CN104475023A - Preparation method of modified amorphophallus konjac gulcomannan carbon microsphere heavy-metal absorption material - Google Patents
Preparation method of modified amorphophallus konjac gulcomannan carbon microsphere heavy-metal absorption material Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention discloses a preparation method of a modified amorphophallus konjac gulcomannan carbon microsphere heavy-metal absorption material. The preparation method comprises the following steps: (1) adding 0.5-1 part by weight of amorphophallus konjac gulcomannan to 30-50 parts by weight of ultrapure water, stirring to obtain a turbid solution, reacting the turbid solution at 160-200 DEG C for 8-16 hours to obtain a reaction liquid, centrifugalizing the reaction liquid at 10000r/m for 20 minutes, cleaning an obtained solid for 3-5 times by using ethanol, and drying to obtain a carbon microsphere; (2) regulating the pH of an alcohol-water solution to 4.5 by using an acid solution with the volume fraction of 1%-5%, adding a silane coupling agent solution with the volume fraction of 1%-3% to the alcohol-water solution, and oscillating for 2 hours to obtain a modified solution; and (3) adding 3-15 parts by weight of carbon microspheres to 100 parts by weight of modified solutions, oscillating for 3-5 hours, filtering, drying a filter cake at 65 DEG C, washing the dried filter cake for 3-5 times by using the ethanol and water, and carrying out vacuum drying to prepare the modified amorphophallus konjac gulcomannan carbon microsphere absorption material. The preparation method disclosed by the invention can be used for overcoming the defects of high process difficulty, severe preparation condition and the like of a traditional heavy-metal waste water adsorption material and preparing the modified amorphophallus konjac gulcomannan carbon microsphere heavy-metal absorption material by adopting a simple and easily-operated process.
Description
Technical field
The invention belongs to Phytochemistry and adsorption science field, be specifically related to the preparation method of konjaku glucomannan carbosphere heavy-metal adsorption material.
Background technology
Heavy metal ion mainly come from mine smelting, machining, plating and, the industries such as petrochemical industry, the waste water that these industries produce mostly directly is discharged into lake, river, ocean, this not only pollutes water environment, water quality is worsened rapidly, and along with industrial expansion, its quantity of wastewater effluent raise year by year, water pollutions especially in water heavy metal pollution seriously become undisputable fact, serious harm different kind organism comprises the existence of the mankind.In recent years, heavy metal pollution threat that is healthy to human body and living environment caused various countries scientist extensive concern, make heavy metal containing wastewater treatment technology obtain develop rapidly.The method of process heavy metal wastewater thereby is various, substantially can be summarized as: chemical method, Physical, bioanalysis.But chemistry and physical method are due to reasons such as treatment effect is undesirable, somewhat expensives, limit they self application prospect.Relative to many drawbacks of first two, bioanalysis has good treatment effect, low cost, waste material easily to process etc. with it to the heavy metal wastewater thereby of low concentration and has advantage, become the focus of water treatment research field now.In the recent period, lot of domestic and international researcher carries out certain modification to agriculture and forestry by-product or agricultural wastes, develops the adsorbent of some different qualities functions.The modified adsorbents of making such as such as wood chip, persimmon slag, mushroom root, tea grounds, but eventually because its processing process is complicated, and well do not promoted.
Konjaku is a kind of perennial grass wood plant, is mainly distributed in the ground such as Southeast Asia, Africa; The states such as China, Japan, Burma, Vietnam, Indonesia, its Chinese Amorphophallus producing region is mainly distributed in cloud, expensive, river, Southern Shaanxi and West of Hubei Province, the abundantest with the Amorphophallus Resources in mountain area around the Sichuan Basin.Its plant height about 40 ~ 70 centimeters, petiole is slightly long, and like stem, cylindrical, light green, has dark violet color spot, palmately compound leaf, opens aubergine flower.There is bulb underground, in oblate, diameter reaches more than 25cm, nutritious, it contains SKGM and reaches more than 45%, SKGM and konjaku glucomannan, also known as KGM, it is a kind of natural macromolecule soluble dietary fiber, have water-soluble, thickening, suspension, gel, film forming, bonding, the multiple physicochemical property such as stable, because its viscosity is high, water suction is many, expand the physicochemical property such as fast, and the processing technology of konjaku is restricted, in existing konjak food, the purity of konjaku glucomannan is generally on the low side, and it is very few that people take in Glucomannan.Konjaku glucomannan contains carbon, hydrogen, oxygen element, and its surface is containing multiple functional group, and as alcoholic extract hydroxyl group, carboxyl anion and be easy to be modified, can make adsorbent, and itself also have the performance of Adsorption of Heavy Metal Ions, adsorption effect is better.
In patent document CN102161711 A, carry out chemical modification to konjaku glucomannan prepared heavy-metal adsorption material, but the preparation method of this sorbing material is complicated, technology difficulty is large, and manufacturing conditions is harsh, realization of industrialization difficulty.A kind of preparation method of sorbing material of cross-linked carboxymethyl modification is then described at Master's thesis " modification of konjaku glucomannan cross-linked carboxymethyl and to metal biosorption and desorption performance research ", and have studied its heavy metal absorption property, scheme complexity prepared by this sorbing material, condition is difficult to control, and gained Modification of Amorphophallus Glucomannan product substitution value is not very high.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that, carry out carbonization and modification to konjaku glucomannan, carbonization treatment can make Amorphophallus rivieri glucomannan sugar become micro-nano ball, and modification makes the absorption property of konjaku glucomannan be greatly improved.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.
Another object of the present invention is to provide a kind of preparation method of modified konjac glucomannan carbosphere heavy-metal adsorption material, Amorphophallus rivieri glucomannan sugar can be made to become micro-nano ball by carbonization treatment, by the modification of silane coupler, the absorption property of konjaku glucomannan is greatly improved.
In order to realize, according to these objects of the present invention and other advantage, providing a kind of preparation method of modified konjac glucomannan carbosphere heavy-metal adsorption material, comprise the following steps:
Step one, 0.5 ~ 1 weight portion konjaku glucomannan is added in 30 ~ 50 weight portion ultra-pure waters, stirring obtains the turbid liquid of gluing shape, at 160 ~ 200 DEG C, turbid for gluing shape liquid is heated 8 ~ 16h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 3 ~ 5 times, then vacuum drying 12 ~ 24h at 50 ~ 80 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 1 ~ 5% acid solution regulate the pH to 4.5 of alcohol solution, be that the silane coupler solution of 1 ~ 3% adds in alcohol solution and shakes 2h by volume fraction, obtain modification liquid; In described alcohol solution, the volume ratio of alcohol and water is 1:1, and the volume ratio of described alcohol solution and silane coupler solution is 1:0.3 ~ 0.5;
Step 3, the konjaku glucomannan carbosphere getting 3 ~ 15 weight portion steps one preparations add in modification liquid prepared by 100 weight portion step 2, concussion 3 ~ 5h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 3 ~ 5 times by the filter cake volume ratio after drying, vacuum drying 12 ~ 24h at 50 ~ 80 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Preferably, the acid in described step 2 in acid solution is the one in acetic acid, hydrochloric acid, sulfuric acid, nitric acid.
Preferably, the alcohol in described step 2 in alcohol solution is the one in methyl alcohol or ethanol.
Preferably, silane coupler described in described step 2 is the one in 3-mercaptopropyltriethoxysilane, 3-aminopropyl trimethoxysilane, vinyltrimethoxy silane, VTES.
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, technology difficulty is large, the shortcomings such as manufacturing conditions is harsh, adopt simple, easy-operating technique has prepared heavy-metal adsorption material, the present invention selects abundance, cheap konjaku glucomannan, carbonization and modification are carried out to it, carbonization treatment can make konjaku glucomannan form micro-carbon ball, the modification of silane coupler makes the absorption property of the konjaku glucomannan of carbonization be greatly improved, 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 modified konjac glucomannan carbosphere prepared by the embodiment of the present invention 1.
Detailed description of the invention:
Below in conjunction with embodiment and 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, 0.7g konjaku glucomannan is added in 40g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 180 DEG C, turbid for gluing shape liquid is heated 12h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 3 times, then vacuum drying 24h at 60 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 5% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 30mL of 1.5% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 5g step one add in modification liquid prepared by 100g step 2, concussion 3h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 3 times by the filter cake volume ratio after drying, vacuum drying 24h at 50 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Figure 1 shows that the surface sweeping Electronic Speculum figure of modified konjac glucomannan carbosphere prepared by the present embodiment.
Embodiment 2:
Step one, 0.5g konjaku glucomannan is added in 30g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 160 DEG C, turbid for gluing shape liquid is heated 8h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 3 times, then vacuum drying 24h at 50 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 1% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 30mL of 1% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 3g step one add in modification liquid prepared by 100g step 2, concussion 3h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 3 times by the filter cake volume ratio after drying, vacuum drying 24h at 50 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Embodiment 3:
Step one, 1g konjaku glucomannan is added in 50g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 200 DEG C, turbid for gluing shape liquid is heated 16h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 5 times, then vacuum drying 12h at 80 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 5% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 50mL of 3% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 15g step one add in modification liquid prepared by 100g step 2, concussion 5h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 5 times by the filter cake volume ratio after drying, vacuum drying 12h at 80 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Embodiment 4:
Step one, 0.8g konjaku glucomannan is added in 40g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 180 DEG C, turbid for gluing shape liquid is heated 12h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 4 times, then vacuum drying 20h at 70 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 3% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 40mL of 2% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 10g step one add in modification liquid prepared by 100g step 2, concussion 4h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 4 times by the filter cake volume ratio after drying, vacuum drying 18h at 60 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
In order to effect of the present invention is described, inventor provides comparative experiments as follows:
Comparative example 1:
Step one, 0.2g konjaku glucomannan is added in 30g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 160 DEG C, turbid for gluing shape liquid is heated 8h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 3 times, then vacuum drying 24h at 50 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 1% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 30mL of 1% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 3g step one add in modification liquid prepared by 100g step 2, concussion 3h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 3 times by the filter cake volume ratio after drying, vacuum drying 24h at 50 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Comparative example 2:
Step one, 2g konjaku glucomannan is added in 30g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 160 DEG C, turbid for gluing shape liquid is heated 8h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 3 times, then vacuum drying 24h at 50 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 1% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 30mL of 1% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 3g step one add in modification liquid prepared by 100g step 2, concussion 3h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 3 times by the filter cake volume ratio after drying, vacuum drying 24h at 50 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Comparative example 3:
Step one, 0.5g konjaku glucomannan is added in 30g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 100 DEG C, turbid for gluing shape liquid is heated 8h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 3 times, then vacuum drying 24h at 50 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 1% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 30mL of 1% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 3g step one add in modification liquid prepared by 100g step 2, concussion 3h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 3 times by the filter cake volume ratio after drying, vacuum drying 24h at 50 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Comparative example 4:
Step one, 1g konjaku glucomannan is added in 50g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 200 DEG C, turbid for gluing shape liquid is heated 16h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 5 times, then vacuum drying 12h at 80 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 5% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 50mL of 3% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 1g step one add in modification liquid prepared by 100g step 2, concussion 5h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 5 times by the filter cake volume ratio after drying, vacuum drying 12h at 80 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Comparative example 5:
Step one, 1g konjaku glucomannan is added in 50g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 200 DEG C, turbid for gluing shape liquid is heated 16h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 5 times, then vacuum drying 12h at 80 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 5% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 50mL of 3% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 20g step one add in modification liquid prepared by 100g step 2, concussion 5h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 5 times by the filter cake volume ratio after drying, vacuum drying 12h at 80 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Comparative example 6:
Step one, 0.8g konjaku glucomannan is added in 40g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 180 DEG C, turbid for gluing shape liquid is heated 12h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 4 times, then vacuum drying 20h at 70 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 3% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 40mL of 0.5% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 10g step one add in modification liquid prepared by 100g step 2, concussion 4h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 4 times by the filter cake volume ratio after drying, vacuum drying 18h at 60 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Comparative example 7:
Step one, 0.8g konjaku glucomannan is added in 40g ultra-pure water, stirring obtains the turbid liquid of gluing shape, at 180 DEG C, turbid for gluing shape liquid is heated 12h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 4 times, then vacuum drying 20h at 70 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 3% acetum regulate the pH to 4.5 of 100mL ethanol water, be that the 3-mercaptopropyltriethoxysilane solution 40mL of 5% adds in ethanol water and shakes 2h by volume fraction, obtain modification liquid; In described ethanol water, the volume ratio of alcohol and water is 1:1;
Step 3, the konjaku glucomannan carbosphere getting the preparation of 10g step one add in modification liquid prepared by 100g step 2, concussion 4h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 4 times by the filter cake volume ratio after drying, vacuum drying 18h at 60 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
Heavy metal lead ion and cadmium ion carry out Static Adsorption research to the sorbing material adopting above embodiment 1 ~ 4 and comparative example 1 ~ 7 to prepare respectively.
Get the lead ion solution mixing of sorbing material 20mg and the 100mL50mg/L of above-described embodiment 1 ~ 4 and comparative example 1 ~ 7 preparation respectively, regulate pH to be 4, be placed in shaking table vibration 2h, rotating speed is 130rpm, and adsorption temp is 25 DEG C;
Get the cadmium-ion solution mixing of sorbing material 20mg and the 100mL40mg/L of above-described embodiment 1 ~ 4 and comparative example 1 ~ 7 preparation respectively, regulate pH to be 4, be placed in shaking table vibration 2h, rotating speed is 130rpm, and adsorption temp is 25 DEG C;
As shown in table 1 to the adsorption effect of two kinds of ions, the clearance of heavy metal ion is calculated by following formula (1),
Clearance=(C
o-C
m)/C
o× 100% (1)
Wherein, C
ofor adsorbing the concentration of front heavy metal ion, C
mfor adsorbing the concentration of rear heavy metal ion.
The adsorbance of sorbing material is calculated by following formula (2),
Adsorbance=(C
o-C
e) V/m (2)
Wherein, C
ofor adsorbing the concentration of front heavy metal ion, C
efor the concentration of heavy metal ion after adsorption equilibrium, V is the volume adding heavy metal solution, and m is the quality of the sorbing material added.
Table 1
As known from Table 1, embodiment 1 ~ 4 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 94%, all 100mg/g is greater than to the adsorbance of lead ion, all 50mg/g is greater than to the adsorbance of cadmium ion.
And the ratio of the raw material adopted in comparative example 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 90%, all 80mg/g is less than to the adsorbance of lead ion, all 40mg/g is less than to the adsorbance of cadmium ion.
Comparative example 1 and comparative example 2 are compared with embodiment 2, the amount of the difference konjaku glucomannan that to be comparative example 1 add in step one is 0.2g, comparative example 2 is 2g in the amount of the konjaku glucomannan that step one is added, both are not all within proportion of the present invention, this is by uneven for the micro-sphere structure caused after konjaku glucomannan carbonization, and the clearance of the sorbing material heavy metal ion obtained and adsorbance are all lower than the sorbing material prepared by embodiment 2.
Comparative example 3 is compared with embodiment 2, difference is the reaction temperature of comparative example 3 in step one is 100 DEG C, this reaction temperature is not in reaction temperature of the present invention 160 ~ 200 DEG C, temperature is lower, the carbonization of konjaku glucomannan is complete not, the particle diameter of the microballoon obtained is comparatively large, and therefore the clearance of sorbing material heavy metal ion and adsorbance are all lower than the sorbing material prepared by embodiment 2.
Comparative example 4 and comparative example 5 are compared with embodiment 3, the amount of the difference konjaku glucomannan carbosphere that to be comparative example 4 add in step 3 is 1g, comparative example 5 is 20g in the amount of the konjaku glucomannan carbosphere that step one is added, both are not all within proportion of the present invention, when the amount of konjaku glucomannan carbosphere is lower than described scope, by cause konjaku glucomannan carbosphere cover by a large amount of 3-mercaptopropyltriethoxysilanes, this is unfavorable for Adsorption of Heavy Metal Ions, when the amount of konjaku glucomannan carbosphere is higher than described scope, by causing, the modification of konjaku glucomannan carbosphere is incomplete, effectively can not play the effect of 3-mercaptopropyltriethoxysilane, the clearance of the sorbing material heavy metal ion therefore obtained and adsorbance are all lower than the sorbing material prepared by embodiment 3.
Comparative example 6 and comparative example 7 are compared with embodiment 4, difference is the volume fraction of the 3-mercaptopropyltriethoxysilane that comparative example 6 adds in the preparation of step 2 modification liquid is 0.5%, the volume fraction of the 3-mercaptopropyltriethoxysilane that comparative example 7 adds in the preparation of step 2 modification liquid is 5%, both are not all within proportion 1 ~ 3% of the present invention, when the volume fraction of 3-mercaptopropyltriethoxysilane is lower than described scope, will be not exclusively to the modification of konjaku glucomannan carbosphere in step 3, effectively can not play the effect of 3-mercaptopropyltriethoxysilane, when the volume fraction of 3-mercaptopropyltriethoxysilane is higher than described scope, in step 3 konjaku glucomannan carbosphere by cover by a large amount of 3-mercaptopropyltriethoxysilanes, the clearance of the sorbing material heavy metal ion therefore obtained and adsorbance are all lower than the sorbing material prepared by embodiment 4.
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 (4)
1. a preparation method for modified konjac glucomannan carbosphere heavy-metal adsorption material, is characterized in that, comprises the following steps:
Step one, 0.5 ~ 1 weight portion konjaku glucomannan is added in 30 ~ 50 weight portion ultra-pure waters, stirring obtains the turbid liquid of gluing shape, at 160 ~ 200 DEG C, turbid for gluing shape liquid is heated 8 ~ 16h in hydrothermal reaction kettle, then by reactant liquor centrifugal 20min under the rotating speed of 10000r/min, the centrifugal solid ethanol purge obtained 3 ~ 5 times, then vacuum drying 12 ~ 24h at 50 ~ 80 DEG C, obtains konjaku glucomannan carbosphere;
Step 2, by volume fraction be 1 ~ 5% acid solution regulate the pH to 4.5 of alcohol solution, be that the silane coupler solution of 1 ~ 3% adds in alcohol solution and shakes 2h by volume fraction, obtain modification liquid; In described alcohol solution, the volume ratio of alcohol and water is 1:1, and the volume ratio of described alcohol solution and silane coupler solution is 1:0.3 ~ 0.5;
Step 3, the konjaku glucomannan carbosphere getting 3 ~ 15 weight portion steps one preparations add in modification liquid prepared by 100 weight portion step 2, concussion 3 ~ 5h, filter, filter cake is dried at 65 DEG C, be the ethanol of 1:1 and water washing 3 ~ 5 times by the filter cake volume ratio after drying, vacuum drying 12 ~ 24h at 50 ~ 80 DEG C, obtained modified konjac glucomannan carbosphere sorbing material.
2. the preparation method of the modified konjac glucomannan carbosphere heavy-metal adsorption material as requested described in 1, is characterized in that, the acid in described step 2 in acid solution is the one in acetic acid, hydrochloric acid, sulfuric acid, nitric acid.
3. the preparation method of the modified konjac glucomannan carbosphere heavy-metal adsorption material as requested described in 1, is characterized in that, the alcohol in described step 2 in alcohol solution is the one in methyl alcohol or ethanol.
4. the preparation method of the modified konjac glucomannan carbosphere heavy-metal adsorption material as requested described in 1, it is characterized in that, silane coupler described in described step 2 is the one in 3-mercaptopropyltriethoxysilane, 3-aminopropyl trimethoxysilane, vinyltrimethoxy silane, VTES.
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