CN103381357A - Preparation method for modified walnut shell cation adsorbent - Google Patents
Preparation method for modified walnut shell cation adsorbent Download PDFInfo
- Publication number
- CN103381357A CN103381357A CN2013103246954A CN201310324695A CN103381357A CN 103381357 A CN103381357 A CN 103381357A CN 2013103246954 A CN2013103246954 A CN 2013103246954A CN 201310324695 A CN201310324695 A CN 201310324695A CN 103381357 A CN103381357 A CN 103381357A
- Authority
- CN
- China
- Prior art keywords
- walnut shell
- modification
- modified
- powder
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method for a modified walnut shell cation adsorbent, belongs to the field of modified adsorbent material preparation, and particularly relates to a preparation method for the modified walnut shell cation adsorbent used for adsorption removal of anionic dye in printing and dyeing wastewater. According to the preparation method, waste materials such as walnut shells are used as raw materials; in an alkaline environment, epichlorohydrin is used as an etherifying agent, diethylenetriamine is used as a crosslinker, modifying is performed in two steps and amino groups are introduced, and the poly-amino-contained modified walnut shell cation adsorbent is prepared in a compound mode. Experiment results show that walnut shells modified through the method can absorb anionic azo dyes to the capacity of 500 mg/g, and the adsorption capacity is nearly 9 times the adsorption capacity of non-modified walnut shells. The modified walnut shell cation adsorbent is wide in raw material source, high in mechanical strength, good in chemical stabilization, low in costs, easy to regenerate, simple in modifying method, applicable to the field of printing and dyeing wastewater treatment and high in removal rate, reliable and efficient and has an extremely good prospect.
Description
Technical field
The invention belongs to the modified adsorbent field of material preparation.Particularly relate to the preparation method for the modification walnut shell cation adsorbent of anionic dye in dyeing waste water.
Background technology
In recent years, along with the develop rapidly of township enterprise and the further quickening of rural urbanization construction, the discharging of various sanitary sewages, industrial wastewater day by day increases, particularly dyeing waste water is day by day serious on the impact of ecological environment and human health, it is carried out respective handling become in environmental improvement more and more distinct issues.The method of traditional dye wastewater treatment using has electrochemical process, coagulant sedimentation, oxidizing process, membrane separation process and active carbon adsorption etc.Wherein charcoal absorption is simple because of its method, and operating simple and easy and removing the high many advantages that waits of efficient has become most widely used dye wastewater treatment technology at present, but consumption is large, cost is high and regeneration can produce secondary pollution etc. and limited its further development and application.
Seek 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 dyeing waste waters as adsorbent and had theory and practical significance.Many scholars use agriculture and forestry by-product, as walnut shell, bagasse, banana skin, peanut shell, tea waste residue, bagasse, Pericarppium Armeniacae Amarum, pomelo peel and stalk etc., process through a series of simple physical and chemical modified, made the adsorbent cheap, that Selective adsorption is high, and proved to have good effect.
The people such as Yu Chunli are in the Agriculture of Anhui science, 2009,37(20): in " the characterization of adsorption research of modified formaldehyde peanut shell to methylene blue " literary composition of delivering in the 9618-9620 periodical, by the adsorption test of modified formaldehyde peanut shell to methylene blue, make to methylene blue have fine adsorptivity sorbing material, but the adsorbance to dyestuff is too little, and consumptive material is large; Patent CN 200510040485.8 discloses a kind of method of utilizing the standby cationic adsorption agent of straw, and the stalk citric acid-modified with after pulverizing refluxed 12 hours, filter, distilled water is washed till neutrality, and whole process is complicated, the property-modifying additive consumption is large, and cost is high; Patent CN201010243990.3, a kind of method for preparing cationic adsorption agent with canna slag, whole process is comparatively loaded down with trivial details, first alkali lye and canna slag is stirred, then adds epoxypropyltrimethylchloride chloride stirring 30min, in baking oven, reaction is a little rear extremely neutral with hydrochloric acid accent pH, filter washing, vacuum drying and getting, the method exists material limited, because collecting the problem of being responsible for being difficult to carry out application; The people such as Huang Jiangsheng refer 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 with modification tealeaves and Fe
3+Reaction makes sorbing material tealeaves matter iron, but all lower to the adsorbance of two kinds of dyestuffs, and best pH is difficult to promote the use of near 1.
The people such as Li Buhai in " research of ethylenediamine modified peanut powder adsorpting anion dyestuff " take the natural products peanut shell as matrix, epoxychloropropane as crosslinking agent, ethylenediamine as modifier has synthesized a kind of new adsorbent, with it, direct indigo plant (DB) and sunset yellow (SY) are adsorbed, but amino less with the crosslinked generation of ethylenediamine, its maximum adsorption capacity to two kinds of dyestuffs is only also 129.1 and 135.2mg/g, from the promotion prospect aspect and little.
Use walnut shell to be used for dyestuff removal aspect as sorbent material in patent or paper and still rarely have discovery, we find or with it directly as the adsorbent absorbing dye, as the SCI paper: Effective removal of Maxilon Red GRL from Aqueous solution by walnut shell:nonlinear Kinetic and Equilibrium Models, but discovery is also bad as the effect of adsorbent adsorption treatment of dye waste water with unmodified walnut shell, and adsorbance is only 10 ~ 50mg/g.Or have it is made active carbon, as the SCI paper: Preparation of activated carbons from walnut shells via vacuum chemical activation and their application for methylene blue removal.But active carbon has cost high, the shortcomings such as difficult life.
Summary of the invention
The technical problem that solves:The present invention overcomes the deficiencies in the prior art and proposes a kind of preparation method who contains the modification walnut shell adsorbent of polyamino, the present invention be large by the contrast table area, mechanical strength is high, chemically stable good and the walnut shell of easy regeneration carries out modification, obtain containing the modification walnut shell adsorbent of polyamino, and utilize the specific physicochemical property give it to remove anionic dye in water body, especially the removal effect for Reactive Brilliant Red K-2BP dyestuff in dyeing waste water is remarkable.
Technical scheme:The present invention is take the biological material walnut shell as material, epoxychloropropane is under etherifying agent, NaOH environment, diethylenetriamine is crosslinking agent and carry out in two steps modification as introducing amino group, a kind of method that contains the modification walnut shell adsorbent of polyamino of compound preparation, the outward appearance of the adsorbent that it makes is the brown color powder.
Anionic dye described in the present invention refers to that a class contains hydroxy, sulfonic group, carboxyl, can be combined with wool or silk fabric ionic bond and the dyestuff that dyes, and electronegative property soluble in water.After this this cation-modified walnut shell adsorbent that contains polyamino adds fuel waste water, because the electrostatic adsorption of zwitterion just can have been played good removal effect to Wastewater Dyes.The azo dyes Reactive Brilliant Red K-2BP that uses in whole process of the test is a kind of typical anionic dye that contains the monoazo key, has the anionic dye representativeness.
Technical solutions according to the invention are: a kind of preparation method of modification walnut shell cation adsorbent, and the preparation process of the method is as follows:
(1) pretreatment:
Clean walnut shell after pulverizer pulverizes and sieves, is obtained the walnut shell powder;
(2) modifications:
Be that 1 ~ 1.25mol/L sodium hydroxide solution and epoxychloropropane add in the walnut shell powder that step (1) obtains with concentration, add the sodium hydroxide solution of 7.5 ~ 22.5mL and the epoxychloropropane of 1 ~ 10mL in every gram walnut shell powder; Then be placed in the constant temperature combined reactor in 40 ~ 65 ℃ of lower whip modified 30 ~ 60min, after then the walnut shell powder after modification being spent ionized water and being washed till neutrality, in 65 ~ 80 ℃ of lower vacuum dryings 3 ~ 5 hours, grinding was sieved, and obtains modification walnut shell powder one time;
(3) twice-modified
Add step (2) to obtain in modification walnut shell powder deionized water, sodium hydroxide powder and diethylenetriamine, modification walnut shell powder of every gram adds the diethylenetriamine of 25 ~ 50mL deionized water, 0.1 ~ 2g sodium hydroxide powder and 1 ~ 20mL, then be placed in the constant temperature combined reactor and stir 60 ~ 120min under 65 ~ 80 ℃, then the walnut shell powder after modification is spent ionized water is washed till neutrality, in 65 ~ 80 ℃ of lower vacuum dryings 3 ~ 5 hours, grinding is sieved, get twice-modified walnut shell powder, be modification walnut shell cation adsorbent finished product.
Described clean walnut shell makes by the following method: walnut shell is boiled 60 ~ 120min with boiling water, remove flesh and pulp; Soak 7 ~ 14 days, replacing every day with deionized water, to wash away except the dust that sticks together and residual pulp, smoke 24 ~ 48h afterwards at 65 ~ 105 ℃ of temperature; After processing like this, decapacitation is effectively removed outside the walnut shell surface impurity, also can effectively improve walnut shell specific area, micropore amount and micropore volume simultaneously, also provides more reaction site for follow-up diethylenetriamine modification simultaneously.
The selected particle diameter of the walnut shell powder of step (1) after pulverizer pulverizes and sieves is 0.065 ~ 0.2mm.
In step (2), every gram walnut shell powder adds 15 ~ 20mL sodium hydroxide solution and 5 ~ 6.25mL epoxychloropropane.
In step (3), modification walnut shell powder of every gram adds the diethylenetriamine of 40 ~ 50mL deionized water, 0.25 ~ 0.5g sodium hydroxide powder and 2.5 ~ 5mL.
Constant temperature combined reactor top described in step 3 is there-necked flask, and the bottom is the magnetic stirring apparatus with function of temperature control.Three mouthfuls of top there-necked flasks are laid respectively and are thermometer boss, and serpentine condenser and cover have the polytetrafluoroethylene (PTFE) plug with holes of magnetic stirring apparatus temperature sense rod.
Mechanism of the present invention:
Adopt epoxychloropropane as etherifying agent, the walnut shell powder to be carried out a modification in preparation method's step 2 of the present invention.Because containing a lot of celluloses in walnut shell, use epoxychloropropane with the cellulose etherificate, the cellulose dissolution degree that is insoluble in water is originally increased, for follow-up modification creates favorable conditions.Adopt simultaneously diethylenetriamine to carry out twice-modified as crosslinking agent to the walnut shell powder in preparation method's step 3 of the present invention.Can make these electronegative cationizations in the aqueous solution usually such as cellulose and hemicellulose after modification, make and contain more polyamino, thereby be converted into the positively charged anionic dye that makes the easy suction band negative electrical charge of cellulose, reach the effect of removing anionic dye waste water.
The modification walnut shell cationic adsorption agent that makes by method of the present invention is used for the removal of dyeing waste water anionic dye.
Make by method of the present invention the removal that described modification walnut shell cationic adsorption agent is used for dyeing waste water Reactive Brilliant Red K-2BP dyestuff.
The application of the modification walnut shell cationic adsorption agent that makes by method of the present invention, method for optimizing is as follows:
Under room temperature, modification walnut shell cation adsorbent dosage is 1 ~ 2g/L, and the pH that regulates anionic azo dyes waste water is about 1 ~ 4, and oscillation rate is 160 ~ 180r/min, continues 2 ~ 3h, and its clearance can be more than 95%.
Beneficial effect:
The walnut shell cation adsorbent of the modification that makes by method of the present invention is applied to the treatment of dyeing wastewater field, and is high to the clearance of anionic dye in dyeing waste water; Through verification experimental verification, its azo dyes Reactive Brilliant Red K-2BP adsorption capacity can reach 500mg/g, is approximately 9 times of unmodified walnut shell powder, is 3 ~ 4 times of coal mass active carbon under equal experimental condition; Simultaneously the required raw material sources of preparation method of the present invention are extensive, and method of modifying technique is simple, and the mechanical strength of the product that it makes is high, chemically stable good, the low easily regeneration of cost.
Description of drawings
Fig. 1 is that in embodiment 8, walnut shell powder and the walnut shell cation adsorbent after modification (being walnut shell powder after modification) before modification is subjected to the pH value to affect figure on anionic dye Reactive Brilliant Red K-2BP in waste water; Wherein the A:pH value on modification after walnut shell powder absorbing dye adsorbance and clearance affect figure, B: before and after modification, walnut shell powder foot couple Dye Adsorption amount size is with pH value variation comparison diagram.
Fig. 2 is that the dosage of the modification walnut shell cation adsorbent that makes of embodiment 8 is on the figure that affects of its absorption azo dyes Reactive Brilliant Red K-2BP;
Fig. 3 is that the modification walnut shell cation adsorbent adsorption time that embodiment 8 makes adsorbs the figure that affects of azo dyes Reactive Brilliant Red K-2BP to it;
Fig. 4 is that in embodiment 8, the walnut shell powder before modification adsorbs with the walnut shell cation adsorbent after modification that in waste water, the azo dyes Reactive Brilliant Red K-2BP is subjected to the dyestuff initial concentration to affect figure.A: the adsorbance of the walnut shell cation adsorbent absorbing dye of dyestuff initial concentration after on modification and the impact of clearance, B: before and after modification, walnut shell powder foot couple Dye Adsorption amount size changes comparison diagram with the dyestuff initial concentration.
Fig. 5 is the ESEM phenogram of the resulting unmodified walnut shell powder of step 1 in embodiment 8,10000 times of multiplication factors.
Fig. 6 is the ESEM phenogram of the prepared modification walnut shell of embodiment 8 cation adsorbent, 10000 times of multiplication factors.
Fig. 7 is the ESEM phenogram after the prepared modification walnut shell of embodiment 8 cation adsorbent absorption azo dyes Reactive Brilliant Red K-2BP, 10000 times of multiplication factors.
Fig. 8 is the infrared spectrogram after the walnut shell powder before modification in embodiment 8, the walnut shell cation adsorbent after modification and walnut shell cation adsorbent absorption azo dyes Reactive Brilliant Red K-2BP.A: the infrared spectrogram of unmodified walnut shell powder, B: the infrared spectrogram of modification walnut shell cation adsorbent, C: the infrared spectrogram after modification walnut shell cation adsorbent absorption azo dyes Reactive Brilliant Red K-2BP.
Fig. 9 is the modification walnut shell cation adsorbent thermogravimetric analysis phenogram that embodiment 8 makes, and selected range of temperature is 25 ~ 800 ℃, and rate temperature change is 20 ℃/min.
Figure 10 is the absorption property figure of the modification walnut shell cation adsorbent desorption that makes of embodiment 8 after repeatedly.
The specific embodiment
Embodiment 1:
The preparation method of a kind of modification walnut shell cation adsorbent that proposes, its manufacturing process comprises the following steps:
Step 1, pretreatment:
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, boil 60min with boiling water, remove remaining flesh and pericarp.Soak 7 days, replacing every day with deionized water, to wash away except the dust that sticks together and residual pulp.Smoke 24 h after a week under 105 ℃ of conditions, getting particle diameter through the plant sample crushing machine grinding and sieving is 0.125 ~ 0.2mm, standby in the wide-mouth bottle of packing into;
Step 2, a modification:
Get the walnut shell powder 2g that step 1 obtains, adding 30mL concentration is sodium hydroxide solution and the 20mL epoxychloropropane solution of 1.25mol/L, 40 ℃ of lower modification 30min in the constant temperature combined reactor, be washed till neutrality with deionized water, and in 65 ℃ of lower vacuum dryings of baking oven 3 hours, grinding sieves got the modification walnut shell that particle diameter is 0.125 ~ 0.2mm;
Get the modification walnut shell powder 1g that step 2 makes and add the 50mL deionized water, add simultaneously 0.25g NaOH end and 5mL diethylenetriamine solution, stir 60min under 65 ℃ of constant temperature combined reactors, be washed till neutrality with deionized water, and in 65 ℃ of lower vacuum dryings 3 hours, grinding is sieved and is got the twice-modified walnut shell that particle diameter is 0.125 ~ 0.2mm, is a kind of modification walnut shell cation adsorbent of indication.
Embodiment 2:
Operating procedure one and three once is modified as in the difference step 2 with embodiment 1:
Get the walnut shell powder 2g that step 1 obtains, adding 15 mL concentration is sodium hydroxide solution and the 20mL epoxychloropropane solution of 1mol/L, 40 ℃ of lower modification 30min in the constant temperature combined reactor, be washed till neutrality with deionized water, and in 65 ℃ of lower vacuum dryings of baking oven 3 hours, grinding sieves got the modification walnut shell that particle diameter is 0.125 ~ 0.2mm;
Embodiment 3:
Operating procedure one and three once is modified as in the difference step 2 with embodiment 1:
Get the walnut shell powder 2g that step 1 obtains, adding 45 mL concentration is sodium hydroxide solution and the 2mL epoxychloropropane solution of 1mol/L, 40 ℃ of lower modification 30min in the constant temperature combined reactor, be washed till neutrality with deionized water, and in 65 ℃ of lower vacuum dryings of baking oven 3 hours, grinding sieves got the modification walnut shell that particle diameter is 0.125 ~ 0.2mm;
Embodiment 4:
Operating procedure one and two is with embodiment 1, twice-modifiedly in the difference step 3 is:
Add step 2 to obtain in modification walnut shell powder deionized water, sodium hydroxide powder and diethylenetriamine, modification walnut shell powder of every gram adds the diethylenetriamine of 25mL deionized water, 0.1g sodium hydroxide powder and 1mL, then be placed in the constant temperature combined reactor and stir 60min under 65 ℃, then the walnut shell powder after modification is spent ionized water is washed till neutrality, in 65 ℃ of lower vacuum dryings 3 hours, grinding sieves got the modification walnut shell cation adsorbent that particle diameter is 0.125 ~ 0.2mm.
Embodiment 5:
Operating procedure one and two is with embodiment 1, twice-modifiedly in the difference step 3 is:
Deionized water, sodium hydroxide powder and diethylenetriamine are added in the modification walnut shell powder that step 2 obtains, modification walnut shell powder of every gram adds the diethylenetriamine of 25mL deionized water, 2g sodium hydroxide powder and 2.5mL, then be placed in the constant temperature combined reactor and stir 120min under 80 ℃, then the walnut shell powder after modification is spent ionized water is washed till neutrality, in 65 ℃ of lower vacuum dryings 5 hours, grinding sieves got the modification walnut shell cation adsorbent that particle diameter is 0.125 ~ 0.2mm.
Embodiment 6:
Operating procedure one and two is with embodiment 1, twice-modifiedly in the difference step 3 is:
Deionized water, sodium hydroxide powder and diethylenetriamine are added in the modification walnut shell powder that step 2 obtains, modification walnut shell powder of every gram adds the diethylenetriamine of 50mL deionized water, 0.1g sodium hydroxide powder and 10mL, then be placed in the constant temperature combined reactor and stir 120min under 70 ℃, then the walnut shell powder after modification is spent ionized water is washed till neutrality, in 65 ℃ of lower vacuum dryings 3 hours, grinding sieves got the modification walnut shell cation adsorbent that particle diameter is 0.125 ~ 0.2mm.
Embodiment 7:
Step 1, pretreatment:
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, boil 60min with boiling water, remove remaining flesh and pericarp.Soak 7 days, replacing every day with deionized water, to wash away except the dust that sticks together and residual pulp.Smoke 24 h after a week under 105 ℃ of conditions, getting particle diameter through the plant sample crushing machine grinding and sieving is 0.075 ~ 0.125mm, standby in the wide-mouth bottle of packing into;
Step 2, a modification:
Get the walnut shell powder 2g that step 1 obtains, adding 30mL concentration is sodium hydroxide solution and the 20mL epoxychloropropane solution of 1.25mol/L, 40 ℃ of lower modification 30min in the constant temperature combined reactor, be washed till neutrality with deionized water, and in 65 ℃ of lower vacuum dryings of baking oven 3 hours, grinding sieves got the modification walnut shell that particle diameter is 0.075 ~ 0.125mm;
Deionized water, sodium hydroxide powder and diethylenetriamine are added in the modification walnut shell powder that step 2 obtains, modification walnut shell powder of every gram adds the diethylenetriamine of 50mL deionized water, 2g sodium hydroxide powder and 20mL, then be placed in the constant temperature combined reactor and stir 120min under 70 ℃, then the walnut shell powder after modification is spent ionized water is washed till neutrality, in 65 ℃ of lower vacuum dryings 3 hours, grinding sieves got the modification walnut shell cation adsorbent that particle diameter is 0.075 ~ 0.125mm.
Embodiment 8:
Step 1, pretreatment:
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, boil 60min with boiling water, remove remaining flesh and pericarp.Soak 7 days, replacing every day with deionized water, to wash away except the dust that sticks together and residual pulp.Smoke 24 h after a week under 105 ℃ of conditions, getting particle diameter through the plant sample crushing machine grinding and sieving is 0.065 ~ 0.075mm, standby in the wide-mouth bottle of packing into;
Step 2, a modification:
Get the walnut shell powder 2g that step 1 obtains, adding 30mL concentration is sodium hydroxide solution and the 20mL epoxychloropropane solution of 1.25mol/L, 40 ℃ of lower modification 30min in the constant temperature combined reactor, be washed till neutrality with deionized water, and in 65 ℃ of lower vacuum dryings of baking oven 3 hours, grinding sieves got the modification walnut shell that particle diameter is 0.065 ~ 0.075mm;
Deionized water, sodium hydroxide powder and diethylenetriamine are added in the modification walnut shell powder that step 2 obtains, modification walnut shell powder of every gram adds the diethylenetriamine of 50mL deionized water, 2g sodium hydroxide powder and 20mL, then be placed in the constant temperature combined reactor and stir 60min under 65 ℃, then the walnut shell powder after modification is spent ionized water is washed till neutrality, in 70 ℃ of lower vacuum dryings 3 hours, grinding sieves got the modification walnut shell cation adsorbent that particle diameter is 0.065 ~ 0.075 mm.
Embodiment 9
Step 1, pretreatment:
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, boil 90min with boiling water, remove remaining flesh and pericarp.Soak 14 days, replacing every day with deionized water, to wash away except the dust that sticks together and residual pulp.Smoke 36 h after a week under 95 ℃ of conditions, getting particle diameter through the plant sample crushing machine grinding and sieving is 0.065 ~ 0.075mm, standby in the wide-mouth bottle of packing into;
Step 2, a modification:
Get the walnut shell powder 2g that step 1 obtains, adding 40mL concentration is sodium hydroxide solution and the 12.5mL epoxychloropropane solution of 1.15mol/L, 65 ℃ of lower modification 45min in the constant temperature combined reactor, be washed till neutrality with deionized water, and in 70 ℃ of lower vacuum dryings of baking oven 5 hours, grinding sieves got the modification walnut shell that particle diameter is 0.065 ~ 0.075mm;
Get the modification walnut shell powder 1g that step 2 makes and add the 40mL deionized water, add simultaneously 1g NaOH end and 15mL diethylenetriamine solution, stir 90min under 70 ℃ of constant temperature combined reactors, be washed till neutrality with deionized water, and in 75 ℃ of lower vacuum dryings 5 hours, grinding is sieved and is got the twice-modified walnut shell that particle diameter is 0.065 ~ 0.075mm, is a kind of modification walnut shell cation adsorbent of indication.
Step 1, pretreatment:
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, boil 120min with boiling water, remove remaining flesh and pericarp.Soak 11 days, replacing every day with deionized water, to wash away except the dust that sticks together and residual pulp.Smoke 48 h after a week under 65 ℃ of conditions, getting particle diameter through the plant sample crushing machine grinding and sieving is 0.065 ~ 0.075mm, standby in the wide-mouth bottle of packing into;
Step 2, a modification:
Get the walnut shell powder 2g that step 1 obtains, adding 35mL concentration is sodium hydroxide solution and the 10mL epoxychloropropane solution of 1.10mol/L, 55 ℃ of lower modification 60min in the constant temperature combined reactor, be washed till neutrality with deionized water, and in 80 ℃ of lower vacuum dryings of baking oven 4 hours, grinding sieves got the modification walnut shell that particle diameter is 0.065 ~ 0.075mm;
Get the modification walnut shell powder 1g that step 2 makes and add the 35mL deionized water, add simultaneously 0.5g NaOH end and 10mL diethylenetriamine solution, stir 90min under 70 ℃ of constant temperature combined reactors, be washed till neutrality with deionized water, and in 80 ℃ of lower vacuum dryings 4 hours, grinding is sieved and is got the twice-modified walnut shell that particle diameter is 0.065 ~ 0.075mm, is a kind of modification walnut shell cation adsorbent of indication.
Embodiment 11:
The walnut shell powder that uses embodiment 8 step 1 to make is that unmodified walnut shell is used for the contrast adsorption test, it is 0.5g/L that dosage is set, pH value of solution is adjusted to 3 left and right, Reactive Brilliant Red K-2BP dyestuff waste liquid concentration is 200mg/L, regulating hunting speed in constant temperature oscillator is 180rpm, measures the dyestuff residual concentration after vibration 120min and calculates to get the adsorbance of adsorbent.
Embodiment 12:
(particle diameter is 0.065 ~ 0.075mm) to be used for the contrast adsorption test to use the coal mass active carbon of 200 mesh sieves, it is 0.5g/L that dosage is set, pH value of solution is adjusted to 3 left and right, Reactive Brilliant Red K-2BP dyestuff waste liquid concentration is 200mg/L, regulating hunting speed in constant temperature oscillator is 180rpm, measures the dyestuff residual concentration after vibration 120min and calculates to get the adsorbance of adsorbent.
Embodiment 13:
The modified cation adsorbent that uses embodiment 8 to make carries out adsorption activity bright red K-2BP test, getting the adsorbent dosage is 2g/L, the dyestuff initial concentration is 200mg/L, pH is adjusted to 3 left and right, fully after the vibration adsorption equilibrium, filter, with deionized water washing several times, take out adsorbent, be used for desorption experiment of lower step.
The use desorption method is as follows: in conical flask, the adsorbent of getting after the 0.1g saturated adsorption joins in the NaOH solution that 20mL concentration is 0.4mol/L, vibration desorb 5h in constant temperature oscillator, filter, with deionized water washing several times, take out adsorbent and can carry out adsorption test again, the adsorption capacity of examination reproducing adsorbent to dyestuff.
Above step repeatedly is to inquire into the power of regeneration of modified cation adsorbent.
Utilize the Reactive Brilliant Red K-2BP in the modified cation adsorbent absorbing dye waste water solution for preparing in embodiment 1-10.The adsorption test condition of each embodiment is as follows:
The dosage of modification walnut shell cation adsorbent is 0.5g/L, pH value of solution is adjusted to 3 left and right, Reactive Brilliant Red K-2BP dyestuff waste liquid concentration is 200mg/L, add the 120min that vibrates in 25 ℃ of constant temperature oscillators after the modification walnut shell cation adsorbent that embodiment 1 ~ 10 makes in the waste water, hunting speed is 180rpm.
Upon adsorption reach balance after, take out solution, and after centrifugal with supercentrifuge, the concentration of residual dye in the mensuration supernatant is according to following formula
Obtain adsorbance.In formula:
Be adsorbance (mg/g),
Be the concentration (mg/L) of adsorbing dyestuff in front solution,
Be the concentration (mg/L) of adsorbing dyestuff in rear solution,
Be liquor capacity (L),
Be adsorbent mass (g).
Embodiment 1 ~ 12 each adsorbent adsorption activity bright red K-2BP dye solution adsorbance such as following table:
| Embodiment | Adsorbance (mg/g) |
| 1 | 179.5 |
| 2 | 150.4 |
| 3 | 176.3 |
| 4 | 152.4 |
| 5 | 163.1 |
| 6 | 165.9 |
| 7 | 235.9 |
| 8 | 245.2 |
| 9 | 247.6 |
| 10 | 235.1 |
| 11 | 63.0 |
| 12 | 72.8 |
The below is the experiment situation of carrying out as an example of the modification walnut shell cation adsorbent of embodiment 8 example under different condition the removal of waste water Reactive Brilliant Red K-2BP.
The impact of pH:
Experiment condition: at room temperature, to the Reactive Brilliant Red K-2BP solution of initial concentration 200mg/L, regulate the pH scope at 1.5 ~ 11, use modification walnut shell powder, it is 0.5g/L that dosage is set, 160rpm vibration absorption 180min.The modification walnut shell is subjected to the impact of the initial pH of solution larger on the absorption of dyestuff, as shown in Fig. 1 A, pH less than 3 o'clock adsorbances all more than 350mg/g.
In addition, walnut shell powder before modification is also carried out the experiment of the same terms, obtain before and after Fig. 1 B modification walnut shell powder foot couple Dye Adsorption amount size with pH value variation comparison diagram.The contrast discovery, the adsorbance of modification walnut shell powder foot couple Reactive Brilliant Red K-2BP is significantly increased, and is about 40 times of unmodified walnut shell.
The impact of adsorbent dosage:
Experiment condition: at room temperature, be the Reactive Brilliant Red K-2BP solution of 200mg/L to initial concentration, vibrating under 160rpm and controlling adsorption time is 180min, and pH is 2.15.As shown in Figure 2, along with the increase of modification walnut shell powder dosage, adsorbent also constantly increases the clearance of Reactive Brilliant Red K-2BP.
The impact of adsorption time:
Experiment condition: at room temperature, the pH of the Reactive Brilliant Red K-2BP solution of 200mg/L is regulated 2.70, controlling the adsorbent dosage is 0.5g/L, vibration absorption 5 ~ 180min under 160rpm.As shown in Figure 3, the increase with adsorption time increases the modification walnut shell to the clearance of Reactive Brilliant Red K-2BP, and 0 ~ 40min rate of adsorption is very fast, then slows down gradually, substantially reaches adsorption equilibrium after 180min, and adsorbance is about 270mg/g.In addition, under equal conditions used the coal mass active carbon powder of 200 mesh sieves to adsorb (being example 12) discovery to Reactive Brilliant Red K-2BP, during adsorption equilibrium, its adsorbance to dyestuff is 72.8mg/g.It is 4 times that under this condition, the modification walnut shell is about coal mass active carbon to the absorption of dyestuff.
The impact of dyestuff initial concentration:
Experiment condition: at room temperature, the pH that keeps waste water from dyestuff is 2.5,160rpm vibration 180min in constant temperature oscillator, and dosage is 0.5g/L, setting the initial concentration excursion is 50 ~ 1400mg/L.As shown in Fig. 4 A, the adsorbance of modified adsorbent azo dyes Reactive Brilliant Red K-2BP is with the rapid extremely approximately 250mg/g of increase of initial concentration when initial concentration is 0 ~ 200mg/L; Concentration slowly increases when 200 ~ 1400mg/L by a small margin; When concentration reaches 1000mg/L balance reached maximum, i.e. the about 500mg/g of saturated adsorption capacity.
As shown in Fig. 4 B, investigate before and after the walnut shell modification adsorption capacity to Reactive Brilliant Red K-2BP, under this condition after modification walnut shell the removal of dyestuff is significantly improved.Under the same terms, unmodified walnut shell is that 63.0mg/g(is example 11 to the saturated extent of adsorption of Reactive Brilliant Red K-2BP), so the modification walnut shell is nearly 9 times of unmodified walnut shell for the saturated extent of adsorption of dyestuff.
In addition, Fig. 9 is modification walnut shell cation adsorbent thermogravimetric analysis phenogram, and range of temperature is 25 ~ 800 ℃, and temperature increase rate is 20 ℃/min.0 ~ 100 ℃ of scope is steam volatilization loss as seen from the figure, and the weight of 100 ~ 300 ℃ of modification walnut shell adsorbents does not have loss, just has weight to descend after 300 ℃, represents the good thermal stability of this modified adsorbent.
Figure 10 is the repeatedly absorption property figure of post-modification walnut shell cation adsorbent of desorption, learns that by figure this modified adsorbent processes the clearance that still can have more than 90% to dyestuff again the 8th desorb, illustrates that the regenerability of this modified adsorbent is good.
Claims (5)
1. the preparation method of a modification walnut shell cation adsorbent is characterized in that this preparation method's step is as follows:
(1) pretreatment:
Clean walnut shell after pulverizer pulverizes and sieves, is obtained the walnut shell powder;
(2) modifications:
Be that 1 ~ 1.25mol/L sodium hydroxide solution and epoxychloropropane add in the walnut shell powder that step (1) obtains with concentration, add the sodium hydroxide solution of 7.5 ~ 22.5mL and the epoxychloropropane of 1 ~ 10mL in every gram walnut shell powder; Then in 40 ~ 65 ℃ of lower constant temperature whip modified 30 ~ 60min, after then the walnut shell powder after modification being spent ionized water and being washed till neutrality, in 65 ~ 80 ℃ of lower vacuum dryings 3 ~ 5 hours, grinding was sieved, and obtains modification walnut shell powder one time;
(3) twice-modified
Add step (2) to obtain in modification walnut shell powder deionized water, sodium hydroxide powder and diethylenetriamine, modification walnut shell powder of every gram adds the diethylenetriamine of 25 ~ 50mL deionized water, 0.1 ~ 2g sodium hydroxide powder and 1 ~ 20mL, then in 65 ~ 80 ℃ of lower constant temperature whip modified 60 ~ 120min, then the walnut shell powder after modification is spent ionized water is washed till neutrality, in 65 ~ 80 ℃ of lower vacuum dryings 3 ~ 5 hours, grinding is sieved, get twice-modified walnut shell powder, be modification walnut shell cation adsorbent finished product.
2. the preparation method of a kind of modification walnut shell cation adsorbent according to claim 1, it is characterized in that: described clean walnut shell makes by the following method: walnut shell is boiled 60 ~ 120min with boiling water, remove flesh and pulp; Then soak 7 ~ 14 days, replacing every day with deionized water, to wash away except the dust that sticks together and residual pulp, smoke 24 ~ 48h afterwards at 65 ~ 105 ℃ of temperature.
3. the preparation method of a kind of modification walnut shell cation adsorbent according to claim 1, it is characterized in that: the selected particle diameter of the walnut shell powder of described step (1) after pulverizer pulverizes and sieves is 0.065 ~ 0.2mm.
4. the preparation method of a kind of modification walnut shell cation adsorbent according to claim 1, it is characterized in that: in described step (2), every gram walnut shell powder adds 15 ~ 20mL sodium hydroxide solution and 5 ~ 6.25mL epoxychloropropane.
5. the preparation method of a kind of modification walnut shell cation adsorbent according to claim 1, it is characterized in that: in described step (3), modification walnut shell powder of every gram adds the diethylenetriamine of 40 ~ 50mL deionized water, 0.25 ~ 0.5g sodium hydroxide powder and 2.5 ~ 5mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103246954A CN103381357A (en) | 2013-07-30 | 2013-07-30 | Preparation method for modified walnut shell cation adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103246954A CN103381357A (en) | 2013-07-30 | 2013-07-30 | Preparation method for modified walnut shell cation adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103381357A true CN103381357A (en) | 2013-11-06 |
Family
ID=49489411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103246954A Pending CN103381357A (en) | 2013-07-30 | 2013-07-30 | Preparation method for modified walnut shell cation adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103381357A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657600A (en) * | 2013-11-28 | 2014-03-26 | 河海大学 | Modified water treatment absorbent and preparation method and application thereof |
| CN103752280A (en) * | 2014-01-07 | 2014-04-30 | 河海大学 | Composite modified walnut shell adsorbent as well as preparation method and application of composite modified walnut shell absorbent |
| CN103752279A (en) * | 2013-11-27 | 2014-04-30 | 河海大学 | Modified walnut-shell adsorbent containing double amidoxime groups and preparation method thereof |
| CN103861560A (en) * | 2014-03-13 | 2014-06-18 | 北京工业大学 | Method for removing reactive brilliant red K-2G dye from wastewater by walnut shell biomass carbon adsorbent |
| CN104084141A (en) * | 2014-07-04 | 2014-10-08 | 河海大学 | Preparation method of amino modified macadimia nut shell adsorbing agent |
| CN104096539A (en) * | 2014-07-04 | 2014-10-15 | 河海大学 | Method for preparing macadamia nut shell adsorbent |
| CN104275159A (en) * | 2014-09-26 | 2015-01-14 | 河海大学 | Preparation method of modified macadamia shell adsorbent |
| CN104815617A (en) * | 2015-04-27 | 2015-08-05 | 宁夏医科大学 | Preparing method of ephedra amination waste biosorbent |
| CN104826577A (en) * | 2015-04-30 | 2015-08-12 | 广东第二师范学院 | Modified slag adsorbent for anion dye wastewater treatment, and preparation method thereof |
| CN105597700A (en) * | 2016-03-16 | 2016-05-25 | 华东交通大学 | Novel amino walnut shell adsorbent with efficient adsorption performance and preparation method thereof |
| CN107433188A (en) * | 2017-08-09 | 2017-12-05 | 陕西科技大学 | A kind of cation adsorbent prepared with vinasse and its preparation method and application |
| CN107456951A (en) * | 2017-08-25 | 2017-12-12 | 河海大学 | A kind of rice straw adsorbent of modification and its preparation method and application |
| CN108212102A (en) * | 2016-12-13 | 2018-06-29 | 西南石油大学 | A kind of ethylenediamine is modified peach-pit cationic adsorption agent and preparation method thereof |
| CN109777741A (en) * | 2019-01-15 | 2019-05-21 | 昆明理工大学 | A kind of method that walnut shell efficiently utilizes |
| CN110773227A (en) * | 2019-10-23 | 2020-02-11 | 华侨大学 | Walnut shell powder acid-base functionalized catalyst, preparation method and application |
| CN110961152A (en) * | 2019-11-27 | 2020-04-07 | 华侨大学 | Preparation method of imidazolium salt functionalized walnut shell powder heterogeneous catalyst and synthesis method of cyclic carbonate based on catalyst |
| CN112108127A (en) * | 2020-10-15 | 2020-12-22 | 桂林理工大学 | Passion fruit peel adsorption material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080227969A1 (en) * | 2004-08-31 | 2008-09-18 | Chuichi Hirayama | Nucleic acid adsorbent; methods for adsorbing, removing, dissociating, and recovering nucleic acids using the same; and method for regenerating the same |
| CN102553538A (en) * | 2012-01-10 | 2012-07-11 | 山东大学 | Modified peanut shell cationic adsorbent, preparation method and application |
-
2013
- 2013-07-30 CN CN2013103246954A patent/CN103381357A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080227969A1 (en) * | 2004-08-31 | 2008-09-18 | Chuichi Hirayama | Nucleic acid adsorbent; methods for adsorbing, removing, dissociating, and recovering nucleic acids using the same; and method for regenerating the same |
| CN102553538A (en) * | 2012-01-10 | 2012-07-11 | 山东大学 | Modified peanut shell cationic adsorbent, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| WEI SHEN ET AL.: "Adsorption of Cu(II) and Pb(II) onto diethylenetriamine-bacterial cellulose", 《CARBOHYDRATE POLYMERS》, vol. 75, 9 July 2008 (2008-07-09), pages 110 - 114, XP025431358, DOI: doi:10.1016/j.carbpol.2008.07.006 * |
| 王秀平等: "二乙烯三胺改性山竹壳吸附水溶液中的Cd2+，Pb2+", 《高师理科学刊》, vol. 32, no. 2, 31 March 2012 (2012-03-31), pages 65 - 68 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752279A (en) * | 2013-11-27 | 2014-04-30 | 河海大学 | Modified walnut-shell adsorbent containing double amidoxime groups and preparation method thereof |
| CN103657600B (en) * | 2013-11-28 | 2016-06-08 | 河海大学 | A kind of modification water treatment absorbent and its preparation method and application |
| CN103657600A (en) * | 2013-11-28 | 2014-03-26 | 河海大学 | Modified water treatment absorbent and preparation method and application thereof |
| CN103752280B (en) * | 2014-01-07 | 2015-09-16 | 河海大学 | Composite modified walnut shell adsorbent and its preparation method and application |
| CN103752280A (en) * | 2014-01-07 | 2014-04-30 | 河海大学 | Composite modified walnut shell adsorbent as well as preparation method and application of composite modified walnut shell absorbent |
| CN103861560A (en) * | 2014-03-13 | 2014-06-18 | 北京工业大学 | Method for removing reactive brilliant red K-2G dye from wastewater by walnut shell biomass carbon adsorbent |
| CN104096539B (en) * | 2014-07-04 | 2016-04-27 | 河海大学 | A kind of preparation method of macadamia shell adsorbent |
| CN104096539A (en) * | 2014-07-04 | 2014-10-15 | 河海大学 | Method for preparing macadamia nut shell adsorbent |
| CN104084141A (en) * | 2014-07-04 | 2014-10-08 | 河海大学 | Preparation method of amino modified macadimia nut shell adsorbing agent |
| CN104275159B (en) * | 2014-09-26 | 2017-01-18 | 河海大学 | Preparation method of modified macadamia shell adsorbent |
| CN104275159A (en) * | 2014-09-26 | 2015-01-14 | 河海大学 | Preparation method of modified macadamia shell adsorbent |
| CN104815617A (en) * | 2015-04-27 | 2015-08-05 | 宁夏医科大学 | Preparing method of ephedra amination waste biosorbent |
| CN104826577A (en) * | 2015-04-30 | 2015-08-12 | 广东第二师范学院 | Modified slag adsorbent for anion dye wastewater treatment, and preparation method thereof |
| CN105597700A (en) * | 2016-03-16 | 2016-05-25 | 华东交通大学 | Novel amino walnut shell adsorbent with efficient adsorption performance and preparation method thereof |
| CN108212102A (en) * | 2016-12-13 | 2018-06-29 | 西南石油大学 | A kind of ethylenediamine is modified peach-pit cationic adsorption agent and preparation method thereof |
| CN107433188A (en) * | 2017-08-09 | 2017-12-05 | 陕西科技大学 | A kind of cation adsorbent prepared with vinasse and its preparation method and application |
| CN107456951A (en) * | 2017-08-25 | 2017-12-12 | 河海大学 | A kind of rice straw adsorbent of modification and its preparation method and application |
| CN109777741A (en) * | 2019-01-15 | 2019-05-21 | 昆明理工大学 | A kind of method that walnut shell efficiently utilizes |
| CN110773227A (en) * | 2019-10-23 | 2020-02-11 | 华侨大学 | Walnut shell powder acid-base functionalized catalyst, preparation method and application |
| CN110961152A (en) * | 2019-11-27 | 2020-04-07 | 华侨大学 | Preparation method of imidazolium salt functionalized walnut shell powder heterogeneous catalyst and synthesis method of cyclic carbonate based on catalyst |
| CN112108127A (en) * | 2020-10-15 | 2020-12-22 | 桂林理工大学 | Passion fruit peel adsorption material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103381357A (en) | Preparation method for modified walnut shell cation adsorbent | |
| CN106914225B (en) | A kind of preparation method of cellulose base bifunctional adsorbent | |
| CN107983300B (en) | The charcoal composite material and preparation method and application of manganese dioxide modification | |
| CN102553538B (en) | Modified peanut shell cationic adsorbent, preparation method and application | |
| CN103752280B (en) | Composite modified walnut shell adsorbent and its preparation method and application | |
| CN103464111B (en) | Softex kw modification walnut shell adsorbent and its preparation method and application | |
| CN103657600B (en) | A kind of modification water treatment absorbent and its preparation method and application | |
| CN103752279A (en) | Modified walnut-shell adsorbent containing double amidoxime groups and preparation method thereof | |
| CN103071463A (en) | Modified peanut shell Pb (II) adsorbent and preparation method and application thereof | |
| CN104226259A (en) | Threonine modified attapulgite adsorbent and application thereof | |
| CN104941575A (en) | Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method | |
| CN103769059B (en) | Surface imprinted sorbing material of straw and preparation method thereof | |
| CN105561922A (en) | Preparation method of alga biological adsorbent | |
| CN108325506A (en) | A kind of preparation method of the modified cellulose aeroge of absorption heavy metal | |
| CN103920466A (en) | Preparation method and application of modified ramie fiber adsorbent | |
| CN103406105A (en) | Modified waste tea leaves absorbent and preparation method and application thereof | |
| CN105080511B (en) | A kind of preparation method and application of corn stalk fiber element xanthic acid magnesium salts | |
| CN104307488A (en) | Magnetic response heavy metal ion adsorbent and application thereof | |
| CN107252678A (en) | A kind of sulfhydryl modified cassava stalk adsorbent and its preparation method and application | |
| CN107552027A (en) | A kind of application that the method for carbon material and its carbon material of preparation are prepared using biomass dead meal | |
| CN104096539A (en) | Method for preparing macadamia nut shell adsorbent | |
| CN109173999A (en) | A kind of preparation method and applications of biology carbon microspheres | |
| CN106824096A (en) | One step hydro thermal method prepares functional amido Carbon Materials adsorbent | |
| CN102417179A (en) | Preparation method of activated carbon material for electrochemical capacitor | |
| CN110201636A (en) | A kind of preparation method of modification biological charcoal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C05 | Deemed withdrawal (patent law before 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131106 |