CN110302749A - A kind of modification biological charcoal and its preparation method and application - Google Patents
A kind of modification biological charcoal and its preparation method and application Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
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- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The present invention relates to a kind of modification biological charcoals and its preparation method and application.The preparation method includes the following steps: S1: charcoal being dispersed, ammonium hydroxide and organic silicon source are sequentially added, reacts, obtains mixed solution；S2: heavy metal chelating agent being added into mixed solution, stirring；S3: adding organic silicon source and ammonium hydroxide, stirs, and washs, dry, grinds up to the modification biological charcoal.Present invention nonloaded silica nano particle first on charcoal, then heavy metal chelating agent is loaded again, it is greatly improved the load capacity of heavy metal chelating agent, the complexing site of absorption of the charcoal for pollutants such as heavy metals is greatly increased, substantially increases absorption property；Meanwhile nonloaded silica nano particle, realization silica coat heavy metal chelating agent, may make heavy metal chelating agent steadily to load, effectively raise modification biological charcoal recycling rate of waterused again after load heavy metal chelating agent.Modification biological charcoal absorption property of the invention is excellent.
Description
Technical field
The invention belongs to bio-organic materials, adsorbent adsorbing domain, and in particular to a kind of modification biological charcoal and its preparation
Methods and applications.
Background technique
Since mankind's activity is as a result, include house refuse, mining, smelting, chemical fertilizer, the application of pesticide and electronic manufacture skill
Art etc., metalliferous waste water quantity just increase in the environment, cause the metallic pollution in water.Metallic pollution in water body is not only right
Environment causes great harm, and also has very big harm to the health of the mankind.The minimizing technology of heavy metal includes in sewage
Chemical method, physical method and biological method.In these methods, biosorption technology is most common and most cost-benefit side
Method.This is because biological adsorption agent have the characteristics that it is environmentally friendly and widely used, wherein most popular biological adsorption agent
First is that charcoal.
Charcoal is the material that biomass leaves after high-temperature process under anoxic conditions.Charcoal itself have it is at low cost,
The advantages that range is wide, prepares that raw material range is wide, porosity is high, large specific surface area, thermal stability are good.Meanwhile charcoal is almost
It is pure carbon, when being embedded in underground, hundreds of thousands year cannot all disappear, it means that carbon consolidating to deposit and will be helpful to slow down the whole world in the soil
It warms.These advantages cause people to the extensive concern of charcoal.It was in recent years, very active always to the research of charcoal,
Various raw materials are widely used in removing heavy metals.For example, studies have reported that using bagasse production charcoal for studying sewage
The absorption situation of middle heavy metal.The most common biological carbon feedstock of absorption in sewage is agricultural wastes, as timber, straw and
Pericarp.Charcoal is made as adsorbent by matrix of corn stover in someone.Sludge, chestnut shell, yak excrement charcoal, ocean
Macro also can be used as the raw material of manufacture charcoal.But directly using existing biological carbon materials as adsorbent, adsorptivity
It can be limited its application there are still limitation.
Therefore, developing a kind of preferable charcoal adsorbent material of adsorption effect has important research significance and economic valence
Value.
Summary of the invention
It is an object of the invention to overcome limitation of the biological carbon materials on absorption property in the prior art, one kind is provided
The preparation method of modification biological charcoal.Then present invention nonloaded silica nano particle first on charcoal loads a huge sum of money again
Belong to agent for capturing, is greatly improved the load capacity of heavy metal chelating agent；The load of heavy metal chelating agent, greatly increases charcoal pair
In the complexing site of the absorption of the pollutants such as heavy metal, absorption property is substantially increased；Meanwhile it being born after loading heavy metal chelating agent
Nano SiO 2 particle is carried, realizes that silica coats heavy metal chelating agent, heavy metal chelating agent may make steadily to bear
It is loaded on material, effectively raises modification biological charcoal recycling rate of waterused.Modification biological charcoal absorption property provided by the invention is excellent
It is different, there is preferable adsorption effect to heavy metal, especially there is excellent adsorption effect to heavy metal Cd (II).
Another object of the present invention is to provide a kind of modification biological charcoals.
Another object of the present invention is to provide above-mentioned modification biological charcoal as adsorbent material absorption heavy metal in answering
With.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of preparation method of modification biological charcoal, includes the following steps:
S1: charcoal is dispersed, and sequentially adds ammonium hydroxide and organic silicon source, and reaction obtains mixed solution；
S2: heavy metal chelating agent being added into mixed solution, stirring；
S3: adding organic silicon source and ammonium hydroxide, stirs, and washs, dry, grinds up to the modification biological charcoal.
Organic silicon source hydrolyzes to form nano SiO 2 particle under the action of ammonium hydroxide in S1 of the present invention, is supported on charcoal
On, it can promote the load that S2 step preferably realizes heavy metal chelating agent.Biology is greatly increased after heavy metal chelating agent load
Charcoal substantially increases absorption property for the complexing site of the absorption of the pollutants such as heavy metal.Then titanium dioxide is loaded again in S3
Nano silicon particles realize that silica coats heavy metal chelating agent, heavy metal chelating agent may make steadily to be supported on material
On, effectively raise modification biological charcoal recycling rate of waterused.
Modification biological charcoal absorption property provided by the invention is excellent, has preferable adsorption effect to heavy metal, especially
There is excellent adsorption effect to heavy metal Cd (II).
Preferably, charcoal is prepared via a method which to obtain in S1: bio-matrix is dry, after being pyrolyzed after grinding to obtain the final product
The charcoal.
The bio-matrix of this field routine is used equally in the present invention.
It is further preferable that the bio-matrix is one or more of kelp, sludge or rice husk.
Most preferably, the bio-matrix is kelp.
Algae is widely distributed in nature.China is one of the most abundant marine algae resource in the world.The processing of China algae
The exploration utilized starts from 20th century 50, the sixties, including food, cosmetics and Chemical Manufacture.Therefore, large ocean algae is a large amount of
Breeding.During appropriate scale of operation, also due to the reasons such as unsalable generate many stale, discarded algae.These algaes
Class, it is generally difficult to handle.In addition, a large amount of sanitary sewage, industrial wastewater enter the content that ocean will increase nitrogen, phosphorus, cause red
Tide, leads to algae raised growth in ocean, these algae are difficult processed.It has been investigated that the charcoal made of algae
Surface has pH value more higher than traditional biological charcoal and various oxygen-containing functional groups, is conducive to remove cationic heavy metal.Select sea
Algae has more excellent absorption property after being modified as charcoal prepared by bio-matrix.
Preferably, the temperature of the pyrolysis is 500~700 DEG C, and the time is 1.5~3h.
Preferably, organic silicon source is tetraethyl orthosilicate in S1.
Preferably, charcoal and the mass ratio of organic silicon source are 1:3~5 in S1；The matter of charcoal and organic silicon source in S3
Amount is than being 1:8~10.
Not only may be implemented the relatively large load of silica under the conditions of the dosage, but can realize to heavy metal chelating agent compared with
Good cladding.
Preferably, charcoal is scattered in the mixed solution of organic solvent and water in S1.
Organic solvent, ammonium hydroxide dosage can be chosen according to actual needs, to realize that organic silicon source preferably hydrolyzes i.e.
It can.
It is further preferable that the organic solvent is in one in dehydrated alcohol or methanol or several.
Preferably, heavy metal chelating agent described in S2 is one or more of TMT-102 or TMT-60.
Liquid TMT-102 and solid-state TMT-60 are more suitable.
Preferably, the mass ratio of charcoal described in S2 and heavy metal chelating agent is 1:1.5~2.5.
Preferably, it and is washed using organic solvent and successively in S3.
It is further preferable that the organic solvent is one or more of dehydrated alcohol, methanol or tert-butyl alcohol.
Preferably, the mixed solution of ammonium hydroxide, organic solvent and water is additionally added in S3.
A kind of modification biological charcoal, is prepared by the above method.
Above-mentioned modification biological charcoal is also within the scope of the present invention as application of the adsorbent material in absorption heavy metal.
Preferably, the heavy metal is Cd2+、Cr3+、Cu2+Or Pb2+One or more of.
It is further preferable that the modification biological charcoal is as adsorbent material in absorption heavy metal Cd2+Answering in (Cd (II))
With.
Compared with prior art, the invention has the following beneficial effects:
Present invention nonloaded silica nano particle first on charcoal, then loads heavy metal chelating agent again, can be big
The big load capacity for improving heavy metal chelating agent；The load of heavy metal chelating agent greatly increases charcoal for dirts such as heavy metals
The complexing site for contaminating the absorption of object, substantially increases absorption property；Meanwhile it loading heavy metal chelating agent back loading silica and receiving
Rice grain realizes that silica coats heavy metal chelating agent, may make heavy metal chelating agent to be steadily supported on material, have
Effect improves modification biological charcoal recycling rate of waterused.Modification biological charcoal absorption property provided by the invention is excellent, has to heavy metal
There is preferable adsorption effect, especially there is excellent adsorption effect to heavy metal Cd (II).
Detailed description of the invention
Fig. 1 is the process flow chart for the modification biological charcoal TMT-102BC that embodiment 1 provides；
Fig. 2 is the infrared figure of charcoal and modification biological charcoal that each embodiment provides；
Fig. 3 is to scheme the case where adsorbing Cd (II) under the charcoal differential responses time that embodiment 1 provides；
Fig. 4 is the influence diagram that the charcoal dosage that embodiment 1 provides adsorbs Cd (II) to charcoal；
Fig. 5 is the influence diagram that the heavy metal cadmium ion initial concentration that embodiment 1 provides adsorbs Cd (II) to charcoal.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replacement belongs to scope of the present invention.
Embodiment 1
The present embodiment provides a kind of modification biological charcoal TMT-102BC, such as Fig. 1 is prepared via a method which to obtain.
(1) discarded kelp is thoroughly cleaned, is air-dried 24 hours, it is then dry under conditions of 70 DEG C in drying box
12h.Kelp is ground into fine particle using grinder.
(2) ground kelp particle is packed into tube furnace and is pyrolyzed.500 are raised the temperature to the rate of 7 DEG C/min
DEG C and be maintained at 2h at corresponding temperature and (before pyrolysis and in pyrolytic process, inert gas be passed through with the rate of 25mL/min
To prevent required organic matter in furnace to be pyrolyzed), then furnace is cooled to room temperature and is taken out, obtains charcoal.
(3) modification biological charcoal: 1g charcoal is added 40mL dehydrated alcohol in beaker, 30 min of ultrasonic disperse, then plus
Enter 20mL dehydrated alcohol, 10mL distilled water and 3mL ammonium hydroxide, stir 6h at room temperature, 2.5mL tetraethyl orthosilicate is added later
(TEOS), acquired solution is solution A.At the same time, 2mL heavy metal chelating agent TMT-102,40mL distilled water, 0.5mL ammonium hydroxide and
30ml dehydrated alcohol is all added in beaker and mixes, and acquired solution is solution B, finally, at room temperature by solution A and solution B
Mixing is added 5 mL TEOS and stirs 6h.After 6h, remaining ammonium hydroxide and a huge sum of money are alternately rinsed with dehydrated alcohol and distilled water
Belong to agent for capturing, 80 DEG C of drying 12h, grinding, the product finally obtained is modification biological charcoal, is denoted as TMT-102BC.
Embodiment 2
The present embodiment provides a kind of modification biological charcoals, are prepared via a method which to obtain.
(1) kelp is ground into fine particle using grinder in the drying 8 hours of 105 DEG C of baking oven by sewage sludge.
(2) ground mud granule is packed into tube furnace and is pyrolyzed.500 are raised the temperature to the rate of 7 DEG C/min
DEG C and be maintained at 2h at corresponding temperature and (before pyrolysis and in pyrolytic process, inert gas be passed through with the rate of 25mL/min
To prevent required organic matter in furnace to be pyrolyzed), then furnace is cooled to room temperature and is taken out, obtains charcoal.
(3) 40mL ethyl alcohol is added in 1g charcoal in beaker, then 20mL ethyl alcohol, 10mL is added in ultrasonic disperse 30min
Distilled water and 3mL ammonium hydroxide, stir 6h at room temperature, 2.5mL tetraethyl orthosilicate are added later, acquired solution is solution A.It is same with this
When, 2mL heavy metal chelating agent TMT-102,40mL distilled water, 0.5mL ammonium hydroxide and 30ml dehydrated alcohol are all added in beaker simultaneously
Mixing, obtained product is solution B, finally, solution A is mixed with solution B at room temperature, 5mLTEOS is added and stirs 6h.6h
Later, remaining ammonium hydroxide and heavy metal chelating agent are alternately rinsed with dehydrated alcohol and distilled water, 80 DEG C of drying 12h are ground, finally
Obtain modification biological charcoal.
Embodiment 3
The present embodiment provides a kind of modification biological charcoals, are prepared via a method which to obtain.
(1) discarded kelp is thoroughly cleaned, is air-dried 24 hours, it is then dry under conditions of 70 DEG C in drying box
12h.Kelp is ground into fine particle using grinder.
(2) ground kelp particle is packed into tube furnace and is pyrolyzed.700 are raised the temperature to the rate of 7 DEG C/min
DEG C and be maintained at 1.5h at corresponding temperature and (before pyrolysis and in pyrolytic process, indifferent gas be passed through with the rate of 25mL/min
Body is to prevent required organic matter in furnace to be pyrolyzed), then furnace is cooled to room temperature and is taken out, obtains charcoal.
(3) modification biological charcoal: 1g charcoal is added 40mL dehydrated alcohol in beaker, 30 min of ultrasonic disperse, then plus
Enter 20mL dehydrated alcohol, 10mL distilled water and 3mL ammonium hydroxide, stir 6h at room temperature, 3.22mL tetraethyl orthosilicate is added later
(TEOS, 3g), acquired solution are solution A.At the same time, 2.5mL heavy metal chelating agent TMT-102 (2.5g), 40mL distillation
Water, 0.5mL ammonium hydroxide and 30ml dehydrated alcohol are all added in beakers and mix, and acquired solution is solution B, finally, by solution A with
Solution B mixes at room temperature, and 8.57mL TEOS (8g) is added and stirs 6h.After 6h, alternately rushed with dehydrated alcohol and distilled water
Remaining ammonium hydroxide and heavy metal chelating agent are washed, 80 DEG C of drying 12h, grinding, the product finally obtained is modification biological charcoal.
Embodiment 4
The present embodiment provides a kind of modification biological charcoals, are prepared via a method which to obtain.
(1) discarded kelp is thoroughly cleaned, is air-dried 24 hours, it is then dry under conditions of 70 DEG C in drying box
12h.Kelp is ground into fine particle using grinder.
(2) ground kelp particle is packed into tube furnace and is pyrolyzed.500 are raised the temperature to the rate of 7 DEG C/min
DEG C and be maintained at 3h at corresponding temperature and (before pyrolysis and in pyrolytic process, inert gas be passed through with the rate of 25mL/min
To prevent required organic matter in furnace to be pyrolyzed), then furnace is cooled to room temperature and is taken out, obtains charcoal.
(3) modification biological charcoal: 1g charcoal is added 40mL dehydrated alcohol in beaker, 30 min of ultrasonic disperse, then plus
Enter 20mL dehydrated alcohol, 10mL distilled water and 3mL ammonium hydroxide, stir 6h at room temperature, later be added 5.4mL tetraethyl orthosilicate (TEOS,
5g), acquired solution is solution A.At the same time, 1.5mL heavy metal chelating agent TMT-102 (1.5g), 40mL distilled water, 0.5mL
Ammonium hydroxide and 30ml dehydrated alcohol are all added in beaker and mix, and acquired solution is solution B, finally, solution A and solution B are existed
It mixes at room temperature, 11mL TEOS (10g) is added and stirs 6h.After 6h, alternately rinsed with dehydrated alcohol and distilled water remaining
Ammonium hydroxide and heavy metal chelating agent, 80 DEG C of drying 12h, grinding, the product finally obtained is modification biological charcoal.
Comparative example 1
This comparative example provides a kind of modification biological charcoal, in addition to step (3) does not add ammonium hydroxide, tetraethyl orthosilicate (TEOS),
Remaining step and condition are consistent with embodiment 1, are only loaded the modification biological charcoal of TMT-102.
Comparative example 2
This comparative example provides a kind of modification biological charcoal, in addition to step (3) does not add heavy metal chelating agent, remaining step and
Condition is consistent with embodiment 1, obtains the modification biological charcoal of only nonloaded silica.
Comparative example 3
This comparative example provides a kind of modification biological charcoal, after mixing solution A at room temperature with solution B in step (3), no
TEOS, directly stirring, flushing is added, drying, grinding obtain the modification biological charcoal not by coated with silica.
The performance of the charcoal and modification biologicals charcoal that obtain to each embodiment and comparative example is tested.
Such as Fig. 2, the infrared spectrogram of charcoal and the infrared spectrogram of the charcoal after pyrolyzing sludge after being pyrolyzed for kelp,
Wherein, former charcoal refers to the charcoal obtained after pyrolysis, and the charcoal absorption heavy metal Cd obtained after pyrolysis is referred to after former charcoal absorption
(II) after, Modified Activated Carbon refers to the modification biological charcoal that embodiment is prepared, and refers to what embodiment was prepared after Modified Activated Carbon absorption
After modification biological charcoal adsorbs heavy metal Cd (II).From figure it is found that kelp and sludge its biological carbon surface after pyrolysis have very much
Oxygen-containing functional group, and kelp biology carbon surface with oxygen-containing functional groups more more than sludge organism carbon surface (kelp have than
The more oxygen-containing functional groups of sludge), be conducive to the absorption of heavy metal cation, in addition, adsorbing oxygen-containing functional group after preceding and absorption
Peak position also changed, show that heavy metal is effectively adsorbed by charcoal.
By taking the absorption Cd (II) for the TMT-102BC that embodiment 1 provides as an example, differential responses time, modification biological charcoal are studied
The influence of dosage and heavy metal initial concentration to absorption property.Test method and result are as follows.
(1) reaction time determines: accurately weighing 0.475g charcoal, is placed in 100mL conical flask, initial concentration, which is added, is
The cadmium chloride solution 25mL of 45mg/L, conical flask is placed in mechnical oscillator, and controlled at 25 DEG C, revolving speed is set as 150r/
Min is sampled in certain interval of time respectively, using Cd (II) concentration in NITRATE BY FLAME ATOMIC spectrophotometry measurement samples taken, and
The removal rate and adsorption capacity of Cd (II) concentration is calculated.
Test result such as Fig. 3.From figure it is found that the reaction time is very big on charcoal absorption Cd (II) influence, before absorption
In 300min, the increase at any time of the adsorbance of Cd (II) and increase, this is the fast phase of absorption；Then 300~
660min basically reaches adsorption equilibrium state, and increase adsorbance at any time is no longer changed, this is the equilibrium stage of absorption,
In conclusion 300min is the optimum balance time of charcoal absorption Cd (II).
(2) the absorption property test of modification biological charcoal dosage: at room temperature, preparation 25mL initial concentration is 45mg/L
10 parts of cadmium chloride solution be respectively placed in 100mL conical flask, charcoal dosage is 0.4~1.3g/L, and adsorption time is
300min determines the optimum amount of TMT-102BC according to atom absorption method.
Test result such as Fig. 4.As seen from the figure, with the increase of modification biological charcoal dosage, modification biological charcoal to cadmium metal from
The adsorption rate of son gradually rises.When modification biological charcoal dosage increases to 1g/L, adsorbance is 34.83 mg/g, and adsorption rate reaches substantially
To saturation, it is further added by charcoal dosage, adsorption rate does not change substantially.Therefore best modification biological charcoal dosage is 1g/L.
(3) the absorption property test under different heavy metal initial concentrations: at room temperature, produce respectively heavy metal cadmium from
Sub- concentration is 5~80mg/L, reaction volume 25mL, and 1g/L TMT-102BC is added, and adsorption time is when balancing achieved
Between, the dosage of TMT-102BC is determined according to the result of previous experiments, only adjusts metal concentration of cadmium ions, carries out a batch-type huge sum of money
Belong to ionic adsorption experiment.
Test result such as Fig. 5, as can be seen from Figure 5, in a certain concentration, as the initial concentration of cadmium ion increases, kelp is raw
Object charcoal is also increasing its adsorbance, and after cadmium ion initial concentration reaches 45mg/L, adsorbance no longer rises, therefore at the beginning of heavy metal
Beginning concentration is optimum condition when being 45mg/L.
The absorption property for the modification biological charcoal that Examples 1 to 4 and comparative example 1~3 are provided under above-mentioned optimum condition into
Row test, it is specific as follows: to accurately weigh 0.025g modification biological charcoal, be placed in 100mL conical flask, initial concentration, which is added, is
The cadmium chloride solution 25mL of 45mg/L, conical flask is placed in mechnical oscillator, and controlled at 25 DEG C, revolving speed is set as 150r/
Min is sampled in certain interval of time respectively, using Cd (II) concentration in NITRATE BY FLAME ATOMIC spectrophotometry measurement samples taken, and
The removal rate and adsorption capacity of Cd (II) concentration is calculated.Test result such as table 1.
The absorption property test result of 1 modification biological charcoal of table
| The removal rate (%) of Cd (II) | The adsorption capacity (mg/g) of Cd (II) concentration | |
| Embodiment 1 | 69.70 | 34.83 |
| Embodiment 2 | 51.10 | 25.36 |
| Embodiment 3 | 54.89 | 26.77 |
| Embodiment 4 | 61.13 | 30.01 |
| Comparative example 1 | 35.71 | 18.47 |
| Comparative example 2 | 32.55 | 16.27 |
| Comparative example 3 | 40.16 | 20.45 |
It carries out repeated circulation experiment according to adsorbent material of the optimum reaction condition to embodiment 1 and comparative example 3 to probe into, often
Material recycle next time before is carried out after the completion of secondary absorption to clean by 1mol/L hydrochloric acid, then continues to inhale by identical condition
It is attached.
After measured, the first time adsorbance for the TMT-102BC that embodiment 1 provides is 34.83mg/g, secondary adsorbance
For 30.01mg/g, the adsorbance of third time is 27.35mg/g, and the 4th adsorbance is 24.03mg/g, the 5th suction
Attached amount 20.21mg/g, although the absorption property of material declines after its circulation, its adsorption effect is better than comparative example, the material
Material is the material with high absorption property, and adsorption site is more.
And the modification biological charcoal absorption that comparative example 3 provides for the first time~the 5th adsorbance be respectively 40.16 mg/g,
10.34mg/g, 5.11mg/g, 1.56mg/g and 0.32mg/g, recycling rate of waterused are poor.
As seen from the table, the modification biological charcoal that various embodiments of the present invention provide has preferable absorption effect to heavy metal Cd (II)
Fruit and recycling rate of waterused.Since for nonloaded silica, the load capacity of heavy metal absorbent is smaller, adsorptivity in comparative example 1
It can be poor；For comparative example 2 due to unsupported heavy metal chelating agent, absorption property is poor；Heavy metal in comparative example 3 due to absorption is caught
It catches agent not coated by silica, absorption property is slightly poor, and recycling rate of waterused is poor.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modification biological charcoal, which comprises the steps of:
S1: charcoal is dispersed, and sequentially adds ammonium hydroxide and organic silicon source, and reaction obtains mixed solution；
S2: heavy metal chelating agent being added into mixed solution, stirring；
S3: adding organic silicon source and ammonium hydroxide, stirs, and washs, dry, grinds up to the modification biological charcoal.
2. preparation method according to claim 1, which is characterized in that charcoal is prepared via a method which to obtain in S1: will
Bio-matrix is dry, up to the charcoal after being pyrolyzed after grinding.
3. preparation method according to claim 2, which is characterized in that the bio-matrix is in kelp, sludge or rice husk
It is one or more of.
4. preparation method according to claim 2, which is characterized in that the temperature of the pyrolysis is 500~700 DEG C, and the time is
1.5~3h.
5. preparation method according to claim 1, which is characterized in that organic silicon source is tetraethyl orthosilicate in S1.
6. preparation method according to claim 1, which is characterized in that charcoal and the mass ratio of organic silicon source are 1:3 in S1
~5；Charcoal and the mass ratio of organic silicon source are 1:8~10 in S3.
7. preparation method according to claim 1, which is characterized in that heavy metal chelating agent described in S2 be TMT-102 or
TMT-60。
8. preparation method according to claim 1, which is characterized in that the quality of charcoal described in S2 and heavy metal chelating agent
Than for 1:1.5~2.5.
9. a kind of modification biological charcoal, which is characterized in that be prepared by any the method for claim 1~8.
10. application of the modification biological charcoal described in claim 9 as adsorbent material in absorption heavy metal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910410186.0A CN110302749B (en) | 2019-05-16 | 2019-05-16 | Modified biochar and preparation method and application thereof |
Applications Claiming Priority (1)
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| CN116371362A (en) * | 2023-04-19 | 2023-07-04 | 哈尔滨工业大学（深圳） | Preparation method of activated carbon adsorbent based on coffee shell, and product and application thereof |
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