CN103349966A - Bamboo shoot shell adsorbing material for treating heavy metal ion wastewater and preparation method thereof - Google Patents
Bamboo shoot shell adsorbing material for treating heavy metal ion wastewater and preparation method thereof Download PDFInfo
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- CN103349966A CN103349966A CN2013102926611A CN201310292661A CN103349966A CN 103349966 A CN103349966 A CN 103349966A CN 2013102926611 A CN2013102926611 A CN 2013102926611A CN 201310292661 A CN201310292661 A CN 201310292661A CN 103349966 A CN103349966 A CN 103349966A
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Abstract
The invention relates to a bamboo shoot shell adsorbing material for treating heavy metal ion wastewater and a preparation method thereof. The bamboo shoot shell adsorbing material is prepared by air-drying, crushing and modifying a bamboo shoot shell serving as a raw material. The preparation method comprises the following steps: crushing the bamboo shoot shell raw material and sieving by 40 to 60 meshes to obtain bamboo shoot shell powder; weighing the bamboo shoot shell powder; mixing the bamboo shoot shell powder with sodium hydroxide and 1,4-butanediol glycerol diether; placing the mixture into a constant-temperature oscillator; reacting; filtering reactants; soaking and washing with acetone; washing with deionized water; drying to obtain an epoxy activated bamboo shoot shell; modifying the epoxy activated bamboo shoot shell by using a gallotannic acid aqueous solution and a sodium borohydride solution; washing with deionized water; drying to obtain the bamboo shoot shell adsorbing material. The adsorbing material prepared by the method has simple method, wide source of materials, low price and strong adsorbing ability on heavy metal ions, and avoids secondary pollution.
Description
Technical field
The invention belongs to exploitation and the applied technical field of environment-friendly novel material, be specifically related to a kind of Compositions of Bamboo Shoot Shell sorbing material and preparation method for the treatment of effluent containing heavy metal ions.
Background technology
The development of the industries such as modern industry such as petrochemical industry, machine-building, wool spinning, leather can produce the waste water that contains in a large number heavy metal inevitably, undressed heavy metal-containing waste water is directly discharged, not only waste resource, also can work the mischief to environmental and human health impacts.In the today of advocating environmental protection, advocating green science, the method of utilizing absorption principle that effluent containing heavy metal ions is processed is used more extensive, particularly cheap in development of new, be easy to get, the environment-friendly materials that adsorption efficiency is high have good development prospect especially, and the research and development of sorbing material will be the keys that promotes development, up to the present, many sorbing materials of having developed, but existing sorbing material also exists adsorption capacity low, selectively not strong, the defectives such as sorbing material price height.
Bamboo grove is the second forest in China, the bamboo shoot case fibre of bamboo shoot shell has porosity characteristic in the bamboo grove, the bamboo shoot shell itself has certain oil absorption, contain more tannin isoreactivity material in the bamboo shoot shell simultaneously, contain a plurality of ortho positions phenolic hydroxyl structure in the tannin, can be used as a kind of multidentate ligand and metal ion generation complex reaction, can be good at Adsorption of Heavy Metal Ions, but there is water-soluble problem in tannin, by method of modifying the tannin in the Compositions of Bamboo Shoot Shell is fixed and the further external tannin of energy, increase the content of tannin in the Compositions of Bamboo Shoot Shell, further improve the ability that it processes heavy metal wastewater thereby, therefore tannin is fixed in some Compositions of Bamboo Shoot Shell carriers, brings into play simultaneously bamboo shoot shell and the effect of tannin counterweight metal biosorption.This technical method is simple, and the Compositions of Bamboo Shoot Shell sorbing material adsorption rate that obtains is high, to the environment non-secondary pollution, can also bring limitless economic benefit.
Summary of the invention
For problems of the prior art, the object of the invention is providing a kind of Compositions of Bamboo Shoot Shell sorbing material and preparation method for the treatment of effluent containing heavy metal ions.
The present invention is realized by the following technical programs:
Described Compositions of Bamboo Shoot Shell sorbing material for the treatment of effluent containing heavy metal ions, it is characterized in that this sorbing material be Compositions of Bamboo Shoot Shell through air-dry pulverizing, and the Compositions of Bamboo Shoot Shell powder of crossing through NaOH, BDO two glycerin ethers and tannic acid aqueous solution modification.
The preparation method of described Compositions of Bamboo Shoot Shell sorbing material for the treatment of effluent containing heavy metal ions is characterized in that may further comprise the steps:
1) preliminary treatment: the Compositions of Bamboo Shoot Shell pulverizer after air-dry is pulverized, cross the 40-60 mesh sieve, get the Compositions of Bamboo Shoot Shell powder, this preliminary treatment is direct air-dry the operation also, need not pulverize, after steps of processing, can carry out adsorption treatment without the Compositions of Bamboo Shoot Shell of pulverization process to heavy metal ion, also can be used for the processing of sewage;
2) the Compositions of Bamboo Shoot Shell powder that step 1) is made carries out modification, and its modification may further comprise the steps:
A) take by weighing Compositions of Bamboo Shoot Shell powder that step 1) makes in volumetric flask, add successively 1 of the sodium hydroxide solution of solid-to-liquid ratio (g/ml) 1:25 and solid-to-liquid ratio (g/ml) 1:0.8-1.2,4-butanediol two glycerin ethers, then insert that isothermal reaction gets reactant in the oscillator, reactant is used the acetone washing by soaking after filtering with sand core funnel, with the deionized water washing, get epoxy activation Compositions of Bamboo Shoot Shell after the drying again;
B) take by weighing epoxy activation Compositions of Bamboo Shoot Shell that step a) makes in reactor; add successively the 2%-4% tannic acid aqueous solution of solid-to-liquid ratio (g/ml) 1:25 and the sodium borohydride solution of solid-to-liquid ratio (g/ml) 1:1-2; then insert in the oscillator; pass into nitrogen; under nitrogen protection, filter after the constant temperature oscillation reaction; filter residue washs with 0.01mol/LHCl, with the deionized water washing, namely gets the Compositions of Bamboo Shoot Shell sorbing material after the drying again.Reactor in this step is the reactor with two openings, and one of them opening is used for adding raw material, and another opening passes into nitrogen, and the reaction of flask interior is carried out under nitrogen.
The preparation method of described Compositions of Bamboo Shoot Shell sorbing material for the treatment of effluent containing heavy metal ions, the concentration that it is characterized in that NaOH in the step a) is 0.7mol/L.
The preparation method of described Compositions of Bamboo Shoot Shell sorbing material for the treatment of effluent containing heavy metal ions is characterized in that oscillator isothermal is set as 20 ℃ in the step a), and the reaction time is 6-10 hour.
The preparation method of described Compositions of Bamboo Shoot Shell sorbing material for the treatment of effluent containing heavy metal ions is characterized in that oscillator isothermal is set as 40 ℃ in the step b), and the reaction time is 10-14 hour.
The present invention is for the treatment of Compositions of Bamboo Shoot Shell sorbing material and the preparation method of effluent containing heavy metal ions, abundant raw material, cheap, adsorption effect is good, the preparation method is simple, easy to operate.By with Compositions of Bamboo Shoot Shell as sorbing material, but effective exploitation utilizes the discarded object in the bamboo grove, and raw material sources are extensively sent out, technique is simple, easily degraded, adsorption efficiency are high, adsorption rate to some heavy metal ion reaches more than 95%, environmentally safe, the theory that is fit to sustainable development also can be bamboo farming and society and brings huge economic benefit.
The specific embodiment
Embodiment 1
Compositions of Bamboo Shoot Shell pulverizer after air-dry was pulverized 40 mesh sieves and was got the Compositions of Bamboo Shoot Shell powder, accurately take by weighing 2g Compositions of Bamboo Shoot Shell powder in the 100ml volumetric flask, add 1 of NaOH 50ml that concentration is 0.7mol/L and 2ml in the volumetric flask, 4-butanediol two glycerin ethers, inserted design temperature after the mixing and be in the constant temperature oscillator under 20 ℃ reaction 8 hours, get reactant, reactant is filtered with sand core funnel, filter residue acetone soln washing by soaking, with a large amount of deionized water washings, obtain epoxy activation Compositions of Bamboo Shoot Shell after the drying again.
Accurately take by weighing epoxy activation Compositions of Bamboo Shoot Shell 2g; 3% the tannic acid aqueous solution that adds 50ml; insert in the oscillator after dripping sodium borohydride solution 3ml; pass into nitrogen; oscillating reactions was filtered after 12 hours under 40 ℃ of conditions of constant temperature under nitrogen protection; filter residue washs with 0.01mol/LHCl, with a large amount of deionized water washings, namely gets the Compositions of Bamboo Shoot Shell sorbing material after the drying again.
Application test one: the Compositions of Bamboo Shoot Shell sorbing material is to ferric absorption
Static Adsorption: accurately taking by weighing Compositions of Bamboo Shoot Shell sorbing material that 0.5g obtains by embodiment 1, to put into 50ml concentration be the 100mg/L ferric chloride solution, with 0.1mol/L sodium hydroxide solution and 0.1mol/L hydrochloric acid solution the pH value of ferric chloride solution is transferred to 4.0, till vibration is adsorbed onto balance in 25 ℃ of constant temperature oscillators, after upon adsorption the finishing, filtration obtains filtrate, with heavy metal concentration in the NITRATE BY FLAME ATOMIC spectrophotometer measurement solution, calculate adsorption rate and adsorbance according to following formula:
W%=100%×(C
0-C
e)/C
0 Q=(C
0-C
e)V/M
C
0For adsorbing the initial concentration mg/L of front metal ion; C
eFor adsorbing the mass concentration mg/L of rear metal ion, V is that M is sorbing material quality g for the simulated wastewater volume mL of reaction.
The optimal adsorption condition pH of Compositions of Bamboo Shoot Shell sorbing material (III) is 4.0, and adsorption time is 120min, and adsorption rate reaches more than 95%, and adsorbance is more than 9mg/g; Can well describe the Compositions of Bamboo Shoot Shell sorbing material to the adsorption dynamics adsorption kinetics of iron (III) with intending the secondary rate equation, the equilibrium adsorption capacity that calculates and measured value differ less, and error is less than 0.5%.And adsorption process can well be carried out match with the Freundlich equation, shows that the absorption of Compositions of Bamboo Shoot Shell sorbing material processing heavy metal iron (III) belongs to mono layer adsorption, and comparatively easy.
Embodiment 2
Compositions of Bamboo Shoot Shell pulverizer after air-dry was pulverized 50 mesh sieves and was got the Compositions of Bamboo Shoot Shell powder, accurately take by weighing 2g Compositions of Bamboo Shoot Shell powder in the 100ml volumetric flask, add 1 of NaOH 50ml that concentration is 0.7mol/L and 1.6ml in the volumetric flask, 4-butanediol two glycerin ethers, inserted design temperature after the mixing and be in the constant temperature oscillator under 20 ℃ reaction 6 hours, get reactant, reactant is filtered with sand core funnel, filter residue acetone soln washing by soaking, with a large amount of deionized water washings, obtain epoxy activation Compositions of Bamboo Shoot Shell after the drying again.
Accurately take by weighing epoxy activation Compositions of Bamboo Shoot Shell 2g; 2% the tannic acid aqueous solution that adds 50ml; insert in the oscillator after dripping sodium borohydride solution 2ml; pass into nitrogen; oscillating reactions was filtered after 14 hours under 40 ℃ of conditions of constant temperature under nitrogen protection; filter residue washs with 0.01mol/LHCl, with a large amount of deionized water washings, namely gets the Compositions of Bamboo Shoot Shell sorbing material after the drying again.
Application test two: the Compositions of Bamboo Shoot Shell sorbing material is to the absorption of manganese (II)
Static Adsorption: accurately taking by weighing Compositions of Bamboo Shoot Shell sorbing material that 0.5g obtains by embodiment 2, to put into 50ml concentration be the 100mg/L manganese sulfate solution, with 0.1mol/LNaOH solution and 0.1mol/LHCL solution the pH value of manganese sulfate solution transferred to 7.0.Till vibration is adsorbed onto balance in 25 ℃ of constant temperature oscillators, after upon adsorption the finishing, filters and obtain filtrate, with heavy metal concentration in the NITRATE BY FLAME ATOMIC spectrophotometer measurement solution, calculate adsorption rate and adsorbance according to following formula:
W%=100%×（C
0-C
e）/ C
0 Q=（C
0-C
e）V/M
C
0For adsorbing the initial concentration mg/L of front metal ion; C
eFor adsorbing the mass concentration mg/L of rear metal ion, V is that M is sorbing material quality g for the simulated wastewater volume mL of reaction.
The Compositions of Bamboo Shoot Shell sorbing material is 7.0 to the optimal adsorption condition pH of manganese (II), and adsorption time is 120min, and adsorption rate reaches more than 93%, and adsorbance is more than 9mg/g; Can well describe the Compositions of Bamboo Shoot Shell sorbing material to the adsorption dynamics adsorption kinetics of manganese (II) with intending the secondary rate equation, the equilibrium adsorption capacity that calculates and measured value differ less, and error is less than 0.3%.And adsorption process can well be carried out match with the Freundlich equation, shows that the absorption of Compositions of Bamboo Shoot Shell sorbing material processing heavy metal manganese (II) belongs to mono layer adsorption, and comparatively easy.
Embodiment 3
Compositions of Bamboo Shoot Shell pulverizer after air-dry was pulverized 60 mesh sieves and was got the Compositions of Bamboo Shoot Shell powder, accurately take by weighing 2g Compositions of Bamboo Shoot Shell powder in the 100ml volumetric flask, add 1 of NaOH 50ml that concentration is 0.7mol/L and 2.4ml in the volumetric flask, 4-butanediol two glycerin ethers, inserted design temperature after the mixing and be in the constant temperature oscillator under 20 ℃ reaction 10 hours, get reactant, reactant is filtered with sand core funnel, filter residue acetone soln washing by soaking, with a large amount of deionized water washings, obtain epoxy activation Compositions of Bamboo Shoot Shell after the drying again.
Accurately take by weighing epoxy activation Compositions of Bamboo Shoot Shell 2g; 4% the tannic acid aqueous solution that adds 50ml; insert in the oscillator after dripping sodium borohydride solution 4ml; pass into nitrogen; oscillating reactions was filtered after 10 hours under 40 ℃ of conditions of constant temperature under nitrogen protection; filter residue washs with 0.01mol/LHCl, with a large amount of deionized water washings, namely gets the Compositions of Bamboo Shoot Shell sorbing material after the drying again.
Application test 3: the absorption of Compositions of Bamboo Shoot Shell sorbing material low plumbous (II)
Static Adsorption: accurately taking by weighing Compositions of Bamboo Shoot Shell sorbing material that 0.5g makes by embodiment 3, to put into 50mL concentration be that the 100mg/L lead nitrate solution is red, with 0.lmol/LNa0H solution and 0.lmol/LHCL solution the pH value of lead nitrate solution transferred to 6.0.Till vibration is adsorbed onto balance in 25 ℃ of constant temperature oscillators, after upon adsorption the finishing, filters and obtain filtrate, with heavy metal concentration in the NITRATE BY FLAME ATOMIC spectrophotometer measurement solution, calculate adsorption rate and adsorbance according to following formula:
W%=100%×(C
0-C
e)/C
0 Q=(C
0-C
e)V/M
C
0For adsorbing the initial concentration mg/L of front metal ion; C
eFor adsorbing the mass concentration mg/L of rear metal ion, V is that M is sorbing material quality g for the simulated wastewater volume mL of reaction.
The Compositions of Bamboo Shoot Shell sorbing material is 6.0 to the optimal adsorption condition pH of plumbous (II), and adsorption time is 120min, and adsorption rate reaches more than 82%, and adsorbance is more than 8mg/g; Can well describe the Compositions of Bamboo Shoot Shell sorbing material to the adsorption dynamics adsorption kinetics of plumbous (II) with intending the secondary rate equation, the equilibrium adsorption capacity that calculates and measured value differ less, and error is less than 0.3%.And adsorption process can well be carried out match with the Freundlich equation, shows that the absorption of Compositions of Bamboo Shoot Shell sorbing material processing heavy metal lead (II) belongs to mono layer adsorption, and comparatively easy.
Claims (5)
1. for the treatment of the Compositions of Bamboo Shoot Shell sorbing material of effluent containing heavy metal ions, it is characterized in that this sorbing material be Compositions of Bamboo Shoot Shell through air-dry pulverizing, and the Compositions of Bamboo Shoot Shell powder of crossing through NaOH, BDO two glycerin ethers and tannic acid aqueous solution modification.
2. for the treatment of the preparation method of the Compositions of Bamboo Shoot Shell sorbing material of effluent containing heavy metal ions, it is characterized in that may further comprise the steps:
1) preliminary treatment: the Compositions of Bamboo Shoot Shell pulverizer after air-dry is pulverized, crossed the 40-60 mesh sieve, get the Compositions of Bamboo Shoot Shell powder;
2) the Compositions of Bamboo Shoot Shell powder that step 1) is made carries out modification, and its modification may further comprise the steps:
A) take by weighing Compositions of Bamboo Shoot Shell powder that step 1) makes in volumetric flask, add successively 1 of the sodium hydroxide solution of solid-to-liquid ratio (g/ml) 1:25 and solid-to-liquid ratio (g/ml) 1:0.8-1.2,4-butanediol two glycerin ethers, then insert that isothermal reaction gets reactant in the oscillator, reactant is used the acetone washing by soaking after filtering with sand core funnel, with the deionized water washing, get epoxy activation Compositions of Bamboo Shoot Shell after the drying again;
B) take by weighing epoxy activation Compositions of Bamboo Shoot Shell that step a) makes in reactor; add successively the 2%-4% tannic acid aqueous solution of solid-to-liquid ratio (g/ml) 1:25 and the sodium borohydride solution of solid-to-liquid ratio (g/ml) 1:1-2; then insert in the oscillator; pass into nitrogen; under nitrogen protection, filter after the constant temperature oscillation reaction; filter residue washs with 0.01mol/LHCl, with the deionized water washing, namely gets the Compositions of Bamboo Shoot Shell sorbing material after the drying again.
3. the preparation method of the Compositions of Bamboo Shoot Shell sorbing material for the treatment of effluent containing heavy metal ions according to claim 2, the concentration that it is characterized in that NaOH in the step a) is 0.7mol/L.
4. the preparation method of the Compositions of Bamboo Shoot Shell sorbing material for the treatment of effluent containing heavy metal ions according to claim 2 is characterized in that oscillator isothermal is set as 20 ℃ in the step a), and the reaction time is 6-10 hour.
5. the preparation method of the Compositions of Bamboo Shoot Shell sorbing material for the treatment of effluent containing heavy metal ions according to claim 2 is characterized in that oscillator isothermal is set as 40 ℃ in the step b), and the reaction time is 10-14 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336345A (en) * | 2018-11-29 | 2019-02-15 | 福州宇澄环保工程设计有限公司 | A kind of black and odorous water bed mud biological modification agent |
Citations (3)
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|---|---|---|---|---|
| CN1382787A (en) * | 2001-04-25 | 2002-12-04 | 马连清 | Composition containing dannin and its appication |
| US20040248975A1 (en) * | 2001-10-24 | 2004-12-09 | Willy Van Brussel | Complexating systems, intermediates for their production and method for obtaining and using the same |
| CN1657157A (en) * | 2004-12-08 | 2005-08-24 | 华东理工大学 | Super large pore ball shaped cellulose fixed tannin adsorbent and its preparation method and application |
-
2013
- 2013-07-12 CN CN201310292661.1A patent/CN103349966B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382787A (en) * | 2001-04-25 | 2002-12-04 | 马连清 | Composition containing dannin and its appication |
| US20040248975A1 (en) * | 2001-10-24 | 2004-12-09 | Willy Van Brussel | Complexating systems, intermediates for their production and method for obtaining and using the same |
| CN1657157A (en) * | 2004-12-08 | 2005-08-24 | 华东理工大学 | Super large pore ball shaped cellulose fixed tannin adsorbent and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 蒋新龙等: ""改性竹笋壳生物吸附剂的制备及其对Cr（VI）的吸附工艺研究"", 《浙江树人大学学报》, vol. 12, no. 1, 31 March 2012 (2012-03-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336345A (en) * | 2018-11-29 | 2019-02-15 | 福州宇澄环保工程设计有限公司 | A kind of black and odorous water bed mud biological modification agent |
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