CN106732358B - A kind of biomass carbonization microballoon loading iron oxide and its preparation and application - Google Patents
A kind of biomass carbonization microballoon loading iron oxide and its preparation and application Download PDFInfo
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- CN106732358B CN106732358B CN201611188873.5A CN201611188873A CN106732358B CN 106732358 B CN106732358 B CN 106732358B CN 201611188873 A CN201611188873 A CN 201611188873A CN 106732358 B CN106732358 B CN 106732358B
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- iron oxide
- microballoon
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
-
- 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 invention discloses a kind of biomass carbonization microballoon for loading iron oxide and its preparations and application, include the following steps: that molysite is added in the cetyl trimethylammonium bromide solution by boiling, and pH is adjusted with sodium hydroxide solution, chilled processing is added, grinds the coconut husk sieved with 100 mesh sieve, stirring evaporation, freeze-day with constant temperature arrives the Carbonized microsphere of load iron oxide in acetic acid zinc solution after hydrothermal carbonization.The material preparation process is simple, easy to operate, low in cost, and physicochemical properties are stablized, good to Pb In Exhausted Water, cadmium absorption property, without secondary pollution, and concentration for the treatment of 20mg/L or less contains cadmium, lead ion waste water, and removal rate can reach 92% or more.
Description
Technical field
The present invention relates to a kind of to prepare the biomass carbonization microballoon of load iron oxide using coconut husk and its give up in Adsorption
Lead in water, the application on cadmium ion belong to the technical field of carbon material preparation and application.
Background technique
The industries such as chemical industry, smelting and processing produce a large amount of heavy metal wastewater thereby, and heavy metal is because of its non-biodegradable and pole
It is easily enriched in vivo by food chain, great threat is constituted to environment and the mankind, therefore how deep purifying is handled
Heavy metal wastewater thereby has become current work urgently to be resolved.
Absorption method is to handle a kind of important physico-chemical process in effluent containing heavy metal ions, wide with adsorbent source,
Plasticity is strong, the advantages such as easy to operate, but traditional adsorbent such as active carbon, zeolite, iron oxide etc. comes with some shortcomings: preparation
Complex process, higher cost, absorption property difference or secondary pollution problems.Therefore seek from a wealth of sources, cheap and absorption
High-efficient sorbent material becomes the key for administering heavy metal wastewater thereby.Charcoal have raw material sources are wide, short texture is porous,
The features such as surface-active functional group is more；More and more paid attention in environmental material field as water treatment absorbent, wherein
Hydrothermal carbonization microballoon has thermal stability, absolute acid stability, large specific surface area, and the easy function in surface compared with other adsorbent materials
Dough forms a large amount of hydroxyl, carboxyl etc., can adsorb simultaneously stabilizing heavy metal ion.
Coconut husk contains a large amount of cellulose and lignin, carbon rich in, but coconut husk is dropped mostly at present, comprehensive
It is low to close utilization rate, using coconut husk as raw material, the good load oxygen of large specific surface area, absorption property is prepared by modified with ferric sulfate
The hydrothermal carbonization microballoon for changing iron is used for the removal of Pb In Exhausted Water, cadmium ion, not only realizes the high level comprehensive utilization of coconut husk, drops significantly
The production cost of low carbon materials, and provide for the processing of heavy metal wastewater thereby that a kind of preparation cost is low, absorption property is strong, environment
Friendly new adsorbent.
Summary of the invention
The present invention is intended to provide a kind of biomass carbonization microballoon for loading iron oxide and its preparation and application, material preparation
Process is simple, and production cost is low, and absorption property is good, and heat, absolute acid stability are high, without secondary pollution, is able to achieve coconut husk biomass resource
Higher value application.The material being prepared is simple applied to leaded, cadmium waste water processing application method, and the time is short, operation side
Just.
To achieve the above object of the invention, insight of the invention is that regulating and controlling to generate iron hydroxide by pH using iron salt solutions
Colloid is thoroughly mixed with the higher coconut husk of phosphorus content, surfactant is added such as: cetyl trimethylammonium bromide
(CTMAB) hydrophilicity that can increase cocoanut shell surface hydrophobicity property, can make molysite be easy to be supported in biomass, improve molysite
Utilization rate and Carbonized microsphere yield.Zinc ion in acetic acid zinc solution can influence biomass carbonization in hydrothermal carbonization process
Structure advantageously forms Carbonized microsphere, increases specific surface area, and hydrothermal carbonization process, the easy function dough in Carbonized microsphere surface, shape
At great amount of hydroxy group, carboxyl etc., increase to heavy metal ion adsorbed active site, thus improve material to Pb In Exhausted Water, cadmium from
The removal efficiency of son.
The purpose of the present invention is what is be accomplished by the following way.
A kind of preparation method for the biomass carbonization microballoon loading iron oxide, includes the following steps: for iron salt solutions to be added
Brownish red colloid is obtained in the surfactant solution of heating；PH is adjusted after cooling, broken coconut husk is added, after stirring is sufficiently mixed
It is dry；It is then added to hydro-thermal reaction in acetic acid zinc solution, after cooling wash products, re-dry is to get to load iron oxide
Biomass carbonization microballoon.
The preparation method of the biomass carbonization microballoon of the load iron oxide, surfactant includes: cetyl three
Methyl bromide ammonium；Molysite is one or both of ferric sulfate, ferric nitrate；Surfactant solution is heated to boiling, dropwise
Iron salt solutions are added, obtain brownish red colloid.
The preparation method of the biomass carbonization microballoon of the load iron oxide, the concentration range of surfactant is:
0.001-0.005mol/L；The concentration range 0.0025-0.05mol/L of molysite；The molar ratio of surfactant and iron is 1:(1-
20), the mixed liquor volume of surfactant and molysite and coconut husk mass ratio are 80-120mL/g.
The preparation method of the biomass carbonization microballoon of the load iron oxide, after brownish red colloid is cooled to room temperature, is used
Sodium hydroxide solution or ammonia spirit adjust pH to 8.0~10.0.
The preparation method of the biomass carbonization microballoon of the described load iron oxide is added and chilled be crushed, sieve with 100 mesh sieve
Coconut husk, heating magnetic agitation are sufficiently mixed 3-8h, dry 24~48h in 60 DEG C of baking ovens.
The preparation method of the biomass carbonization microballoon of the described load iron oxide, the sample of drying is added to 0.002~
In 0.01mol/L acetic acid zinc solution；Acetic acid zinc solution volume and coconut husk mass ratio are 10~50mL/g.
The preparation method of the biomass carbonization microballoon of the load iron oxide, hydrothermal temperature are 160~200 DEG C,
Reaction time 6-10 hour.
The preparation method of the biomass carbonization microballoon of the load iron oxide, it is clear with water and ethyl alcohol after hydrothermal product is cooling
It washes, then is placed in baking oven and dries 12~24 hours to get the biomass carbonization microballoon for arriving load iron oxide.
A kind of biomass carbonization microballoon loading iron oxide, is prepared by above-mentioned preparation method.
The biomass carbonization microballoon of above-mentioned load iron oxide is applied to for removing the lead in waste water, cadmium ion.
Specifically refer to take the material be added in leaded, cadmium waste water (20~1000mg/L of plumbum ion concentration, cadmium from
Sub- 10~400mg/L of concentration), adsorbent is 0.1-1g.L according to adsorbent mass and wastewater volume ratio-1, magnetic force under room temperature
After being stirred to react 5-720min, filtering.
Beneficial effects of the present invention:
(1) the present invention provides one kind using coconut husk, molysite as raw material, the biomass carbonization microballoon of preparation load iron oxide,
Preparation method is simple, and production cost is low, and physicochemical properties are stablized, without secondary pollution, and industrial application prospect is high, the coconut palm of use
Shell source is wide, yield is big, make a low multiple use, it can be achieved that coconut husk resource higher value application.
(2) the biomass carbonization microballoon of load iron oxide provided by the invention, good dispersion have biggish specific surface
Product, surface functional group is abundant, and absorption heavy metal ion active site is more, can be handed over by electrostatic interaction, surface engagement reaction, ion
It changes, realizes the efficient removal of Pb In Exhausted Water, cadmium ion.
(3) the biomass carbonization microballoon of load iron oxide of the invention, it is right compared to the non-modified hot charcoal of pure water
Lead, cadmium adsorption effect be significantly improved.20mg/L concentration of cadmium ions is handled, addition quantity of sorbent is 0.5g/L, pure water heat
The removal rate of charcoal is 58.5%, and loads the Carbonized microsphere removal rate of iron oxide up to 92%.To lead ion, pure water heat is raw
The adsorption capacity of object charcoal is 396.2mg/g, loads the Carbonized microsphere of iron oxide up to 562.08mg/g.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the biomass carbonization microballoon of present invention load iron oxide；
Fig. 2 is the scanning electron microscope (SEM) photograph of the biological carbon materials without ferric sulfate and acetic acid zinc modification.
Specific embodiment
Illustrate that the present invention is described further below with specific embodiment, but it is necessary to note that following embodiment is only used
In the further explanation to summary of the invention, limitation of the present invention not will form.
Embodiment 1
After 80mL 0.001mol/L CTMAB is boiled, 20mL0.025mol/L ferrum sulfuricum oxydatum solutum is added dropwise, it is to be cooled
PH to 9.0 is adjusted with sodium hydroxide solution afterwards.Cocoanut shell is shredded and is immersed in liquid nitrogen, then immediately turns the cocoanut shell after freezing
It moves to and is ground to powdery in mortar rapidly, sieve with 100 mesh sieve, 1g cocoanut shell is added into solution, magnetic agitation is sufficiently mixed.It will be molten
Liquid heating stirring is evaporated to total volume about 20mL, 24 hours dry in 60 DEG C of baking ovens.The sample of drying is placed in 10mL
In 0.005mol/L acetic acid zinc solution, hydrothermal carbonization final temperature is 200 DEG C, the time 8 hours, is produced after cooling with water and ethyl alcohol rinse
Object, then be placed in baking oven and dry 24 hours to get the biomass carbonization microballoon for arriving load iron oxide.
Embodiment 2
After 80mL 0.001mol/L CTMAB is boiled, 20mL0.05mol/L iron nitrate solution is added, uses after cooling
Sodium hydroxide solution adjusts pH to 9.0.Cocoanut shell is shredded and is immersed in liquid nitrogen, then is immediately transferred to the cocoanut shell after freezing
Powdery is ground in mortar rapidly, is sieved with 100 mesh sieve, 1g cocoanut shell is added into solution, magnetic agitation is sufficiently mixed.By solution plus
Thermal agitation is evaporated to total volume about 20mL, 24 hours dry in 60 DEG C of baking ovens.The sample of drying is placed in 10mL
In 0.005mol/L acetic acid zinc solution, hydrothermal carbonization final temperature is 200 DEG C, the time 8 hours, is produced after cooling with water and ethyl alcohol rinse
Object, then be placed in baking oven and dry 24 hours to get the biomass carbonization microballoon for arriving load iron oxide.
Embodiment 3
It under room temperature, is respectively 11.58,26.53,30.29 to 20mL concentration with material prepared by 0.01g embodiment 1
Adsorption reaction is carried out containing lead solution with 40.96mg/L, wherein the reaction time is 12 hours, the plumbum ion concentration inductance in filtrate
The measurement of coupled plasma optical emission spectrometer, material reach 95% or more to the removal rate of lead ion.
Embodiment 4
Under room temperature, with 0.01g embodiment 1 prepare material respectively to 20mL concentration be 100mg/L, 600mg/L and
1000mg/L's carries out adsorption reaction containing lead solution, and wherein the reaction time is 12 hours, the plumbum ion concentration inductance in filtrate
The measurement of coupled plasma optical emission spectrometer, lead ion adsorbance is respectively 139.28mg/g, 323.42mg/g and 562.08mg/
g。
Embodiment 5
It under room temperature, is respectively that 20mg/L cadmium-containing solution carries out to 20mL concentration with material prepared by 0.01g embodiment 2
Adsorption reaction, wherein the reaction time is 12 hours, the concentration of cadmium ions inductive coupling plasma emission spectrograph in filtrate
Measurement, the removal rate of cadmium ion are 92.2%.
Claims (9)
1. a kind of preparation method for the biomass carbonization microballoon for loading iron oxide, which comprises the steps of: by molysite
Brownish red colloid, which is obtained, in the surfactant solution of solution addition heating uses sodium hydroxide after brownish red colloid is cooled to room temperature
Solution or ammonia spirit adjust pH to 8.0 ~ 10.0；Broken coconut husk is added, stirring is dry after being sufficiently mixed；It is then added to acetic acid
Hydro-thermal reaction in zinc solution, wash products, re-dry load the biomass carbonization microballoon of iron oxide to get arriving after cooling.
2. the preparation method of the biomass carbonization microballoon of load iron oxide according to claim 1, which is characterized in that surface
Activating agent includes: cetyl trimethylammonium bromide；Molysite is one or both of ferric sulfate, ferric nitrate；By surface-active
Agent solution is heated to boiling, and iron salt solutions are added dropwise, and obtains brownish red colloid.
3. the preparation method of the biomass carbonization microballoon of load iron oxide according to claim 1, which is characterized in that surface
The concentration range of activating agent is: 0.001-0.005mol/L；The concentration range 0.0025-0.05mol/L of molysite；Surfactant
Molar ratio with iron is 1:(1-20), the mixed liquor volume and coconut husk mass ratio of surfactant and molysite are 80-120mL/
g。
4. the preparation method of the biomass carbonization microballoon of load iron oxide according to claim 1, which is characterized in that be added
The chilled coconut husk for being crushed, sieving with 100 mesh sieve, heating magnetic agitation are sufficiently mixed 3-8h, dry 24 ~ 48h in 60 DEG C of baking ovens.
5. the preparation method of the biomass carbonization microballoon of load iron oxide according to claim 1, which is characterized in that will dry
Dry sample is added in 0.002 ~ 0.01 mol/L acetic acid zinc solution；Acetic acid zinc solution volume and coconut husk mass ratio be 10 ~
50mL/g。
6. the preparation method of the biomass carbonization microballoon of load iron oxide according to claim 1, which is characterized in that hydro-thermal
Reaction temperature is 160 ~ 200oC, reaction time 6-10 hour.
7. the preparation method of the biomass carbonization microballoon of load iron oxide according to claim 1, which is characterized in that hydro-thermal
Product is cleaned after cooling down with water and ethyl alcohol, then is placed in baking oven and is dried 12 ~ 24 hours to get the biomass carbon for arriving load iron oxide
Change microballoon.
8. a kind of biomass carbonization microballoon for loading iron oxide is by the described in any item preparation method preparations of claim 1-7
It obtains.
9. it is according to any one of claims 8 load iron oxide biomass carbonization microballoon be applied to for remove the lead in waste water, cadmium from
Son.
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| CN107262044A (en) * | 2017-07-01 | 2017-10-20 | 湘潭大学 | It is a kind of to Congo red magnetic coupling functional material with efficient clearance and preparation method thereof in water |
| CN108745305B (en) * | 2018-06-21 | 2019-11-12 | 福州大学 | A kind of super-hydrophobicity carries zinc biomass adsorbent and its preparation and application |
| CN109847695A (en) * | 2019-01-19 | 2019-06-07 | 桂林理工大学 | The preparation method of magnetic mulberry tree bar biology carbon adsorbent |
| CN110508243B (en) * | 2019-08-14 | 2022-05-31 | 贵州大学 | Preparation method and application of biomass-based porous carbon loaded iron floc adsorption material |
| CN111573882A (en) * | 2020-04-16 | 2020-08-25 | 中南大学 | Process for deeply removing heavy metals in water body |
| CN113260244B (en) * | 2021-05-14 | 2022-10-04 | 同济大学 | Composite material and preparation method and application thereof |
| CN113648974A (en) * | 2021-09-29 | 2021-11-16 | 长春工业大学 | Preparation of magnetic charcoal adsorbent |
| CN114130392A (en) * | 2021-11-29 | 2022-03-04 | 哈尔滨工业大学 | Preparation method of iron-carbon-based material, product and application thereof |
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