CN108658071A - It is a kind of using chromium skin as biomass porous carbon of raw material and its preparation method and application - Google Patents
It is a kind of using chromium skin as biomass porous carbon of raw material and its preparation method and application Download PDFInfo
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- CN108658071A CN108658071A CN201710207416.4A CN201710207416A CN108658071A CN 108658071 A CN108658071 A CN 108658071A CN 201710207416 A CN201710207416 A CN 201710207416A CN 108658071 A CN108658071 A CN 108658071A
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- chromium
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Carbon And Carbon Compounds (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to a kind of using chromium skin as biomass porous carbon of raw material and its preparation method and application, is that biomass porous Carbon Materials are made in its carbonization-activation by raw material using tanning waste chromium skin.It is acted on using the high-specific surface area of porous charcoal, abundant pore structure and metal oxide, is applied to the purification containing chromium and dye wastewater.
Description
Technical field
The invention belongs to field of new materials, and in particular to a kind of using chromium skin as the biomass porous carbon of raw material and its preparation side
Method and application.
Background technology
Porous charcoal physical characteristic is unique, has many advantages, such as good absorption property, mechanical strength and surface characteristic, is a kind of
Excellent sorbing material is widely used in environmental protection and chemical field, while in liquid phase adsorption, Gas Phase Adsorption, energy storage material, lithium
The fields such as ion battery, lithium-sulfur cell, biosensor, catalyst and catalyst carrier show good application prospect, are
One research hotspot of current Carbon Materials.
The raw material for preparing porous charcoal is very extensive, mainly there is mineral substance raw material, synthesis high molecular material, waste high polymer material
Material, biological material etc..Mineral substance raw material has many advantages, such as that steady sources, cost are relatively low, preparation method is ripe, is currently to prepare
The primary raw material of porous charcoal.In order to further decrease achievement, reduces mineral origin and rely on, especially have to agriculture and industry waste
Effect utilizes, and achievees the purpose that give up with useless administer, and currently preparing porous charcoal as raw material using biological material becomes research hotspot, such as rice
Shell, corncob, bamboo and wood, shell, fruit stone, bagasse, Animal Skin and bone etc..
Process hides scrap leather is Leather Factory by the tanned leftover bits and pieces of skin, is commonly called as " chromium skin ", is equally rich in collagen, Ke Yiyong
It is extremely cheap relative to edible gelatin and pharmagel in production technical-grade gelatine.But its chromium content is high, it is stringent to prohibit
Only it is used for the fields such as food and medicine.How to guide it is this not only be rich in collagen again be rich in chromium cladding can resource it is effectively sharp
With, it is correct to guide market development direction, it realizes maximizing the benefits, is an important research topic.
Chinese patent CN104588388.A discloses a kind of method of comprehensive utilization of the leather castoff containing chromium, solves existing
In the art to containing the problem of chromium skin waste cannot make full use of.Include the following steps：（1）It is carried out to containing chromium leather castoff
It tears up；（2）Drying and processing is carried out to the fragment of leather castoff containing chromium after tearing up；（3）To the leather castoff containing chromium after drying
Fragment carries out high-temp combustion；（4）The extraction of chromated oxide is carried out to the leather ash of the leather castoff containing chromium after high-temp combustion.By upper
State design scheme, can to contain the burning of chromium leather castoff and using its thermal energy and to containing waste liqouor in chromium leather castoff it is sharp again
With, and then complete to make full use of leather castoff containing chromium.But the patented method underuses collagen abundant in chromium skin
Albumen and activated carbon resource.
Chinese patent CN103145126.A discloses a kind of method preparing activated carbon as raw material microwave method using waste leather,
Realize that resource repeats to recycle, preparation speed is fast, simple for process, and the adsorption effect of activated carbon in water of preparation is good, includes the following steps：
（1）Washed with impurities are dried, and crush, leather particles are made；（2）Leather particles are impregnated in a period of time in acid；（3）Set micro-wave oven
Middle carbonization-activation；（4）It is boiled in acid, is washed to neutrality, dry to obtain leather activated carbon.But the patented method is using microwave
Legal system takes porous charcoal, and the specific surface area of porous charcoal is 638.24-639.52m2/g.But the specific surface of the standby porous charcoal of the patent system
Product does not have advantage compared with the activated carbon of document report, and does not utilize chromium resource abundant in chromium skin.
Carbon source and chromium source abundant in leather castoff are made full use of, waste resource is efficiently used, solves environmental pollution
Problem and food and drug safety problem are of great significance.Through retrieval, there is presently no find about utilization chromium leather for chromium-rich work
The report of property charcoal and its concrete application.
Invention content
It is raw material using tanning waste chromium skin to overcome problems of the prior art, the present invention, is carbonized
Activation, is made biomass porous Carbon Materials.Made using the high-specific surface area of porous charcoal, abundant pore structure and metal oxide
With the purification of purification and the sewage containing methylene blue dye applied to high concentration chrome wastewater.
The present invention adopts the following technical scheme that：It is a kind of using chromium skin as the biomass porous carbon of raw material, make as follows
It is standby to obtain：
（1）Pre-treatment step：By process hides scrap leather（Chromium skin）Drying crushes, and heating removing grease obtains chromium skin pretreatment product；
（2）Pre- carburising step：Chromium skin pretreatment product is carbonized in advance, obtains the pre- carbonized product of chromium skin；
（3）Carbonization-activation step：After the pre- carbonized product of chromium skin is mixed with activator, carbonization-activation is carried out, is then washed, dried,
Obtain chromium scytoblastema porous charcoal.
In the preferred embodiments of the present invention, step（1）In, by process hides scrap leather（Chromium skin）Natural drying is crushed to
About 0.5cm × 0.5cm, heating removing grease to smokeless generate, and obtain chromium skin pretreatment product.
In the preferred embodiments of the present invention, step（2）In, chromium skin pretreatment product is placed in electric tube furnace,
In N2Or CO2Under gas shield, 0.5 ~ 3h of pre- carbonization is carried out at 400 ~ 600 DEG C, obtains the pre- carbonized product of chromium skin.
In the preferred embodiments of the present invention, step（3）In, the pre- carbonized product of chromium skin presses charcoal/activation with activator
Agent=3:1~1:3 ratio mixing, 0.5 ~ 3h of carbonization-activation is carried out at 600 ~ 1000 DEG C, is then washed to neutrality, and 105 ~ 120
It is dried at DEG C, obtains chromium scytoblastema porous charcoal.
In the preferred embodiments of the present invention, step（1）In, heating and temperature control is at 200 DEG C hereinafter, it is preferred that 160
DEG C or less.
In the preferred embodiments of the present invention, step（2）In, protective gas N2, pre- carburizing temperature is 500 DEG C,
Pre- carbonization time is 1 ~ 2h.
In the preferred embodiments of the present invention, step（3）In, activator KOH, charcoal/activator is 2:1~1:2,
Carburizing temperature is 650 ~ 850 DEG C, and carbonization time is 1 ~ 2h, and drying temperature is 105 ~ 110 DEG C.
On the other hand, the present invention also protects application of the above-mentioned biomass porous carbon in handling sewage containing Cr VI.
On the other hand, the present invention also protects above-mentioned biomass porous carbon answering in handling sewage containing methylene blue dye
With.
Compared with the prior art, the advantages of the present invention are as follows：
（1）There is provided it is a kind of using chromium skin as the preparation method of the biomass carbon of raw material, it is of low cost, craft science rationally, be easy to grasp
Make, prepare chromium scytoblastema porous charcoal by raw material of tanning waste chromium skin, in chromium skin carbon resource and chromium resource carried out fully
It recycles, the comprehensive reutilization and new application for being conducive to chromium skin excavate.
（2）The present invention will be prepared is applied to sewage disposal containing Cr VI by the biomass porous carbon of raw material of chromium skin
Field and sewage treatment field containing methylene blue dye.Carbon source is enriched using it to prepare with adsorptive selectivity and high-ratio surface
Long-pending porous carbon material, activated carbon hole obtained is flourishing, and specific surface area is more than 2000 m2/ g, especially to containing Cr VI dirt
The adsorption effect of water is better than commercial activated carbons；Realize the comprehensive reutilization of chromium skin.
Description of the drawings
Fig. 1 is the electromicroscopic photograph of the chromium scytoblastema porous charcoal prepared under 750 DEG C of Carbonization Conditions；
Fig. 2 is the pore-size distribution and N of the chromium scytoblastema porous charcoal prepared under 750 DEG C of Carbonization Conditions2Absorption takes off curve；
Fig. 3 is the electromicroscopic photograph of the chromium scytoblastema porous charcoal prepared under 650 DEG C of Carbonization Conditions；
Fig. 4 is the pore-size distribution and N of the chromium scytoblastema porous charcoal prepared under 650 DEG C of Carbonization Conditions2Absorption takes off curve.
Specific implementation mode
With reference to embodiment, the present invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
（1）Pre-treatment step：By process hides scrap leather（Chromium skin）Natural drying is crushed to about 0.5cm × 0.5cm, and heating is de- on electric furnace
Except grease to smokeless generates, chromium skin pretreatment product is obtained.
（2）Pre- carburising step：Chromium skin pretreatment product is placed in electric tube furnace, in N2Under protection, carried out at 500 DEG C
Pre- carbonization 1h, obtains the pre- carbonized product of chromium skin.
（3）Carbonization-activation step：The pre- carbonized product of chromium skin presses charcoal/activator=1 with KOH:1 ratio mixing, in 750 DEG C
Lower progress carbonization-activation 1h, is then washed to neutrality, is dried at 110 DEG C, obtain chromium scytoblastema porous charcoal.
Gained chromium scytoblastema porous charcoal electromicroscopic photograph is as shown in Figure 1, pore-size distribution and N2Absorption take off curve as shown in Fig. 2, by
As a result it is found that the obtained active porous charcoal of chromium scytoblastema has hierarchical porous structure, large specific surface area（Higher than 2000 m2/g）.
Embodiment 2
（1）Pre-treatment step：By process hides scrap leather（Chromium skin）Natural drying is crushed to about 0.5cm × 0.5cm, and heating is de- on electric furnace
Except grease to smokeless generates, chromium skin pretreatment product is obtained.
（2）Pre- carburising step：Chromium skin pretreatment product is placed in electric tube furnace, in N2Under protection, carried out at 500 DEG C
Pre- carbonization 2h, obtains the pre- carbonized product of chromium skin.
（3）Carbonization-activation step：The pre- carbonized product of chromium skin presses charcoal/activator=1 with KOH:1 ratio mixing, in 650 DEG C
Lower progress carbonization-activation 1h, is then washed to neutrality, is dried at 110 DEG C, obtain chromium scytoblastema porous charcoal.
Gained chromium scytoblastema porous charcoal electromicroscopic photograph is as shown in figure 3, pore-size distribution and N2Absorption take off curve as shown in figure 4, by
As a result it is found that obtained chromium scytoblastema porous charcoal has hierarchical porous structure, large specific surface area.
Embodiment 3
By chromium scytoblastema porous charcoal for purifying sewage containing Cr VI.
（1）It is 2.0 to prepare initial pH value, different initial concentrations（100-700mg/L）Cr (VI) solution, chromium scytoblastema is porous
Charcoal dosage is 1.0g/L.
（2）In thermostatic control oscillator vibration（30 DEG C of temperature, hunting speed 130r/min）Staticadsorption experiment is carried out, for 24 hours
After take supernatant to measure remaining Cr (VI) concentration.
（3）By Langmuir adsorption isotherm models, obtain chromium scytoblastema porous charcoal in 30 DEG C of maximum adsorptions to Cr VI
Measure about 400mg/g.
Embodiment 4
By chromium scytoblastema porous charcoal for purifying sewage containing methylene blue dye.
（1）It is 7.0 to prepare initial pH value, different initial concentrations（100-800mg/L）Methylene blue solution, chromium scytoblastema is more
Hole charcoal dosage is 1.0g/L.
（2）In thermostatic control oscillator vibration（30 DEG C of temperature, hunting speed 130r/min）Staticadsorption experiment is carried out, for 24 hours
After take supernatant to measure remaining Cr (VI) concentration.
（3）By Langmuir adsorption isotherm models, obtain chromium scytoblastema porous charcoal 30 DEG C to methylene blue dye most
Big adsorbance is 565mg/g.
Although by referring to the preferred embodiment of the present invention, invention has been described, this field it is common
It will be appreciated by the skilled person that various changes can be made to it in the form and details, without departing from appended right
The spirit and scope of the present invention defined by claim.
Claims (9)
1. a kind of using chromium skin as the biomass porous carbon of raw material, which is characterized in that be made by the steps to obtain：
（1）Pre-treatment step：By process hides scrap leather（Chromium skin）Drying crushes, and heating removing grease obtains chromium skin pretreatment product；
（2）Pre- carburising step：Chromium skin pretreatment product is carbonized in advance, obtains the pre- carbonized product of chromium skin；
（3）Carbonization-activation step：After the pre- carbonized product of chromium skin is mixed with activator, carbonization-activation is carried out, is then washed, dried,
Obtain chromium scytoblastema porous charcoal.
2. biomass porous carbon according to claim 1, which is characterized in that step（1）In, by process hides scrap leather（Chromium skin）From
So drying is crushed to about 0.5cm × 0.5cm, and heating removing grease to smokeless generates, and obtains chromium skin pretreatment product.
3. biomass porous carbon according to claim 1, which is characterized in that step（2）In, chromium skin pretreatment product is set
In electric tube furnace, in N2Or CO2Under gas shield, 0.5 ~ 3h of pre- carbonization is carried out at 400 ~ 600 DEG C, chromium skin is obtained and is carbonized in advance
Product.
4. biomass porous carbon according to claim 1, which is characterized in that step（3）In, the pre- carbonized product of chromium skin and work
Agent presses charcoal/activator=3:1~1:3 ratio mixing, 0.5 ~ 3h of carbonization-activation is carried out at 600 ~ 1000 DEG C, is then washed to
Neutrality dries at 105 ~ 120 DEG C, obtains chromium scytoblastema porous charcoal.
5. biomass porous carbon according to claim 1, which is characterized in that step（1）In, heating and temperature control is 200
DEG C hereinafter, it is preferred that 160 DEG C or less.
6. biomass porous carbon according to claim 1, which is characterized in that step（2）In, protective gas N2, pre- to be carbonized
Temperature is 500 DEG C, and pre- carbonization time is 1 ~ 2h.
7. biomass porous carbon according to claim 1, which is characterized in that step（3）In, activator KOH, charcoal/work
Agent is 2:1~1:2, carburizing temperature is 650 ~ 850 DEG C, and carbonization time is 1 ~ 2h, and drying temperature is 105 ~ 110 DEG C.
8. application of the biomass porous carbon in handling sewage containing Cr VI described in any one of claim 1-7.
9. application of the biomass carbon in handling sewage containing methylene blue dye described in any one of claim 1-7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678134A (en) * | 2019-01-25 | 2019-04-26 | 齐鲁工业大学 | A method of porous carbon materials are prepared using the waste in aldehyde-plant combination tannage process hides |
| CN110217789A (en) * | 2019-06-10 | 2019-09-10 | 陕西科技大学 | A kind of leather base capacitor Carbon Materials and its preparation method and application |
| CN112221465A (en) * | 2020-09-10 | 2021-01-15 | 昆明理工大学 | Method for preparing porous biochar through waste-free biological refining and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678134A (en) * | 2019-01-25 | 2019-04-26 | 齐鲁工业大学 | A method of porous carbon materials are prepared using the waste in aldehyde-plant combination tannage process hides |
| CN110217789A (en) * | 2019-06-10 | 2019-09-10 | 陕西科技大学 | A kind of leather base capacitor Carbon Materials and its preparation method and application |
| CN112221465A (en) * | 2020-09-10 | 2021-01-15 | 昆明理工大学 | Method for preparing porous biochar through waste-free biological refining and application |
| CN112221465B (en) * | 2020-09-10 | 2021-07-16 | 昆明理工大学 | Method for preparing porous biochar through waste-free biological refining and application |
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| CN108658071B (en) | 2021-02-19 |
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