CN107694546A - A kind of acrylic acid modified walnut shell adsorbent and preparation method thereof - Google Patents
A kind of acrylic acid modified walnut shell adsorbent and preparation method thereof Download PDFInfo
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- CN107694546A CN107694546A CN201710980875.6A CN201710980875A CN107694546A CN 107694546 A CN107694546 A CN 107694546A CN 201710980875 A CN201710980875 A CN 201710980875A CN 107694546 A CN107694546 A CN 107694546A
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- walnut shell
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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
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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
- C02F2101/20—Heavy metals or heavy metal compounds
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- Hydrology & Water Resources (AREA)
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Abstract
It is used for acrylic acid modified walnut shell adsorbent and preparation method thereof the invention provides a kind of, mainly comprises the following steps：（1）Washing, crushing, the sieving of walnut shell, choose the walnut shell particle of 60 ~ 80 mesh；（2）With liquor potassic permanganate soaking step（1）Gained walnut shell particle is at initiation state；（3）By step（2）The walnut shell that gained walnut shell reacts acrylic acid modified with acrylic acid and n-hexane mixed liquor heating generation chemical graft；（4）By step（3）Gained is modified walnut shell and is extracted with ethyl acetate, and is washed with the deionized water of certain temperature, and product is collected after drying, obtains acrylic acid modified walnut shell adsorbent.Gained adsorbent of the invention is suitable for adsorbing the metal ion all kinds of sewage, particularly harmful heavy metal ions.
Description
Technical field
The present invention relates to a kind of preparation method of the modified walnut shell adsorbent of acid, particularly it is a kind of be used for adsorbing metal from
The preparation method of the acrylic acid modified walnut shell adsorbent of son.
Background technology
In China, water resource critical shortage, and along with the fast development of industry and the great growth of population, great Liang Gong
Industry waste water and sanitary wastewater is unprocessed is just discharged into environment, can cause seriously to pollute to water body, especially heavy metal and
Body eutrophication, they cause pollution the most serious to water body.For heavy metal pollution, not but not it is biodegradable,
But also can retain, be enriched with and migrate in animal and plant body by food chain, once into human body, human body will be produced for a long time
And irreversible influence.Therefore, the improvement to Heavy Metals in Waters pollution is very urgent.Metal is dirty in common removal water body
The method of dye thing has chemical precipitation method, ion-exchange, solvent extraction, electroosmose process, hyperfiltration, ultrafiltration etc., wherein,
Adsorb and ion-exchange is because the features such as its effect is good, cost is low, easy to operate is widely used in metal ion industrial wastewater
Processing in.
Walnut shell structural property such as porosity, specific surface area is all higher；Functional groups property as containing more hydroxyl,
Carboxyl etc., all adsorb heavy metal ion for walnut shell and provide substantial amounts of avtive spot, therefore, walnut shell can be directly as suction
Attached dose of use.Be presently used for absorption, separating metal ions relevant walnut shell adsorbent most modified techniques be all with
Generation activated carbon is final product.Because substantial amounts of functional group such as hydroxyl, carboxyl etc., their chemistry are contained in walnut shell powder surface
Property is more active, therefore walnut shell powder can be modified by a variety of chemical reactions, and introducing some has adsorption capacity
Group, such as amino, carboxyl, phosphate.Therefore, researcher has synthesized polytype modification or compound in recent years
Modified walnut shell adsorbent, applied in many industry and environmental area.The A of patent CN 103007897 propose a kind of hard
Resin acid is modified the preparation method of walnut shell petroleum adsorbent, and this method is to add stearic acid, n-hexane, the concentrated sulfuric acid, walnut shell
In reaction vessel, flowed back 6 hours in 65 ± 2 DEG C of water-baths.Nylon net filter is used in reaction after terminating, then rinses material with n-hexane
Material, is then placed in 60 DEG C of electric heating constant-temperature blowing drying boxes and is dried to constant weight, that is, stearic acid modified walnut shell petroleum absorption is made
Agent.It is etherifying agent that the A of patent CN 103752280, which are proposed with epoxychloropropane, diethylenetriamine is that crosslinking agent introduces amino base
Group, it is that composite modified walnut shell is inhaled that modified powder, which is made, using the further composite modified reactions of silane coupler kh550 afterwards
Attached dose.Relevant acrylic acid modified patent is there is no at present, and many Patents are used for absorption dyestuff, to metal ion
Absorption it is less, therefore the present invention proposes following scheme, obtains acrylic acid modified walnut shell adsorbent, and for metal from
The research of son absorption.
The content of the invention
The purpose of the present invention is to prepare a kind of modified walnut shell adsorbent of acid, and the adsorbent can be used in adsorbed water body
Metal ion（Pb2+,Ni2+Deng）.
The method of the present invention comprises the following steps：
（1）Appropriate walnut shell is weighed, is washed with clear water, dries to constant weight, crushes and screens at 90 DEG C after filtering, collects 60
The particle of ~ 80 mesh, and particle is soaked into 24 h with deionized water, dried after filtering at 90 DEG C to constant weight, it is standby；
（2）Weigh appropriate step（1）Gained walnut shell particle, with concentration it is 12.0-18.0 mmol L at 30 DEG C-1It is high
After potassium manganate solution immersion certain time, filter and be washed with deionized, it is colourless to wash to supernatant；
（3）By step（2）Gained walnut shell and appropriate acrylic acid and n-hexane are added in three-necked flask, are added under agitation
Heat 1 ~ 2 h of backflow, adds appropriate ethyl acetate and continues the min of stirring 10 ~ 15, filter while hot；
（4）By step（3）Obtained solid soaks 20 ~ 30 min with 70 ~ 80 DEG C of deionized water, filtering, is done at 90 DEG C
It is dry to constant weight, obtain acrylic graft-modified walnut shell particle.
On the basis of every gram of walnut shell particle, the step（2）Middle liquor potassic permanganate volume is 10 ~ 15 mL, the step
Suddenly（3）The quality of middle acrylic acid is 1.0 ~ 2.0 g, and the volume of n-hexane is 10 ~ 20 mL, and the volume of ethyl acetate is 10 ~ 15
ML, the step（4）The volume of middle deionized water is 20 ~ 30 mL.
The step（2）Middle soak time is 15 ~ 30 min.
The innovative point of the present invention is to carry out walnut shell in graft modification, gained modification walnut shell adsorbent with acrylic acid
Acrylic acid quality grafting rate be more than 18%, significantly improved when more unmodified to the absorption property of metal ion, and its circulation profit
Performance is been significantly enhanced.
Embodiment
Embodiment 1
Appropriate walnut shell is weighed, is washed with clear water, dries to constant weight, crushes and screens at 90 DEG C after filtering, collects 60 ~ 80
Purpose particle, and particle is soaked into 24 h with deionized water, dried after filtering at 90 DEG C to constant weight, it is standby；Weigh 3 g warps
The gained walnut shell particle of above-mentioned processing is crossed, with concentration is 12.0 mmol L at 30 DEG C-1The mL of liquor potassic permanganate 40 soaks
20 min after certain time, filter and be washed with deionized, it is colourless to wash to supernatant；Then by walnut shell and 3.0 g
Acrylic acid and 60 mL n-hexanes are added in three-necked flask, are heated to reflux 2 h under agitation, add 30 mL ethyl acetate
Continue to stir 10 min, filter while hot；Obtained solid soaks 20 min, filtering, 90 with 70 DEG C of the mL of deionized water 75
Dried at DEG C to constant weight, obtain acrylic graft-modified walnut shell particle.
Obtained acrylic acid modified walnut shell adsorbent, available for the metal ion in adsorption aqueous solution.Weigh about 45
In the conical flask with cover that mg modification walnut shell is placed in, 25 mL initial concentrations are 5.0 mmol L-1Pb2+In solution, 25
DEG C h of Static Adsorption 48, filters and collects filtrate, dilutes and simultaneously determines Pb in solution with flame atomic absorption spectrophotometer2+It is residual
Remaining concentration.The quality grafting rate for obtaining being modified walnut shell is 18.15%, and the adsorption capacity to Pb ions is 95.28 mgg−1, follow
Adsorption capacity after ring uses 4 times is 85.38mgg−1。
Embodiment 2
Appropriate walnut shell is weighed, is washed with clear water, dries to constant weight, crushes and screens at 90 DEG C after filtering, collects 60 ~ 80
Purpose particle, and particle is soaked into 24 h with deionized water, dried after filtering at 90 DEG C to constant weight, it is standby；Weigh 3 g warps
The gained walnut shell particle of above-mentioned processing is crossed, with concentration is 18.0 mmol L at 30 DEG C-1The mL of liquor potassic permanganate 30 soaks
15 min after certain time, filter and be washed with deionized, it is colourless to wash to supernatant；Then by walnut shell and 5.0 g
Acrylic acid and 45 mL n-hexanes are added in three-necked flask, are heated to reflux 1 h under agitation, add 35 mL ethyl acetate
Continue to stir 15 min, filter while hot；Obtained solid soaks 20 min, filtering, 90 with 80 DEG C of the mL of deionized water 90
Dried at DEG C to constant weight, obtain acrylic graft-modified walnut shell particle.
Obtained acrylic acid modified walnut shell adsorbent, available for the metal ion in adsorption aqueous solution.Weigh about 45
In the conical flask with cover that mg modification walnut shell is placed in, 25 mL initial concentrations are 5.0 mmol L-1Ni2+In solution, 25
DEG C h of Static Adsorption 48, filters and collects filtrate, dilutes and with Ni in the EDTA solution volumetric soiutions of concentration known2+It is remaining dense
Degree.The quality grafting rate for obtaining being modified walnut shell is 20.16%, and the adsorption capacity to Ni ions is 32.19 mgg−1, circulation makes
It is 28.84 mgg with the adsorption capacity after 4 times−1。
Embodiment 3
Appropriate walnut shell is weighed, is washed with clear water, dries to constant weight, crushes and screens at 90 DEG C after filtering, collects 60 ~ 80
Purpose particle, and particle is soaked into 24 h with deionized water, dried after filtering at 90 DEG C to constant weight, it is standby；Weigh 3 g warps
The gained walnut shell particle of above-mentioned processing is crossed, with concentration is 16.0 mmol L at 30 DEG C-1The mL of liquor potassic permanganate 45 soaks
30 min after certain time, filter and be washed with deionized, it is colourless to wash to supernatant；Then by walnut shell and 4.5 g
Acrylic acid and 30 mL n-hexanes are added in three-necked flask, are heated to reflux 1 h under agitation, add 45 mL ethyl acetate
Continue to stir 15 min, filter while hot；Obtained solid soaks 25 min, filtering, 90 with 80 DEG C of the mL of deionized water 60
Dried at DEG C to constant weight, obtain acrylic graft-modified walnut shell particle.
Obtained acrylic acid modified walnut shell adsorbent, available for the metal ion in adsorption aqueous solution.Weigh about
In the conical flask with cover that 45mg modification walnut shell is placed in, 25mL initial concentrations are 5.0mmol L-1Pb2+In solution, 25 DEG C
Static Adsorption 48h, filter and collect filtrate, dilute and determine Pb in solution with flame atomic absorption spectrophotometer2+Remnants
Concentration.The quality grafting rate for obtaining being modified walnut shell is 21.02%, and the adsorption capacity to Pb ions is 107.62 mgg−1, follow
Adsorption capacity after ring uses 4 times is 96.39 mgg−1。
Embodiment 4
Appropriate walnut shell is weighed, is washed with clear water, dries to constant weight, crushes and screens at 90 DEG C after filtering, collects 60 ~ 80
Purpose particle, and particle is soaked into 24 h with deionized water, dried after filtering at 90 DEG C to constant weight, it is standby；Weigh 3g processes
The gained walnut shell particle of above-mentioned processing, with concentration it is 16.0 mmol L at 30 DEG C-1The mL of liquor potassic permanganate 30 immersions one
25 min after fixing time, filter and be washed with deionized, it is colourless to wash to supernatant；Then by walnut shell and 6.0 g third
Olefin(e) acid and 30 mL n-hexanes are added in three-necked flask, are heated to reflux 1.5 h under agitation, add 40 mL ethyl acetate
Continue to stir 10 min, filter while hot；Obtained solid soaks 30 min, filtering, 90 with 70 DEG C of the mL of deionized water 75
Dried at DEG C to constant weight, obtain acrylic graft-modified walnut shell particle.
Obtained acrylic acid modified walnut shell adsorbent, available for the metal ion in adsorption aqueous solution.Weigh about 45
In the conical flask with cover that mg modification walnut shell is placed in, 25 mL initial concentrations are 5.0 mmol L-1Ni2+In solution, 25
DEG C h of Static Adsorption 48, filters and collects filtrate, dilutes and with Ni in the EDTA solution volumetric soiutions of concentration known2+It is remaining dense
Degree.The quality grafting rate for obtaining being modified walnut shell is 22.10%, and the adsorption capacity to Ni ions is 34.54 mgg−1, circulation makes
It is 30.95 mgg with the adsorption capacity after 4 times−1。
Comparative example
Appropriate walnut shell is weighed, is washed with clear water, dries to constant weight, crushes and screens at 90 DEG C after filtering, collects 60 ~ 80
Purpose particle, and particle is soaked into 24 h with deionized water, dried after filtering at 90 DEG C to constant weight, it is standby；Obtain unmodified
Walnut shell particle.
Weigh in the conical flask with cover that about 45mg unmodified walnut shell is placed in, 25mL initial concentrations are 5.0mmol L-1
Pb2+In solution, 25 DEG C of Static Adsorption 48h, filter and collect filtrate, dilute and determined with flame atomic absorption spectrophotometer
Pb in solution2+Residual concentration.It is 11.08 mgg to the adsorption capacity of Pb ions to obtain unmodified walnut shell−1。
Claims (3)
1. a kind of acrylic acid modified walnut shell adsorbent and preparation method thereof, it is characterised in that comprise the following steps：
（1）Appropriate walnut shell is weighed, is washed with clear water, dries to constant weight, crushes and screens at 90 DEG C after filtering, collects 60
The particle of ~ 80 mesh, and particle is soaked into 24 h with deionized water, dried after filtering at 90 DEG C to constant weight, it is standby；
（2）Weigh appropriate step（1）Gained walnut shell particle, with concentration it is 12.0 ~ 18.0 mmol L at 30 DEG C-1Gao Meng
After sour potassium solution immersion certain time, filter and be washed with deionized, it is colourless to wash to supernatant；
（3）By step（2）Gained walnut shell and appropriate acrylic acid and n-hexane are added in three-necked flask, are added under agitation
Heat 1 ~ 2 h of backflow, adds appropriate ethyl acetate and continues the min of stirring 10 ~ 15, filter while hot；
（4）By step（3）Obtained solid soaks 20 ~ 30 min with 70 ~ 80 DEG C of deionized water, filtering, is done at 90 DEG C
It is dry to constant weight, obtain acrylic graft-modified walnut shell particle.
2. method according to claim 1, it is characterised in that on the basis of every gram of walnut shell particle, the step（2）Middle height
Potassium manganate solution volume is 10 ~ 15 mL, the step（3）The quality of middle acrylic acid is 1.0 ~ 2.0 g, and the volume of n-hexane is
10 ~ 20 mL, the volume of ethyl acetate are 10 ~ 15 mL, the step（4）The volume of middle deionized water is 20 ~ 30 mL.
3. according to claim 1 ~ 2 methods described, it is characterised in that the step（2）Middle soak time is 15 ~ 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710980875.6A CN107694546A (en) | 2017-10-20 | 2017-10-20 | A kind of acrylic acid modified walnut shell adsorbent and preparation method thereof |
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| CN201710980875.6A CN107694546A (en) | 2017-10-20 | 2017-10-20 | A kind of acrylic acid modified walnut shell adsorbent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225162A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of the modified walnut shell adsorbent of aspartic acid |
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- 2017-10-20 CN CN201710980875.6A patent/CN107694546A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225162A (en) * | 2018-11-09 | 2019-01-18 | 华东理工大学 | A kind of preparation method of the modified walnut shell adsorbent of aspartic acid |
| CN109225162B (en) * | 2018-11-09 | 2022-03-01 | 华东理工大学 | Preparation method of aspartic acid modified walnut shell adsorbent |
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Application publication date: 20180216 |