CN103203217A - Interlayer silane modified bentonite and application thereof - Google Patents
Interlayer silane modified bentonite and application thereof Download PDFInfo
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Abstract
The invention discloses an interlayer silane modified bentonite and an application thereof. A preparation method of the interlayer silane modified bentonite comprises: (1) drying the calcium bentonite under a temperature of 100-110 DEG C for 3-4 hours, cooling to a room temperature, grinding, and sieving with a mesh of 80-100 meshes to obtain bentonite powder; (2) taking the bentonite powder into a mixed solution of 1-7 mol/L nitric acid and ethyl orthosilicate, uniformly mixing and stirring, conveying to a crystallization reactor to crystallize for 12-48 hours under 100-200 DEG C, centrifuging the reaction solution, separating precipitate, washing, and drying to obtain crude products; and (3) roasting the crude product for 5-20 hours under 350-750 DEG C, grinding, and sieving with a sieve of 80-100 meshes to obtain the interlayer silane modified bentonite. The interlayer silane modified bentonite can be used as an adsorbent applied in treating copper-containing wastewater. According to the invention, sources of raw materials are abundant, preparation technology is simple, and production cost is low; and the obtained modified bentonite is stable in structure, high in adsorption rate for copper ions and good in reusability.
Description
Technical field
The present invention relates to the organosilane-modified bentonite of a kind of interlayer and as the application of adsorbent in copper-containing wastewater.
Background technology
Problem of environmental pollution has become the focus that the world today pays close attention to the most.The important pollution sources of contaminated environment water quality are the heavy metal ion in the industrial wastewater, said heavy metal aspect environmental pollution, mainly comprise the significant heavy metals of bio-toxicity such as mercury, cadmium, lead and metallic arsenic, also comprise heavy metal copper with toxicity, zinc, cobalt, nickel etc.The waste water of manufacturing enterprises such as colliery, metal sulfide mineral, iron ore, metallurgy, plating discharging is the main source of the metal ion waste water of contaminant water environment.Special picture electroplating industry, except the electro-coppering that plating piece requires, copper plate Chang Zuowei nickel plating, zinc-plated, chromium plating, silver-plated, gold-plated bottom are to improve parent metal and the adhesion of overlay coating and the Corrosion Protection of coating, this shows that copper-containing wastewater is very general in electroplating industry.Thereby, safety and the heavy metal ion such as copper handled effectively in the waste water are significant to the improvement of environment and human sustainable development how.
At present, mainly adopt chemical method, ion-exchange, membrane separation process, bioanalysis, absorption method etc. for the processing of heavy metal ion-containing waste water.Chemical method can be divided into neutralization precipitation method, sulphide precipitation and electrochemical process.Neutralization precipitation method characteristics are can neutralize when removing heavy metal ion various acid and mixed liquor thereof, because be subjected to the influence of complex ions such as cyanogen, ammonium in pH value and the waste water, bad to the water outlet effect of composite waste, sediment weight is big, go out water hardness height, can make soil, water body alkalization; Though sulphide precipitation pH value wider range, sulfide precipitation is tiny, and free settling does not form secondary pollution, and vulcanizing agent itself is poisonous, and is expensive, also limited its application.Though the common employed ion exchange resin of ion-exchange its have selectively good, adsorption capacity is big, advantage such as quick, it is expensive, still rests on experimental stage at present.Membrane separation technique has advantage such as treatment effect and non-secondary pollution preferably to heavy metal ion-containing waste water, but its bargain price is relatively more expensive, has also limited the extensive use of this technology; Bioanalysis has more advantage in application, and stronger as comprehensive treatment capability, processing method is easy etc., yet biological treatment exists the function bacterium reproduction speed and reaction rate is slow, handles shipwreck with the shortcoming of reuse.Therefore, absorption method has become one of emphasis of the research of water treatment in recent years owing to have characteristics such as absorbing process is easy, environmental friendliness.
The key of absorption method Treatment of Copper waste water is the exploitation of high-efficiency adsorbent, and in recent years, the researcher has carried out research comparatively widely in this respect.Hui etc. (Hui K S, Chao C Y H.Journal of Hazardous Materials, 2005,127 (3), 89-101.) find that the 4A zeolite is to multiple metal ion (Co
2+, Cr
3+, Cu
2+, Zn
2+, Ni
2+) good adsorption property is arranged, especially to Cu
2+Absorption property the best.In order to improve the absorption property of material, people have further carried out the research of modification.(Rengaraj S such as Rengaraj, Kim Y.Journal of Colloid and Interface Science, 2004,273 (1): 14-21.) by after porous seepage of water vanadine is carried out ammonification and protonated modification, realized that mass concentration to cupric is that the waste water of 100mg/L is removed and reached 95%.People such as Walcarius (Walcarius A, L ü thi N, Blin J L, Su B L, Lamberts L.Electrochimica Acta, 1999,44 (25), 4601-4610.) discover, amino (NH is carried out on the surface of MCM-41
2-) material that obtains of modification is to Cu
2+Have good selection absorption property, can be to the Cu in the water
2+Follow the tracks of quantitative detection.People such as Liu (Liu A M, Hidajat K, Kawi S, Zhao D Y.Chemical Communications, 2000,13,1145-1146.) also find, to the surface, duct of SBA-15 carry out amino modified after, by it to Hg
2+, Cu
2+, Zn
2+, Cr
3+, Ni
2+Etc. the absorption research of several heavy metal ion, find that this material is to Cu
2+Good adsorption property is arranged, Cu
2+Clearance reaches 99.8%.Recently, Li Aiyang etc. (Li Aiyang, Chu Hongwei. material protection, 2004,37 (6): 37-41.) by the study on the modification of clinoptilolite is found that it is to Cu
2+Adsorption capacity obviously improve, and simultaneously can remove heavy metal ion such as zinc, cadmium, lead.Above-mentioned studies show that, numerous porous materials are to Cu
2+All have certain absorption property, particularly amidized processing is carried out on the surface of material after, absorption property has great raising.Yet, because the synthetic price of general porous material is higher, limited the extensive use of such material, therefore, await further to develop for cheap efficient sorbing material.
Bentonite is to be the clay mineral of main component with the montmorillonite, is the natural layer silicate mineral of a class 2:1 type, and its construction unit is two dimension to the Si-O tetrahedron of arranging and two dimension to the Al(or the Mg that arrange)-the O-OH octahedral sheet.Bentonite mineral products resource is very abundant, widely distributed in China, and reserves are at the forefront in the world.Because the Si-OH that the montmorillonite surface exists can be fixed on heavy metal ion between cheating engaging layer by the mode of coordination or co-precipitation.Therefore, natural montmorillonite itself also have certain heavy metal ion adsorbed performance, but absorption property is relatively poor as adsorbent, so, be an important job to STUDY OF BENTONITE MODIFICATION.There are some researches show that the organobentonite that makes after to the sodium bentonite modification with lauryl sodium sulfate and softex kw is to Cu
2+Clearance be that sieve 97.8%(becomes beautiful, the friend is refined in department, Liu Xiaohong, Zhu Zhengzhong.Modified alta-mud is to Cu in the waste water
2+, Zn
2+The research of removal effect.Agricultural University Of Anhui's journal, 1997,34(1): 34-39.).(Montarges E such as Mortarges, Michot L J, Lhote F, Fabien T, Vilieras F.Clays and Clay Minerals, 1995,43 (4): 417-426.) with the reaction of hydroxy Al imvite and polymerization of ethylene oxide obtain a kind of inorganic-organic montmorillonite composite material, this modified montmorillonoid can be removed the Cu in the aqueous solution effectively
2+, Hg
2+, Cd
2+, Ni
2+Etc. heavy metal ion.
Summary of the invention
First technical problem that the present invention will solve provides the silane-modified bentonite of a kind of interlayer, and its preparation raw material sources are abundant, preparation technology is simple, production cost is low, gained modified alta-mud Stability Analysis of Structures, and to copper ion adsorption rate height, reusability is good.
Second technical problem that the present invention will solve is the silane-modified bentonite of described interlayer to be used for copper-containing wastewater as adsorbent handle.
Below technical scheme of the present invention is done and specified.
The invention provides the silane-modified bentonite of a kind of interlayer, its preparation method may further comprise the steps:
(1) with calcium-base bentonite under 100～110 ℃ of temperature dry 3～4 hours, be cooled to room temperature, grind by 80～100 orders sieve bentonite in powder;
(2) getting bentonite in powder joins in the mixed liquor that the configuration of 1～7mol/L nitric acid and ethyl orthosilicate obtains, be transferred to after the mixing and stirring in the crystallizing kettle in 100～200 ℃ of crystallization 12～48h, the reactant liquor centrifugation is gone out precipitation, and washing, drying obtain crude product;
(3) with crude product at 350～750 ℃ of roasting 5～20h, product ground to sieve by 80～100 orders namely get the silane-modified bentonite of interlayer.
In the described step (2), the mass ratio that feeds intake of bentonite in powder and mixed liquor is 1:10～50.Described mixed liquor is to be that 1:3～0.05 configuration obtains by 1～7mol/L nitric acid and ethyl orthosilicate according to mass ratio, and preferred mass most preferably is 1:0.43 than being 1:1.5～0.1.
In the described step (2), the concentration of nitric acid is preferably 2-4mol/L.
In the described step (2), crystallization temperature is preferably 100～150 ℃; Most preferably crystallization temperature is 100 ℃, and crystallization time is 20 hours.
In the described step (2), preferred baking temperature is 80～120 ℃, and be 4～6 hours drying time.
In the described step (3), sintering temperature is preferably 550 ℃, and roasting time is preferably 10 hours.
The present invention also provides the silane-modified bentonite of described interlayer as the application of adsorbent in copper-containing wastewater is handled.
In the described application, control the pH of described copper-containing wastewater 4～7, preferably control the pH value 5.
In the described application, the silane-modified bentonitic addition of described interlayer is counted 0.2～4g/mg with the quality of copper ion in the copper-containing wastewater.
In the described application, adsorption temp is 25～55 ℃, is preferably 30 ℃; Adsorption time was preferably 1 hour at 0.5～2 hour.
The silane-modified bentonite of interlayer of the present invention can be regenerated after use by the following method: get the silane-modified bentonite of the interlayer that reaches adsorption equilibrium, with clear water washing 2～3 times, ammonia scrubbing with 0.5～1.0mol/L soaked 12～24 hours again, being washed till the pH value of solution value with pure water then is 3～6, filter the back and collect the filtrate utilization to be recycled that contains copper ion, filter cake was placed 110～120 ℃ of oven for drying 5～7 hours simultaneously, grind back 80～100 orders and sieve, namely get the silane-modified bentonite of interlayer of regeneration.
Compared with prior art, the invention has the advantages that:
A) used raw material is bentonite, and mineral resources are abundant, and cheap, easy to utilize, and the silane-modified bentonite preparation technology of interlayer is simple, easy to operate.
B) the silane-modified bentonite of gained interlayer is to the adsorption rate height of copper ion in the waste water.
C) organosilan passes through covalent bonding between bentonite bed, therefore, the bentone adsorbent Stability Analysis of Structures of gained, reusability is good, meets the requirement of energy-saving and emission-reduction.
Description of drawings
Fig. 1 is the silane-modified bentonitic synthetic schematic diagram of interlayer.
Fig. 2 is the silane-modified bentonitic SEM figure of interlayer.
The specific embodiment:
Below by specific embodiment technical scheme of the present invention is described further, but protection scope of the present invention is not limited thereto:
The specification of table 1 main material and source
Tester and method:
722 type grating spectrophotometers: adopt the sodium diethyldithiocarbamate AAS.
Preparation of adsorbent:
The preparation method of bentone adsorbent, its feature may further comprise the steps:
(1) calcium-base bentonite is put in the electric drying oven with forced convection under 100～110 ℃ of temperature dry 3～4 hours, is cooled to room temperature, grind by 80～100 orders sieve bentonite in powder.
(2) get above-mentioned calcium-base bentonite, join nitric acid and ethyl orthosilicate (TEOS) mixed liquor of 50g2mol/L, mix and stir 30min, be transferred to 100-200 ℃ of crystallization 20h in the crystallizing kettle.
(3) with above-mentioned mixed liquor centrifugation, spend deionised water three times, then at 120 ℃ of dry 10h, at last with product at 550 ℃ of roasting 10h.Product is ground, and 80～100 orders sieve and namely get bentone adsorbent.Its sem photograph as shown in Figure 2.
Embodiment 1-5: different crystallization temperatures are to the influence of absorption property
In the 250ml conical flask that 50mL, 10mg/L copper ion are housed, the bentone adsorbent that add 0.5g, 2M nitric acid and TEOS consumption and be 35g and 15g, under different crystallization temperatures, obtains, in 30 ℃ constant temperature shaking bath, adsorb 1h, centrifugation is immediately got supernatant liquor and is surveyed its copper ion concentration.Be colour reagent with the sodium diethyldithiocarbamate, detect the concentration of copper ion at 722 type grating spectrophotometers.The result is as shown in table 2.
The influence of table 2 adsorbent crystallization temperature
As seen from the above table, the preferable crystallization temperature of bentone adsorbent is 100 ℃.
Embodiment 6-8: nitric acid and ethyl orthosilicate (TEOS) consumption is to the adsorbents adsorb Effect on Performance
In the 250ml conical flask that 50mL, 10mg/L copper ion are housed, nitric acid in the adjusting bentone adsorbent preparation process and the ratio of TEOS, add the bentone adsorbent that 0.5g obtains 100 ℃ of following crystallization, in 30 ℃ constant temperature shaking bath, adsorb 1h, centrifugation is immediately got supernatant liquor and is surveyed its copper ion concentration.Be colour reagent with the sodium diethyldithiocarbamate, detect the concentration of copper ion at 722 type grating spectrophotometers.The result is as shown in table 3.
Table 3
As seen from the above table, preferable nitric acid and ethyl orthosilicate (TEOS) amount ratio are 7:3.
Embodiment 9-14: the pH value of solution value is to the influence of absorption property
Getting 0.5g, is the bentone adsorbent that crystallization obtains under 35g and the 15g condition at 100 ℃, 2M nitric acid and TEOS consumption, mixes with 50mL, 10mg/L copper ion solution.In pH value 1,2,3,4, adsorb 1h under 5,6,7 conditions in 30 ℃ of constant temperature shaking baths respectively, centrifugation is immediately got supernatant liquor and is surveyed its copper ion concentration.Be colour reagent with the sodium diethyldithiocarbamate, detect the concentration of copper ion at 722 type grating spectrophotometers.The result is as shown in table 4.
Table 4
| Embodiment | The pH value | Cu 2+Clearance (%) |
| 9 | 1 | 78.2 |
| 10 | 2 | 82.5 |
[0053]?
| 11 | 3 | 88.7 |
| 12 | 4 | 92.3 |
| 1 | 5 | 97.5 |
| 13 | 6 | 97.7 |
| 14 | 7 | 98.1 |
As seen from the above table, after the pH value of solution value is greater than 5, Cu
2+Clearance change not quite, consider the Cu for preparing
2+The pH of solution is about 5, and therefore, selecting preferable pH value is 5.
Embodiment 15-18: the adsorbent consumption is to the influence of absorption property
Getting a certain amount of is the bentone adsorbent that crystallization obtains under 35g and the 15g condition at 100 ℃, 2M nitric acid and TEOS consumption, mix with 50mL, 10mg/L copper ion solution, be in 30 ℃ of constant temperature shaking baths, to adsorb 1h under 5 conditions in the pH value, centrifugation is immediately got supernatant liquor and is surveyed its copper ion concentration.Be colour reagent with the sodium diethyldithiocarbamate, detect the concentration of copper ion at 722 type grating spectrophotometers.The result is as shown in table 5.
Table 5
| Embodiment | Catalyst amount (g) | Cu 2+Clearance (%) |
| 15 | 0.1 | 84.2 |
| 1 | 0.5 | 97.5 |
| 16 | 1.0 | 98.1 |
| 17 | 1.5 | 98.8 |
| 18 | 2.0 | 99.1 |
As seen from the above table, preferable catalyst amount is 0.5g.
The influence of embodiment 19-21 adsorption time
Getting 0.5g is the bentone adsorbent that crystallization obtains under 35g and the 15g condition at 100 ℃, 2M nitric acid and TEOS consumption, mix for the 10mg/L copper ion solution with 50mL, concentration, be in 30 ℃ of constant temperature shaking baths, to adsorb 0.5h, 1h, 1.5h, 2h under 5 conditions in the pH value, centrifugation is immediately got supernatant liquor and is surveyed its copper ion concentration.Be colour reagent with the sodium diethyldithiocarbamate, detect the concentration of copper ion at 722 type grating spectrophotometers.The result is as shown in table 6.
Table 6
| Embodiment | Adsorption time (h) | Cu 2+Clearance (%) |
| 19 | 0.5 | 89.6 |
| 1 | 1.0 | 97.5 |
| 20 | 1.5 | 99.0 |
| 21 | 2.0 | 99.2 |
As seen from the above table, be 5 times in the pH value, preferable adsorption time is 1h.
The regeneration serviceability of embodiment 22-24 adsorbent
Get the bentone adsorbent filter cake that reaches adsorption equilibrium, with clear water washing 3 times, ammonia scrubbing with 1.0mol/L soaked 12 hours again, being washed till the pH value of solution value with pure water then is 6, filter the back and collect the filtrate utilization to be recycled that contains copper ion, filter cake was placed 110 ℃ of oven for drying 5 hours simultaneously, grind back 80 orders and sieve, namely get the regeneration bentone adsorbent.
Getting the bentone adsorbent of 0.5g regeneration, mix for the 10mg/L copper ion solution with 50ml concentration, is to adsorb 1h under 5 conditions in 30 ℃ of constant temperature shaking baths in the pH value, and centrifugation is immediately got supernatant liquor and surveyed its copper ion concentration.Be colour reagent with the sodium diethyldithiocarbamate, detect the concentration of copper ion at 722 type grating spectrophotometers.The result is as shown in table 7.
Table 7
| Embodiment | Reclaim access times | Cu 2+Clearance (%) |
| 22 | 1 | 95.2 |
| 23 | 2 | 93.8 |
| 24 | 3 | 93.0 |
As seen from the above table, the bentone adsorbent repeat performance is good, 4 use back Cu
2+Clearance still reach 93.0%.
Claims (9)
1. silane-modified bentonite of interlayer, its preparation method may further comprise the steps:
(1) with calcium-base bentonite under 100 ~ 110 ℃ of temperature dry 3～4 hours, be cooled to room temperature, grind by 80～100 orders sieve bentonite in powder;
(2) getting bentonite in powder joins in the mixed liquor that the configuration of 1 ~ 7 mol/L nitric acid and ethyl orthosilicate obtains, be transferred to after the mixing and stirring in the crystallizing kettle in 100 ~ 200 ℃ of crystallization 12 ~ 48 h, the reactant liquor centrifugation is gone out precipitation, and washing, drying obtain crude product;
(3) with crude product at 350 ~ 750 ℃ of roasting 5 ~ 20 h, product ground to sieve by 80～100 orders namely get the silane-modified bentonite of interlayer.
2. the silane-modified bentonite of interlayer as claimed in claim 1, it is characterized in that: in the described step (2), the mass ratio that feeds intake of bentonite in powder and mixed liquor is 1:10 ~ 50, and described mixed liquor is to be obtained according to mass ratio 1:3 ~ 0.05 configuration by 1-7mol/L nitric acid and ethyl orthosilicate.
3. the silane-modified bentonite of interlayer as claimed in claim 1, it is characterized in that: the concentration of described nitric acid is 2-4 mol/L, described mixed liquor is to be obtained according to mass ratio 1:1.5 ~ 0.1 configuration by 2-4mol/L nitric acid and ethyl orthosilicate.
4. as the silane-modified bentonite of the described interlayer of one of claim 1 ~ 3, it is characterized in that: in the described step (2), crystallization temperature is 100 ~ 150 ℃.
5. as the silane-modified bentonite of the described interlayer of one of claim 1 ~ 3, it is characterized in that: in the described step (2), baking temperature is 80 ~ 120 ℃, and be 4 ~ 6 hours drying time.
6. the silane-modified bentonite of interlayer as claimed in claim 5, it is characterized in that: in the described step (2), crystallization temperature is 100 ℃, and crystallization time is 20 hours; In the described step (3), sintering temperature is 550 ℃, and roasting time is 10 hours.
7. the silane-modified bentonite of interlayer as claimed in claim 1 is as the application of adsorbent in copper-containing wastewater is handled.
8. application as claimed in claim 7 is characterized in that: control the pH of described copper-containing wastewater 4 ~ 7.
9. application as claimed in claim 8 is characterized in that: adsorption temp is 25 ~ 55 ℃, and adsorption time is 0.5 ~ 2 hour.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624172A (en) * | 2014-12-31 | 2015-05-20 | 芜湖恒杰膨润土科技有限公司 | Modified bentonite, and preparation method and application thereof |
| CN105170120A (en) * | 2015-09-30 | 2015-12-23 | 西北师范大学 | Method for preparing functional loess-based adsorbent through surface graft polymerization |
| CN112337427A (en) * | 2020-10-15 | 2021-02-09 | 四川轻化工大学 | La @ Zr @ SiO2Preparation method of @ bentonite composite phosphorus removal adsorbent |
| CN112812714A (en) * | 2021-02-06 | 2021-05-18 | 惠州东铭新能源研究院有限公司 | Fireproof flame-retardant buffer aerogel product capable of absorbing stress and manufacturing method thereof |
| CN113929250A (en) * | 2020-06-29 | 2022-01-14 | 宝山钢铁股份有限公司 | Cold rolling reverse osmosis concentrated water zero-discharge process and treatment system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624172A (en) * | 2014-12-31 | 2015-05-20 | 芜湖恒杰膨润土科技有限公司 | Modified bentonite, and preparation method and application thereof |
| CN105170120A (en) * | 2015-09-30 | 2015-12-23 | 西北师范大学 | Method for preparing functional loess-based adsorbent through surface graft polymerization |
| CN113929250A (en) * | 2020-06-29 | 2022-01-14 | 宝山钢铁股份有限公司 | Cold rolling reverse osmosis concentrated water zero-discharge process and treatment system |
| CN113929250B (en) * | 2020-06-29 | 2023-07-11 | 宝山钢铁股份有限公司 | Cold rolling reverse osmosis concentrated water zero discharge process and treatment system |
| CN112337427A (en) * | 2020-10-15 | 2021-02-09 | 四川轻化工大学 | La @ Zr @ SiO2Preparation method of @ bentonite composite phosphorus removal adsorbent |
| CN112812714A (en) * | 2021-02-06 | 2021-05-18 | 惠州东铭新能源研究院有限公司 | Fireproof flame-retardant buffer aerogel product capable of absorbing stress and manufacturing method thereof |
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Application publication date: 20130717 |