CN108176361A - Sulfhydryl modified charcoal based on agricultural wastes and its preparation method and application - Google Patents
Sulfhydryl modified charcoal based on agricultural wastes and its preparation method and application Download PDFInfo
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- CN108176361A CN108176361A CN201810119241.6A CN201810119241A CN108176361A CN 108176361 A CN108176361 A CN 108176361A CN 201810119241 A CN201810119241 A CN 201810119241A CN 108176361 A CN108176361 A CN 108176361A
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- charcoal
- agricultural wastes
- sulfhydryl modified
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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
- 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
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- Hydrology & Water Resources (AREA)
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Abstract
Sulfhydryl modified charcoal provided by the invention based on agricultural wastes and its preparation method and application, is related to environmental protection technical field.A kind of preparation method of the sulfhydryl modified charcoal based on agricultural wastes, including：By agriculture waste raw material under conditions of anaerobism or anoxic, charcoal is obtained by pyrolysis.Charcoal is crossed into 50~70 mesh sieve, the first screenings is taken to obtain oxidative biological charcoal with concentrated nitric acid mixed oxidization.Oxidative biological charcoal is crossed into 70~90 mesh sieve, the second screenings is taken to mix ultrasound with compounds containing thiol groups, then filter, dry.The preparation method is simple for process, and controllability is strong, is easy to industrialized production.The sulfhydryl modified charcoal being made by the preparation method of the above-mentioned sulfhydryl modified charcoal based on agricultural wastes, absorption property is good, and stability is good, and adsorption time is short.
Description
Technical field
The present invention relates to environmental protection technical field, and sulfhydryl modified charcoal more particularly to based on agricultural wastes and
Preparation method and application.
Background technology
Agricultural wastes refer to the organic species being dropped in entire agricultural production process, mainly include：Agriculture and forestry
The plant remnants class wastes generated in production process, the animal class remnants wastes generated during herding fish production, agriculture
The processing class remnants wastes generated in industry process and rural urbanization house refuse etc..China is agricultural wastes in the world
The country of quantum of output maximum, every year about more than 40 hundred million tons of output.With the continuous development of agricultural economy, the yield of crops is therewith
It improves, while livestock and poultry cultivation quantity also gradually increases so that agriculture waste species and total amount are gradually increasing.
There are many current heavy metal absorbent, but cost is higher, and effect is irregular.Charcoal is a kind of carbon rich material
Matter is a kind of potential economical heavy metal absorbent.Current agricultural wastes prepare the method for charcoal, and there are techniques to answer
It is miscellaneous, not environmentally the shortcomings that.
Invention content
The purpose of the present invention is to provide a kind of preparation method of the sulfhydryl modified charcoal based on agricultural wastes, the systems
Preparation Method is simple for process, and controllability is strong, is easy to industrialized production.
Another object of the present invention is to provide a kind of sulfhydryl modified charcoal based on agricultural wastes, absorption property
Good, stability is good, and adsorption time is short.
The present invention is solved its technical problem and is realized using following technical scheme：
A kind of preparation method of the sulfhydryl modified charcoal based on agricultural wastes, including：
By agriculture waste raw material under conditions of anaerobism or anoxic, charcoal is obtained by pyrolysis.
Charcoal is crossed into 50~70 mesh sieve, the first screenings is taken to obtain oxidative biological charcoal with concentrated nitric acid mixed oxidization.
Oxidative biological charcoal is crossed into 70~90 mesh sieve, the second screenings is taken to mix ultrasound with compounds containing thiol groups, then filter, dry
It is dry.
A kind of sulfhydryl modified charcoal based on agricultural wastes, by the above-mentioned sulfhydryl modified biology based on agricultural wastes
The preparation method of charcoal is made.
The sulfhydryl modified charcoal based on agricultural wastes of the embodiment of the present invention and its preparation method and application it is beneficial
Effect is：
The present invention uses agricultural wastes to prepare sulfhydryl modified charcoal for raw material, and preparation process is simple, based on industrialization
Production, and the strong sulfhydryl modified charcoal of absorption property has been obtained, agricultural wastes recycling is realized, realizes guarantor
The purpose in retaining ring border has good social benefit and environmental benefit.The sulfhydryl modified charcoal is given birth to existing charcoal or class
Object carbon adsorbent is compared, and the absorption property of heavy metal is greatly improved, and has preferable stability, adsorption time is short, after absorption
Desorption and regeneration may be reused.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to sulfhydryl modified charcoal based on agricultural wastes of the embodiment of the present invention and its preparation method and application
It is specifically described.
A kind of preparation method of sulfhydryl modified charcoal based on agricultural wastes provided in an embodiment of the present invention, including：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.Detesting
Oxygen or anoxic under conditions of 300~700 DEG C, agriculture waste composition granule are carried out to heat to obtain charcoal.The product is crude product,
Charcoal is crossed 50~70 mesh sieve by the uniform and easy to process charcoal of particle in order to obtain, and it is first to take the charcoal under sieve
Screenings, it is spare.In the present invention, agricultural wastes mainly include fruit peel, peanut skin, useless leaf etc..
The first screenings is taken, adds in concentrated nitric acid, 24~48h of magnetic agitation makes concentrated nitric acid oxidation under conditions of 40~70 DEG C
Charcoal under sieve, mixed liquor is filtered, and washing filter residue is dried again, obtains oxidative biological charcoal.In the present invention, filter,
Washing and drying use the common processes of the art, and the present invention does not limit it.It is obtained according to experimental study, first
The mass ratio of screenings and concentrated nitric acid is 1:It when 1~5, fully reacts, oxidation is uniformly abundant.
Particle uniformly and performance preferably oxidative biological charcoal, helps to react with compounds containing thiol groups in order to obtain, will
Oxidative biological charcoal crosses 70~90 mesh sieve, and it is the second screenings to take the oxidative biological charcoal under sieve, is saved backup.
The second screenings is taken to be dispersed in distilled water under ultrasound condition, addition compounds containing thiol groups mixing ultrasound 0.5~
2h makes oxidative biological charcoal sulfhydrylation.Mixed liquor is filtered, filter residue is washed and is dried, obtains sulfhydryl modified biology
Charcoal.It is obtained according to experimental study, the mass ratio of the second screenings and compounds containing thiol groups is 1:1~5, under the dosage, the second sieve
Lower object reacts abundant with compounds containing thiol groups, stablizes, is rapid, and radical amount is more.
Further, in the present invention preferably in embodiment, compounds containing thiol groups include thioacetic acid, L-cysteine,
In dithiocar-bamate, 2- amino -5- sulfydryl -1,3,4- thiadiazoles, ethyl mercaptan and thioxanthamide extremely
Few one kind.
This method uses agricultural wastes to prepare sulfhydryl modified charcoal for raw material, and preparation process is simple, based on industrialization
Production, and the strong sulfhydryl modified charcoal of absorption property has been obtained, agricultural wastes recycling is realized, realizes guarantor
The purpose in retaining ring border has good social benefit and environmental benefit.
The present invention provides a kind of sulfhydryl modified charcoal based on agricultural wastes, by above-mentioned based on agricultural wastes
The preparation method of sulfhydryl modified charcoal is made.The sulfhydryl modified charcoal and existing charcoal or class biology carbon adsorbent
It compares, the absorption property of heavy metal is greatly improved, there is preferable stability, adsorption time is short, and desorption and regeneration can after absorption
To reuse.
Sulfhydryl modified charcoal provided by the invention based on agricultural wastes has stronger absorption property to heavy metal,
In terms of can be used for environmental protection, there is preferable effect.
With reference to embodiments to this, the feature and performance of invention are described in further detail.
Embodiment 1
Present embodiments provide a kind of sulfhydryl modified charcoal based on agricultural wastes, mainly by following steps make and
Into：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.It is limiting
Under conditions of oxygen and 300 DEG C, agriculture waste composition granule is carried out to heat to obtain charcoal.Charcoal is crossed into 50 mesh sieve, is taken under sieve
Charcoal is the first screenings.
It takes the first screenings, adds in concentrated nitric acid, the life under magnetic agitation for 24 hours sieves concentrated nitric acid oxidation under conditions of 40 DEG C
Object charcoal, mixed liquor is filtered, and washing filter residue is dried again, obtains oxidative biological charcoal.The quality of first screenings and concentrated nitric acid
Than being 1:2.Oxidative biological charcoal is crossed into 70 mesh sieve, it is the second screenings to take the oxidative biological charcoal under sieve, is saved backup.
The second screenings is taken to be dispersed in distilled water under ultrasound condition, thioacetic acid mixing ultrasound 0.5h is added in, makes oxygen
Change charcoal sulfhydrylation.Mixed liquor is filtered, filter residue is washed and is dried, obtains sulfhydryl modified charcoal.Second
Screenings and the mass ratio of thioacetic acid are 1:1.
Embodiment 2
Present embodiments provide a kind of sulfhydryl modified charcoal based on agricultural wastes, mainly by following steps make and
Into：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.It is limiting
Under conditions of oxygen and 700 DEG C, agriculture waste composition granule is carried out to heat to obtain charcoal.Charcoal is crossed into 70 mesh sieve, is taken under sieve
Charcoal is the first screenings.
It takes the first screenings, adds in concentrated nitric acid, the life under magnetic agitation 48h sieves concentrated nitric acid oxidation under conditions of 70 DEG C
Object charcoal, mixed liquor is filtered, and washing filter residue is dried again, obtains oxidative biological charcoal.The quality of first screenings and concentrated nitric acid
Than being 1:5.Oxidative biological charcoal is crossed into 90 mesh sieve, it is the second screenings to take the oxidative biological charcoal under sieve, is saved backup.
The second screenings is taken to be dispersed in distilled water under ultrasound condition, L-cysteine mixing ultrasound 2h is added in, makes oxygen
Change charcoal sulfhydrylation.Mixed liquor is filtered, filter residue is washed and is dried, obtains sulfhydryl modified charcoal.Second
Screenings and the mass ratio of L-cysteine are 1:5.
Embodiment 3
Present embodiments provide a kind of sulfhydryl modified charcoal based on agricultural wastes, mainly by following steps make and
Into：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.It is limiting
Under conditions of oxygen and 500 DEG C, agriculture waste composition granule is carried out to heat to obtain charcoal.Charcoal is crossed into 60 mesh sieve, is taken under sieve
Charcoal is the first screenings.
It takes the first screenings, adds in concentrated nitric acid, the life under magnetic agitation 36h sieves concentrated nitric acid oxidation under conditions of 60 DEG C
Object charcoal, mixed liquor is filtered, and washing filter residue is dried again, obtains oxidative biological charcoal.The quality of first screenings and concentrated nitric acid
Than being 1:3.Oxidative biological charcoal is crossed into 80 mesh sieve, it is the second screenings to take the oxidative biological charcoal under sieve, is saved backup.
The second screenings is taken to be dispersed in distilled water under ultrasound condition, adds in dithiocar-bamate mixing ultrasound
1.5h makes oxidative biological charcoal sulfhydrylation.Mixed liquor is filtered, filter residue is washed and is dried, obtains sulfhydryl modified life
Object charcoal.The mass ratio of second screenings and dithiocar-bamate is 1:3.
Embodiment 4
Present embodiments provide a kind of sulfhydryl modified charcoal based on agricultural wastes, mainly by following steps make and
Into：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.It is limiting
Under conditions of oxygen and 500 DEG C, agriculture waste composition granule is carried out to heat to obtain charcoal.Charcoal is crossed into 70 mesh sieve, is taken under sieve
Charcoal is the first screenings.
It takes the first screenings, adds in concentrated nitric acid, the life under magnetic agitation 38h sieves concentrated nitric acid oxidation under conditions of 60 DEG C
Object charcoal, mixed liquor is filtered, and washing filter residue is dried again, obtains oxidative biological charcoal.The quality of first screenings and concentrated nitric acid
Than being 1:2.Oxidative biological charcoal is crossed into 90 mesh sieve, it is the second screenings to take the oxidative biological charcoal under sieve, is saved backup.
The second screenings is taken to be dispersed in distilled water under ultrasound condition, adds in thioxanthamide mixing ultrasound
2h makes oxidative biological charcoal sulfhydrylation.Mixed liquor is filtered, filter residue is washed and is dried, obtains sulfhydryl modified biology
Charcoal.The mass ratio of second screenings and thioxanthamide is 1:2.
Comparative example 1
This comparative example provides a kind of sulfhydryl modified charcoal based on agricultural wastes, mainly by following steps make and
Into：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.Detesting
Under conditions of oxygen and 300 DEG C, agriculture waste composition granule is carried out to heat to obtain charcoal.Charcoal is crossed into 50 mesh sieve, is taken under sieve
Charcoal.
Comparative example 2
This comparative example provides a kind of sulfhydryl modified charcoal based on agricultural wastes, mainly by following steps make and
Into：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.It is lacking
Under conditions of oxygen and 700 DEG C, agriculture waste composition granule is carried out to heat to obtain charcoal.Charcoal is crossed into 70 mesh sieve, is taken under sieve
Charcoal.
Comparative example 3
This comparative example provides a kind of sulfhydryl modified charcoal based on agricultural wastes, mainly by following steps make and
Into：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.It is limiting
Under conditions of oxygen and 500 DEG C, agriculture waste composition granule is carried out to heat to obtain charcoal.Charcoal is crossed into 60 mesh sieve, is taken under sieve
Charcoal.
Comparative example 4
This comparative example provides a kind of sulfhydryl modified charcoal based on agricultural wastes, mainly by following steps make and
Into：
Suitable agricultural wastes are taken, it is smashed, dried and is ground, it is graininess to make agricultural wastes.It is limiting
Under conditions of oxygen and 500 DEG C, agriculture waste composition granule is carried out to heat to obtain charcoal.Charcoal is crossed into 70 mesh sieve, is taken under sieve
Charcoal.
The Examples 1 to 4 of equivalent, the charcoal that comparative example 1~4 provides and sulfhydryl modified charcoal are chosen, be in pH value
Under conditions of 5-6, temperature are 20 ± 2 DEG C, the adsorption experiment of heavy metal, adsorpting data such as following table are carried out：
1 adsorpting data result of table
As shown in Table 1, compared to comparative example 1~4, the sulfhydryl modified charcoal that Examples 1 to 4 provides is to heavy metal ion
Adsorptivity is stronger, Pb2+Removal rate more than 88%, Cd2+Removal rate more than 91%.The mercapto that Examples 1 to 4 is provided
Base modification biological charcoal is tested again after placing in room conditions 6 months, and data result is similar to the result in table 1.Explanation
Pass through the good sulfhydryl modified charcoal of the available strong adsorption of preparation method provided by the invention, stability.Comparative example 1~
4 compare Examples 1 to 4, due in preparation process to charcoal progress sulfhydrylation, the charcoal adsorptivity of preparation compared with
Difference.
Embodiments described above is part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the sulfhydryl modified charcoal based on agricultural wastes, which is characterized in that including：
By agriculture waste raw material under conditions of anaerobism or anoxic, charcoal is obtained by pyrolysis；
The charcoal is crossed into 50~70 mesh sieve, the first screenings is taken to obtain oxidative biological charcoal with concentrated nitric acid mixed oxidization；
The oxidative biological charcoal is crossed into 70~90 mesh sieve, the second screenings is taken to mix ultrasound with compounds containing thiol groups, then filter, dry
It is dry.
2. the preparation method of the sulfhydryl modified charcoal according to claim 1 based on agricultural wastes, which is characterized in that
The agriculture waste raw material heats to obtain the life after smashing, drying, grind under conditions of limit oxygen and 300~700 DEG C
Object charcoal.
3. the preparation method of the sulfhydryl modified charcoal according to claim 1 based on agricultural wastes, which is characterized in that
After first screenings is mixed with the concentrated nitric acid, under conditions of 40~70 DEG C after 24~48h of magnetic agitation, then taken out
Filter, washing, drying.
4. the preparation method of the sulfhydryl modified charcoal according to claim 3 based on agricultural wastes, which is characterized in that
The mass ratio of first screenings and the concentrated nitric acid is 1:1~5.
5. the preparation method of the sulfhydryl modified charcoal according to claim 1 based on agricultural wastes, which is characterized in that
Second screenings is dispersed in water under ultrasound condition, then add in compounds containing thiol groups mixing ultrasound 0.5~
It after 2h, filtered, washed, dried.
6. the preparation method of the sulfhydryl modified charcoal according to claim 5 based on agricultural wastes, which is characterized in that
The mass ratio of second screenings and the compounds containing thiol groups is 1:1~5.
7. the preparation method of the sulfhydryl modified charcoal according to claim 1 based on agricultural wastes, which is characterized in that
The compounds containing thiol groups include thioacetic acid, L-cysteine, dithiocar-bamate, 2- amino -5- sulfydryls -1,3,4-
At least one of thiadiazoles, ethyl mercaptan and thioxanthamide.
8. the preparation method of the sulfhydryl modified charcoal according to claim 1 based on agricultural wastes, which is characterized in that
The agriculture waste raw material includes at least one of fruit peel, peanut shell, useless leaf.
9. a kind of sulfhydryl modified charcoal based on agricultural wastes, which is characterized in that by any one of such as claim 1~8 institute
The preparation method of the sulfhydryl modified charcoal based on agricultural wastes stated is made.
10. application of the sulfhydryl modified charcoal in terms of environmental protection based on agricultural wastes as claimed in claim 9.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943345A (en) * | 2019-04-17 | 2019-06-28 | 湖南清之源环保科技有限公司 | Reparation medicament and its preparation method and application for handling heavy-metal contaminated soil |
| CN110639471A (en) * | 2019-09-24 | 2020-01-03 | 南开大学 | Ball-milling oxidation-sulfhydrylation modified biochar and preparation method and application thereof |
| CN111117641A (en) * | 2019-12-25 | 2020-05-08 | 厦门顷刻环境材料科技有限公司 | Heavy metal passivator for water and soil remediation |
| CN111545167A (en) * | 2020-04-13 | 2020-08-18 | 南昌航空大学 | Method for preparing silver ion selective adsorbent by using pasture |
| CN112063385A (en) * | 2020-09-16 | 2020-12-11 | 南京大学 | Passivating agent for efficiently fixing trivalent arsenic under anaerobic condition, and preparation method and application thereof |
| CN113046569A (en) * | 2021-03-03 | 2021-06-29 | 南昌航空大学 | Method for selectively recovering gold from waste circuit board |
| CN115557653A (en) * | 2022-11-28 | 2023-01-03 | 湖南子宏生态科技股份有限公司 | Method for removing nitrogen and phosphorus elements in aquaculture wastewater |
| CN116272856A (en) * | 2022-12-28 | 2023-06-23 | 南方电网电力科技股份有限公司 | Sulfhydryl modified biochar for removing polychlorinated biphenyl in water, and preparation method and application thereof |
| CN116328731A (en) * | 2023-04-19 | 2023-06-27 | 西北农林科技大学 | Preparation method of sulfur-calcium loaded biochar material |
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| CN113046569A (en) * | 2021-03-03 | 2021-06-29 | 南昌航空大学 | Method for selectively recovering gold from waste circuit board |
| CN115557653A (en) * | 2022-11-28 | 2023-01-03 | 湖南子宏生态科技股份有限公司 | Method for removing nitrogen and phosphorus elements in aquaculture wastewater |
| CN116272856A (en) * | 2022-12-28 | 2023-06-23 | 南方电网电力科技股份有限公司 | Sulfhydryl modified biochar for removing polychlorinated biphenyl in water, and preparation method and application thereof |
| CN116328731A (en) * | 2023-04-19 | 2023-06-27 | 西北农林科技大学 | Preparation method of sulfur-calcium loaded biochar material |
| CN116328731B (en) * | 2023-04-19 | 2024-08-23 | 西北农林科技大学 | Preparation method of sulfur-calcium loaded biochar material |
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Application publication date: 20180619 |