CN104475021B - Rich nitrogen tea seed episperm activated carbon and its preparation method and application - Google Patents
Rich nitrogen tea seed episperm activated carbon and its preparation method and application Download PDFInfo
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- CN104475021B CN104475021B CN201410684179.7A CN201410684179A CN104475021B CN 104475021 B CN104475021 B CN 104475021B CN 201410684179 A CN201410684179 A CN 201410684179A CN 104475021 B CN104475021 B CN 104475021B
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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
- C02F2101/12—Halogens or halogen-containing compounds
Abstract
The invention discloses a kind of rich nitrogen tea seed episperm activated carbon and its preparation method and application.This richness nitrogen tea seed episperm activated carbon is with tea seed episperm as raw material, prepare through alkali liquor heat treatment, activation processing, pyrolysis processing, oxidation processes and ammoniated treatment, in this richness nitrogen tea seed episperm activated carbon, the atomic percentage of nitrogen is 8.03%～9.52%, and specific surface area is 990 m2/ g～1005 m2/g.Its preparation method includes alkali liquor heat treatment, activation processing, pyrolysis processing, oxidation processes and five steps of ammoniated treatment.The rich nitrogen tea seed episperm activated carbon adsorption capacity utilization high, repeatable of the present invention, greatly reduce processing cost, preparation method is simple, with low cost, the rich nitrogen tea seed episperm activated carbon prepared can effectively process high concentration perchlorate waste water, not result in secondary pollution, it is achieved that the recycling to agricultural wastes.
Description
Technical field
The present invention relates to sewage treatment area, be specifically related to a kind of rich nitrogen tea seed episperm activated carbon and preparation method thereof and the application in processing perchlorate waste water of this richness nitrogen tea seed episperm activated carbon.
Background technology
Perchlorate is the salt that perchloric acid is formed, the perchlorate (ClO containing tetrahedral4 -), it is widely used in the fields such as propellant, pyrotechnics manufacture, army's industry, air bag, highway safety Flash board, also serves as in the production that additive is used for lubricating oil, fabric fixative, electroplate liquid, fuel coating, the smelting product such as aluminum and magnesium cell simultaneously.Owing to people use perchlorate in productive life widely, substantial amounts of perchlorate is caused to enter among natural water, perchlorate has that dissolubility is high, diffusion velocity is fast, the high-leveled and difficult feature with degraded of stability, therefore becomes a kind of novel persistent pollutant.Perchlorate in water body by directly drinking or can enter human body by the way of food chain.The perchlorate entering human body can disturb the thyroid absorption to iodide ion, affects thyroid normal function, causes the minimizing of thyroxin synthetic quantity, affects the growth of human brain tissue.Owing to thyroid hormone secretion is not enough, hinder the synthesis of hemoglobin, affect cardio-pulmonary function and the growth of skeleton, the maintenance of immunity, the normal function etc. of organon auditus.
The research of American National research center shows, the perchlorate amount that human body daily intakes not can exceed that 0.7 μ g/kg body weight, and health, not above 25 μ g/L, otherwise will be impacted by the content of Perchlorate in Drinking Water.Environmental Protection in America general administration specifies that perchlorate safety criterion in drinking water is 18 μ g/L, and the area that some damage ratios are more serious has been formulated lower safety criterion value.
At present, the removal technology of perchlorate specifically includes that microorganism remediation, physical absorption and electronation three major types.But although utilizing micro-reduction perchlorate effectively to there are problems, such as reducing condition requires height, there is pathogenic microorganism harm etc..Utilizing chemical method to remove perchlorate processing cost high, operation is loaded down with trivial details, easily causes secondary pollution, and subsequent concentration liquid difficult treatment.Utilize activated carbon or the perchlorate in the absorbent charcoal material absorption waste water of N doping, be a kind of simple, easily operated and widely used method.Existing commercial activated carbons used is the most undesirable for the adsorption effect of perchlorate.At present, the correlational study utilizing the rich nitrogen activated carbon adsorption perchlorate of tea seed episperm preparation is the most fewer, does not find the method that in active adsorption water prepared by perchlorate richness nitrogen tea seed episperm activated carbon.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is provided that a kind of prepare simple, with low cost, can effectively process high concentration perchlorate waste water, the rich nitrogen tea seed episperm activated carbon not resulting in secondary pollution, repeatable utilization and its preparation method and application.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of rich nitrogen tea seed episperm activated carbon, described rich nitrogen tea seed episperm activated carbon is with tea seed episperm as raw material, prepares through alkali liquor heat treatment, activation processing, pyrolysis processing, oxidation processes and ammoniated treatment；In described rich nitrogen tea seed episperm activated carbon, the atomic percentage of nitrogen is 8.03%～9.52%, and specific surface area is 990 m2/ g～1005 m2/g。
As total technology design, the present invention also provides for the preparation method of a kind of above-mentioned rich nitrogen tea seed episperm activated carbon, comprises the following steps:
(1), there is pyrolytic reaction in alkali liquor heat treatment: be placed in alkali liquor by tea seed episperm and carry out water-bath vibration, washing alkali liquid being vacuum dried after reaction, obtains tea seed episperm activation raw material；
(2) activation processing: above-mentioned tea seed episperm activation raw material is joined in liquor zinci chloridi and stirs, heating in water bath, and carry out vacuum drying treatment, obtain tea seed episperm activated feedstock；
(3), there is pyrolytic reaction, cool down after reaction, wash, be vacuum dried, obtain tea seed episperm activated carbon powdered carbon raw material in pyrolysis processing: heated under nitrogen protection by above-mentioned tea seed episperm activated feedstock；
(4) oxidation processes: above-mentioned tea seed episperm activated carbon powdered carbon raw material is added in the mixed solution of nitric acid and hydrogen peroxide, after vibration oxidation reaction, wash, be vacuum dried, obtain tea seed episperm activated carbon oxidation powdered carbon raw material；
(5) ammoniated treatment: above-mentioned tea seed episperm activated carbon oxidation powdered carbon raw material is placed in heater, first it is passed through the air in nitrogen emptying heater, then pass to ammonification gas and carry out aminating reaction, it is passed through nitrogen again and is cooled to room temperature, after scrubbed and vacuum drying, obtain rich nitrogen tea seed episperm activated carbon.
In above-mentioned preparation method, it is preferred that in described step (1): the concentration of described alkali liquor is 1mol/L～2mol/L；The quality of described tea seed episperm is 1g: 10ml～30ml with the ratio of the volume of described alkali liquor；The condition of described water-bath vibration is: bath temperature is 95 DEG C～100 DEG C, and rotating speed is 140r/min～160r/min, and the time is 2h～4h；Described vacuum drying temperature is 90 DEG C～110 DEG C, and the time is 12h～24h.
In above-mentioned preparation method, it is preferred that in described step (1), described alkali liquor is sodium hydroxide solution or potassium hydroxide solution.
In above-mentioned preparation method, it is preferred that in described step (2): the mass concentration of described liquor zinci chloridi is 30%～50%, the quality of described tea seed episperm activation raw material is 1g: 4ml～6ml with the ratio of the volume of described liquor zinci chloridi；The temperature of described heating in water bath is 95 DEG C～100 DEG C, and the time is 10h～12h；Described vacuum drying temperature is 105 DEG C～110 DEG C, and the time is 24h～48h.
In above-mentioned preparation method, preferably, in described step (3): the step of described pyrolytic reaction is, first with the ramp of 20 DEG C/min～30 DEG C/min to 200 DEG C, after stopping 5min～10min, again with the ramp of 20 DEG C/min～30 DEG C/min to end reaction temperature 600 DEG C, stop 90min～120min；Described washing uses hydrochloric acid solution, and the molar concentration of described hydrochloric acid solution is 1mol/L～2mol/L；Described vacuum drying temperature is 105 DEG C～110 DEG C, and the time is 8h～12h.
In above-mentioned preparation method, it is preferred that in described step (4): the described quality of tea seed episperm activated carbon powdered carbon raw material is 1g: 50ml～100ml with the ratio of the volume of described nitric acid and the mixed solution of hydrogen peroxide；In the mixed solution of described nitric acid and hydrogen peroxide, nitric acid is 1～4: 1 with the volume ratio of hydrogen peroxide；The temperature of described vibration oxidation reaction is 90 DEG C～100 DEG C, and rotating speed is 140r/min～160r/min, and the time is 2h～4h；Described vacuum drying temperature is 105 DEG C～110 DEG C, and the time is 5h～8h.
In above-mentioned preparation method, it is preferred that in described step (5): described in be passed through the step of the air in nitrogen emptying heater be to be passed through nitrogen 5min～10min with the flow velocity of 20mL/min～50mL/min；The step of described aminating reaction is, it is passed through described nitrogen to stopping when 200 DEG C～300 DEG C with 20 DEG C/min～30 DEG C/min ramp, it is passed through ammonification gas with the flow velocity of 100mL/min～150mL/min, with the ramp of 20 DEG C/min～30 DEG C/min to aminating reaction temperature 500 DEG C～900 DEG C, and stop 90min～120min；Described vacuum drying temperature is 105 DEG C～110 DEG C, and the time is 5h～8h.
As total technology design, the present invention also provides for the application in processing perchlorate waste water of rich nitrogen tea seed episperm activated carbon that a kind of above-mentioned rich nitrogen tea seed episperm activated carbon or above-mentioned preparation method prepare, comprise the following steps: described rich nitrogen tea seed episperm activated carbon and perchlorate waste water are joined and carry out adsorption reaction in adsorption system, measure rich nitrogen tea seed episperm activated carbon to the absorbability of perchlorate in waste water.
In above-mentioned application, it is preferred that the concentration of described perchlorate waste water is 1mg/L～100mg/L；The described rich quality of nitrogen tea seed episperm activated carbon is 1g: 500ml～1000ml with the ratio of the volume of described perchlorate waste water；Perchlorate in described perchlorate waste water is sodium perchlorate and/or potassium hyperchlorate；Described adsorption system is conventional vessel, and described conventional vessel includes triangular flask.
In the preparation method of the present invention, in described step (1): described tea seed episperm is the discarded tea seed episperm of oil pressing mill；The drying condition of described tea seed episperm is: temperature is 70 DEG C～80 DEG C, and drying time is 24h～48h.
In the preparation method of the present invention, in described step (4): before described tea seed episperm activated carbon powdered carbon raw material adds mixed solution, can first be ground, cross 80 mesh sieves；The molar concentration of described nitric acid is 1mol/L～2mol/L, and the mass concentration of described hydrogen peroxide is 30%.
In the preparation method of the present invention, in described step (5), described ammonification gas is ammonia.
In the present invention, the rich nitrogen tea seed episperm activated carbon processing perchlorate waste water can pass through micro wave regeneration, and can again process perchlorate waste water.Micro wave regeneration comprises the following steps: will process the rich nitrogen tea seed episperm activated carbon of perchlorate waste water after 105 DEG C～110 DEG C of dry 12h～24h, it is placed in microwave oven, under conditions of steam and carbon dioxide exist, heat 60min～120min in 800 DEG C～1000 DEG C, obtain regenerating rich nitrogen tea seed episperm activated carbon.Utilizing the rich nitrogen tea seed episperm activated carbon of regeneration to process perchlorate waste water, its treatment conditions are identical with the treatment conditions of rich nitrogen tea seed episperm activated carbon.
Compared with prior art, it is an advantage of the current invention that:
1, the rich nitrogen tea seed episperm activated carbon of the present invention has adsorption capacity utilization high, repeatable, does not results in secondary pollution, prepares the advantages such as simple, with low cost.Compared to existing activated carbon, the rich nitrogen tea seed episperm activated carbon of the present invention is easier to N doping, it is possible to significantly improve nitrogen content；The effect that perchlorate is adsorbed by the rich nitrogen tea seed episperm activated carbon of the present invention simultaneously is more preferable, and this makes the rich nitrogen tea seed episperm activated carbon of the present invention can effectively adsorb perchlorate waste water.The rich nitrogen tea seed episperm activated carbon of the present invention is with the garbage tea seed episperm of camellia oleosa seed oil plant as raw material, after discarded tea seed episperm is carried out a series of process, has obtained rich nitrogen tea seed episperm activated carbon, it is achieved the recycling to agricultural wastes.
2, the preparation method of the present invention is simple, with low cost, first uses alkali liquor heat treatment can dissolve the polysaccharide in tea seed episperm and partial lignin, beneficially tea seed episperm and softens and the release of cellulose；Then utilize liquor zinci chloridi to carry out activation processing, advantageously form the tea seed episperm activated carbon of high-specific surface area；Recycling nitric acid and hydrogen peroxide mixed solution carry out oxidation processes, make tea seed episperm activated carbon surface form substantial amounts of oxidative function group；Finally by ammoniated treatment, ammonia reacts with tea seed episperm activated carbon surface oxidative function group, will form nitrogen-dopped activated carbon, and prepare rich nitrogen tea seed episperm absorbent charcoal material on nitrogen atom doping to carbocyclic ring.
3, the rich nitrogen tea seed episperm activated carbon of the present invention can active adsorption perchlorate waste water, particularly concentration be the high concentration perchlorate waste water of 1mg/L～100mg/L.The present invention processed the rich nitrogen tea seed episperm activated carbon of perchlorate waste water through micro wave regeneration, can again process perchlorate waste water, and i.e. rich nitrogen tea seed episperm activated carbon can be reused, and greatly reduces processing cost.
Accompanying drawing explanation
Fig. 1 is the microscopic appearance figure (amplifying 800 times) of tea seed episperm activated carbon in the embodiment of the present invention 1.
Fig. 2 is the microscopic appearance figure (amplifying 800 times) of rich nitrogen tea seed episperm activated carbon in the embodiment of the present invention 1.
Fig. 3 be in the embodiment of the present invention 1 XPS to rich nitrogen tea seed episperm activated carbon surface each elementary analysis result figure.
Fig. 4 is the XPS peak spectrum fitted figure of rich nitrogen tea seed episperm activated carbon surface nitrogen substance in the embodiment of the present invention 1.
Fig. 5 is the rich nitrogen tea seed episperm activated carbon absorption isotherm to perchlorate in the embodiment of the present invention 2.
Fig. 6 is the perchlorate absorption dynamic curve of rich nitrogen tea seed episperm activated carbon in the embodiment of the present invention 2.
Fig. 7 is the comparison diagram of the rich nitrogen tea seed episperm activated carbon nitrogen content of preparation in different embodiments of the invention.
Detailed description of the invention
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
Material and instrument employed in following example are commercially available.
Embodiment
1
:
A kind of rich nitrogen tea seed episperm activated carbon of the present invention, this richness nitrogen tea seed episperm activated carbon is with tea seed episperm as raw material, prepare after alkali liquor heat treatment, activation processing, pyrolysis processing, oxidation processes and ammoniated treatment, in this richness nitrogen tea seed episperm activated carbon, the atomic percentage of nitrogen is 8.7%, and the specific surface area of rich nitrogen tea seed episperm activated carbon is 997 m2/g。
The preparation method of the rich nitrogen tea seed episperm activated carbon of a kind of above-mentioned the present embodiment, comprises the following steps:
(1) alkali liquor heat treatment: cleaned by the discarded tea seed episperm taking from oil pressing mill, is dried 24h at 80 DEG C.Dry tea seed episperm is ground for soybean grain size, take 10g grind after tea seed episperm join 100ml, concentration be 1mol/L sodium hydroxide solution in, in 98 DEG C, water-bath vibration 2h under the conditions of 150r/min, filter after being cooled to room temperature, deionized water wash by heat, last vacuum drying 24h at a temperature of 105 DEG C, obtains tea seed episperm activation raw material.
(2) activation processing: take 10g tea seed episperm activation raw material and add to the liquor zinci chloridi that 40ml mass concentration is 30%, heating in water bath 12h at 98 DEG C, this is conducive to zinc chloride and the reaction of tea seed episperm activation raw material, and slough unnecessary moisture, finally it is vacuum dried 24h in 105 DEG C, obtains tea seed episperm activated feedstock.
(3) pyrolysis processing: take 2g tea seed episperm activated feedstock and be positioned in tube type resistance furnace, be passed through nitrogen 5min with the air in drain with the flow velocity of 50mL/min.The most under nitrogen protection with the ramp of 20 DEG C/min to 200 DEG C, stop 5min, then with 20 DEG C/min ramp to end reaction temperature 600 DEG C, stop 90min, stop the heating and continuous nitrogen that is passed through and be cooled to room temperature.With the vibration washing of hydrochloric acid solution that concentration is 1mol/L, then with the unnecessary hydrochloric acid of deionized water rinsing, finally vacuum drying 10h at 105 DEG C, obtains tea seed episperm activated carbon powdered carbon raw material, as shown in Figure 1.
(4) oxidation processes: the tea seed episperm activated carbon powdered carbon raw material of 1g is ground, cross 80 mesh sieves, it is then added in the triangular flask of 150ml, add 40ml concentration and be the salpeter solution of 1mol/L and 10ml mass concentration is the hydrogen peroxide solution of 30%, in 90 DEG C, after the 2h that vibrates under the conditions of 150r/min, with deionized water cyclic washing to pH=6.5, at 105 DEG C, finally it is vacuum dried 8h, obtains tea seed episperm activated carbon oxidation powdered carbon raw material.
(5) ammoniated treatment: 2g tea seed episperm activated carbon oxidation powdered carbon raw material is positioned in tube type resistance furnace, it is passed through nitrogen 10min with the air in drain with the flow velocity of 50mL/min, it is passed through nitrogen to stopping when 200 DEG C again with 20 DEG C/min ramp, now, it is passed through ammonia with the flow velocity of 100mL/min, and to 600 DEG C and stop 120min with the ramp of 20 DEG C/min, stop being passed through ammonia, then it is passed through nitrogen with the speed of 50mL/min, it is cooled to room temperature, with deionized water rinsing to pH=6.5, last vacuum drying 8h at 105 DEG C, obtain rich nitrogen tea seed episperm activated carbon.
Tea seed episperm activated carbon and the microscopic pattern of rich nitrogen tea seed episperm activated carbon is watched, the most as depicted in figs. 1 and 2 with mirror field scanning electron microscope.As shown in Figure 1, tea seed episperm activated carbon surface is smooth and with the presence of substantial amounts of hole.As shown in Figure 2, the surface of rich nitrogen tea seed episperm activated carbon by ammonia corrode very serious, present rough form, illustrate that substantial amounts of ammonia reacts at tea seed episperm activated carbon surface, in the middle of nitrogen atom doping to carbocyclic ring.Characterizing the surface mass of rich nitrogen tea seed episperm activated carbon with x-ray photoelectron spectroscopy (XPS), result is as shown in Figure 3.Result shows, the atomic percentage of rich nitrogen tea seed episperm activated carbon surface nitrogen is 8.7%.Having obtained the open score about N by the peak near 400eV is carried out high power analysis, result is as shown in Figure 4.Can be obtained, by Fig. 4, the peak spectrum that the peak spectrogram of N is not simple a kind of nitrogen substance (nitrogen-containing functional group), but be composed mixing by the peak of multiple nitrogen substance and form.
Due to pyridine structure (N-6), amine substance (Amines), pyrrole structure (N-5), quaternary ammonium salt structure (N-Q) and oxynitride (N-Ox) combination can be respectively as follows: 398.7 ± 0.3eV, 399.4eV, 400.3 ± 0.3eV, 401.4eV and 402eV～405eV, and pyridine structure and quaternary ammonium salt can be with the ClO in aqueous solution4 -In conjunction with.Peak spectrum to nitrogen element carries out the matching of above-mentioned nitrogen substance, and result is as shown in Figure 4.As shown in Figure 4, the nitrogen substance of the rich nitrogen tea seed episperm activated carbon surface prepared by the present invention mainly has: pyridine structure, pyrrole structure, quaternary ammonium salt structure, amine substance and oxynitride, and the rich nitrogen tea seed episperm activated carbon of the present invention can adsorb the perchlorate in water.
Embodiment
2
:
The application (i.e. adsorbing and absorption power determination) in processing high concentration perchlorate waste water of the rich nitrogen tea seed episperm activated carbon of a kind of present invention, this richness nitrogen tea seed episperm activated carbon takes from the rich nitrogen tea seed episperm activated carbon of embodiment 1 preparation, and application process comprises the following steps:
The perchlorate solution (specially sodium perchlorate solution) of 12 variable concentrations of configuration, its concentration is respectively 1mg/L, 5 mg/L, 10 mg/L, 20 mg/L, 30 mg/L, 40 mg/L, 50 mg/L, 60 mg/L, 70 mg/L, 80 mg/L, 90 mg/L, 100 mg/L, respectively take 50ml, put in the triangular flask (i.e. adsorption system) of 250ml；Taking rich nitrogen tea seed episperm activated carbon 0.1g and join in the triangular flask of the 250ml equipped with variable concentrations perchlorate solution, vibrate under the conditions of room temperature, 150r/min 24h, and after having reacted, the concentration of sampling and measuring perchlorate, result is as shown in Figure 5.
Absorption power determination: take in the triangular flask that 0.1g richness nitrogen tea seed episperm activated carbon joins 250ml, add the perchlorate solution that 50ml concentration is 50mg/L, vibrate under the conditions of room temperature, 150r/min 24h, and at 1min, 5 min, 10 min, 20 min, 30 min, 60 min, 90 min, 120 min, 150 min, 180 min, 1440 min, water sampling measures the perchlorate solution concentration of different time points, and result is as shown in Figure 6.
Being shown by the result of Fig. 5 and Fig. 6, rich nitrogen tea seed episperm activated carbon has stronger adsorption effect for perchlorate.As shown in Figure 5 the adsorption capacity of rich nitrogen tea seed episperm activated carbon along with in solution the increase of perchlorate concentration and improve constantly, when perchlorate solution concentration reaches 100mg/L, absorption reaches maximum saturation value.It is 6.8mg/g by being calculated rich nitrogen tea seed episperm activated carbon to the maximum adsorption capacity of perchlorate.Absorption power determination result as shown in Figure 6 shows, the rich nitrogen tea seed episperm activated carbon absorption to perchlorate solution, reaches to adsorb saturated at about 120min.
Embodiment
3
:
A kind of process of the present invention the regeneration of rich nitrogen tea seed episperm activated carbon of perchlorate waste water and application thereof, the process in the present embodiment the rich nitrogen tea seed episperm activated carbon of perchlorate waste water derive from embodiment 2.
Regeneration: by the process in embodiment 2 the rich nitrogen tea seed episperm activated carbon of perchlorate waste water after 105 DEG C of dry 12h, be placed in microwave oven, under conditions of steam and carbon dioxide exist, heat 90min in 900 DEG C, must regenerate richness nitrogen tea seed episperm activated carbon.
Application: utilizing the rich nitrogen tea seed episperm activated carbon of regeneration to process perchlorate waste water, its treatment conditions are identical with the treatment conditions of the rich nitrogen tea seed episperm activated carbon in embodiment 2.
Result shows, makes rich nitrogen tea seed episperm activated carbon that the adsorption capacity of sodium perchlorate is obtained the biggest recovery through micro wave regeneration, and recovery rate is 87.4%, is 5.9mg/g through calculating the maximum adsorption capacity of the rich nitrogen tea seed episperm activated carbon of regeneration.
Embodiment
4
:
The preparation method and application of the rich nitrogen tea seed episperm activated carbon of the present embodiment, comprises the following steps:
Preparation process is basically identical with embodiment 1, and difference is: in step (1), and the concentration of sodium hydroxide solution is 2 mol/L, and the quality of tea seed episperm is 1g: 30ml with the ratio of the volume of alkali liquor；In step (2), the mass concentration of liquor zinci chloridi is 50%；In step (3), being warming up to end reaction temperature when being 600 DEG C, the time of staying of pyrolytic reaction is 120 min；In step (4), in the mixed solution of nitric acid and hydrogen peroxide, nitric acid is 3: 1 with the ratio of the volume of hydrogen peroxide；In step (5), the flow velocity of ammonia is 120 ml/min, and aminating reaction temperature is 500 DEG C.In rich nitrogen tea seed episperm activated carbon, the atomic percentage of nitrogen is 8.03%, and specific surface area is 990 m2/g。
By the rich nitrogen tea seed episperm activated carbon obtained according to being that 1～100 mg/L sodium perchlorate aqueous solutions adsorb to concentration under conditions of same as in Example 2.Result shows, rich nitrogen tea seed episperm activated carbon is 5.8 to the maximum adsorption capacity of sodium perchlorate
mg/g。
Embodiment
5
:
The preparation method and application of the rich nitrogen tea seed episperm activated carbon of the present embodiment, comprises the following steps:
Preparation process is basically identical with embodiment 1, and difference is: in step (1), and the quality of tea seed episperm is 1g: 20ml with the ratio of the volume of alkali liquor；In step (2), the mass concentration of liquor zinci chloridi is 40%, and the quality of tea seed episperm activation raw material is 1g: 5ml with the ratio of the volume of liquor zinci chloridi；In step (3), the concentration of hydrochloric acid is 2 mol/L；In step (4), the quality of tea seed episperm activated carbon powdered carbon raw material and ratio 1g: 100ml of the volume of nitric acid and the mixed solution of hydrogen peroxide, nitric acid is 2: 1 with the volume ratio of hydrogen peroxide；In step (5), aminating reaction temperature is 700 DEG C.In rich nitrogen tea seed episperm activated carbon, the atomic percentage of nitrogen is 8.56%, and specific surface area is 996 m2/g。
By the rich nitrogen tea seed episperm activated carbon obtained according to being that 1～100 mg/L sodium perchlorate aqueous solutions adsorb to concentration under conditions of same as in Example 2.Result shows, rich nitrogen tea seed episperm activated carbon is 6.4 to the maximum adsorption capacity of sodium perchlorate
mg/g。
Embodiment
6
:
The preparation method and application of the rich nitrogen tea seed episperm activated carbon of the present embodiment, comprises the following steps:
Preparation process is basically identical with embodiment 1, and difference is: in step (1), and the concentration of sodium hydroxide solution is 2 mol/L, and the quality of tea seed episperm is 1g: 30ml with the ratio of the volume of alkali liquor；In step (2), the mass concentration of liquor zinci chloridi is 40%, and the quality of tea seed episperm activation raw material is 1g: 6ml with the ratio of the volume of liquor zinci chloridi；In step (3), when being warming up to end reaction temperature 600 DEG C, the time of staying of pyrolytic reaction is 120 min；In step (4), in the mixed solution of nitric acid and hydrogen peroxide, nitric acid is 1: 1 with the volume ratio of hydrogen peroxide；In step (5), the flow velocity of ammonia is 150 ml/min, and aminating reaction temperature is 800 DEG C.In rich nitrogen tea seed episperm activated carbon, the atomic percentage of nitrogen is 8.96%, and specific surface area is 998 m2/g。
By the rich nitrogen tea seed episperm activated carbon obtained according to being that 1～100 mg/L sodium perchlorate aqueous solutions adsorb to concentration under conditions of same as in Example 2.Result shows, rich nitrogen tea seed episperm activated carbon is 6.7 to the maximum adsorption capacity of sodium perchlorate
mg/g。
Embodiment
7
:
The preparation method and application of the rich nitrogen tea seed episperm activated carbon of the present embodiment, comprises the following steps:
Preparation process is basically identical with embodiment 1, and difference is: in step (1), and the quality of tea seed episperm is 1g: 20ml with the ratio of the volume of alkali liquor；In step (2), the mass concentration of liquor zinci chloridi is 50%, and the quality of tea seed episperm activation raw material is 1g: 5ml with the ratio of the volume of liquor zinci chloridi；In step (3), when being warming up to end reaction temperature 600 DEG C, the time of staying of pyrolytic reaction is 120min；In step (4), the quality of tea seed episperm activated carbon powdered carbon raw material and ratio 1g: 100ml of the volume of nitric acid and the mixed solution of hydrogen peroxide；In step (5), aminating reaction temperature is 900 DEG C.In rich nitrogen tea seed episperm activated carbon, the atomic percentage of nitrogen is 9.52%, and specific surface area is 1005
m2/g。
By the rich nitrogen tea seed episperm activated carbon obtained according to being that 1～100 mg/L sodium perchlorate aqueous solutions adsorb to concentration under conditions of same as in Example 2.Result shows, rich nitrogen tea seed episperm activated carbon is 7.1 to the maximum adsorption capacity of sodium perchlorate
mg/g。
As it is shown in fig. 7, be the nitrogen content (i.e. the atomic percentage of nitrogen) being respectively adopted in the rich nitrogen tea seed episperm activated carbon of tea seed episperm activated carbon powdered carbon raw material, embodiment 1,4,5,6,7 preparation.By contrast, after tea seed episperm activated carbon is carried out oxidation processes and ammoniated treatment, can effectively improve the nitrogen content in tea seed episperm activated carbon, form the tea seed episperm activated carbon of rich nitrogen, the atomic percentage of its nitrogen can reach 8.03%～9.52%, and can effectively adsorb perchlorate in water.
In addition to the sodium perchlorate aqueous solution gone out given in above example, rich nitrogen tea seed episperm activated carbon also can process high concentration potassium hyperchlorate aqueous solution.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-described embodiment.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.Iting is noted that for those skilled in the art, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. a preparation method for rich nitrogen tea seed episperm activated carbon, comprises the following steps:
(1), there is pyrolytic reaction in alkali liquor heat treatment: be placed in alkali liquor by tea seed episperm and carry out water-bath vibration, washing alkali liquid being vacuum dried after reaction, obtains tea seed episperm activation raw material；
(2) activation processing: above-mentioned tea seed episperm activation raw material is joined in liquor zinci chloridi and stirs, heating in water bath, and carry out vacuum drying treatment, obtain tea seed episperm activated feedstock；
(3), there is pyrolytic reaction, cool down after reaction, wash, be vacuum dried, obtain tea seed episperm activated carbon powdered carbon raw material in pyrolysis processing: heated under nitrogen protection by above-mentioned tea seed episperm activated feedstock；The step of described pyrolytic reaction is, first with the ramp of 20 DEG C/min～30 DEG C/min to 200 DEG C, after stopping 5min～10min, then with the ramp of 20 DEG C/min～30 DEG C/min to end reaction temperature 600 DEG C, stops 90min～120min；
(4) oxidation processes: above-mentioned tea seed episperm activated carbon powdered carbon raw material is added in the mixed solution of nitric acid and hydrogen peroxide, after vibration oxidation reaction, wash, be vacuum dried, obtain tea seed episperm activated carbon oxidation powdered carbon raw material；
(5) ammoniated treatment: above-mentioned tea seed episperm activated carbon oxidation powdered carbon raw material is placed in heater, first it is passed through the air in nitrogen emptying heater, then pass to ammonification gas and carry out aminating reaction, it is passed through nitrogen again and is cooled to room temperature, after scrubbed and vacuum drying, obtain rich nitrogen tea seed episperm activated carbon.
Preparation method the most according to claim 1, it is characterised in that in described step (1): the concentration of described alkali liquor is 1mol/L～2mol/L；The quality of described tea seed episperm is 1g: 10mL～30mL with the ratio of the volume of described alkali liquor；The condition of described water-bath vibration is: bath temperature is 95 DEG C～100 DEG C, and rotating speed is 140r/min～160r/min, and the time is 2h～4h；Described vacuum drying temperature is 90 DEG C～110 DEG C, and the time is 12h～24h.
Preparation method the most according to claim 2, it is characterised in that in described step (1), described alkali liquor is sodium hydroxide solution or potassium hydroxide solution.
Preparation method the most according to claim 1, it is characterised in that in described step (2): the mass concentration of described liquor zinci chloridi is 30%～50%, the quality of described tea seed episperm activation raw material is 1g: 4mL～6mL with the ratio of the volume of described liquor zinci chloridi；The temperature of described heating in water bath is 95 DEG C～100 DEG C, and the time is 10h～12h；Described vacuum drying temperature is 105 DEG C～110 DEG C, and the time is 24h～48h.
5. according to the preparation method according to any one of Claims 1 to 4, it is characterised in that in described step (3): described washing uses hydrochloric acid solution, and the molar concentration of described hydrochloric acid solution is 1mol/L～2mol/L；Described vacuum drying temperature is 105 DEG C～110 DEG C, and the time is 8h～12h.
6. according to the preparation method according to any one of Claims 1 to 4, it is characterised in that in described step (4): the described quality of tea seed episperm activated carbon powdered carbon raw material is 1g: 50mL～100mL with the ratio of the volume of described nitric acid and the mixed solution of hydrogen peroxide；In the mixed solution of described nitric acid and hydrogen peroxide, nitric acid is 1～4: 1 with the volume ratio of hydrogen peroxide；The temperature of described vibration oxidation reaction is 90 DEG C～100 DEG C, and rotating speed is 140r/min～160r/min, and the time is 2h～4h；Described vacuum drying temperature is 105 DEG C～110 DEG C, and the time is 5h～8h.
7. according to the preparation method according to any one of Claims 1 to 4, it is characterised in that in described step (5): described in be passed through the step of the air in nitrogen emptying heater be to be passed through nitrogen 5min～10min with the flow velocity of 20mL/min～50mL/min；The step of described aminating reaction is, it is passed through described nitrogen to stopping when 200 DEG C～300 DEG C with 20 DEG C/min～30 DEG C/min ramp, it is passed through ammonification gas with the flow velocity of 100mL/min～150mL/min, with the ramp of 20 DEG C/min～30 DEG C/min to aminating reaction temperature 500 DEG C～900 DEG C, and stop 90min～120min；Described vacuum drying temperature is 105 DEG C～110 DEG C, and the time is 5h～8h.
8. the rich nitrogen tea seed episperm activated carbon that the preparation method as according to any one of claim 1～7 prepares application in processing perchlorate waste water, comprise the following steps: described rich nitrogen tea seed episperm activated carbon and perchlorate waste water are joined and carry out adsorption reaction in adsorption system, measure rich nitrogen tea seed episperm activated carbon to the absorbability of perchlorate in waste water.
Application the most according to claim 8, it is characterised in that the concentration of described perchlorate waste water is 1mg/L～100mg/L；The described rich quality of nitrogen tea seed episperm activated carbon is 1g: 500mL～1000mL with the ratio of the volume of described perchlorate waste water；Perchlorate in described perchlorate waste water is sodium perchlorate and/or potassium hyperchlorate；Described adsorption system is conventional vessel, and described conventional vessel includes triangular flask.
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| CN102513061A (en) * | 2011-12-29 | 2012-06-27 | 翟云波 | Modified active carbon and preparation method and application thereof |
| CN103495399A (en) * | 2013-10-23 | 2014-01-08 | 湖南大学 | Preparation method and application of sludge activated carbon |
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| CN102513061A (en) * | 2011-12-29 | 2012-06-27 | 翟云波 | Modified active carbon and preparation method and application thereof |
| CN103495399A (en) * | 2013-10-23 | 2014-01-08 | 湖南大学 | Preparation method and application of sludge activated carbon |
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