CN106345429B - A kind of bagasse base anion adsorbent and its preparation method and application - Google Patents
A kind of bagasse base anion adsorbent and its preparation method and application Download PDFInfo
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- CN106345429B CN106345429B CN201610989111.9A CN201610989111A CN106345429B CN 106345429 B CN106345429 B CN 106345429B CN 201610989111 A CN201610989111 A CN 201610989111A CN 106345429 B CN106345429 B CN 106345429B
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- Prior art keywords
- bagasse
- base anion
- preparation
- anion adsorbent
- bagasse base
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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
- B01J20/22—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
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Abstract
The present invention provides a kind of bagasse base anion adsorbents and preparation method thereof and its purposes.The preparation method of the bagasse base anion adsorbent includes the following steps: (1) esterification: bagasse raw material being mixed with nitric acid, glacial acetic acid, a period of time is stirred to react under certain temperature, obtains bagasse nitrate；(2) complexation reaction: the bagasse nitrate that step (1) obtains is mixed with ferric chloride solution, and a period of time is stirred to react under certain temperature, and reaction product is washed to neutrality, is filtered, dry, obtains bagasse base anion adsorbent.The preparation method raw material sources are wide, and cheap, preparation process is simple, and equipment requirement is low, high production efficiency.Bagasse base anion adsorbent obtained by this method can be used for adsorbing the anion in eutrophication water.
Description
Technical field
The present invention relates to bagasse base anion adsorbent and its preparation method and application design, belong to biological material and
Adsorbing separation field.
Background technique
Water eutrophication refer in water body the nutrient concentrations such as N, P it is excessively high caused by contamination phenomenon.Industrial production, agriculture
The excessive fertilization of industry all makes the eutrophication in surrounding city lake serious.In order to solve this problem, common at present biological
Method, ecological method and absorption method, and wherein often expense cost is excessively high and energy consumption is larger for bioanalysis and ecological method.So preparation is rich
Nutrient laden anion adsorbent is to comply with Times ' Demand, benefits following important development strategy, can especially be prepared a kind of at low cost
Honest and clean, the adsorbent of the treatment of wastes with processes of wastes against one another is with regard to even more important.
The purification device (CN 205087963U) of phosphate radical is adsorbed in Li Mingshun once invention with PERFORMANCE OF MODIFIED VERMICULITE, and Yue Wenwen was once sent out
It is bright that with modified wheat straw waste absorption phosphate radical, (Yue Wenwen, Wang Yu, Gao Baoyu, modified wheat straw waste imitate Phosphateadsorption in water
The research of fruit, ACTA Scientiae Circumstantiae, 2006,26 (12), 1983-1986), once a kind of phosphoric acid was made with inorganic mineral in Dong Qingjie etc.
Root adsorbent (CN 1748857A), can obtain relatively good adsorption effect, thus for low concentration eutrophication yin from
The processing of son is also the research project full of vigour for having numerous inventors to participate in.
Bagasse derives from the by-product of cane sugar manufacture, is a kind of from a wealth of sources, low-cost biomass material, for a long time
Since largely directly burned, cause environmental pollution and the wasting of resources.Bagasse is mainly by cellulose, hemicellulose and wooden
Element is constituted, and constituting the not single of substance makes it be difficult to be utilized.
Summary of the invention
The purpose of the present invention is being directed to above-mentioned the problems of the prior art, provide a kind of bagasse base anion adsorbent and
Preparation method and use.Bagasse base anion adsorbent provided by the invention for processing eutrophication water in yin from
Son has fabulous effect, and preparation method is simple, low raw-material cost.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of bagasse base anion adsorbent, which is characterized in that include the following steps:
(1) esterification: bagasse raw material is mixed with nitric acid, glacial acetic acid, when being stirred to react one section under certain temperature
Between, obtain bagasse nitrate；
(2) complexation reaction: the bagasse nitrate that step (1) obtains is mixed with ferric chloride solution, under certain temperature
It is stirred to react a period of time, reaction product is washed to neutrality, is filtered, it is dry, obtain bagasse base anion adsorbent.
According to the above scheme, it is preferable that bagasse raw material described in step (1) is the sugarcane by washing and drying and processing
Slag.
According to the above scheme, it is preferable that bagasse raw material described in step (1), nitric acid, glacial acetic acid amount ratio be 1g:4~
10mL:1~6mL.
According to the above scheme, it is highly preferred that the mass concentration score of the nitric acid is 10%~65%.
According to the above method, it is preferable that in step (1), the reaction temperature is 0~100 DEG C, and the reaction time is 0.5
~10 hours.
According to the above method, it is preferable that described bagasse raw material in ferric chloride solution described in step (2) and step (1)
Amount ratio is 3~6mL:1g.
According to the above scheme, it is highly preferred that the mass concentration score of the ferric chloride solution is 1~13%.
According to the above method, it is preferable that in step (2), the reaction temperature is 10~70 DEG C, and the reaction time is 2~6
Hour.
According to the above method, it is preferable that dry temperature described in step (2) is 15-105 DEG C.
The present invention also provides the bagasse base anion adsorbents being prepared according to above-mentioned preparation method.
The present invention also provides the applications of above-mentioned bagasse base anion adsorbent, which is characterized in that can be used for adsorbing rich battalion
Anion in feedingization water body, especially phosphate anion.
Reaction principle of the present invention is as follows:
Wherein, (a) is that the first step reacts to obtain bagasse nitrate；(b) for second step react to obtain bagasse Ji Yin from
Son absorption；R is other parts in bagasse.
Compared with the prior art, beneficial effects of the present invention are as follows:
1, novel bagasse base anion adsorbent provided by the invention can be used in adsorbing the yin in eutrophication water
Ion, it is especially fabulous to the adsorption effect of phosphate anion.
2, bagasse is mainly made of cellulose, hemicellulose and lignin, and constituting the not single of substance keeps it often difficult
To be utilized.And these three substances of the positive good utilisation of present invention active hydrogen all rich in, esterification can occur with nitric acid,
Using the method being coordinated afterwards is first esterified, bagasse base anion adsorbent is prepared, achieving the effect that give up well, it is useless to control,
Both the utilization rate for the biomass energy for having reduced resource waste or having improved.
3, the present invention is using the natural plants residue of industrial waste gas as raw material, and raw material sources are wide, cheap, preparation process stream
Journey is simple, low for equipment requirements, high production efficiency, environment friendly and pollution-free and good in economic efficiency, is anion in eutrophication water
Processing provide a kind of new adsorbent and preparation method thereof.
4, the present invention, can be by changing nitric acid and iron chloride during preparing bagasse base anion adsorbent
Concentration adjusts the absorption property of product adsorbent.
Detailed description of the invention:
Fig. 1 inhales for raw materials used, intermediate products in bagasse in the present invention modified process flow and embodiment 1 and finished product
Attached dose of photo；
Fig. 2 is that bagasse raw material, intermediate products (bagasse nitrate) and final finished (change in the embodiment of the present invention 2
Property bagasse base anion adsorbent) infrared spectrum comparison diagram；
Fig. 3 is bagasse base anion adsorbent made from the embodiment of the present invention 5, and at 25 DEG C is 5mg/L to concentration
The adsorbance of phosphate radical solution change over time curve.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation of bagasse base anion adsorbent, the specific steps are as follows:
1) washing and drying is handled: using discarded bagasse as raw material, cleaning removes soil and dust after first being impregnated with clear water,
Again wash with distilled water, then drying to constant weight, and bagasse raw material is made with spare.
2) esterification: taking 50g bagasse raw material, first mixed with 450mL nitric acid (mass fraction 63%) and 150mL glacial acetic acid
It closes, is stirred under 30 DEG C of condition of normal pressure, esterification 4 hours, obtain bagasse ester.
3) complexation reaction: the bagasse ester that step 2) obtains is mixed with 300mL iron chloride (mass fraction 6%) solution,
It is stirred 4 hours under 35 DEG C of condition of normal pressure, reaction product is repeatedly washed with distilled water to neutrality, is filtered, is dried, obtain in 35 DEG C
The modified bagasse base anion adsorbent (finished product adsorbent) being coordinated to Fe.
Absorption property experiment, the specific steps are as follows:
1, using the concentration of P-Mo blue spectrophotometry calibration phosphate radical solution: take 0 respectively, 0.1,0.2,0.6,1.0,
1.4, each 5mL of 1.8mg/L phosphate radical standard solution is in 7 little Lan lid bottles, is added 0.1mL ascorbic acid thereto, after 30s again
0.2mL ammonium molybdate is added thereto, shakes up, uses Shimadzu UV-1800 ultraviolet-visible spectrophotometer after placing 5min at room temperature
It is measured in 720nm wavelength, obtains its absorbance-phosphate concentration standard curve: y=0.3466x+0.01219；Y is absorbance,
X is phosphate concentration.
2, absorption test: modified bagasse base anion adsorbent made from 1g the present embodiment is taken to be put into 100mL conical flask
In, adding 80mL concentration is 5mg/L phosphate radical solution, and conical flask is placed in shaking table and is shaken, and guarantees adsorbent and phosphate radical
Solution is sufficiently mixed, and the temperature of shaking table is controlled at 25 DEG C.Phosphate radical solution after 5min takes 5mL to adsorb is in little Lan lid bottle
In, 0.1mL ascorbic acid is first added, 0.2mL ammonium molybdate is added thereto again after 30s, shakes up, is used after placing 5min at room temperature
Shimadzu UV-1800 ultraviolet-visible spectrophotometer measures to obtain absorbance in 720nm wavelength, and the standard obtained by step 1 is bent
Line converts adsorbed after phosphate radical solution concentration.
3, the calculation formula of adsorption efficiency is as follows:
Wherein η is adsorption efficiency, C0For the initial concentration of phosphate radical solution, C is the concentration for being adsorbed rear phosphate radical solution,
According to the above method, it measures, modified bagasse base anion adsorbent made from the present embodiment is to 80mL 5mg/L phosphorus
Acid group solution reached adsorption equilibrium in 1 hour, and when reaching adsorption equilibrium, the concentration of the phosphate radical solution after being adsorbed is
0.5mg/L, adsorption efficiency highest, reaches 90% at this time.
Bagasse raw material used, intermediate products and finished product adsorbent pattern photo are as shown in Figure 1 in the present embodiment.
Embodiment 2
The preparation of bagasse base anion adsorbent, the specific steps are the same as those in embodiment 1, only by institute in step 2) esterification
The mass fraction of nitric acid is changed to 65%, and the mass fraction of iron chloride used in step 3) complexation reaction is changed to 8%, and
The temperature of complexation reaction is changed to 55 DEG C.
In the present embodiment, bagasse nitrate and step 3) that bagasse raw material that step 1) obtains, step 2) obtain
The infrared spectrum comparison diagram of obtained modified bagasse base anion adsorbent is as shown in Figure 2.It compares (a), (b) 1700cm-1It is left
It is right, it was demonstrated that nitric acid esterification has NO group, 1300cm-1Left and right is proved with the presence of C-N, so being esterified successfully；In comparison (b), (c) send out
Existing 1300cm-1Stretching vibration is weakened, and is illustrated that the coordination of Fe shortens C-N key, its Oscillation Amplitude is reduced, so also turning out
The success of complexation reaction.
It is measured according to absorption property test method described in embodiment 1, modified bagasse base made from 1g the present embodiment
When anion adsorbent adsorbs 80mL 5mg/L phosphate radical solution under the conditions of 25 DEG C, phosphate radical solution reaches suction in 1 hour
Attached balance, when reaching adsorption equilibrium, the concentration of the phosphate radical solution after being adsorbed is 0.35mg/L, at this time adsorption efficiency highest,
Reach 93%.
Embodiment 3
The preparation of bagasse base anion adsorbent, the specific steps are the same as those in embodiment 1, only by institute in step 2) esterification
The mass fraction of nitric acid is changed to 53%, and volumetric usage is changed to 400mL, by iron chloride used in step 3) complexation reaction
Mass fraction is changed to 4%, and dosage volume is changed to 250mL.
It is measured according to absorption property test method described in embodiment 1, bagasse Ji Yin made from 0.5g the present embodiment
When ionic adsorption adsorbs 80mL 5mg/L phosphate radical solution under the conditions of 25 DEG C, it is flat that phosphate radical solution reaches absorption in 45min
Weighing apparatus, when reaching adsorption equilibrium, the concentration of the phosphate radical solution after being adsorbed is 2.15mg/L, and adsorption efficiency highest, reaches at this time
57%.
Embodiment 4
The preparation of bagasse base anion adsorbent, the specific steps are the same as those in embodiment 1, only by institute in step 2) esterification
The quality of bagasse raw material is changed to 30g, and volumetric usage is changed to 250mL and the mass fraction of nitric acid is changed to 53%, by step
3) mass fraction of iron chloride used in complexation reaction is changed to 4%, and drying temperature is changed to 105 DEG C.
It is measured according to absorption property test method described in embodiment 1, bagasse Ji Yin made from 0.7g the present embodiment
When ion adsorbent adsorbs 80mL 5mg/L phosphate radical solution under the conditions of 25 DEG C, phosphate radical solution reaches absorption in 45min
Balance, when reaching adsorption equilibrium, the concentration of the phosphate radical solution after being adsorbed is 0.9mg/L, and adsorption efficiency highest, reaches at this time
82%.
Embodiment 5
The preparation of bagasse base anion adsorbent, the specific steps are the same as those in embodiment 1, only by institute in step 2) esterification
The quality of bagasse raw material is changed to 25g, and the volumetric usage of nitric acid is changed to 200mL, the volumetric usage of glacial acetic acid is changed to
The volumetric usage of iron chloride used in step 3) complexation reaction is changed to 150mL by 80mL, and drying temperature is changed to 65 DEG C.
Measured according to absorption property test method described in embodiment 1, bagasse Ji Yin made from 1g the present embodiment from
When sub- adsorbent adsorbs 80mL 5mg/L phosphate radical solution under the conditions of 25 DEG C, it is flat that phosphate radical solution reaches absorption in 60min
Weighing apparatus, when reaching adsorption equilibrium, the concentration 0.5mg/L of the phosphate radical solution after being adsorbed, adsorption efficiency highest, reaches at this time
90%.Influence of the adsorption time to adsorbance such as Fig. 3.
Claims (9)
1. a kind of preparation method of bagasse base anion adsorbent, which is characterized in that include the following steps:
(1) esterification: 1g bagasse raw material is mixed with nitric acid, glacial acetic acid, and a period of time is stirred to react under certain temperature,
Obtain bagasse nitrate；
(2) complexation reaction: the bagasse nitrate that step (1) obtains is mixed with 3~6mL ferric chloride solution, in 10~70 DEG C
Lower the reaction was stirred for 2 to 6 hours, and reaction product is washed to neutrality, is filtered, dry, obtains bagasse base anion adsorbent.
2. the preparation method of bagasse base anion adsorbent according to claim 1, which is characterized in that in step (1)
The bagasse raw material is the bagasse by washing and drying and processing.
3. the preparation method of bagasse base anion adsorbent according to claim 1, which is characterized in that in step (1)
The bagasse raw material, nitric acid, glacial acetic acid amount ratio be 1g:4~10mL:1~6mL.
4. the preparation method of bagasse base anion adsorbent according to claim 3, which is characterized in that the nitric acid
Mass concentration score is 10%~65%.
5. the preparation method of bagasse base anion adsorbent according to claim 1, which is characterized in that in step (1),
The reaction temperature is 0~100 DEG C, and the reaction time is 0.5~10 hour.
6. the preparation method of bagasse base anion adsorbent according to claim 1, which is characterized in that the iron chloride
The mass concentration score of solution is 1~13%.
7. the preparation method of bagasse base anion adsorbent according to claim 1, which is characterized in that in step (2)
The temperature of the drying is 15-105 DEG C.
8. the bagasse base anion adsorbent being prepared by the described in any item preparation methods of claim 1-7.
9. the application of bagasse base anion adsorbent according to any one of claims 8, which is characterized in that can be used for adsorbing eutrophication
Anion in water body.
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| CN109647351B (en) * | 2019-01-07 | 2022-10-21 | 武汉工程大学 | Bagasse loaded iron hydroxide adsorbent and preparation method and application thereof |
| CN110314655B (en) * | 2019-06-03 | 2022-05-10 | 武汉工程大学 | Bagasse-loaded zero-valent iron adsorbent and preparation method and application thereof |
| CN111420975B (en) * | 2020-05-06 | 2021-06-08 | 浙江大学 | Modified bagasse and preparation method and application thereof |
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| GB2166140B (en) * | 1984-10-27 | 1989-06-07 | Ion Exchange | Novel adsorbents for use in the purification of water and other chemicals and a process for preparing same |
| JP5319192B2 (en) * | 2007-08-03 | 2013-10-16 | 株式会社東芝 | Phosphorus compound adsorbent, phosphorus compound adsorption system, and method of using phosphorous compound adsorbent |
| CN102218303B (en) * | 2011-06-22 | 2012-07-11 | 广东石油化工学院 | Method for preparing heavy metal adsorbent by using modified bagasse |
| CN102964605B (en) * | 2012-11-30 | 2015-02-18 | 南京林业大学 | Esterification modification method for wood fiber biomasses |
| CN104815624A (en) * | 2015-04-30 | 2015-08-05 | 广东第二师范学院 | Efficient adsorbent of inorganic modified sugarcane residues and preparation method and application thereof |
| CN104986822B (en) * | 2015-06-19 | 2017-03-08 | 华东理工大学 | A kind of chemical modification carries the preparation of iron peanut shell dephosphorization material and renovation process |
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