CN103464111B - Softex kw modification walnut shell adsorbent and its preparation method and application - Google Patents
Softex kw modification walnut shell adsorbent and its preparation method and application Download PDFInfo
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Abstract
Softex kw modification walnut shell adsorbent and its preparation method and application, the present invention is prepared by following steps and obtains: step one, prepares walnut shell powder; Step 2, prepares modification liquid; Step 3, modification: step 2 gained modification liquid is dropwise added in walnut shell powder prepared by step one, after intensification stirring, reactant liquor is transferred in ultrasound reactor and reacts, reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight, grinding is sieved and obtains finished product of the present invention.Azo dyes Reactive Brilliant Red K-2BP of the present invention has excellent adsorption capacity, and saturated extent of adsorption can, up to 203.5mg/g, be 4 ~ 5 times of unmodified walnut shell, and abundant raw material source, easy regeneration with low cost.Preparation method of the present invention is simple, has boundless application prospect in treatment of dyeing wastewater field.
Description
Technical field
The invention belongs to 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 further quickening that develop rapidly and the rural urbanization of township enterprise are built, the demand of water resource constantly increases, but what produce together is various sanitary sewage, the discharge of industrial wastewater day by day increases, particularly azo dyes is day by day serious on the impact of ecological environment and human health, carries out respective handling to have become in environmental improvement more and more distinct issues to it.The method of traditional dye wastewater treatment has membrane separation process, flocculence, electrochemical process, bioanalysis, advanced oxidation processes and active carbon adsorption etc.Wherein charcoal absorption because of its method simple, operating simple and easy and removal efficiency height waits many advantages to become dye wastewater treatment technology most widely used at present, but consumption is large, cost is high and regeneration can produce the undesirable elements such as secondary pollution and limits its further development and application.
The agriculture and forestry organic waste material finding a kind of acquisition with low cost, easy and advantages of good adsorption effect has theory and practical significance as adsorbent to process various azo dyeing waste water.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., through the process of series of physical chemical modification, prepare the adsorbent cheap, 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 " modified formaldehyde peanut shell is studied the characterization of adsorption of methylene blue " literary composition that 9618-9620 delivers, by the adsorption test of modified formaldehyde peanut shell to methylene blue, obtained to methylene blue have fine adsorptivity sorbing material, but still there is 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, this patent is by the stalk citric acid-modified after pulverizing, reflux 12 hours, filter, distilled water is washed till neutrality, and this preparation method exists the deficiency that whole process is complicated, property-modifying additive consumption is large, cost is high; Chinese patent CN201010243990.3, a kind of canna slag prepares the method for cationic adsorption agent, first alkali lye and canna slag are stirred, add epoxypropyltrimethylchloride chloride again and stir 30min, in baking oven, adjust pH to neutral with hydrochloric acid after reaction, filter, washing, vacuum drying and obtaining, there is the deficiencies such as raw material is limited, material collection is difficult, preparation process is loaded down with trivial details in the method; The people such as Huang Jiangsheng refer to modification tealeaves and Fe in " tealeaves matter iron is to the Study on adsorption properties of Reactive Brilliant Red K-2BP dyestuff and reactive brilliant yellow K-6G dyestuff " literary composition
3+reaction, obtained sorbing material tealeaves matter iron, but all lower to the adsorbance of two kinds of dyestuffs, and Optimal pH is close to 1, is difficult to promote the use of.
Although the existing adsorbent obtained about utilizing cationic surfactant modification at present; but all there is the shortcoming of azo dyes adsorption capacity difference in majority; 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 made biological adsorption agent dosage is 15g/L, and namely prepared adsorbent is not high to the adsorbance of dyestuff; Have employed cationic surfactant softex kw equally in paper Adsorption of dye from wastewater usingchitosan-CTAB modified bentonites. and modification is carried out to shitosan, but its maximal absorptive capacity scarlet to dyestuff weak acid is also only 102.0mg/g.
Not enough in order to overcome these, the present invention is large by specific area, mechanical strength is high, chemical stability is good and the walnut shell cationic surfactant softex kw of easy regeneration carries out modification, adsorbs azo dyes with it.
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 azo dyes Reactive Brilliant Red K-2BP has excellent adsorption capacity.
Technical scheme: the present invention with biological material walnut shell for raw material, cationic surfactant softex kw is used to carry out modification to it, prepare a kind of softex kw modification walnut shell adsorbent, obtained adsorbent is chocolate brown powder.
Softex kw modification walnut shell adsorbent of the present invention, prepared by following steps and obtain:
Step one, prepare walnut shell powder:
Clean walnut shell is pulverized and sieved, obtains walnut shell powder;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 50 ~ 75 DEG C, is dissolved in deionized water by cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 0.05 ~ 1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 1 ~ 5 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 4 ~ 10:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder prepared by step one, stir 1 ~ 4 hour at 45 ~ 75 DEG C, reactant liquor is transferred in ultrasound reactor, temperature setting 45 ~ 75 DEG C, ultrasonic 30 ~ 60min, reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 ~ 85 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Clean walnut shell is pulverized and sieved, obtains walnut shell powder;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 50 ~ 75 DEG C, is dissolved in deionized water by cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 0.05 ~ 1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 1 ~ 5 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 4 ~ 10:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder prepared by step one, stir 1 ~ 4 hour at 45 ~ 75 DEG C, reactant liquor is transferred in ultrasound reactor, temperature setting 45 ~ 75 DEG C, ultrasonic 30 ~ 60min, reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 ~ 85 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
The preparation method of described softex kw modification walnut shell adsorbent, the walnut shell cleaned described in step one is prepared by the following method and obtains: walnut shell boiling water is boiled 60 ~ 120min, removing flesh and pulp; Soak 7 ~ 14 days by deionized water, every day is changed, to remove the dust that sticks together and residual pulp, after at 65 ~ 105 DEG C, dry 24 ~ 48h.
The particle diameter of the walnut shell powder after pulverizing in described step one and step 3 is 65 ~ 200 microns.
Use hydrochloric acid that isopropyl alcohol pH value is adjusted to 2.5 ~ 3.5 in described step 2 (2).
Described isopropyl alcohol is pure for analyzing.
The application of softex kw modification walnut shell adsorbent in absorption waste water in azo dyes.
The application of described softex kw modification walnut shell adsorbent in absorption waste water in azo dyes, described azo dyes is Reactive Brilliant Red K-2BP.
Beneficial effect: the present invention make use of the feature that walnut shell powder specific area is large, mechanical strength is high and chemically stable is good preferably, with softex kw, modification is carried out to it, obtain the modification walnut shell adsorbent that azo dyes Reactive Brilliant Red K-2BP has excellent adsorption capacity, saturated extent of adsorption can up to 203.5mg/g, 4 ~ 5 times of unmodified walnut shell, and abundant raw material source, easy regeneration with low cost; Preparation method of the present invention is simple, has boundless application prospect in treatment of dyeing wastewater field.
Accompanying drawing illustrates:
Fig. 1 is modification walnut shell adsorbent to Reactive Brilliant Red K-2BP adsorbance in waste water from dyestuff and the clearance Changing Pattern figure with pH value;
Fig. 2 be before modified after walnut shell to the Changing Pattern figure of Reactive Brilliant Red K-2BP adsorbance in waste water from dyestuff with pH value;
Fig. 3 is modification walnut shell adsorbent to the graph of a relation of the clearance of Reactive Brilliant Red K-2BP in waste water from dyestuff and modified adsorbent consumption;
Fig. 4 is the clearance of modification walnut shell adsorbent to Reactive Brilliant Red K-2BP in waste water from dyestuff and the graph of a relation of adsorption time;
Fig. 5 is modification walnut shell adsorbent to the adsorbance of Reactive Brilliant Red K-2BP in waste water from dyestuff and the clearance variation diagram with waste water from dyestuff initial concentration;
Fig. 6 be before modified after walnut shell to the variation relation figure of the adsorbance of Reactive Brilliant Red K-2BP in waste water from dyestuff with dyestuff initial concentration;
Fig. 7 is the scanning electron microscope (SEM) photograph of unmodified walnut shell adsorbent;
Fig. 8 is the scanning electron microscope (SEM) photograph of modification walnut shell adsorbent.
Detailed description of the invention
Following embodiment is of the present invention further illustrating, instead of limits the scope of the invention.
Embodiment 1:
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 120min, removes remaining flesh and pericarp; Soak 7 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 105 DEG C, dry 24h after one week, get through plant sample crushing machine grinding and sieving the powder that particle diameter is 65 ~ 75 microns, load in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 65 DEG C, is dissolved in deionized water by 2g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 3 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 4:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in 5g walnut shell powder prepared by step one, stir 4 hours in 75 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 45 DEG C, ultrasonic 30min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
Embodiment 2:
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 120min, removes remaining flesh and pericarp; Soak 7 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 105 DEG C, dry 48h after one week, get through plant sample crushing machine grinding and sieving the powder that particle diameter is 65 ~ 75 microns, load in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 50 DEG C, is dissolved in deionized water by 2g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 3 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 10:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder 5g prepared by step one, stir 4 hours in 75 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 45 DEG C, ultrasonic 60min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
Embodiment 3:
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 60min, removes remaining flesh and pericarp; Soak 10 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 65 DEG C, dry 24h after one week, get through plant sample crushing machine grinding and sieving the powder that particle diameter is 75 ~ 125 microns, load in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 75 DEG C, is dissolved in deionized water by 0.05g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 0.05%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 3 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 10:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder 5g prepared by step one, stir 1 hour in 75 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 45 DEG C, ultrasonic 30min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 85 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
Embodiment 4:
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 60min, removes remaining flesh and pericarp; Soak 10 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 65 DEG C, dry 24h after one week, get through plant sample crushing machine grinding and sieving the powder that particle diameter is 75 ~ 125 microns, load in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 75 DEG C, is dissolved in deionized water by 0.05g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 0.05%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 1 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 10:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder 5g prepared by step one, stir 1 hour in 45 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 45 DEG C, ultrasonic 30min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
Embodiment 5:
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 90min, removes remaining flesh and pericarp; Soak 14 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 85 DEG C, dry 36h after one week, get through plant sample crushing machine grinding and sieving the powder that particle diameter is 75 ~ 125 microns (120 order ~ 200 orders), load in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 50 DEG C, is dissolved in deionized water by 0.1g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 0.1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 2.5 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 5:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder 5g prepared by step one, stir 4 hours in 45 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 75 DEG C, ultrasonic 60min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 85 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
Embodiment 6:
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 90min, removes remaining flesh and pericarp; Soak 14 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 85 DEG C, dry 36h after one week, get through plant sample crushing machine grinding and sieving the powder that particle diameter is 125 ~ 200 microns, load in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 50 DEG C, is dissolved in ionized water by 0.1g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 0.1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 5 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 5:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder 5g prepared by step one, stir 1 hour in 75 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 75 DEG C, ultrasonic 40min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
Embodiment 7:
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 90min, removes remaining flesh and pericarp; Soak 14 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 105 DEG C, dry 48h after one week, get through plant sample crushing machine grinding and sieving the powder that particle diameter is 65 ~ 75 microns, load in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 75 DEG C, is dissolved in deionized water by 0.1g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 0.1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 5 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 5:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder 5g prepared by step one, stir 2 hours in 75 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 45 DEG C, ultrasonic 60min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
Embodiment 8:
The preparation method of softex kw modification walnut shell adsorbent, comprises the following steps:
Step one, prepare walnut shell powder:
Buy a small amount of walnut in the local market of farm produce, go flesh to stay shell, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 90min, removes remaining flesh and pericarp; Soak 14 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 105 DEG C, dry 48h after one week, get through plant sample crushing machine grinding and sieving the powder that particle diameter is 65 ~ 75 microns (200 order ~ 220 orders), load in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 65 DEG C, is dissolved in deionized water by 0.1g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 0.1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 3.5 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 5:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in walnut shell powder 5g prepared by step one, stir 2 hours in 60 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 60 DEG C, ultrasonic 60min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 70 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
Utilize the Reactive Brilliant Red K-2BP in the modification walnut shell adsorbent waste water from dyestuff 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 vibrate add modification walnut shell adsorbent in waste water after 120min in 25 DEG C of constant temperature oscillators, and hunting speed is 180rpm.
Upon adsorption reach balance after, take out solution, and centrifugal with supercentrifuge after, the concentration of residual activity bright red K-2BP in mensuration supernatant, according to following formula
obtain adsorbance.In formula: Q is adsorbance (mg/g), C
0for adsorbing the concentration (mg/L) of Reactive Brilliant Red K-2BP in front solution, C
efor adsorbing the concentration (mg/L) of Reactive Brilliant Red K-2BP in rear solution, V is liquor capacity (L), W is adsorbent mass (g).
Application examples 1:
Be applied in adsorption test by example 1 gained modification walnut shell adsorbent, modification walnut shell adsorbent dosage is 2g/L, regulates pH to be 3.07, 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:
Be applied in adsorption test by example 2 gained modification walnut shell adsorbent, modification walnut shell adsorbent dosage is 1g/L, regulates pH to be 3.07, result of the test: modification walnut shell adsorbent is 80.49% to the clearance of Reactive Brilliant Red K-2BP dye solution;
Adsorbent dosage is 2g/L, regulates pH to be 3.07, 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:
Be applied in adsorption test by example 3 gained modification walnut shell adsorbent, modification walnut shell adsorbent dosage is 1g/L, regulates pH to be 3.07, result of the test: modification walnut shell adsorbent is 66.32% to the clearance of Reactive Brilliant Red K-2BP dye solution;
Adsorbent addition is 2g/L, result of the test when regulating pH to be 3.07: modification walnut shell adsorbent is 82.54% to the clearance of Reactive Brilliant Red K-2BP dye solution.
Application examples 4:
Be applied in adsorption test by example 4 gained modification walnut shell adsorbent, modification walnut shell adsorbent dosage is 2g/L, regulates pH to be 2.72, result of the test: modification walnut shell adsorbent is 89.56% to the clearance of Reactive Brilliant Red K-2BP dye solution;
Adsorbent addition is 2g/L, regulates pH to be 6.17(initial pH value), 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:
Be applied in adsorption test by example 5 gained modification walnut shell adsorbent, modification walnut shell adsorbent dosage is 2g/L, regulates pH to be 3.07, 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:
Be applied in adsorption test by example 6 gained modification walnut shell adsorbent, modification walnut shell adsorbent dosage is 2g/L, regulates pH to be 3.07, 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:
Be applied in adsorption test by example 7 gained modification walnut shell adsorbent, modification walnut shell adsorbent dosage is 2g/L, regulates pH to be 3.07, 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
Be applied in adsorption test by example 8 gained modification walnut shell adsorbent, modification walnut shell adsorbent dosage is 2g/L, regulates pH to be 3.07, 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 obtains has good absorption property to the Reactive Brilliant Red K-2BP in waste water from dyestuff solution.
Below for the modification walnut shell adsorbent that embodiment 1 is obtained, under investigating different condition, modified adsorbent is to the removal situation of Reactive Brilliant Red K-2BP in waste water.
(1) impact of pH:
At room temperature, the initial concentration of Reactive Brilliant Red K-2BP solution is 200mg/L, regulates pH to be 1.5 ~ 10, and modification walnut shell addition is 2g/L, 160rpm vibration absorption 240min.As shown in Figure 1, modification walnut shell is comparatively large by the impact of the initial pH of solution on the absorption of Reactive Brilliant Red K-2BP in waste water from dyestuff, and when pH is less than 3, adsorbance is all in higher level; PH is 3 ~ 10, and adsorbance and clearance all start to decline rapidly, according to probing into 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, pH value is on rear walnut shell is on the impact of the adsorbance of Reactive Brilliant Red K-2BP in waste water from dyestuff before modified, and contrast finds, the adsorbance of modification walnut shell to Reactive Brilliant Red K-2BP is significantly increased, and when pH is 3, is about 12 times of unmodified walnut shell.
(2) impact of adsorbent addition:
At room temperature, respectively the modification walnut shell adsorbent of different quality to be added to initial concentration be 200mg/L, pH is in the Reactive Brilliant Red K-2BP solution of 3, vibration absorption 210min under 160rpm.As shown in Figure 3, along with the increase of modification walnut shell adsorbent addition, it also constantly increases the clearance of Reactive Brilliant Red K-2BP.Consider adsorbance and cost factor, the addition selecting modification walnut shell is 2g/L.
(3) impact of adsorption time:
At room temperature, be that the pH of the Reactive Brilliant Red K-2BP solution of 200mg/L is adjusted to 3 by initial concentration, adsorbent addition is the absorption 0 ~ 360min that vibrates under 2g/L, 160rpm.As shown in Figure 4, the clearance of modification walnut shell adsorbent to Reactive Brilliant Red K-2BP increases with the increase of adsorption time, 0 ~ 10min rate of adsorption is very fast, after slow down gradually, during 10min, eliminating rate of absorption just reaches 88.9%, substantially adsorption equilibrium is reached, so the adsorption selection time is 20min after 20min.
(4) impact of dyestuff initial concentration:
At room temperature, to get a series of initial concentration be 25 ~ 2000mg/L, pH be 3 waste water from dyestuff, modification walnut shell adsorbent addition is 2g/L, and in constant temperature oscillator, 160rpm vibrates 20min.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, it is last that along with adsorption site position is saturated gradually, the adsorbance that reaches capacity is 203.5mg/g, and clearance declines with the increase of dyestuff initial concentration, this is because modified adsorbent dosage is certain, and the adsorption site on its surface causes clearance to decline after being filled by dyestuff.
At room temperature, getting two groups of a series of initial concentrations is 25 ~ 2000mg/L, pH is the waste water from dyestuff of 3, add modification walnut shell adsorbent and unmodified walnut shell adsorbent respectively, addition is 2g/L, in constant temperature oscillator, 160rpm vibrates 20min as shown in Figure 6, the walnut shell adsorbent azo dyes Reactive Brilliant Red K-2BP modified with softex kw has excellent adsorption capacity, saturated extent of adsorption can up to 203.5mg/g, it is 4 ~ 5 times of unmodified walnut shell, this is because walnut shell space can be being embedded through the modified cationic surfactant of the method by ionic bond, surfactant layer is formed on whole walnut shell surface, not only because the hydrophobicity of cationic surfactant enhances the absorption to organic dyestuff Reactive Brilliant Red K-2BP, in addition, the apolar surfaces on walnut shell surface has adsorbed the hydrophobic alkyl end of surfactant in solution by Van der Waals force, change walnut shell surface chemistry, modified walnut shell electronegativity is strengthened, thus the adsorption capacity of anionic dye is strengthened.
Fig. 7 and Fig. 8 is respectively the scanning electron microscope (SEM) photograph of unmodified walnut shell adsorbent and modification walnut shell adsorbent, multiplication factor 10000 times.Contrast two width figure can find, it is smooth that unmodified walnut shell adsorbent surface compared by the walnut shell adsorbent through modification, is because modifier and softex kw chemical action have successfully been attached to walnut shell surface.
Claims (3)
1. softex kw modification walnut shell adsorbent, is characterized in that being prepared by following steps and obtaining:
Step one, prepare walnut shell powder:
Go flesh to stay shell walnut, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 120min, removes remaining flesh and pericarp; Soak 7 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 105 DEG C, dry 24h after one week, getting particle diameter through plant sample crushing machine grinding and sieving is
The powder of 65 ~ 75 μm, loads in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 65 DEG C, is dissolved in deionized water by 2g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 3 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 4:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in 5g walnut shell powder prepared by step one, stir 4 hours in 75 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 45 DEG C, ultrasonic 30min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 DEG C, grinding is sieved and obtains 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 one, prepare walnut shell powder:
Go flesh to stay shell walnut, and remove pericarp and the seed coat of inner side, walnut shell boiling water is boiled 120min, removes remaining flesh and pericarp; Soak 7 days by deionized water, every day is changed, to remove the dust and residual pulp that stick together; At 105 DEG C, dry 24h after one week, getting particle diameter through plant sample crushing machine grinding and sieving is
The powder of 65 ~ 75 μm, loads in wide-mouth bottle for subsequent use;
Step 2, prepare modification liquid:
(1) preparation of modification liquid A: at 65 DEG C, is dissolved in deionized water by 2g cationic surfactant softex kw, and preparation mass fraction is the softex kw aqueous solution of 1%, is modification liquid A;
(2) preparation of modification liquid B: regulate isopropyl alcohol pH value to be 3 with hydrochloric acid, gained solution is modification liquid B;
(3) mix: drop in modification liquid A by modification liquid B under stirring, the volume ratio of modification liquid A and modification liquid B is 4:1, is uniformly mixed, obtains modification liquid;
Step 3, modification:
Step 2 gained modification liquid is dropwise added in 5g walnut shell powder prepared by step one, stir 4 hours in 75 DEG C of heating water baths, reactant liquor is transferred in ultrasound reactor, temperature sets 45 DEG C, ultrasonic 30min, and reaction terminates rear filtration, obtain softex kw modification walnut shell adsorbent crude product, spend deionized water to neutral, dry to constant weight at 65 DEG C, grinding is sieved and obtains softex kw modification walnut shell adsorbent finished product.
3. the application of softex kw modification walnut shell adsorbent according to claim 1 in absorption waste water in Reactive Brilliant Red K-2BP.
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| 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 |
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