CN109289787A - A kind of preparation method of the co-modified biological carbon composite of iron, cyclodextrin - Google Patents
A kind of preparation method of the co-modified biological carbon composite of iron, cyclodextrin Download PDFInfo
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- CN109289787A CN109289787A CN201811290968.7A CN201811290968A CN109289787A CN 109289787 A CN109289787 A CN 109289787A CN 201811290968 A CN201811290968 A CN 201811290968A CN 109289787 A CN109289787 A CN 109289787A
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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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
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C02F2101/103—Arsenic compounds
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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
- C02F2101/12—Halogens or halogen-containing compounds
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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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- 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
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
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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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The present invention relates to the preparation methods of a kind of iron, the co-modified biological carbon composite of cyclodextrin, beta-cyclodextrin, iron by being introduced into the surface of charcoal by the present invention, the co-modified biological carbon composite of obtained iron, beta-cyclodextrin, the material has good absorption property and catalytic degradation performance, there is absorption and catalytic degradation performance simultaneously to organic pollutant and heavy metal, on the one hand the co-modified charcoal of iron, beta-cyclodextrin improves the water solubility of material, on the other hand, the active site for increasing material greatly improves absorption property and catalytic degradation performance.
Description
Technical field
The present invention relates to the preparation methods of a kind of iron, the co-modified biological carbon composite of cyclodextrin, belong to materials synthesis skill
Art field.
Background technique
Water pollution is mainly divided into three broad aspect of chemical contamination, physical contamination and biological pollution, wherein chemical pollutant
Matter mostlys come from sanitary sewage and industrial wastewater, has the characteristics that complicated component, pollution range are wide, it is difficult to administer.Currently, changing
The main component for learning pollutant is inorganic noxious material (if any heavy metals such as copper, barium, chromium, selenium, vanadium), and organic toxic substance is (such as
Various organic agricultural chemicals, polycyclic aromatic hydrocarbon, phenols, dyestuff etc.), aerobic pollution matter (such as sanitary sewage, livestock sewage and certain industry
The organic substances such as carbohydrate, protein contained in waste water, fat, lignin and phenol) etc. a variety of pollution sources.Find raw material
Inexpensively, the simple pollutant control material of preparation process is one of research field most active at present.
As the concept of the propulsion of pollution control, " treatment of wastes with processes of wastes against one another " gradually gets the nod, the especially biological raw material of wood-charcoal of carbon material
Material has played huge potential in terms of pollution control.Charcoal is bio-organic materials (biomass) in anoxic or anoxybiotic ring
In border, the loose porous solid product generated after high temperature pyrolysis has the characteristics that porosity height, large specific surface area, thus
The source of charcoal wide (such as stalk, timber, bamboo etc.) and to produce preparation simple, however, charcoal is to a huge sum of money in water body
The absorption of category is mainly physical absorption, limited sorption capacity.
Green, environmental-friendly coating material beta-cyclodextrin (β-CDs) is just receiving extensive attention.It is super as the second generation
β-the CDs of molecules present is a kind of cyclic oligosaccharide generated by 7 D- glucopyranose units, each glucose unit with 1,
4- glycosidic bond is combined into the annulus tapered slightly, and the special nature of " center cavity is hydrophobic, and outer rim is hydrophilic " is presented, but his is thin
Water area and catalytic activity are limited, are subject to certain restrictions it above in application.It, can by the cyclodextrin modified surface to other materials
To improve water solubility, the biocompatibility of material, to further improve the physicochemical properties of material, thus controlled in environment
The fields such as reason, quasi-enzyme catalytic, bioprobe are widely used, and application prospect is huge.
But charcoal and beta-cyclodextrin have the shortcomings that common a, position for shortage catalytic degradation on charcoal and beta-cyclodextrin
Point can not carry out catalytic degradation to organic matter, cause to be adsorbed onto the blocking of charcoal/cyclodextrin material surface organic pollutant
Duct, hole seriously hinder charcoal/cyclodextrin adsorption treatment effect, and seriously affect reuse effect.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides the preparation of a kind of iron, the co-modified biological carbon composite of cyclodextrin
Method, beta-cyclodextrin, iron by being introduced into the surface of charcoal, the co-modified charcoal of obtained iron, beta-cyclodextrin by the present invention
Composite material, the material have good absorption property and catalytic degradation performance, have simultaneously to organic pollutant and heavy metal
There are absorption and catalytic degradation performance, on the one hand the co-modified charcoal of iron, beta-cyclodextrin improves the water solubility of material, another party
Face increases the active site of material, greatly improves absorption property and catalytic degradation performance.
The present invention is achieved through the following technical solutions:
A kind of preparation method of the co-modified biological carbon composite of iron, cyclodextrin, comprises the following steps that
(1) molysite, cyclodextrin, charcoal, sodium citrate are added in solvent, regulation system pH to 8-11, stirring is anti-
Answer 0.5~10h, the mass ratio of molysite and cyclodextrin are as follows: (0.1~20): the mass ratio of (0.1~60), molysite and charcoal are as follows:
(0.1~20): the mass ratio of (0.1~60), molysite and sodium citrate: (0.1~20): the matter of (0.1~20), molysite and solvent
Measure volume ratio are as follows: (0.1~20): (20~1000), unit: g/mL;
(2) reaction is moved back into autoclave, and 1~48h is reacted under 80~180 DEG C of temperature, pressure 0.1MPa~1.6MPa,
It reacts obtained black solid and uses deionized water, washes of absolute alcohol respectively, obtain the co-modified biology of iron, beta-cyclodextrin after dry
Carbon composite.
As a currently preferred technical solution, the molysite be ferric chloride hexahydrate, ferric sulfate, ferric nitrate or
Ironic citrate.
As a currently preferred technical solution, the molysite is ferric chloride hexahydrate.
As a currently preferred technical solution, the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin or γ-ring paste
Essence.
As a currently preferred technical solution, the cyclodextrin is beta-cyclodextrin.
As a currently preferred technical solution, the mass ratio of molysite and beta-cyclodextrin are as follows: (0.5~15): (0.1
~30), it is preferred that the mass ratio of molysite and beta-cyclodextrin are as follows: (2~10): (2~10).
As a currently preferred technical solution, the charcoal be sludge organism charcoal, feces of livestock and poultry charcoal,
Wooden charcoal, stalk, shell class charcoal or bamboo charcoal.
As a currently preferred technical solution, the charcoal is bamboo charcoal.
As a currently preferred technical solution, the mass ratio of molysite and charcoal are as follows: (0.5~15): (0.1~
30), it is preferred that the mass ratio of molysite and charcoal are as follows: (2~10): (2~10).
As a currently preferred technical solution, the mass ratio of molysite and sodium citrate are as follows: (0.5~15): (0.1
~5), it is preferred that the mass ratio of molysite and sodium citrate are as follows: (2~6): (1~3).
As a currently preferred technical solution, the solvent is water or alcohols solvent, the alcohols solvent
For alcohols solvents more than 2 hydroxyls, it is further preferred that the alcohols material is selected from ethylene glycol, diethylene glycol, 1,2- third
Glycol, 1,3- propylene glycol, glycerol, 1,3 butylene glycol, 1,4- butanediol, neopentyl glycol, Diethylene Glycol, dipropylene glycol
One or more of mixture.
As a currently preferred technical solution, the solvent is water.
As a currently preferred technical solution, the mass volume ratio of molysite and solvent are as follows: (0.1~20): (20~
500)g/mL;It is highly preferred, the mass volume ratio of molysite and solvent are as follows: (0.1~10): 200, unit: g/mL.
As a currently preferred technical solution, the reaction time is 0.5~10h in step (1), further preferably
, the reaction time is 1~3h in step (1), and the reaction time is 1.5h in step (1).
As a currently preferred technical solution, ammonia water conditioning system pH to 8-11, optimal pH are utilized in step (1)
It is 10.
As a currently preferred technical solution, the reaction time is 1~48h in step (2), it is further preferred that
The reaction time is 20~30h in step (2), highly preferred, and the reaction time is for 24 hours in step (2).
As a currently preferred technical solution, reaction temperature is 80~180 DEG C in step (2), it is preferred that step
(2) reaction temperature is 80~120 DEG C in, highly preferred, and reaction temperature is 100 DEG C in step (2).
As a currently preferred technical solution, drying described in step (2) be placed in a vacuum drying oven into
Row drying, drying temperature are 50~70 DEG C, 10~20h of drying time.
A currently preferred technical solution, the preparation method of the co-modified biological carbon composite of Yi Zhongtie, cyclodextrin,
It comprises the following steps that
(1) molysite, cyclodextrin, charcoal, sodium citrate are added to the water, the pH to 10 of solution are adjusted using ammonium hydroxide,
It is stirred to react 1~3h, the mass ratio of molysite and beta-cyclodextrin are as follows: (0.5~15): the mass ratio of (0.1~30), molysite and bamboo charcoal
Are as follows: (0.5~15): the mass ratio of (0.1~30), molysite and sodium citrate: (0.5~15): (0.1~5), molysite and solvent
Mass volume ratio are as follows: (0.1~10): 200, unit g/mL.
(2) reaction is moved back into autoclave, and 1~48h is reacted under 80~180 DEG C of temperature, pressure 0.5MPa~1.0MPa,
It reacts obtained black solid and uses deionized water, washes of absolute alcohol respectively, obtain the co-modified biology of iron, beta-cyclodextrin after dry
Carbon composite.
The raw materials used in the present invention and equipment are the prior art.
Technical characterstic and advantage of the invention is as follows:
1, the bamboo charcoal that the present invention uses is one kind of charcoal, has big pore structure and higher specific surface area, can
To bamboo charcoal surface, the carboxyl class on bamboo charcoal surface and hydroxy kind group can be with bamboo charcoal surfaces for adsorbing metal ions and beta-cyclodextrin
Hydroxyl forms hydrogen bond, and cyclodextrin and metal ion is enable firmly to modify on bamboo charcoal surface, then under high pressure hydrothermal condition, increases
The crystallinity for having added cyclodextrin and metal ion keeps cyclodextrin and metal ion stronger in conjunction with charcoal, it is not easy to deintercalation.
2, the present invention uses metal ion and the common modified biological charcoal of beta-cyclodextrin, assigns charcoal to organic pollutant
There is absorption and catalytic degradation performance, metal ion especially iron ion, first is that beta-cyclodextrin and biology simultaneously with heavy metal
The further reaming of the cavity of charcoal, further increases absorption property, second is that increasing catalytic degradation on beta-cyclodextrin and charcoal
Active site, make its catalytic degradation organic pollutant, avoid blocking duct, improve repeat performance.
3, the raw materials used in the present invention and equipment are the prior art, and raw material is cheap and easy to get.Obtaining composite material has well
Physical adsorption property, and the host -guest inclusion complex with cyclodextrin supermolecule, therefore for the suspension in sewage system
The ingredients such as substance, complicated organic matter (phenol, benzene, chlorine, halomethane etc.), heavy metal ion (silver, cadmium, arsenic, mercury, lead etc.) have good
The ability of good adsorption capacity and catalytic degradation organic pollutant, it will play an important role in terms of water pollution improvement.
Detailed description of the invention
Fig. 1 is Fu of iron, beta-cyclodextrin co-modified biological carbon composite and bamboo charcoal, beta-cyclodextrin prepared by embodiment 1
In leaf transform infrared spectroscopy (FTIR) compare map.Using German Bruker ALPHA-T fourier transform infrared spectroscopy instrument, inspection
Survey device: RT-DLATGS.
Fig. 2 is the scanning electricity of iron, beta-cyclodextrin co-modified biological carbon composite (a) and bamboo charcoal (b) prepared by embodiment 1
Sub- microscope (SEM) map (A) and elemental analysis map (B).Using the SM-6700F of Japan Electronics JEOL.
Fig. 3 is the transmission electricity of iron, beta-cyclodextrin co-modified biological carbon composite (a) and bamboo charcoal (b) prepared by embodiment 1
Sub- microscope (TEM) map.Using the JEM-2100 of Japan Electronics JEOL.
Fig. 4 is that the catalyzing hydrogen peroxide degradation of the co-modified biological carbon composite of iron, beta-cyclodextrin prepared by embodiment 1 is double
Phenol degradation curve.
Fig. 5 is that iron made from embodiment 1, the co-modified biological carbon composite of beta-cyclodextrin, bamboo charcoal and beta-cyclodextrin carry out
The adsorption effect figure (maximum absorption wavelength 665nm) of dyestuff (methylene blue).
Specific embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
Raw materials used following embodiment is commercial products, is analyzed pure.
Embodiment 1
The preparation method of the co-modified biological carbon composite of iron, beta-cyclodextrin, steps are as follows:
(1) 0.5~15 gram of ferric chloride hexahydrate, 0.1~10 gram of sodium citrate, 0.1~30 gram of beta-cyclodextrin are weighed
Bamboo charcoal with 0.1~30 gram is placed in conical flask, pours into the water of 200mL, and using ammonium hydroxide tune pH 10, room-temperature dissolution is stirred, instead
Answer 1.5h.
(2) it is transferred in autoclave again, reacts the black solid for 24 hours, being prepared under 100 DEG C of temperature, pressure 1.0MPa
It is cleaned respectively with dehydrated alcohol, deionized water, it is dry that the co-modified biological carbon composite of iron, beta-cyclodextrin can be obtained.
Obtained iron, beta-cyclodextrin co-modified biological carbon composite fourier transform infrared spectroscopy (FTIR) such as Fig. 1 institute
Show, scanning electron microscope (SEM) and elemental analysis are as shown in Fig. 2, can be seen that method elder generation of the invention by Fig. 1, Fig. 2
It is stirred to react, is then reacted under high pressure, realize the co-modified charcoal of iron, beta-cyclodextrin.
The transmission electron microscope (TEM) of the co-modified biological carbon composite of obtained iron, beta-cyclodextrin as shown in Figure 3,
From figure 3, it can be seen that being modified with substance on bamboo charcoal surface, and there is apparent hole.
Embodiment 2:
Preparation method as described in Example 1, except that: step (1) replaces ferric chloride hexahydrate with ferric sulfate.
Embodiment 3:
Preparation method as described in Example 1, except that: step (1) replaces ferric chloride hexahydrate with ferric nitrate.
Embodiment 4:
Preparation method as described in Example 1, except that: step (1) replaces ferric chloride hexahydrate with ironic citrate.
Embodiment 5:
Preparation method as described in Example 1, except that: step (1) replaces beta-cyclodextrin with alpha-cyclodextrin.
Embodiment 6:
Preparation method as described in Example 1, except that: step (1) replaces beta-cyclodextrin with gamma-cyclodextrin.
Embodiment 7:
Preparation method as described in Example 1, except that: step (1) replaces water with ethyl alcohol.
Embodiment 8:
Preparation method as described in Example 1, except that: step (1) replaces water with glycerol.
Embodiment 9:
Preparation method as described in Example 1, except that: it is 8 that step (1), which adjusts pH using ammonium hydroxide,.
Embodiment 10:
Preparation method as described in Example 1, except that: it is 11 that step (1), which adjusts pH using ammonium hydroxide,.
Embodiment 11:
Preparation method as described in Example 1, except that: step (1) is stirred to react the time as 1h.
Embodiment 12:
Preparation method as described in Example 1, except that: step (1) is stirred to react the time as 3h.
Embodiment 13:
Preparation method as described in Example 1, except that: step (1) is stirred to react the time as 10h.
Embodiment 14:
Preparation method as described in Example 1, except that: step (2) autoclave interior reaction temperature is 80 DEG C, reaction
Pressure is 1.2MPa.
Embodiment 15:
Preparation method as described in Example 1, except that: step (2) autoclave interior reaction temperature is 120 DEG C, instead
Answering pressure is 1.1MPa.
Embodiment 16:
Preparation method as described in Example 1, except that: the reaction time is 6h in step (2) autoclave.
Embodiment 17:
Preparation method as described in Example 1, except that: step (2) autoclave interior reaction temperature is 10h.
Embodiment 18:
Preparation method as described in Example 1, except that: step (2) autoclave interior reaction temperature is for 24 hours.
Embodiment 19:
Preparation method as described in Example 1, except that: step (2) autoclave interior reaction temperature is 36h.
Embodiment 20:
Preparation method as described in Example 1, except that: the additional amount of step (1) water is 400mL.
Embodiment 21:
Preparation method as described in Example 1, except that: the additional amount of step (1) water is 1000mL.
Embodiment 22:
Preparation method as described in Example 1, except that: the additional amount of step (1) water is 1500mL.
Experimental example 1: absorption+catalytic degradation
By iron made from the embodiment of the present invention 1, the co-modified biological carbon composite catalyzing hydrogen peroxide degradation of beta-cyclodextrin
Bisphenol-A (BPA).Laboratory apparatus: high performance liquid chromatography (HPLC), model ELITE P1201, instrument assemble Diode Array Detector
Device and C18 reversed-phase column (5 μm, 4.6mm*150mm), mobile phase are 30 DEG C of column temperature of methanol/water (70:30, v/v) flow velocity 1mL/min,
BPA Detection wavelength 278nm.
Experimental formula: concentration is the co-modified biological carbon composite of iron, the beta-cyclodextrin of 0.1g/L, bamboo charcoal and β-ring paste
Essence, 30mM H2O2,20ppm bisphenol-A (PH=3), is stirred at room temperature, and different time points high performance liquid chromatography (HPLC) is taken to survey
Try the content of bisphenol A in reaction solution.The co-modified biological carbon composite of iron, the beta-cyclodextrin of 0.1g/L, 0.1g/L bamboo charcoal and
0.1g/L beta-cyclodextrin to the degradation effect of bisphenol-A as shown in Figure 4.
Experimental example 2: adsorption experiment
By the co-modified biological carbon composite of iron made from the embodiment of the present invention 1, beta-cyclodextrin, bamboo charcoal and beta-cyclodextrin into
The adsorption experiment of row dyestuff (methylene blue).Laboratory apparatus: ultraviolet-visible spectrophotometer (TU-1901, the general analysis in Beijing).
As shown in Figure 5 to the adsorption effect of methylene blue, the biological carbon composite of beta-cyclodextrin, iron, is still protected in modification
It holds the good biological property of charcoal or even adsorption effect is greater than charcoal.
Experimental formula: concentration be 0.3758g L bamboo charcoal, beta-cyclodextrin and beta-cyclodextrin/bamboo charcoal composite material, 20mg L
Methylene blue.
Claims (10)
1. a kind of preparation method of the co-modified biological carbon composite of iron, beta-cyclodextrin, comprises the following steps that
(1) molysite, cyclodextrin, charcoal, sodium citrate are added in solvent, regulation system pH to 8-11 is stirred to react 0.5
The mass ratio of~10h, molysite and cyclodextrin are as follows: (0.1~20): the mass ratio of (0.1~60), molysite and charcoal are as follows: (0.1
~20): the mass ratio of (0.1~60), molysite and sodium citrate: (0.1~20): the mass body of (0.1~20), molysite and solvent
Product ratio are as follows: (0.1~20): (20~1000), unit: g/mL;
(2) reaction is moved back into autoclave, and 1~48h, reaction are reacted under 80~180 DEG C of temperature, pressure 0.1MPa~1.6MPa
Obtained black solid uses deionized water, washes of absolute alcohol respectively, and it is multiple that the co-modified charcoal of iron, beta-cyclodextrin is obtained after dry
Condensation material.
2. preparation method according to claim 1, which is characterized in that in step (1), the molysite is six chloride hydrates
Iron, ferric sulfate, ferric nitrate or ironic citrate, it is preferred that the molysite is ferric chloride hexahydrate, and the cyclodextrin is α-ring
Dextrin, beta-cyclodextrin or gamma-cyclodextrin, it is preferred that the cyclodextrin is beta-cyclodextrin.
3. preparation method according to claim 1, which is characterized in that in step (1), the mass ratio of molysite and beta-cyclodextrin
Are as follows: (0.5~15): (0.1~30), it is preferred that the mass ratio of molysite and beta-cyclodextrin are as follows: (2~10): (2~10).
4. preparation method according to claim 1, which is characterized in that in step (1), the charcoal is sludge organism
Charcoal, feces of livestock and poultry charcoal, wooden charcoal, stalk, shell class charcoal or bamboo charcoal, it is preferred that the charcoal is bamboo charcoal,
The mass ratio of molysite and charcoal are as follows: (0.5~15): (0.1~30), it is preferred that the mass ratio of molysite and charcoal are as follows: (2~
10): the mass ratio of (2~10), molysite and sodium citrate are as follows: (0.5~15): (0.1~5), it is preferred that molysite and sodium citrate
Mass ratio are as follows: (2~6): (1~3).
5. preparation method according to claim 1, which is characterized in that in step (1), the solvent is that water or alcohols are molten
Agent, the alcohols solvent is the alcohols solvent of 2 hydroxyls or more, it is further preferred that the alcohols material is selected from second two
Alcohol, diethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, glycerol, 1,3 butylene glycol, 1,4- butanediol, neopentyl glycol, two contractings two
The mixture of one or more of ethylene glycol, dipropylene glycol, it is preferred that the solvent is water.
6. preparation method according to claim 1, which is characterized in that in step (1), the mass volume ratio of molysite and solvent
Are as follows: (0.1~20): (20~500) g/mL;It is highly preferred, the mass volume ratio of molysite and solvent are as follows: (0.1~10): 200,
Unit: g/mL.
7. preparation method according to claim 1, which is characterized in that in step (1), the reaction time is 0.5~10h, into
One step is preferred, and the reaction time is 1~3h in step (1), and the reaction time is 1.5h in step (1), utilizes ammonium hydroxide in step (1)
Regulation system pH to 8-11, optimal pH are 10.
8. preparation method according to claim 1, which is characterized in that the reaction time is 1~48h in step (2), further
Preferably, the reaction time is 20~30h in step (2), highly preferred, and the reaction time is for 24 hours in step (2).
9. preparation method according to claim 1, which is characterized in that reaction temperature is 80~180 DEG C in step (2), excellent
Choosing, reaction temperature is 80~120 DEG C in step (2), and highly preferred, reaction temperature is 100 DEG C in step (2), described
Dry to be dried to be placed in a vacuum drying oven, drying temperature is 50~70 DEG C, 10~20h of drying time.
10. a kind of preparation method of the co-modified biological carbon composite of iron, beta-cyclodextrin, comprises the following steps that
(1) molysite, cyclodextrin, charcoal, sodium citrate are added to the water, the pH to 10 of solution, stirring is adjusted using ammonium hydroxide
React 1~3h, the mass ratio of molysite and beta-cyclodextrin are as follows: (0.5~15): the mass ratio of (0.1~30), molysite and bamboo charcoal are as follows:
(0.5~15): the mass ratio of (0.1~30), molysite and sodium citrate: (0.5~15): the matter of (0.1~5), molysite and solvent
Measure volume ratio are as follows: (0.1~10): 200, unit g/mL.
(2) reaction is moved back into autoclave, and 1~48h, reaction are reacted under 80~180 DEG C of temperature, pressure 0.5MPa~1.0MPa
Obtained black solid uses deionized water, washes of absolute alcohol respectively, and it is multiple that the co-modified charcoal of iron, beta-cyclodextrin is obtained after dry
Condensation material.
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