp shell as the nitrogenous biomass carbon adsorbent of raw material SEM scheme；
Fig. 4 is the energy spectrum analysis figure of the spectrogram A in SEM figure shown in Fig. 3.
Specific embodiment
Present invention will be further described below with reference to the accompanying drawings and specific embodiments, not to the limit of its protection scope
System.
To avoid repeating, shrimp shell first will be discarded involved in present embodiment and diluted acid agreement is described as follows, is implemented
It is repeated no more in example:
The discarded shrimp shell is the discarded outer of the red shrimp in the South Pole, freshwater shrimp, river prawn, Procambius clarkii, prawn, prawn and lobster
Shell；In the discarded shrimp shell: the content of chitin is 20~30wt%, and the content of protein is 20~30wt%, CaCO3Contain
Amount is 40~50wt%.
The diluted acid is dilute hydrochloric acid or is spirit of vinegar, and the concentration of the diluted acid is 1~5vol%.
Embodiment 1
It is a kind of using discarded shrimp shell as nitrogenous biomass carbon adsorbent of raw material and preparation method thereof.It is prepared described in the present embodiment
The step of method, is:
Step 1: discarded shrimp shell clear water is rinsed 5~8 times, it is 7~8 hours dry under the conditions of 60~65 DEG C, it is crushed
It is 0.15~2.0mm to partial size, obtains shrimp shell broken material.
Step 2: the shrimp shell broken material is placed in electric tube furnace, with the rate of 5~7 DEG C/min in nitrogen atmosphere
400~550 DEG C are warming up to, 2~3 hours is kept the temperature, is cooled to room temperature, obtains nitrogenous biomass carbon material.
Step 3: by the nitrogenous biomass carbon material dilute acid wash, then rinsed 5~8 times with deionized water, 90~
It is 8~10 hours dry under the conditions of 95 DEG C, it obtains using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material.
Manufactured in the present embodiment using discarded shrimp shell is the nitrogenous biomass carbon adsorbent of raw material through detecting: to lead (II) ion
Adsorbance is 58.739~69.782mg/g；It is 46.735~56.715mg/g to cupric ion adsorption.
Embodiment 2
It is a kind of using discarded shrimp shell as nitrogenous biomass carbon adsorbent of raw material and preparation method thereof.It is prepared described in the present embodiment
The step of method, is:
Step 1: discarded shrimp shell clear water is rinsed 5~8 times, it is 6~7 hours dry under the conditions of 65~70 DEG C, it is crushed
It is 0.15~2.0mm to partial size, obtains shrimp shell broken material.
Step 2: the shrimp shell broken material is placed in electric tube furnace, with the rate of 6~8 DEG C/min in nitrogen atmosphere
550~700 DEG C are warming up to, 2~3 hours is kept the temperature, is cooled to room temperature, obtains nitrogenous biomass carbon material.
Step 3: by the nitrogenous biomass carbon material dilute acid wash, then rinsed 5~8 times with deionized water, 95~
It is 8~10 hours dry under the conditions of 100 DEG C, it obtains using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material.
Manufactured in the present embodiment using discarded shrimp shell is the nitrogenous biomass carbon adsorbent of raw material through detecting: to lead (II) ion
Adsorbance is 62.179~79.643mg/g；It is 50.831~59.7mg/g to cupric ion adsorption.
Embodiment 3
It is a kind of using discarded shrimp shell as nitrogenous biomass carbon adsorbent of raw material and preparation method thereof.It is prepared described in the present embodiment
The step of method, is:
Step 1: discarded shrimp shell clear water is rinsed 5~8 times, it is 5~6 hours dry under the conditions of 70~75 DEG C, it is crushed
It is 0.15~2.0mm to partial size, obtains shrimp shell broken material.
Step 2: the shrimp shell broken material is placed in electric tube furnace, with the rate of 7~9 DEG C/min in nitrogen atmosphere
700~850 DEG C are warming up to, 2~3 hours is kept the temperature, is cooled to room temperature, obtains nitrogenous biomass carbon material.
Step 3: being rinsed 5~8 times by the nitrogenous biomass carbon material dilute acid wash, then with deionized water, 100
It is 8~10 hours dry under the conditions of~105 DEG C, it obtains using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material.
Manufactured in the present embodiment using discarded shrimp shell is the nitrogenous biomass carbon adsorbent of raw material through detecting: to lead (II) ion
Adsorbance is 78.855~120.27mg/g；It is 62.303~94.394mg/g to cupric ion adsorption.
Embodiment 4
It is a kind of using discarded shrimp shell as nitrogenous biomass carbon adsorbent of raw material and preparation method thereof.It is prepared described in the present embodiment
The step of method, is:
Step 1: discarded shrimp shell clear water is rinsed 5~8 times, it is 4~5 hours dry under the conditions of 75~80 DEG C, it is crushed
It is 0.15~2.0mm to partial size, obtains shrimp shell broken material.
Step 2: the shrimp shell broken material is placed in electric tube furnace, with the rate of 8~10 DEG C/min in nitrogen atmosphere
850~1000 DEG C are warming up to, 2~3 hours is kept the temperature, is cooled to room temperature, obtains nitrogenous biomass carbon material.
Step 3: being rinsed 5~8 times by the nitrogenous biomass carbon material dilute acid wash, then with deionized water, 105
It is 8~10 hours dry under the conditions of~110 DEG C, it obtains using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material.
Manufactured in the present embodiment using discarded shrimp shell is the nitrogenous biomass carbon adsorbent of raw material through detecting: to lead (II) ion
Adsorbance is 72.194~98.263mg/g；It is 58.736~89.254mg/g to cupric ion adsorption.
Present embodiment has following technical effect that compared with prior art
Present embodiment is prepared as a raw material with the high discarded shrimp shell of nitrogen content, due to having in discarded shrimp shell
The presence of the nitrogen substances such as chitin, protein, so that being prepared using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material
The troublesome operation that substep introduces nitrogen-atoms is eliminated in the process, simplifies technical process.
Present embodiment uses discarded shrimp shell as raw material, due to there is a large amount of discarded shrimp shell to be taken as rubbish every year
Rubbish abandons in the environment, therefore discards carrying out source electrode extensively and measuring greatly for shrimp shell, becomes one kind and is easy to get and does not directly affect food chain
Nitrogenous biomass source, it is at low cost.Using discard shrimp shell be the nitrogenous biomass carbon adsorbent for preparing of raw material with height texture,
The features such as high surface area, high high pore volume and nitrogen content, because it is rich in nitrogen-atoms, relatively unazotized biomass carbon has more
Good hydrophily and adsorption capacity.
Nitrogenous biomass carbon material is carried out pickling by present embodiment, removes the CaCO in nitrogenous biomass carbon3,
To which porous structure be formed in situ, make the prepared nitrogenous biomass carbon adsorbent such as attached drawing institute to discard shrimp shell raw material
Show: Fig. 1 is that a kind of of the preparation of the present embodiment 1 is schemed using discarding shrimp shell as the SEM of the nitrogenous biomass carbon adsorbent of raw material；Fig. 2 is
Embodiment 2 is prepared a kind of to discard shrimp shell as the SEM of the nitrogenous biomass carbon adsorbent of raw material figure；Fig. 3 is the preparation of embodiment 3
It is a kind of using discard shrimp shell as the nitrogenous biomass carbon adsorbent of raw material SEM scheme；Fig. 4 is the spectrogram A in SEM figure shown in Fig. 3
Energy spectrum analysis figure.
It will be seen from figure 1 that the surface texture of made product is close, hole is intensive, rough surface；Figure it is seen that
The surface of made product is layer structure, and layer and layer centre are fluffy, and surface is still coarse；From figure 3, it can be seen that the table of made product
Face is extremely coarse and fluffy, and Carbon Materials hole is intensive, and the pore size of hole is uniform；From fig. 4, it can be seen that the energy of made product
N element atomic percentage content has accounted for 4.73% to spectrum analysis as the result is shown, because be rich in nitrogen-atoms due to have better hydrophily with
Adsorption capacity.Therefore the made product of present embodiment has the characteristics that high porosity, large specific surface area and absorption property are strong, energy
Pb in efficient absorption water2+And Cu2+。
Present embodiment preparation is the nitrogenous biomass carbon adsorbent of raw material through detecting using discarded shrimp shell: to divalent
Lead ion adsorbance is 58.739~120.27mg/g；It is 46.735~94.394mg/g to cupric ion adsorption.
Therefore, present embodiment has the characteristics that production cost is low and simple process, prepared to discard shrimp shell
It is good to the absorption property of heavy metal for the nitrogenous biomass carbon adsorbent porosity height and large specific surface area of raw material.
Claims (4)
1. a kind of using discarded shrimp shell as the preparation method of the nitrogenous biomass carbon adsorbent of raw material, it is characterised in that the preparation side
The step of method, is:
Step 1: discarded shrimp shell clear water is rinsed 5~8 times, it is 4~8 hours dry under the conditions of 60~80 DEG C, it is crushed to grain
Diameter is 0.15~2.0mm, obtains shrimp shell broken material；
Step 2: the shrimp shell broken material is placed in electric tube furnace, heated up in nitrogen atmosphere with the rate of 5~10 DEG C/min
To 400~1000 DEG C, 2~3 hours are kept the temperature, is cooled to room temperature, obtains nitrogenous biomass carbon material；
Step 3: being rinsed 5~8 times by the nitrogenous biomass carbon material dilute acid wash, then with deionized water, 90~110
It is 8~10 hours dry under the conditions of DEG C, it obtains using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material.
2. it is according to claim 1 using discarded shrimp shell as the preparation method of the nitrogenous biomass carbon adsorbent of raw material, it is special
Sign is that the discarded shrimp shell is the discarded shell of the red shrimp in the South Pole, freshwater shrimp, river prawn, Procambius clarkii, prawn, prawn and lobster；
In the discarded shrimp shell: the content of chitin is 20~30wt%, and the content of protein is 20~30wt%, CaCO3Content
For 40~50wt%.
3. it is according to claim 1 using discarded shrimp shell as the preparation method of the nitrogenous biomass carbon adsorbent of raw material, it is special
Sign is that the diluted acid is dilute hydrochloric acid or is spirit of vinegar, and the concentration of the diluted acid is 1~5vol%.
4. a kind of using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material, it is characterised in that described to discard shrimp shell as original
The nitrogenous biomass carbon adsorbent of material be any one of according to claim 1~3 described in to discard shrimp shell containing as raw material
Using discarded shrimp shell as the nitrogenous biomass carbon adsorbent of raw material prepared by the preparation method of nitrogen biomass carbon adsorbent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111715258A (en) * | 2020-06-15 | 2020-09-29 | 上海大学 | Nitrogen-doped carbon-based catalyst and application thereof in preparation of vinyl chloride by catalyzing hydrochlorination of acetylene |
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| CN106268681A (en) * | 2016-10-12 | 2017-01-04 | 厦门大学嘉庚学院 | A kind of method utilizing shrimp and crab shells to prepare environmentally friendly dye sorbent |
| JP2017109905A (en) * | 2015-12-17 | 2017-06-22 | 有限会社ケーティーワイ | Biomass carbon manufacturing system |
| CN109046240A (en) * | 2018-08-15 | 2018-12-21 | 浙江海洋大学 | A kind of heavy metal absorbent preparation method based on high-specific surface area shrimp shell biomass carbon |
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2019
- 2019-05-07 CN CN201910376751.6A patent/CN110124613A/en active Pending
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| CN102000552A (en) * | 2010-12-06 | 2011-04-06 | 河海大学 | Novel heavy metal adsorbent mainly prepared from shrimp shells and preparation method thereof |
| CN105271171A (en) * | 2015-11-05 | 2016-01-27 | 江苏大学 | Preparation method of N-doped hierarchical pore carbon material with shrimp shells as carbon sources |
| JP2017109905A (en) * | 2015-12-17 | 2017-06-22 | 有限会社ケーティーワイ | Biomass carbon manufacturing system |
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| CN111715258A (en) * | 2020-06-15 | 2020-09-29 | 上海大学 | Nitrogen-doped carbon-based catalyst and application thereof in preparation of vinyl chloride by catalyzing hydrochlorination of acetylene |
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