CN104941589A - Preparation method of porous biological carbon heavy metal adsorbing material based on cotton straw - Google Patents
Preparation method of porous biological carbon heavy metal adsorbing material based on cotton straw Download PDFInfo
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Abstract
The invention discloses a preparation method of a porous biological carbon heavy metal adsorbing material based on cotton straw. The preparation method comprises the following steps: (1) adding the cotton straw into a ZnCl2 solution, carrying out stirring and impregnation for a certain time, and drying; (2) placing the dried cotton straw into an electric tube furnace for high-temperature calcination, grinding the calcined product into powder, adding the powder and ultrapure water into a hydrothermal reaction kettle, stirring till swelling is sufficient, heating for a reaction, and conducting centrifugal drying on the reaction product, so as to obtain a biological carbon material; (3) adjusting the pH of an ethanol aqueous solution with an acetic acid solution, adding 3-mercaptopropyl triethoxy silane into the ethanol aqueous solution, and carrying out oscillation to obtain a modified liquid; adding the biological carbon material into the modified liquid, carrying out oscillation and filtration, drying the obtained solid, washing the dried solid with an ethanol aqueous solution, and drying to obtain the biological carbon heavy metal adsorbing material. The preparation method is simple, and easy to operate; the biological carbon heavy metal adsorbing material prepared according to the method adopts a porous honeycomb-shaped structure, is large in specific surface area, high in heavy metal adsorbing property, and high in economic value and environment-friendly meaning.
Description
Technical field
The invention belongs to and belong to Phytochemistry and adsorption science field, be specifically related to the preparation method of the multiporous biological carbon heavy-metal adsorption material based on cotton stalk.
Background technology
In recent years, due to developing rapidly of industry, dye industry, petroleum chemical industry, the fast development in succession of Electroplating Operations and mechanical processing industry, the waste water that these industries produce mostly directly is discharged into lake, river, ocean, its water body is all more or less containing harmful heavy metal ions, this not only pollutes water environment, water quality is worsened rapidly, and its quantity of wastewater effluent raises year by year, water pollutions especially in water heavy-metal pollution become undisputable fact, serious harm different kind organism comprises the existence of the mankind.Heavy-metal pollution threat that is healthy to human body and living environment caused various countries scientist extensive concern, meanwhile, also just make heavy metal containing wastewater treatment technology obtain develop rapidly.The method of process heavy metal wastewater thereby is various, substantially can be divided at present: chemical method, Physical, bioanalysis.But chemistry and physical method, because treatment effect is undesirable, somewhat expensive, easily cause the reasons such as secondary pollution, limit they self application prospect.Relative to many defects of first two, bioanalysis has good treatment effect with it to the heavy metal wastewater thereby of low concentration, and with low cost, the advantage such as waste material easily processes, become the focus of water treatment research field now.In recent years, lot of domestic and international researcher is studied agriculture and forestry by-product or agricultural wastes, develops some different qualities, the adsorbent of difference in functionality.Such as chestnut shell, persimmon slag, mushroom root, tea grounds etc. make adsorbent after special modification, but eventually because of its processing complex process, could not extensively be promoted.
Cotton, is the seed fiber of Malvaceae cotton, originates in subtropical zone.Plant is shrub shape, is generally 1 to 2 meters, and in torrid areas, cultivation is 6 meters.Flower is milky, and Post flowering changes into peony soon, then withers, and leaves green small-sized capsule, is called cotton boll.Have cottonseed in brocade bell, the fine hair on cottonseed grows from cottonseed skins, fills up cotton boll inside.Cotton boll splits time ripe, exposes soft fiber.Fiber white, is about 2 to 4 centimetres, containing a large amount of cellulose.There are China, the U.S., India etc. in the country that output of cotton is the highest.Its stalk is rich in nitrogen, phosphorus, potassium, calcium, magnesium and organic matter etc., is that one has multiduty renewable biological source, and feature is containing a large amount of crude fibre and lignin etc.Though lignocellulose can not be utilized by pig, chicken, can be absorbed by ox, sheep etc. and utilize.Before industrialization, peasant is multifarious to utilizing of stalk, and such as, rice straw is dried storage by people, can be used as firewood, and the household wares such as braiding seat cushion, mattress, broom, even for making the roof etc. of simple building, are seldom directly wasted.But abundant due to coal, electricity, natural gas and various industrial product in recent years, the demand of rural area to stalk greatly reduces, a large amount of stalk be processed in order to a serious social concern, the direct burning straw in the fields of a lot of local peasant, cause air pollution, the problem that burning straw pollutes constantly occurs.Cotton stalk is selected to make the adsorbent of heavy metal, its utilization rate can be improved, can turn waste into wealth, the general employing cotton stalk method of preparing adsorbent as after adopting aqueous slkali to process cotton stalk in scientific paper " NaOH modification cotton stalk is studied the absorption of Cu ~ (2+), Pb ~ (2+); Yu Baoqing etc.; Shandong chemical industry, 09 phase in 2014 " as heavy metal absorbent.This method still relies on the structure heavy metal of cotton stalk itself to have adsorption effect and prepares, and its adsorption effect is relatively poor.In addition cotton stalk is carried out carbonization treatment, obtain the sorbing material that specific area is large, method as adopted in scientific paper " KOH activation method prepares the research of cotton stalk active carbon; Jiao Qishuai, Hu Yongqi etc.; chemistry of forest product and industry, 2012,32 (1) " is: pretreatment of raw material: segment cotton stalk being cut into about 2cm, peace and quiet with water, at 105 DEG C, be dried to constant mass; Charing: quantitative raw material is contained in the stainless steel closed container of 1000mL and (fills), be placed in Muffle furnace, with the ramp of 15 DEG C/min to predetermined temperature, and constant temperature 1h, be down to normal temperature, take out, weigh and calculate the yield carbonizing rear cotton stalk charcoal (abbreviation charcoal); Dipping: take 5g charcoal respectively, mix with the KOH solution of 25mL variable concentrations, stir, dipping more than 24h, is dried to constant mass at 105 DEG C; Activation: the charcoal being impregnated with activator is moved in 30mL crucible, is placed in Muffle furnace, activate certain hour under uniform temperature; Activation post processing: first clean activating the activated carbon sample obtained with boiling water, reclaim activator, then repeatedly clean with the HCl of 0.1mol/L, more repeatedly clean to neutrality with boiling water, filter, filter cake is dried to constant mass at 110 DEG C, waits until analysis.Char-forming material prepared by this method does not carry out pre-treatment to cotton stalk, and the micropore that carbonized product is formed is few, and carbonized product does not have the chemical modification of postorder to increase the functional group of adsorbable heavy metal, and the adsorption effect of its heavy metal is bad.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that, the adsorption effect of the ABSORBENTS ABSORPTION metal obtained after reacting with 3-mercaptopropyltriethoxysilane carry out liquor zinci chloridi dipping and carbonization before cotton stalk high temperature cabonization after is better, based on this discovery, complete the present invention.
An object of the present invention is to solve at least the problems referred to above and/or defect, and the advantage will illustrated at least is below provided.
A further object of the invention is the method for flooding by carrying out liquor zinci chloridi before cotton stalk high temperature cabonization and carrying out being obtained by reacting biological carbon after carbonization with 3-mercaptopropyltriethoxysilane, improve surface pore formation rate and the adsorption group of carbonized product, to obtain the high biological carbon of heavy metal adsorption efficiency.
In order to realize, according to these objects of the present invention and other advantage, providing a kind of preparation method of the multiporous biological carbon heavy-metal adsorption material based on cotton stalk, comprise the following steps:
Step one, get cotton stalk ultra-pure water cleaning 5 ~ 10 times, then cotton stalk is immersed in the ZnCl that mass fraction is 20 ~ 50%
2in solution, under normal temperature, stir dipping 10 ~ 15h, then the cotton stalk flooded is dried at 50 ~ 70 DEG C;
Step 2, get in step one dry cotton stalk put into electric tube furnace, logical nitrogen protection, with ramp to 600 ~ 850 DEG C of 10 DEG C/min, be then incubated calcining 1 ~ 3h, the product after calcining is ground to form powder, 0.5 ~ 1 weight portion powder and 30 ~ 50 weight portion ultra-pure waters are added in hydrothermal reaction kettle, stir 8 ~ 12h to complete swelling, be then heated to 150 ~ 200 DEG C, reaction 10 ~ 15h, by product centrifugal drying, obtain biological carbon material;
Step 3, by volume fraction be 6 ~ 10% acetum regulate pH to 3 ~ 4 of ethanol water, 3-mercaptopropyltriethoxysilane is added in the ethanol water of modulated pH and shakes 1 ~ 3h, obtain modification liquid; Biological carbon material step 2 obtained adds in described modification liquid, concussion 1 ~ 3h, filter, the solid obtained is dried at 45 ~ 65 DEG C, then solid is washed 5 ~ 10 times with the ethanol-water solution that volume ratio is 1:1 ~ 3, at 40 ~ 60 DEG C, dry 12 ~ 24h, namely obtains multiporous biological carbon heavy-metal adsorption material.
Preferably, in described step one, the diameter of cotton stalk selects 0.3 ~ 0.5cm, is cut into the rod that length is 2 ~ 5cm before using.
Preferably, the mixing speed in described step one is 300 ~ 500r/min; The speed of shaking in described step 3 is 500 ~ 1000r/min.
Preferably, ZnCl in described step one
2solution can be substituted by KOH solution.
Preferably, described electric tube furnace can be substituted by microwave tube type oven.
Preferably, in described step 3 volume fraction be 6 ~ 10% acetum can be 6 ~ 8% by volume fraction hydrochloric acid, sulfuric acid and salpeter solution substitute.
Preferably, in described step 3, in ethanol water, the volume ratio of ethanol and water is 1:2 ~ 3.
Preferably, the addition of described 3-mercaptopropyltriethoxysilane is 1.5 ~ 3% of described ethanol water cumulative volume.
Preferably, described 3-mercaptopropyltriethoxysilane can be substituted by one or more in 3-aminopropyl trimethoxysilane, vinyltrimethoxy silane, VTES.
Preferably, between described step 2 and step 3, also comprise alkaline solution treatment step: biological carbon material soaking step 2 obtained, in volume ratio is the NaOH of 1:2 and urea liquid, stirs 12 ~ 24 hours, obtains the biological carbon material of alkaline solution process; The concentration of described NaOH is 1 ~ 3mol/L, and the concentration of described urea liquid is 1 ~ 3mol/L.
First cotton stalk stirs dipping in liquor zinci chloridi in the present invention, its objective is and obtains a large amount of micropores in order to allow zinc chloride enter into cotton stalk to make cotton stalk at high temperature calcine.
Biological carbon after cotton stalk carbonization in the present invention and 3-mercaptopropyltriethoxysilane react, and the hydroxyl in biological carbon can react with 3-mercaptopropyltriethoxysilane, adds adsorption group, and then improves the adsorption effect of biological carbon heavy metal.
In the present invention between step 2 and step 3, also comprise the alkaline solution treatment step to biological carbon, the object of alkaline solution process is adopted to be the activity increasing biological carbon, be conducive to the reaction with 3-mercaptopropyltriethoxysilane, the one-tenth porosity of biological carbon can be increased simultaneously, improve the adsorption effect of biological carbon.
Electric tube furnace in the present invention can be substituted by microwave tube type oven, microwave is a kind of electromagnetic wave with special nature, its frequency is between radio wave and light wave, its rate of heat addition is fast, raw material can be made in short-term to reach curing reaction temperature required, therefore energy consumption is lower, sintering time is also shorter, simultaneously in microwave heating process, material is self-heating, relative to the mode of existing air conduction, the projecting environment temperature of temperature of charge, therefore heating using microwave is adopted to reduce sintering temperature, and the hot environment of material inside and outside homogeneous temperature is provided, fully can penetrate into the inside of material, microwave is adopted to carry out carbonization to cotton stalk, the biological carbon structure obtained is trickle, become porosity high, be conducive to the absorption of heavy metal.
The present invention at least comprises following beneficial effect: the cost that the sorbing material that this preparation method overcomes prior art process heavy metal wastewater thereby exists is high, processed complex, the shortcomings such as utilization rate is low, and a kind of multiporous biological carbon adsorbing material and preparation method thereof is provided, namely cheap cotton stalk is selected, pretreatment is carried out to it, high temperature cabonization process and chemical modification process, it is made to be porous honeycomb, specific area is large, absorption property is greatly improved, and cotton stalk multiporous biological carbon adsorbing material source is wide, abundant, cheap, method for making is simple, easy to operate, for the treatment of in effluent containing heavy metal ions technique, can significantly reduce effluent containing heavy metal ions processing cost, there is economic worth and environment protection significance.
Part is embodied by explanation below by other advantage of the present invention, target and feature, part also will by research and practice of the present invention by those skilled in the art is understood.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscope (SEM) photograph of biological carbon heavy-metal adsorption material prepared by the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of biological carbon heavy-metal adsorption material prepared by the embodiment of the present invention 2;
Fig. 3 is the scanning electron microscope (SEM) photograph of biological carbon heavy-metal adsorption material prepared by the embodiment of the present invention 3;
Fig. 4 is the scanning electron microscope (SEM) photograph of biological carbon heavy-metal adsorption material prepared by the embodiment of the present invention 4.
Detailed description of the invention:
Below in conjunction with accompanying drawing, the present invention is described in further detail, can implement according to this with reference to description word to make those skilled in the art.
Should be appreciated that used hereinly such as " to have ", other element one or more do not allotted in " comprising " and " comprising " term or the existence of its combination or interpolation.
Embodiment 1:
Step one, get cotton stalk ultra-pure water and clean 5 times, then cotton stalk is immersed in the ZnCl that mass fraction is 20%
2in solution, stir dipping 10h under normal temperature, then the cotton stalk flooded is dried at 50 DEG C;
Step 2, get in step one dry cotton stalk put into electric tube furnace, logical nitrogen protection, with the ramp to 600 DEG C of 10 DEG C/min, then insulation calcining 1h, grinds to form powder by the product after calcining, 0.5 weight portion powder and 30 weight portion ultra-pure waters are added in hydrothermal reaction kettle, stir 8h to complete swelling, be then heated to 150 DEG C, reaction 10h, by product centrifugal drying, obtain biological carbon material;
Step 3, by volume fraction be 6% acetum regulate the pH to 3 of ethanol water, 3-mercaptopropyltriethoxysilane is added in the ethanol water of modulated pH and shake 1h, obtain modification liquid, in described ethanol water, the volume ratio of ethanol and water is 1:1, and the addition of described 3-mercaptopropyltriethoxysilane is 1.5% of described ethanol water cumulative volume; Biological carbon material step 2 obtained adds in described modification liquid, and concussion 1h, filters, the solid obtained is dried at 45 DEG C, then wash solid 5 times with the ethanol-water solution that volume ratio is 1:1, dry 12h at 40 DEG C, namely obtains multiporous biological carbon heavy-metal adsorption material.
Embodiment 2:
Step one, get cotton stalk ultra-pure water and clean 10 times, then cotton stalk is immersed in the ZnCl that mass fraction is 50%
2in solution, stir dipping 15h under normal temperature, then the cotton stalk flooded is dried at 70 DEG C;
Step 2, get in step one dry cotton stalk put into electric tube furnace, logical nitrogen protection, with the ramp to 850 DEG C of 10 DEG C/min, then insulation calcining 3h, grinds to form powder by the product after calcining, 1 weight portion powder and 50 weight portion ultra-pure waters are added in hydrothermal reaction kettle, stir 12h to complete swelling, be then heated to 200 DEG C, reaction 15h, by product centrifugal drying, obtain biological carbon material;
Step 3, by volume fraction be 10% acetum regulate the pH to 4 of ethanol water, 3-mercaptopropyltriethoxysilane is added in the ethanol water of modulated pH and shake 3h, obtain modification liquid, in described ethanol water, the volume ratio of ethanol and water is 1:2, and the addition of described 3-mercaptopropyltriethoxysilane is 1.5% of described ethanol water cumulative volume; Biological carbon material step 2 obtained adds in described modification liquid, and concussion 3h, filters, the solid obtained is dried at 65 DEG C, then wash solid 10 times with the ethanol-water solution that volume ratio is 1:3, dry 24h at 60 DEG C, namely obtains multiporous biological carbon heavy-metal adsorption material.Fig. 2 is the scanning electron microscope (SEM) photograph of biological carbon heavy-metal adsorption material prepared by the present embodiment, can see that there is a large amount of nano-pores on the surface of biological carbon from figure, and this will be conducive to the absorption of heavy metal.
Embodiment 3:
Step one, get cotton stalk ultra-pure water and clean 8 times, then cotton stalk is immersed in the ZnCl that mass fraction is 30%
2in solution, stir dipping 12h under normal temperature, then the cotton stalk flooded is dried at 60 DEG C;
Step 2, get in step one dry cotton stalk put into electric tube furnace, logical nitrogen protection, with the ramp to 800 DEG C of 10 DEG C/min, then insulation calcining 2h, grinds to form powder by the product after calcining, 0.5 weight portion powder and 40 weight portion ultra-pure waters are added in hydrothermal reaction kettle, stir 10h to complete swelling, be then heated to 180 DEG C, reaction 12h, by product centrifugal drying, obtain biological carbon material;
Step 3, by volume fraction be 7% acetum regulate the pH to 3.5 of ethanol water, 3-mercaptopropyltriethoxysilane is added in the ethanol water of modulated pH and shake 2h, obtain modification liquid, in described ethanol water, the volume ratio of ethanol and water is 1:1, and the addition of described 3-mercaptopropyltriethoxysilane is 3% of described ethanol water cumulative volume; Biological carbon material step 2 obtained adds in described modification liquid, and concussion 2h, filters, the solid obtained is dried at 60 DEG C, then wash solid 8 times with the ethanol-water solution that volume ratio is 1:2, dry 18h at 50 DEG C, namely obtains multiporous biological carbon heavy-metal adsorption material.
Embodiment 4:
Step one, get cotton stalk ultra-pure water and clean 8 times, then cotton stalk being immersed in mass fraction is in the KOH solution of 50%, stirs dipping 10h, then dried at 50 DEG C by the cotton stalk flooded under normal temperature;
Step 2, get in step one dry cotton stalk put into electric tube furnace, logical nitrogen protection, with the ramp to 800 DEG C of 10 DEG C/min, then insulation calcining 2h, grinds to form powder by the product after calcining, 1 weight portion powder and 40 weight portion ultra-pure waters are added in hydrothermal reaction kettle, stir 10h to complete swelling, be then heated to 180 DEG C, reaction 12h, by product centrifugal drying, obtain biological carbon material;
Step 3, by volume fraction be 8% acetum regulate the pH to 4 of ethanol water, 3-mercaptopropyltriethoxysilane is added in the ethanol water of modulated pH and shake 3h, obtain modification liquid, the addition of described 3-mercaptopropyltriethoxysilane is 1.5% of described ethanol water cumulative volume; Biological carbon material step 2 obtained adds in described modification liquid, and concussion 2h, filters, the solid obtained is dried at 45 DEG C, then wash solid 5 times with the ethanol-water solution that volume ratio is 1:1, dry 24h at 40 DEG C, namely obtains multiporous biological carbon heavy-metal adsorption material.
Embodiment 5:
Step one, to get long be 3cm, and diameter is that the cotton stalk ultra-pure water of 0.5cm cleans 10 times, then cotton stalk is immersed in the ZnCl that mass fraction is 40%
2in solution, stir dipping 10h with the mixing speed of 300r/min under normal temperature, then the cotton stalk flooded is dried at 70 DEG C;
Step 2, get in step one dry cotton stalk put into microwave tube type oven, logical nitrogen protection, with the ramp to 850 DEG C of 10 DEG C/min, then insulation calcining 2h, grinds to form powder by the product after calcining, 0.5g powder and 40g ultra-pure water is added in hydrothermal reaction kettle, stir 8h to complete swelling, be then heated to 150 DEG C, reaction 10h, by product centrifugal drying, obtain biological carbon material;
Step 3, by volume fraction be 6% hydrochloric acid acid solution regulate the pH to 3 of ethanol water, 3-mercaptopropyltriethoxysilane is added in the ethanol water of modulated pH and shake 1 ~ 3h, obtain modification liquid, in described ethanol water, the volume ratio of ethanol and water is 1:2, and the addition of described 3-mercaptopropyltriethoxysilane is 2% of described ethanol water cumulative volume; Biological carbon material step 2 obtained adds in described modification liquid, with the concussion speed of 1000r/min concussion 1h, filter, the solid obtained is dried at 65 DEG C, then solid is washed 5 times with the ethanol-water solution that volume ratio is 1:1, dry 12h at 60 DEG C, namely obtains multiporous biological carbon heavy-metal adsorption material.
Embodiment 6:
Step one, to get long be 3cm, diameter is that the cotton stalk ultra-pure water of 0.5cm cleans 8 times, then cotton stalk being immersed in mass fraction is in the KOH solution of 20%, stirs dipping 15h, then dried at 60 DEG C by the cotton stalk flooded under normal temperature with the mixing speed of 400r/min;
Step 2, get in step one dry cotton stalk put into microwave tube type oven, logical nitrogen protection, with the ramp to 800 DEG C of 10 DEG C/min, then insulation calcining 3h, grinds to form powder by the product after calcining, 1g powder and 50g ultra-pure water is added in hydrothermal reaction kettle, stir 12h to complete swelling, be then heated to 180 DEG C, reaction 12h, by product centrifugal drying, obtain biological carbon material;
Step 3, the biological carbon material soaking that step 2 obtained, in volume ratio is the NaOH of 1:2 and urea liquid, stirs 12 hours, obtain the biological carbon material of alkaline solution process; The concentration of described NaOH is 3mol/L, and the concentration of described urea liquid is 3mol/L;
Step 4, by volume fraction be 7% salpeter solution regulate the pH to 3 of ethanol water, 3-aminopropyl trimethoxysilane is added in the ethanol water of modulated pH and shake 1 ~ 3h, obtain modification liquid, in described ethanol water, the volume ratio of ethanol and water is 1:2, and the addition of described 3-aminopropyl trimethoxysilane is 3% of described ethanol water cumulative volume; Biological carbon material step 3 obtained adds in described modification liquid, with the concussion speed of 800r/min concussion 1h, filter, the solid obtained is dried at 65 DEG C, then solid is washed 5 times with the ethanol-water solution that volume ratio is 1:1, dry 12h at 60 DEG C, namely obtains multiporous biological carbon heavy-metal adsorption material.
Embodiment 7:
Step one, to get long be 3cm, diameter is that the cotton stalk ultra-pure water of 0.5cm cleans 8 times, then cotton stalk being immersed in mass fraction is in the liquor zinci chloridi of 30%, stir dipping 15h with the mixing speed of 500r/min under normal temperature, then the cotton stalk flooded is dried at 60 DEG C;
Step 2, get in step one dry cotton stalk put into microwave tube type oven, logical nitrogen protection, with the ramp to 850 DEG C of 10 DEG C/min, then insulation calcining 2h, grinds to form powder by the product after calcining, 1g powder and 40g ultra-pure water is added in hydrothermal reaction kettle, stir 12h to complete swelling, be then heated to 180 DEG C, reaction 12h, by product centrifugal drying, obtain biological carbon material;
Step 3, the biological carbon material soaking that step 2 obtained, in volume ratio is the NaOH of 1:2 and urea liquid, stirs 24 hours, obtain the biological carbon material of alkaline solution process; The concentration of described NaOH is 2mol/L, and the concentration of described urea liquid is 3mol/L;
Step 4, by volume fraction be 6% hydrochloric acid solution regulate the pH to 3 of ethanol water, VTES is added in the ethanol water of modulated pH and shake 1 ~ 3h, obtain modification liquid, in described ethanol water, the volume ratio of ethanol and water is 1:2, and the addition of described VTES is 2% of described ethanol water cumulative volume; Biological carbon material step 3 obtained adds in described modification liquid, with the concussion speed of 800r/min concussion 1h, filter, the solid obtained is dried at 65 DEG C, then solid is washed 5 times with the ethanol-water solution that volume ratio is 1:1, dry 12h at 60 DEG C, namely obtains multiporous biological carbon heavy-metal adsorption material.
In order to effect of the present invention is described, inventor provides contrast experiment as follows:
Comparative example 1: contrast with embodiment 3, before cotton stalk high temperature cabonization, just do not carry out the dipping stir process of liquor zinci chloridi, namely do not have the process of the step one in embodiment 3, identical with embodiment 3 of all the other parameters, technical process is also identical.
Comparative example 2: contrast with embodiment 3, just after cotton stalk high temperature cabonization, do not carry out the reaction with 3-mercaptopropyltriethoxysilane, both do not had the process of the step 3 of embodiment 3, identical with embodiment 3 of all the other parameters, technical process is also identical.
Comparative example 3: choose the liquor zinci chloridi that mass fraction is 15% in step one, identical with embodiment 2 of all the other parameters, technical process is also identical.
Comparative example 4: choose the liquor zinci chloridi that mass fraction is 55% in step one, identical with embodiment 2 of all the other parameters, technical process is also identical.
Comparative example 5: the addition of the mercaptopropyltriethoxysilane of 3-described in step 3 is 1% of described ethanol water cumulative volume, identical with embodiment 5 of all the other parameters, technical process is also identical.
Comparative example 6: the addition of the mercaptopropyltriethoxysilane of 3-described in step 3 is 4% of described ethanol water cumulative volume, identical with embodiment 5 of all the other parameters, technical process is also identical.
Heavy metal lead ion and cadmium ion carry out Static Adsorption research to the sorbing material adopting above embodiment 1 ~ 7 and comparative example 1 ~ 6 to prepare respectively.
Get the lead ion solution mixing of biological carbon adsorbing material 5mg and the 50mL50mg/L of above-described embodiment 1 ~ 7 and comparative example 1 ~ 6 preparation respectively, regulate pH to be 5, be placed in shaking table vibration 24h, rotating speed is 130rpm, and adsorption temp is 25 DEG C;
Get the cadmium-ion solution mixing of sorbing material 5mg and the 50mL50mg/L of above-described embodiment 1 ~ 7 and comparative example 1 ~ 6 preparation respectively, regulate pH to be 4.5, be placed in shaking table vibration 24h, rotating speed is 130rpm, and adsorption temp is 25 DEG C.
Calculate adsorption rate and adsorbance, the adsorption effect of two kinds of ions is as shown in table 1;
Table 1
As known from Table 1, embodiment 1 ~ 7 is owing to have employed raw material in proportion of the present invention and technological parameter, the adsorption effect of its heavy metal lead ion and cadmium-ion solution is better, clearance is all greater than 68%, all 220mg/g is greater than to the adsorbance of lead ion, all 117mg/g is greater than to the adsorbance of cadmium ion.
And the ratio of the raw material adopted in comparative example 1 ~ 6 and technological parameter is not within proportion of the present invention, therefore the adsorption effect of heavy metal lead ion and cadmium-ion solution is poor, clearance is all less than 68%, all 216mg/g is less than to the adsorbance of lead ion, all 114mg/g is less than to the adsorbance of cadmium ion.
Comparative example 1 and comparative example 2 are compared with embodiment 3, in comparative example 1, cotton stalk does not carry out the impregnation process of liquor zinci chloridi before carbonization, when high-temperature calcination, cotton stalk can not rely on zinc chloride to form micropore, and flood afterchlorinate zinc in embodiment 3 and enter into cotton stalk to make cotton stalk at high temperature calcine and obtain a large amount of micropores, this is conducive to Adsorption of Heavy Metal Ions.Do not react with 3-mercaptopropyltriethoxysilane after straw-carbonized in comparative example 2, biological carbon does not introduce adsorption group, and therefore compared with embodiment 3, its adsorption effect is poor.
Comparative example 3 and comparative example 4 are compared with embodiment 2, in comparative example 3, the mass fraction of liquor zinci chloridi is lower than scope of the present invention, the adsorption effect of the adsorbent obtained is poor, this is because the content of zinc chloride is low, a large amount of micropores can not be formed when calcining, cause adsorption effect poor, in comparative example 4, the mass fraction of liquor zinci chloridi is higher than scope of the present invention, the adsorption effect of the adsorbent obtained is poor, this is because zinc chloride is excessive, the excessive micropore formed may be caused, adjacent micropore combines the larger micropore of diameter of composition, be unfavorable for the absorption of heavy metal like this.
Comparative example 5 and comparative example 6 are compared with embodiment 5, in comparative example 5, the consumption of 3-mercaptopropyltriethoxysilane is lower than scope of the present invention, the adsorption effect of the adsorbent obtained is poor, this is because the consumption of 3-mercaptopropyltriethoxysilane is low, cause adsorption group content that biological carbon is introduced low, so adsorption effect is poor, in comparative example 6, the consumption of 3-mercaptopropyltriethoxysilane is higher than scope of the present invention, the adsorption effect of the adsorbent obtained is poor, this is because the consumption of 3-mercaptopropyltriethoxysilane is too high, the a large amount of micropore in biological carbon surface may be caused to disappear, be unfavorable for the absorption of heavy metal like this.
After cotton stalk carbonization completes, the processing procedure of alkaline solution has been carried out in embodiment 6 and embodiment 7, the method that the adsorption effect of the adsorbent obtained adopts significantly better than other embodiments, illustrate that alkaline solution process adds the activity of biological carbon, be conducive to the reaction with 3-mercaptopropyltriethoxysilane, add the one-tenth porosity of biological carbon simultaneously, improve the adsorption effect of biological carbon.
Visible, the raw material adopted in the present invention is in described ratio, and in the preparation process of sorbing material, parameters is in described scope, and the absorption property of the sorbing material heavy metal ion of preparation is better.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (10)
1., based on a preparation method for the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, comprise the following steps:
Step one, get cotton stalk ultra-pure water cleaning 5 ~ 10 times, then cotton stalk is immersed in the ZnCl that mass fraction is 20 ~ 50%
2in solution, under normal temperature, stir dipping 10 ~ 15h, then the cotton stalk flooded is dried at 50 ~ 70 DEG C;
Step 2, get in step one dry cotton stalk put into electric tube furnace, logical nitrogen protection, with ramp to 600 ~ 850 DEG C of 10 DEG C/min, be then incubated calcining 1 ~ 3h, the product after calcining is ground to form powder, 0.5 ~ 1 weight portion powder and 30 ~ 50 weight portion ultra-pure waters are added in hydrothermal reaction kettle, stir 8 ~ 12h to complete swelling, be then heated to 150 ~ 200 DEG C, reaction 10 ~ 15h, by product centrifugal drying, obtain biological carbon material;
Step 3, by volume fraction be 6 ~ 10% acetum regulate pH to 3 ~ 4 of ethanol water, 3-mercaptopropyltriethoxysilane is added in the ethanol water of modulated pH and shakes 1 ~ 3h, obtain modification liquid; Biological carbon material step 2 obtained adds in described modification liquid, concussion 1 ~ 3h, filter, the solid obtained is dried at 45 ~ 65 DEG C, then solid is washed 5 ~ 10 times with the ethanol-water solution that volume ratio is 1:1 ~ 3, at 40 ~ 60 DEG C, dry 12 ~ 24h, namely obtains multiporous biological carbon heavy-metal adsorption material.
2., as claimed in claim 1 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, in described step one, the diameter of cotton stalk selects 0.3 ~ 0.5cm, is cut into the rod that length is 2 ~ 5cm before using.
3., as claimed in claim 1 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, the mixing speed in described step one is 300 ~ 500r/min; The speed of shaking in described step 3 is 500 ~ 1000r/min.
4., as claimed in claim 1 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, ZnCl in described step one
2solution can be substituted by KOH solution.
5., as claimed in claim 1 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, described electric tube furnace can be substituted by microwave tube type oven.
6. as claimed in claim 1 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, in described step 3, volume fraction is that hydrochloric acid, sulfuric acid and the salpeter solution that the acetum of 6 ~ 10% can be 6 ~ 8% by volume fraction substitutes.
7., as claimed in claim 1 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, in described step 3, in ethanol water, the volume ratio of ethanol and water is 1:2 ~ 3.
8., as claimed in claim 1 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, the addition of described 3-mercaptopropyltriethoxysilane is 1.5 ~ 3% of described ethanol water cumulative volume.
9. as claimed in claim 8 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, described 3-mercaptopropyltriethoxysilane can be substituted by one or more in 3-aminopropyl trimethoxysilane, vinyltrimethoxy silane, VTES.
10. as claimed in claim 1 based on the preparation method of the multiporous biological carbon heavy-metal adsorption material of cotton stalk, it is characterized in that, between described step 2 and step 3, also comprise alkaline solution treatment step: biological carbon material soaking step 2 obtained is in volume ratio is the NaOH of 1:2 and urea liquid, stir 12 ~ 24 hours, obtain the biological carbon material of alkaline solution process; The concentration of described NaOH is 1 ~ 3mol/L, and the concentration of described urea liquid is 1 ~ 3mol/L.
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