CN103464111A - Cetyl trimethyl ammonium bromide modified walnut shell absorbent, and preparation method and application thereof - Google Patents
Cetyl trimethyl ammonium bromide modified walnut shell absorbent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a cetyl trimethyl ammonium bromide modified walnut shell absorbent, and a preparation method and application thereof. The cetyl trimethyl ammonium bromide modified walnut shell absorbent is prepared by the following steps: step one, preparing walnut shell powder; step two, preparing modified liquid; step three, modifying, namely dropwise adding the modified liquid prepared in the step two into the walnut shell powder prepared in the step one, warming, stirring, transferring reaction liquid to an ultrasonic reactor to react, filtering after the reaction is finished, obtaining a cetyl trimethyl ammonium bromide modified walnut shell absorbent crude product, washing the crude product to be neutral by deionized water, drying to enable the product with constant weight, grinding, screening, and obtaining a finished product provided by the invention. The cetyl trimethyl ammonium bromide modified walnut shell absorbent has excellent adsorption capacity on azo dye reactive brilliant red K-2BP, the saturation adsorption capacity can reach up to 203.5 mg/g which is 4 to 5 times of that of unmodified walnut shells, the raw material source is abundant, low in cost and easy to regenerate, and the preparation method is simple and feasible, and has a very wide application prospect in the field of printing and dyeing wastewater treatment.
Description
Technical field
The invention belongs to the modified adsorbent field of material preparation, be specifically related to a kind of softex kw modification walnut shell adsorbent and its preparation method and application.
Background technology
In recent years, along with the develop rapidly of township enterprise and the further quickening of rural urbanization construction, the demand of water resource constantly increases, but what produce together is that the discharge of various sanitary sewages, industrial wastewater day by day increases, particularly azo dyes is day by day serious on the impact of ecological environment and human health, it is carried out to respective handling and become in environmental improvement more and more distinct issues.The method of traditional dye wastewater treatment using has membrane separation process, flocculence, electrochemical process, bioanalysis, advanced oxidation processes and active carbon adsorption etc.Wherein charcoal absorption is simple because of its method, operate simple and easy and remove the high many advantages that waits of efficiency and become most widely used dye wastewater treatment technology at present, but consumption is large, cost is high and regeneration can produce the undesirable element such as secondary pollution and limited its further development and application.
Find a kind of with low cost, easily obtain and the agriculture and forestry organic waste material of advantages of good adsorption effect is processed various azo dyeing waste waters as adsorbent and had theory and practical significance.Many scholars use agriculture and forestry by-product, as bagasse, banana skin, peanut shell, tea waste residue, bagasse, Pericarppium Armeniacae Amarum, pomelo peel and stalk etc., process through the series of physical chemical modification, prepared the adsorbent cheap, that Selective adsorption is high, and proved that it has good effect.
The people such as Yu Chunli are in " Agriculture of Anhui science ", 2009,37(20): in " the characterization of adsorption research of modified formaldehyde peanut shell to methylene blue " literary composition that 9618-9620 delivers, adsorption test by the modified formaldehyde peanut shell to methylene blue, make to methylene blue have fine adsorptivity sorbing material, but still have the deficiency that adsorbance is too little, consumptive material is large to dyestuff; Chinese patent CN200510040485.8, a kind of preparation method of cation adsorbent and application, stalk citric acid-modified after this patent will be pulverized, reflux 12 hours, filter, distilled water is washed till neutrality, and there is the deficiency that whole process is complicated, the property-modifying additive consumption is large, cost is high in this preparation method; Chinese patent CN201010243990.3, a kind of method for preparing cationic adsorption agent with canna slag, first alkali lye and canna slag are stirred, add again epoxypropyltrimethylchloride chloride to stir 30min, in baking oven, after reaction, with hydrochloric acid, adjust pH to neutral, filter washing, vacuum drying and obtaining, there are the deficiencies such as raw material is limited, raw material is collected difficulty, preparation process is loaded down with trivial details in the method; The people such as Huang Jiangsheng refer to modification tealeaves and Fe in " Study on adsorption properties of tealeaves matter iron to Reactive Brilliant Red K-2BP dyestuff and reactive brilliant yellow K-6G dyestuff " literary composition
3+reaction, make sorbing material tealeaves matter iron, but all lower to the adsorbance of two kinds of dyestuffs, and best pH approaches 1, is difficult to promote the use of.
Although have at present the adsorbent obtained about utilizing the cationic surfactant modification; but most poor shortcomings of azo dyes adsorption capacity that all exist; as Chinese patent CN201210017766.1; a kind of chitosan magnetic/cationic surfactant modified zeolite adsorbent and its preparation method and application, it is only 84mg/g to Congo red adsorbance; Patent CN201110219902.0, a kind of preparation method of dye sorbent and application, be only 78% to dye decolored rate when the biological adsorption agent dosage of made is 15g/L, prepared adsorbent is not high to the adsorbance of dyestuff; In paper Adsorption of dye from wastewater using chitosan-CTAB modified bentonites., adopted equally the cationic surfactant softex kw to carry out modification to shitosan, but its maximal absorptive capacity scarlet to dyestuff weak acid is only also 102.0mg/g.
In order to overcome these deficiencies, the present invention is large by specific area, mechanical strength is high, chemical stability is good and the walnut shell of easy regeneration carries out modification with the cationic surfactant softex kw, with it, adsorbs azo dyes.
Summary of the invention
The technical problem solved: the present invention overcomes the deficiencies in the prior art and proposes a kind of softex kw modification walnut shell adsorbent and its preparation method and application, the present invention utilizes that cationic surfactant softex kw contrast table area is large, mechanical strength is high, chemically stable good and the walnut shell of easy regeneration carries out modification, obtains the modification walnut shell adsorbent that the azo dyes Reactive Brilliant Red K-2BP has excellent adsorption capacity.
Technical scheme: the present invention be take the biological material walnut shell as raw material, use the cationic surfactant softex kw to carry out modification to it, prepare a kind of softex kw modification walnut shell adsorbent, the adsorbent made is chocolate brown powder.
Softex kw modification walnut shell adsorbent of the present invention is obtained by the following steps preparation:
Step 1 prepares the walnut shell powder:
Clean walnut shell is pulverized and sieved, obtain the walnut shell powder;
(1) preparation of modification liquid A: under 50～75 ℃, the cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.05～1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 1～5, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 4～10:1, is uniformly mixed, and obtains modification liquid;
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Clean walnut shell is pulverized and sieved, obtain the walnut shell powder;
(1) preparation of modification liquid A: under 50～75 ℃, the cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.05～1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 1～5, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 4～10:1, is uniformly mixed, and obtains modification liquid;
The preparation method of described softex kw modification walnut shell adsorbent, described in step 1, clean walnut shell prepares by the following method and obtains: walnut shell is boiled to 60～120min with boiling water, remove flesh and pulp; By deionized water, soak 7～14 days, change every day, the dust sticked together with removal and residual pulp, after dry 24～48h under 65～105 ℃.
The particle diameter of the walnut shell powder after pulverizing in described step 1 and step 3 is 65～200 microns.
In described step 2 (2), use hydrochloric acid that isopropyl alcohol pH value is adjusted to 2.5～3.5.
Described isopropyl alcohol is pure for analyzing.
Softex kw modification walnut shell adsorbent is the application in azo dyes in absorption waste water.
Described softex kw modification walnut shell adsorbent is the application in azo dyes in absorption waste water, and described azo dyes is Reactive Brilliant Red K-2BP.
Beneficial effect: the present invention has utilized the characteristics that the walnut shell powder specific area is large, mechanical strength is high and chemically stable is good preferably, with softex kw, it is carried out to modification, obtaining the azo dyes Reactive Brilliant Red K-2BP has the modification walnut shell adsorbent of excellent adsorption capacity, saturated extent of adsorption can be up to 203.5mg/g, be 4～5 times of unmodified walnut shell, and raw material sources are abundant, easy regeneration with low cost; Preparation method of the present invention is simple, in the treatment of dyeing wastewater field, has boundless application prospect.
The accompanying drawing explanation:
Fig. 1 be modification walnut shell adsorbent to Reactive Brilliant Red K-2BP adsorbance and clearance in waste water from dyestuff the Changing Pattern figure with the pH value;
Fig. 2 be before and after modification walnut shell to Reactive Brilliant Red K-2BP adsorbance in waste water from dyestuff the Changing Pattern figure with the pH value;
Fig. 3 is that modification walnut shell adsorbent is to the clearance of Reactive Brilliant Red K-2BP in waste water from dyestuff and the graph of a relation of modified adsorbent consumption;
Fig. 4 is that modification walnut shell adsorbent is to the clearance of Reactive Brilliant Red K-2BP in waste water from dyestuff and the graph of a relation of adsorption time;
Fig. 5 variation diagram with the waste water from dyestuff initial concentration that is modification walnut shell adsorbent to the adsorbance of Reactive Brilliant Red K-2BP in waste water from dyestuff and clearance;
Fig. 6 be before and after modification walnut shell to the adsorbance of Reactive Brilliant Red K-2BP in waste water from dyestuff the variation relation figure with the dyestuff initial concentration;
The scanning electron microscope (SEM) photograph that Fig. 7 is unmodified walnut shell adsorbent;
The scanning electron microscope (SEM) photograph that Fig. 8 is modification walnut shell adsorbent.
The specific embodiment
Following embodiment is of the present invention further illustrating, rather than limits the scope of the invention.
Embodiment 1:
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove inboard pericarp and plant skin, walnut shell is boiled to 120min with boiling water, remove remaining flesh and pericarp; By deionized water, soak 7 days, change every day, the dust sticked together with removal and residual pulp; Dry 24h after one week under 105 ℃, through the plant sample crushing machine grinding and sieving, get the powder that particle diameter is 65～75 microns, standby in the wide-mouth bottle of packing into;
(1) preparation of modification liquid A: under 65 ℃, 2g cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 3, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 4:1, is uniformly mixed, and obtains modification liquid;
Embodiment 2:
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove inboard pericarp and plant skin, walnut shell is boiled to 120min with boiling water, remove remaining flesh and pericarp; By deionized water, soak 7 days, change every day, the dust sticked together with removal and residual pulp; Dry 48h after one week under 105 ℃, through the plant sample crushing machine grinding and sieving, get the powder that particle diameter is 65～75 microns, standby in the wide-mouth bottle of packing into;
(1) preparation of modification liquid A: under 50 ℃, 2g cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 3, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 10:1, is uniformly mixed, and obtains modification liquid;
Embodiment 3:
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove inboard pericarp and plant skin, walnut shell is boiled to 60min with boiling water, remove remaining flesh and pericarp; By deionized water, soak 10 days, change every day, the dust sticked together with removal and residual pulp; Dry 24h after one week under 65 ℃, through the plant sample crushing machine grinding and sieving, get the powder that particle diameter is 75～125 microns, standby in the wide-mouth bottle of packing into;
(1) preparation of modification liquid A: under 75 ℃, 0.05g cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.05%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 3, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 10:1, is uniformly mixed, and obtains modification liquid;
Embodiment 4:
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove inboard pericarp and plant skin, walnut shell is boiled to 60min with boiling water, remove remaining flesh and pericarp; By deionized water, soak 10 days, change every day, the dust sticked together with removal and residual pulp; Dry 24h after one week under 65 ℃, through the plant sample crushing machine grinding and sieving, get the powder that particle diameter is 75～125 microns, standby in the wide-mouth bottle of packing into;
(1) preparation of modification liquid A: under 75 ℃, 0.05g cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.05%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 1, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 10:1, is uniformly mixed, and obtains modification liquid;
Embodiment 5:
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove inboard pericarp and plant skin, walnut shell is boiled to 90min with boiling water, remove remaining flesh and pericarp; By deionized water, soak 14 days, change every day, the dust sticked together with removal and residual pulp; Dry 36h after one week under 85 ℃, through the plant sample crushing machine grinding and sieving, get the powder that particle diameter is 75～125 microns (120 orders～200 orders), standby in the wide-mouth bottle of packing into;
(1) preparation of modification liquid A: under 50 ℃, 0.1g cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 2.5, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 5:1, is uniformly mixed, and obtains modification liquid;
Embodiment 6:
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove inboard pericarp and plant skin, walnut shell is boiled to 90min with boiling water, remove remaining flesh and pericarp; By deionized water, soak 14 days, change every day, the dust sticked together with removal and residual pulp; Dry 36h after one week under 85 ℃, through the plant sample crushing machine grinding and sieving, get the powder that particle diameter is 125～200 microns, standby in the wide-mouth bottle of packing into;
(1) preparation of modification liquid A: under 50 ℃, 0.1g cationic surfactant softex kw is dissolved in ionized water, the softex kw aqueous solution that the preparation mass fraction is 0.1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 5, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 5:1, is uniformly mixed, and obtains modification liquid;
Embodiment 7:
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove inboard pericarp and plant skin, walnut shell is boiled to 90min with boiling water, remove remaining flesh and pericarp; By deionized water, soak 14 days, change every day, the dust sticked together with removal and residual pulp; Dry 48h after one week under 105 ℃, through the plant sample crushing machine grinding and sieving, get the powder that particle diameter is 65～75 microns, standby in the wide-mouth bottle of packing into;
(1) preparation of modification liquid A: under 75 ℃, 0.1g cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 5, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 5:1, is uniformly mixed, and obtains modification liquid;
Embodiment 8:
The preparation method of softex kw modification walnut shell adsorbent comprises the following steps:
Step 1 prepares the walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove inboard pericarp and plant skin, walnut shell is boiled to 90min with boiling water, remove remaining flesh and pericarp; By deionized water, soak 14 days, change every day, the dust sticked together with removal and residual pulp; Dry 48h after one week under 105 ℃, through the plant sample crushing machine grinding and sieving, get the powder that particle diameter is 65～75 microns (200 orders～220 orders), standby in the wide-mouth bottle of packing into;
(1) preparation of modification liquid A: under 65 ℃, 0.1g cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 3.5, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 5:1, is uniformly mixed, and obtains modification liquid;
Utilize the Reactive Brilliant Red K-2BP in the modification walnut shell adsorbent absorbing dye waste water solution prepared in embodiment 1-8.The adsorption test condition of each embodiment is as follows:
Reactive Brilliant Red K-2BP dyestuff waste liquid concentration is 200mg/L, and to add after modification walnut shell adsorbent the 120min that vibrates in waste water in 25 ℃ of constant temperature oscillators, hunting speed is 180rpm.
Upon adsorption reach balance after, take out solution, and, after centrifugal with supercentrifuge, the concentration of residual activity bright red K-2BP in the mensuration supernatant, according to following formula
obtain adsorbance.In formula: Q is adsorbance (mg/g), C
0for the concentration (mg/L) of adsorbing Reactive Brilliant Red K-2BP in front solution, C
efor the concentration (mg/L) of adsorbing Reactive Brilliant Red K-2BP in rear solution, V is liquor capacity (L), and W is adsorbent mass (g).
Application examples 1:
Example 1 gained modification walnut shell adsorbent is applied in adsorption test, and modification walnut shell adsorbent dosage is 2g/L, and regulating pH is 3.07, and result of the test: modification walnut shell adsorbent is 99.46% to the clearance of Reactive Brilliant Red K-2BP dye solution.
Application examples 2:
Example 2 gained modification walnut shell adsorbents are applied in adsorption test, and modification walnut shell adsorbent dosage is 1g/L, and regulating pH is 3.07, and result of the test: modification walnut shell adsorbent is 80.49% to the clearance of Reactive Brilliant Red K-2BP dye solution;
The adsorbent dosage is 2g/L, and regulating pH is 3.07, and result of the test: modification walnut shell adsorbent is 92.94% to the clearance of Reactive Brilliant Red K-2BP dye solution.
Application examples 3:
Example 3 gained modification walnut shell adsorbents are applied in adsorption test, and modification walnut shell adsorbent dosage is 1g/L, and regulating pH is 3.07, and result of the test: modification walnut shell adsorbent is 66.32% to the clearance of Reactive Brilliant Red K-2BP dye solution;
The adsorbent addition is 2g/L, and the result of the test that adjusting pH is 3.07 o'clock: modification walnut shell adsorbent is 82.54% to the clearance of Reactive Brilliant Red K-2BP dye solution.
Application examples 4:
Example 4 gained modification walnut shell adsorbents are applied in adsorption test, and modification walnut shell adsorbent dosage is 2g/L, and regulating pH is 2.72, and result of the test: modification walnut shell adsorbent is 89.56% to the clearance of Reactive Brilliant Red K-2BP dye solution;
The adsorbent addition is 2g/L, and regulating pH is the 6.17(original ph), result of the test: modification walnut shell cation adsorbent is 61.06% to the clearance of Reactive Brilliant Red K-2BP dye solution.
Application examples 5:
Example 5 gained modification walnut shell adsorbents are applied in adsorption test, and modification walnut shell adsorbent dosage is 2g/L, and regulating pH is 3.07, and result of the test: modification walnut shell adsorbent is 92.25% to the clearance of Reactive Brilliant Red K-2BP dye solution.
Application examples 6:
Example 6 gained modification walnut shell adsorbents are applied in adsorption test, and modification walnut shell adsorbent dosage is 2g/L, and regulating pH is 3.07, and result of the test: modification walnut shell adsorbent is 86.92% to the clearance of Reactive Brilliant Red K-2BP dye solution.
Application examples 7:
Example 7 gained modification walnut shell adsorbents are applied in adsorption test, and modification walnut shell adsorbent dosage is 2g/L, and regulating pH is 3.07, and result of the test: modification walnut shell adsorbent is 98.95% to the clearance of Reactive Brilliant Red K-2BP dye solution.
Application examples 8
Example 8 gained modification walnut shell adsorbents are applied in adsorption test, and modification walnut shell adsorbent dosage is 2g/L, and regulating pH is 3.07, and result of the test: modification walnut shell adsorbent is 99.15% to the clearance of Reactive Brilliant Red K-2BP dye solution.In sum, under same experimental conditions, the modification walnut shell adsorbent that embodiment 1 makes has absorption property preferably to the Reactive Brilliant Red K-2BP in waste water from dyestuff solution.
The modification walnut shell adsorbent that the embodiment 1 of below take makes is example, investigates the removal situation of modified adsorbent to Reactive Brilliant Red K-2BP in waste water under different condition.
(1) impact of pH:
At room temperature, the initial concentration of Reactive Brilliant Red K-2BP solution is 200mg/L, and regulating pH is 1.5～10, and modification walnut shell addition is 2g/L, 160rpm vibration absorption 240min.As shown in Figure 1, the modification walnut shell is subject to the impact of the initial pH of solution larger on the absorption of Reactive Brilliant Red K-2BP in waste water from dyestuff, and pH is less than 3 o'clock adsorbances and is in higher level; PH is 3～10, and adsorbance and clearance all start to descend rapidly, according to the probing into of pH influence factor, and considers economy and feasibility simultaneously, and the appropriate pH of modification walnut shell absorption is 3.0.
As shown in Figure 2, the pH value is the impact on the adsorbance of Reactive Brilliant Red K-2BP in waste water from dyestuff on walnut shell before and after modification, the contrast discovery, and the modification walnut shell is significantly increased the adsorbance of Reactive Brilliant Red K-2BP, at pH, is 3 o'clock, is about 12 times of unmodified walnut shell.
(2) impact of adsorbent addition:
At room temperature, in the Reactive Brilliant Red K-2BP solution that respectively the modification walnut shell adsorbent of different quality to be added to initial concentration and to be 200mg/L, pH be 3, vibration absorption 210min under 160rpm.As shown in Figure 3, along with the increase of modification walnut shell adsorbent addition, its clearance to Reactive Brilliant Red K-2BP also constantly increases.Consider adsorbance and cost factor, selecting the addition of modification walnut shell is 2g/L.
(3) impact of adsorption time:
At room temperature, the pH of the Reactive Brilliant Red K-2BP solution that is 200mg/L by initial concentration is adjusted to 3, and the adsorbent addition is 2g/L, vibration absorption 0～360min under 160rpm.As shown in Figure 4, to the clearance of Reactive Brilliant Red K-2BP, the increase with adsorption time increases modification walnut shell adsorbent, 0～10min rate of adsorption is very fast, after slow down gradually, during 10min, eliminating rate of absorption just reaches 88.9%, substantially reach adsorption equilibrium after 20min, so the selection adsorption time is 20min.
(4) impact of dyestuff initial concentration:
At room temperature, getting a series of initial concentrations is the waste water from dyestuff that 25～2000mg/L, pH are 3, and modification walnut shell adsorbent addition is 2g/L, 160rpm vibration 20min in constant temperature oscillator.As shown in Figure 5, when initial concentration is 0～500mg/L, the adsorbance of modification walnut shell adsorbent azo dyes Reactive Brilliant Red K-2BP increases sharply, finally along with the adsorption site position is saturated and the adsorbance that reaches capacity is 203.5mg/g gradually, and clearance descends with the increase of dyestuff initial concentration, this is because the modified adsorbent dosage is certain, and its surperficial adsorption site causes clearance to descend after being filled by dyestuff.
At room temperature, getting two groups of a series of initial concentrations is 25～2000mg/L, the waste water from dyestuff that pH is 3, add respectively modification walnut shell adsorbent and unmodified walnut shell adsorbent, addition is 2g/L, in constant temperature oscillator, 160rpm vibration 20min as shown in Figure 6, with the walnut shell adsorbent azo dyes Reactive Brilliant Red K-2BP after the softex kw modification, excellent adsorption capacity is arranged, saturated extent of adsorption can be up to 203.5mg/g, 4～5 times of unmodified walnut shell, this is because can embed the walnut shell space at cationic surfactant after the method modification by ionic bond, form surfactant layer on whole walnut shell surface, not only the hydrophobicity because of cationic surfactant has strengthened the absorption to the organic dyestuff Reactive Brilliant Red K-2BP, in addition, the apolar surfaces on walnut shell surface has been adsorbed the hydrophobic alkyl end of surfactant in solution by Van der Waals force, changed the walnut shell surface chemistry, walnut shell electronegativity after modification is strengthened, thereby the adsorption capacity to anionic dye strengthens.
Fig. 7 and Fig. 8 are respectively the scanning electron microscope (SEM) photograph of unmodified walnut shell adsorbent and modification walnut shell adsorbent, 10000 times of multiplication factors.Contrasting two width figure can find, compares unmodified walnut shell adsorbent surface through the walnut shell adsorbent of modification smooth, is because modifier is that the softex kw chemical action successfully has been attached to the walnut shell surface.
Claims (8)
1. softex kw modification walnut shell adsorbent is characterized in that by the following steps preparation and obtains:
Step 1 prepares the walnut shell powder:
Clean walnut shell is pulverized and sieved, obtain the walnut shell powder;
Step 2 prepares modification liquid:
(1) preparation of modification liquid A: under 50 ~ 75 ℃, the cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.05 ~ 1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 1 ~ 5, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 4 ~ 10:1, is uniformly mixed, and obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid dropwise is added in walnut shell powder prepared by step 1, under 45 ~ 75 ℃, stir 1 ~ 4 hour, reactant liquor is transferred in ultrasound reactor, 45 ~ 75 ℃ of Temperature Settings, ultrasonic 30 ~ 60min, filter after reaction finishes, obtain softex kw modification walnut shell adsorbent crude product, with the deionized water washing, to neutral, under 65 ~ 85 ℃, dry to constant weight, grinding is sieved and is obtained softex kw modification walnut shell adsorbent finished product.
2. the preparation method of softex kw modification walnut shell adsorbent is characterized in that comprising the following steps:
Step 1 prepares the walnut shell powder:
Clean walnut shell is pulverized and sieved, obtain the walnut shell powder;
Step 2 prepares modification liquid:
(1) preparation of modification liquid A: under 50 ~ 75 ℃, the cationic surfactant softex kw is dissolved in deionized water, the softex kw aqueous solution that the preparation mass fraction is 0.05 ~ 1%, be modification liquid A;
(2) preparation of modification liquid B: regulating isopropyl alcohol pH value with hydrochloric acid is 1 ~ 5, and gained solution is modification liquid B;
(3) mix: under stirring, modification liquid B is dropped in modification liquid A, the volume ratio of modification liquid A and modification liquid B is 4 ~ 10:1, is uniformly mixed, and obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid dropwise is added in walnut shell powder prepared by step 1, under 45 ~ 75 ℃, stir 1 ~ 4 hour, reactant liquor is transferred in ultrasound reactor, 45 ~ 75 ℃ of Temperature Settings, ultrasonic 30 ~ 60min, filter after reaction finishes, obtain softex kw modification walnut shell adsorbent crude product, with the deionized water washing, to neutral, under 65 ~ 85 ℃, dry to constant weight, grinding is sieved and is obtained softex kw modification walnut shell adsorbent finished product.
3. the preparation method of softex kw modification walnut shell adsorbent according to claim 2, it is characterized in that walnut shell clean described in step 1 prepares by the following method and obtains: walnut shell is boiled to 60 ~ 120min with boiling water, remove flesh and pulp; By deionized water, soak 7 ~ 14 days, change every day, the dust sticked together with removal and residual pulp, after dry 24 ~ 48h under 65 ~ 105 ℃.
4. the preparation method of softex kw modification walnut shell adsorbent according to claim 2 is characterized in that: the particle diameter of the walnut shell powder after pulverizing in step 1 and step 3 is 65 ~ 200 microns.
5. the preparation method of softex kw modification walnut shell adsorbent according to claim 2, is characterized in that in step 2 (2) using hydrochloric acid that isopropyl alcohol pH value is adjusted to 2.5 ~ 3.5.
6. the preparation method of softex kw modification walnut shell adsorbent according to claim 2, is characterized in that described isopropyl alcohol is pure for analyzing.
7. softex kw modification walnut shell adsorbent application in azo dyes in absorption waste water.
8. softex kw modification walnut shell adsorbent according to claim 7 application in azo dyes in absorption waste water, is characterized in that described azo dyes is Reactive Brilliant Red K-2BP.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096539A (en) * | 2014-07-04 | 2014-10-15 | 河海大学 | Method for preparing macadamia nut shell adsorbent |
| CN104258820A (en) * | 2014-09-26 | 2015-01-07 | 河海大学 | Method for preparing modified macadamia shell absorbing agent by nitration and reduction |
| CN106268677A (en) * | 2016-09-08 | 2017-01-04 | 河海大学 | A kind of preparation method of modified watermelon peel adsorbent |
| CN106544078A (en) * | 2016-10-07 | 2017-03-29 | 常州创索新材料科技有限公司 | A kind of preparation method of antifriction material |
| CN107159139A (en) * | 2017-05-31 | 2017-09-15 | 华南理工大学 | A kind of pineapple bran radical dye adsorbent of CTAB processing and preparation method and application |
| CN112934191A (en) * | 2021-02-25 | 2021-06-11 | 广东轻工职业技术学院 | Dye adsorbent and preparation method and application thereof |
| CN115569636A (en) * | 2022-08-12 | 2023-01-06 | 济南大学 | Hexavalent chromium efficient removing material for pine bark modified by surfactant and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721978A (en) * | 2009-12-18 | 2010-06-09 | 华东理工大学 | Adsorbent for polyaromatic hydrocarbon pollutant, preparation method and application thereof |
| CN102218299A (en) * | 2010-08-03 | 2011-10-19 | 福建师范大学 | Method for preparation of biological adsorbent with canna edulis ker slags |
-
2013
- 2013-08-22 CN CN201310367160.5A patent/CN103464111B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721978A (en) * | 2009-12-18 | 2010-06-09 | 华东理工大学 | Adsorbent for polyaromatic hydrocarbon pollutant, preparation method and application thereof |
| CN102218299A (en) * | 2010-08-03 | 2011-10-19 | 福建师范大学 | Method for preparation of biological adsorbent with canna edulis ker slags |
Non-Patent Citations (2)
| Title |
|---|
| 朱慧敏: ""CTAB及CPB改性花生壳对LG及AK吸附性能研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》, no. 9, 15 September 2012 (2012-09-15) * |
| 钟璐: ""核桃壳与花生壳对模拟废水中Cr（VI）的吸附特性研究"", 《中国优秀硕士学位论文全文数据库工程科技I辑》, no. 2, 15 February 2013 (2013-02-15) * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096539A (en) * | 2014-07-04 | 2014-10-15 | 河海大学 | Method for preparing macadamia nut shell adsorbent |
| CN104096539B (en) * | 2014-07-04 | 2016-04-27 | 河海大学 | A kind of preparation method of macadamia shell adsorbent |
| CN104258820A (en) * | 2014-09-26 | 2015-01-07 | 河海大学 | Method for preparing modified macadamia shell absorbing agent by nitration and reduction |
| CN106268677A (en) * | 2016-09-08 | 2017-01-04 | 河海大学 | A kind of preparation method of modified watermelon peel adsorbent |
| CN106268677B (en) * | 2016-09-08 | 2018-12-14 | 河海大学 | A kind of preparation method of modified watermelon peel adsorbent |
| CN106544078A (en) * | 2016-10-07 | 2017-03-29 | 常州创索新材料科技有限公司 | A kind of preparation method of antifriction material |
| CN107159139A (en) * | 2017-05-31 | 2017-09-15 | 华南理工大学 | A kind of pineapple bran radical dye adsorbent of CTAB processing and preparation method and application |
| CN112934191A (en) * | 2021-02-25 | 2021-06-11 | 广东轻工职业技术学院 | Dye adsorbent and preparation method and application thereof |
| CN115569636A (en) * | 2022-08-12 | 2023-01-06 | 济南大学 | Hexavalent chromium efficient removing material for pine bark modified by surfactant and preparation method thereof |
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