CN104841382A - Modified peanut shell adsorbent and preparation method and application thereof - Google Patents
Modified peanut shell adsorbent and preparation method and application thereof Download PDFInfo
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- CN104841382A CN104841382A CN201510216996.4A CN201510216996A CN104841382A CN 104841382 A CN104841382 A CN 104841382A CN 201510216996 A CN201510216996 A CN 201510216996A CN 104841382 A CN104841382 A CN 104841382A
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Abstract
The invention discloses a modified peanut shell adsorbent and a preparation method and an application thereof. The method comprises pre-treating and smashing peanut shells to be sieved; adding epoxy chloropropane into the sieved peanut shell powder to be mixed uniformly, adding a NaOH solution into the mixture to be reacted, and performing filtering, washing and drying after reaction to obtain the modified peanut shell adsorbent. By means of the modified peanut shell adsorbent and the preparation method and the application thereof, the peanut shells are modified through the epoxy chloropropane, the modified peanut absorbent physical strength is improved, the number of surface active functional groups is increased greatly, and the peanut shell absorption effect is improved. Besides, waste water is treated through the peanut shells, so that the waste water treatment cost can be reduced effectively, a large number of prior cheap green resources can be used, and a novel approach is provided for comprehensive use of agricultural wastes.
Description
Technical field
The present invention relates to a kind of modified peanut adsorbent, be specifically related to a kind of modified peanut adsorbent and its preparation method and application.
Background technology
China produces peanut pod about 6,000,000 tons per year, in peanut processing process, the peanut shell of about 2,000,000 tons can be produced, these peanut shells only have small part to be used as the raw material of fiberboard, other mostly idle or be used as fuel incinerate, thus cause a large amount of wastings of resources, so people start the Appropriate application approach seeking peanut shell.Consider that peanut shell porosity is higher, there is larger specific area, and the lignin that peanut shell contains, cellulose, the composition surfaces such as hemicellulose are containing hydroxyl, carboxyl isoreactivity functional group, therefore, people process the dyestuff in waste water used as adsorbent, if but directly use, adsorption effect is unsatisfactory, trace it to its cause and be that surface active composition content is less, the dissolving of soluble organic matter can cause chemical oxygen consumption (COC) in water to increase, simultaneously for peanut shell, its physical strength is poor, usually sufficient intensity is not had for wastewater treatment.Therefore, people consider the adsorption effect improving peanut shell further by chemical modification.
Famille rose, have another name called No. 102, edible redness of the skin or complexion (Japan), edible No. 7, redness, ponceau 4R, bright red, brilliant scarlet G, being water-soluble azo class dyestuff, is the isomers of amaranth.Carmine (Ponceau 4R) is a kind of monoazo class synthetic food color that current China uses the most extensively, consumption is maximum.In recent years, report is had to point out, carmine forbid with EU criteria Sudan redly belong to azo pigment, azo-compound metabolism can generate mutagen precursor in vivo---aromatic amine compounds, phenyl ring in addition in its structure is high inhibition effect to biology, therefore, is difficult to Bian biological method and famille rose is degraded into inorganic molecules, and then need to carry out further advanced treating to this waste water from dyestuff, to reduce its pollution to environment.At present, research for this type of dyeing waste water mainly concentrates on the aspects such as physical absorption, chemical reagent oxidizes, film process, photochemical catalytic oxidation and microbial degradation process, but mostly there is the problems such as high cost, complex operation, energy consumption be large in these methods, causes it to apply and be restricted.Therefore, seeking a kind of inexpensive, efficient, pollution-free, easy to operate adsorbent is current research personnel issues that need special attention.
Therefore, use discarded agricultural biomaterials peanut shell to prepare adsorbent for base material, adsorption bleaching research is carried out to famille rose in waste water and has great importance.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of modified peanut adsorbent, described adsorbent significantly can remove the famille rose in waste water; Present invention also offers preparation method and the application of this adsorbent.
The present invention takes following technical scheme to realize foregoing invention object:
1, a modified peanut adsorbent, the preparation process of described modified peanut adsorbent is as follows:
(1) pulverize after peanut shell cleaning, sieve, obtaining particle diameter is 60 ~ 100 object peanut hull meals;
(2) get step (1) described peanut hull meal, add the epoxychloropropane that volume is peanut hull meal weight 10 ~ 30 times, mixing, add NaOH solution again to react, filter after completion of the reaction, be washed to neutrality, dry, obtain modified peanut adsorbent.
Further, in described step (1), peanut hull meal particle diameter is 100 orders.
Further, in NaOH solution described in described step (2), the content of NaOH and the weight ratio of peanut hull meal addition are 1:1.8.
Further, described in described step (2), the temperature of reaction is 20 ~ 80 DEG C, and the time of reaction is 0.5 ~ 10h.
Further, in described step (2) epoxychloropropane add 15 times that volume is peanut hull meal weight, the temperature of described reaction is 45 DEG C, and the time of reaction is 2h.
Further, dry as to dry under 50 ~ 70 DEG C of conditions described in described step (2).
2, the preparation method of modified peanut adsorbent, comprises the steps:
(1) pulverize after peanut shell cleaning, sieve, obtaining particle diameter is 60 ~ 100 object peanut hull meals;
(2) get step (1) described peanut hull meal, add the epoxychloropropane that volume is peanut hull meal weight 10 ~ 30 times, mixing, add NaOH solution again to react, filter after completion of the reaction, be washed to neutrality, dry, obtain modified peanut adsorbent.
3, the application of modified peanut adsorbent in process cochineal dye waste water.
Further, the ratio of 0.013 ~ 0.33g/mL peanut shell adsorbent is added in 100mg/L cochineal dye waste water, joined by peanut shell adsorbent in cochineal dye waste water, the pH regulating waste water is 1.0 ~ 3.0, then stirs at 30 DEG C or vibration absorption 1 ~ 21h.
Further, add the ratio of 0.02g/mL peanut shell adsorbent in 100mg/L cochineal dye waste water, joined by peanut shell adsorbent in cochineal dye waste water, the pH regulating waste water is 2.0, then stirs at 30 DEG C or vibration absorption 10h.
Beneficial effect of the present invention is: the present invention carries out modification by epoxychloropropane to peanut shell, modified peanut shell adsorbent physical strength improves, and surface-active functional group's number increases substantially, further enhancing the adsorption effect of peanut shell, known by experimental result of the present invention, this peanut shell adsorbent reaches 90% to the waste water dyestuff clearance that carmine concentration is 100mg/L.In addition, process waste water with peanut shell, not only effectively can reduce the processing cost of waste water, existing a large amount of cheap green resource can also be utilized, thus provide new way for the comprehensive utilization of agricultural wastes.
Detailed description of the invention
Below the preferred embodiments of the present invention are described in detail.The experimental technique of unreceipted actual conditions in embodiment, the usually conveniently conditioned disjunction condition of advising according to manufacturer.
The preparation process of modified peanut adsorbent is as follows:
(1) pulverize after peanut shell cleaning, sieve, obtaining particle diameter is 60 ~ 100 object peanut hull meals;
(2) get step (1) described peanut hull meal, add the epoxychloropropane that volume is peanut hull meal weight 10 ~ 30 times, mixing, add NaOH solution again to react, filter after completion of the reaction, be washed to neutrality, dry, obtain modified peanut adsorbent; In described NaOH solution, the content of NaOH and the weight ratio of peanut hull meal addition are 1:1.8; The temperature of described reaction is 20 ~ 80 DEG C, and the time of reaction is 0.5 ~ 10h; Described oven dry for dry under 50 ~ 70 DEG C of conditions.
Embodiment 1 reaction time is on the impact of adsorbent effect
First prepare peanut shell modified adsorbent, preparation process is as follows:
(1) pulverize after peanut shell cleaning, cross 60 mesh sieves, obtain peanut hull meal;
(2) get 2.0g peanut hull meal, add 15mL epoxychloropropane, mixing, then the NaOH solution 45mL adding 1.0mol/L reacts, and filters after completion of the reaction, is washed to neutrality, then dry under 65 DEG C of conditions, obtain modified peanut adsorbent; The temperature of described reaction is 30 DEG C, and the time of reaction is 0.5 ~ 10h.
Accurately take the above-mentioned modified peanut adsorbent 0.2g prepared under the differential responses time respectively, add the cochineal solution of 30mL concentration 240mg/L, pH is regulated to be about 2.0, be placed in water bath with thermostatic control oscillator, vibrate 15h at 30 DEG C, and rotating speed is 150 turns/min, measures carmine concentration in residual solution, calculate clearance, the results are shown in Table 1.
Table 1 reaction time is on the impact of modified peanut adsorbent effect
| Reaction time (h) | 0.5 | 1 | 1.5 | 2 | 2.5 | 4 | 6 | 8 | 10 |
| Clearance (%) | 48.2 | 43.6 | 44.6 | 50.4 | 49.1 | 44.7 | 46.1 | 48.7 | 47.2 |
As shown in Table 1, when being when reacted 2h, prepared peanut shell modified adsorbent adsorption effect is best, and adsorbent is 50.4% to the clearance of dyestuff.
Embodiment 2 reaction temperature is on the impact of adsorbent effect
First prepare peanut shell modified adsorbent, preparation process is as follows:
(1) pulverize after peanut shell cleaning, cross 60 mesh sieves, obtain peanut hull meal;
(2) get 2.0g peanut hull meal, add 15mL epoxychloropropane, mixing, then the NaOH solution 45mL adding 1.0mol/L reacts, and filters after completion of the reaction, is washed to neutrality, then dry under 65 DEG C of conditions, obtain modified peanut adsorbent; The temperature of described reaction is 20 ~ 80 DEG C, and the time of reaction is 2h.
Accurately take the above-mentioned modified peanut adsorbent 0.2g prepared at differential responses temperature respectively, add the cochineal solution of 30mL concentration 116.8mg/L, regulate about pH to 2.0, be placed in water bath with thermostatic control oscillator, vibrate 15h at 30 DEG C, and rotating speed is 150 turns/min, measures carmine concentration in residual solution, calculate clearance, the results are shown in Table 2.
Table 2 reaction temperature is on the impact of peanut shell modified adsorbent adsorption effect
| Reaction temperature (DEG C) | 20 | 25 | 30 | 35 | 40 | 45 | 50 | 60 | 70 | 80 |
| Clearance (%) | 73.1 | 81.2 | 79.9 | 84.4 | 78.0 | 85.1 | 81.8 | 83.1 | 86.3 | 85.2 |
As shown in Table 2, when reaction temperature is more than 45 DEG C, prepared peanut shell modified adsorbent all more than 80%, considers Energy Consumption Factors to the clearance of famille rose, selects 45 DEG C as optimal reaction temperature.
Embodiment 3 expoxy propane addition is on the impact of adsorbent effect
First prepare peanut shell modified adsorbent, preparation process is as follows:
(1) pulverize after peanut shell cleaning, cross 60 mesh sieves, obtain peanut hull meal;
(2) get 2.0g peanut hull meal, add a certain amount of epoxychloropropane, mixing, then the NaOH solution 45mL adding 1.0mol/L reacts, and filters after completion of the reaction, is washed to neutrality, then dry under 50 ~ 70 DEG C of conditions, obtain modified peanut adsorbent; The temperature of described reaction is 45 DEG C, and the time of reaction is 2h.
Accurately take peanut shell modified adsorbent 0.2g prepared by above-mentioned interpolation difference amount epoxychloropropane respectively, add the cochineal solution of 30mL concentration 116.8mg/L, regulate about pH to 2.0, be placed in water bath with thermostatic control oscillator, vibrate 15h at 30 DEG C, and rotating speed is 150 turns/min, measures carmine concentration in residual solution, calculate clearance, the results are shown in Table 3.
The different epoxychloropropane addition of table 3 is on the impact of peanut shell modified adsorbent adsorption effect
| Peanut shell: epoxychloropropane (w/v) | 1：10 | 1：15 | 1：20 | 1：25 | 1：30 | Unmodified |
| Clearance (%) | 59.1 | 60.6 | 57.4 | 60.3 | 67.6 | 49.2 |
As shown in Table 3, when pulp furnish is 1:30, the clearance of prepared peanut shell modified adsorbent to famille rose is maximum, reaches 67.6%, considers solvent consumption, selects secondary good proportioning 1:15 as optimum response pulp furnish.
Embodiment 4 peanut hull meal order number is on the impact of peanut shell modified adsorbent adsorption effect
First prepare peanut shell modified adsorbent, preparation process is as follows:
(1) pulverize after peanut shell cleaning, cross 20 ~ 100 mesh sieves, obtain peanut hull meal;
(2) get 2.0g peanut hull meal, add 30mL epoxychloropropane, mixing, then the NaOH solution 45mL adding 1.0mol/L reacts, and filters after completion of the reaction, is washed to neutrality, then dry under 65 DEG C of conditions, obtain modified peanut adsorbent; The temperature of described reaction is 45 DEG C, and the time of reaction is 2h.
Accurately take above-mentioned peanut shell modified adsorbent 0.2g respectively, add the cochineal solution of 30mL concentration 66.1mg/L, adjust ph to 2.0, be placed in water bath with thermostatic control oscillator, vibrate 15 hours at 30 DEG C, rotating speed is 150 turns/min, measures carmine concentration in residual solution, calculate clearance, the results are shown in Table 4.
Table 4 peanut hull meal order number is on the impact of peanut shell modified adsorbent adsorption effect
| Particle size (order) | 20 | 40 | 60 | 80 | 100 |
| Dyestuff clearance (%) | 17.2 | 34.0 | 50.5 | 82.4 | 92.4 |
As shown in Table 4, when peanut shell particle diameter is greater than 100 order, prepared peanut hull meal will more than 90% to the maximum material removal rate of famille rose.
The pH value of embodiment 5 dyestuff is on the impact of peanut shell modified adsorbent adsorption effect
First prepare peanut shell modified adsorbent, preparation process is as follows:
(1) pulverize after peanut shell cleaning, cross 60 mesh sieves, obtain peanut hull meal;
(2) get 2.0g peanut hull meal, add 30mL epoxychloropropane, mixing, then the NaOH solution 45mL adding 1.0mol/L reacts, and filters after completion of the reaction, is washed to neutrality, then dry under 65 DEG C of conditions, obtain modified peanut adsorbent; The temperature of described reaction is 45 DEG C, and the time of reaction is 2h.
Accurately take the peanut shell modified adsorbent 0.2g of preparation, add the cochineal solution of 30mL concentration 109.7mg/L, regulate solution ph, be placed in water bath with thermostatic control oscillator, vibrate 24h at 30 DEG C, and rotating speed is 150 turns/min, measures carmine concentration in residual solution, calculate clearance, the results are shown in Table 5.
Table 5 dyestuff pH is on the impact of peanut shell modified adsorbent adsorption effect
| PH value | 1 | 2 | 3 | 5 | 7 | 9 | 12 |
| Dyestuff clearance (%) | 49.5 | 40.0 | 6.4 | 2.8 | 2.5 | 0 | 0 |
As shown in Table 5, under strong acidic environment, prepared peanut hull meal is better to the removal effect of famille rose, and consider that acid mistake can destroy this body structure of peanut shell by force, selection pH=2 is optimum condition, and under this pH value, carmine clearance is 40.0%.
Embodiment 6 adsorption time is on the impact of peanut shell modified adsorbent adsorption effect
First prepare peanut shell modified adsorbent, preparation process is as follows:
(1) pulverize after peanut shell cleaning, cross 60 mesh sieves, obtain peanut hull meal;
(2) get 2.0g peanut hull meal, add 30mL epoxychloropropane, mixing, then the NaOH solution 45mL adding 1.0mol/L reacts, and filters after completion of the reaction, is washed to neutrality, then dry under 65 DEG C of conditions, obtain modified peanut adsorbent; The temperature of described reaction is 45 DEG C, and the time of reaction is 2h.
Accurately take 0.1g peanut shell modified adsorbent, add the cochineal solution of 30mL concentration 26.5mg/L, adjust ph is 2.0, be placed in water bath with thermostatic control oscillator, at 30 DEG C of vibration different times, rotating speed is 150 turns/min, measure carmine concentration in residual solution, calculate clearance, the results are shown in Table 6.
Table 6 adsorption time is on the impact of peanut shell modified adsorbent adsorption effect
As shown in Table 6, after adsorption time is 10h, the clearance change of prepared peanut hull meal to kermes is little, and clearance can reach 70%.
Embodiment 7 adsorbent amount is on the impact of adsorption effect
First prepare peanut shell modified adsorbent, preparation process is as follows:
(1) pulverize after peanut shell cleaning, cross 100 mesh sieves, obtain peanut hull meal;
(2) get 2.0g peanut hull meal, add 30mL epoxychloropropane, mixing, then the NaOH solution 45mL adding 1.0mol/L reacts, and filters after completion of the reaction, is washed to neutrality, then dry under 65 DEG C of conditions, obtain modified peanut adsorbent; The temperature of described reaction is 45 DEG C, and the time of reaction is 2h.
Get the peanut shell modified adsorbent of the above-mentioned preparation of different amount, add the cochineal solution of 30mL concentration 100mg/L respectively, adjust ph is 2.0, be placed in water bath with thermostatic control oscillator, vibrate 15h at 30 DEG C, and rotating speed is 150 turns/min, measures carmine concentration in residual solution, calculate clearance, the results are shown in Table 7.
Table 7 peanut shell modified adsorbent addition is on the impact of adsorption effect
| Adsorbent amount (g) | 0.2 | 0.4 | 0.6 | 0.8 | 1.0 |
| Dyestuff clearance (%) | 43.3 | 81.2 | 91.9 | 95.8 | 98.5 |
As shown in Table 7, when adsorbent amount is more than 0.6g, prepared peanut hull meal will reach 90% to the clearance of famille rose.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (10)
1. a modified peanut adsorbent, is characterized in that, the preparation process of described modified peanut adsorbent is as follows:
(1) pulverize after peanut shell cleaning, sieve, obtaining particle diameter is 60 ~ 100 object peanut hull meals;
(2) get step (1) described peanut hull meal, add the epoxychloropropane that volume is peanut hull meal weight 10 ~ 30 times, mixing, add NaOH solution again to react, filter after completion of the reaction, be washed to neutrality, dry, obtain modified peanut adsorbent.
2. modified peanut adsorbent as claimed in claim 1, is characterized in that, in described step (1), peanut hull meal particle diameter is 100 orders.
3. modified peanut adsorbent as claimed in claim 1, it is characterized in that, in NaOH solution described in described step (2), the content of NaOH and the weight ratio of peanut hull meal addition are 1:1.8.
4. modified peanut adsorbent as claimed in claim 1, is characterized in that, described in described step (2), the temperature of reaction is 20 ~ 80 DEG C, and the time of reaction is 0.5 ~ 10h.
5. modified peanut adsorbent as claimed in claim 1, is characterized in that, in described step (2) epoxychloropropane add 15 times that volume is peanut hull meal weight, the temperature of described reaction is 45 DEG C, and the time of reaction is 2h.
6. modified peanut adsorbent as claimed in claim 1, is characterized in that, dries as to dry under 50 ~ 70 DEG C of conditions described in described step (2).
7. the preparation method of modified peanut adsorbent according to claim 1, is characterized in that, comprise the steps:
(1) pulverize after peanut shell cleaning, sieve, obtaining particle diameter is 60 ~ 100 object peanut hull meals;
(2) get step (1) described peanut hull meal, add the epoxychloropropane that volume is peanut hull meal weight 10 ~ 30 times, mixing, add NaOH solution again to react, filter after completion of the reaction, be washed to neutrality, dry, obtain modified peanut adsorbent.
8. the application of modified peanut adsorbent according to claim 1 in process cochineal dye waste water.
9. apply as claimed in claim 8, it is characterized in that, the ratio of 0.013 ~ 0.33g/mL peanut shell adsorbent is added in 100mg/L cochineal dye waste water, peanut shell adsorbent is joined in cochineal dye waste water, the pH regulating waste water is 1.0 ~ 3.0, then stirs at 30 DEG C or vibration absorption 1 ~ 21h.
10. apply as claimed in claim 9, it is characterized in that, the ratio of 0.02g/mL peanut shell adsorbent is added in 100mg/L cochineal dye waste water, peanut shell adsorbent is joined in cochineal dye waste water, the pH regulating waste water is 2.0, then stirs at 30 DEG C or vibration absorption 10h.
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Cited By (2)
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| CN108685105A (en) * | 2018-06-04 | 2018-10-23 | 信阳学院 | A kind of modified peanut mushroom culture medium and preparation method thereof |
| CN115404063A (en) * | 2021-05-26 | 2022-11-29 | 中国石油化工股份有限公司 | Environment-friendly plugging agent for water-based drilling fluid and preparation method thereof |
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| CN103272568A (en) * | 2013-05-29 | 2013-09-04 | 浙江大学宁波理工学院 | Method for preparing bifunctional modified cellulose adsorbing agent from peanut shells and application of method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108685105A (en) * | 2018-06-04 | 2018-10-23 | 信阳学院 | A kind of modified peanut mushroom culture medium and preparation method thereof |
| CN108685105B (en) * | 2018-06-04 | 2021-04-09 | 信阳学院 | Modified peanut shell mushroom culture medium and preparation method thereof |
| CN115404063A (en) * | 2021-05-26 | 2022-11-29 | 中国石油化工股份有限公司 | Environment-friendly plugging agent for water-based drilling fluid and preparation method thereof |
| CN115404063B (en) * | 2021-05-26 | 2023-08-01 | 中国石油化工股份有限公司 | Environment-friendly plugging agent for water-based drilling fluid and preparation method thereof |
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Application publication date: 20150819 |