CN105126741A - Heavy metal inorganic adsorption material, preparation method and application thereof - Google Patents
Heavy metal inorganic adsorption material, preparation method and application thereof Download PDFInfo
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- CN105126741A CN105126741A CN201510412017.2A CN201510412017A CN105126741A CN 105126741 A CN105126741 A CN 105126741A CN 201510412017 A CN201510412017 A CN 201510412017A CN 105126741 A CN105126741 A CN 105126741A
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Abstract
The invention discloses a preparation method of a heavy metal inorganic adsorption material. The preparation method includes following steps: with natural clay mineral as a main raw material, adding a bonding agent and a pore-forming agent, mixing the materials uniformly with addition of water to obtain semi-dry raw meal, performing extrusion moulding, pre-drying the raw meal, performing granulation and roasting the raw meal granules to prepare the porous granular material. The adsorption material is high in mechanical strength, is good in acid and alkaline resistance, can be used in high-effective adsorption on manganese ion in heavy metal sewage, is good in treatment effect, is free of secondary pollution, can be recycled and provides possibility to high-effective and low-cost treatment on the heavy metal sewage.
Description
Technical field
The present invention relates to water treatment field, particularly relate to heavy metal species inorganic adsorbing material and preparation method thereof and the application in Treatment of Wastewater With Manganese.
Background technology
China's manganese resource is relatively deficient, but consumes in manganese ore year and occupy first place in the world, and particularly at steel industry, the restriction of the use of a large amount of manganese ore and equipment and technology, creates a large amount of containing manganese waste material and Mn-bearing waste water.One of important Testing index of Meng Shi China water quality heavy metal, the discharge of Mn-bearing waste water can cause serious environmental hazard, especially easily corrosion pipeline, hinders plant growth, and even polluted source and then affect human health.Fe content in water is limited in below 0.1mg/L by drinking water standard, thus, has great importance to the demanganization process of Mn-bearing waste water.
In the processing method of Mn-bearing waste water, traditional chemical demanganization process reagent toxicity is large, easily causes secondary pollution, and processing cost is high simultaneously; Greatly, long processing period, involves great expense for bioanalysis or catalytic oxidation rule floor space; The adsorption effect of physisorphtion to manganese is poor, is difficult to achieve the goal.Therefore a kind of operation is needed badly easy, the process material and progress that can meet again environmental emission standard with low cost.
Summary of the invention
The invention provides heavy metal species inorganic adsorbing material and preparation method thereof and the application in Treatment of Wastewater With Manganese, which overcome the weak point existing for prior art.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of a heavy metal species inorganic adsorbing material, comprises the following steps:
1) natural clay mineral, binding agent and pore former are mixed with the ratio of mass ratio 10:0.5 ~ 3:0.1 ~ 10, wherein natural clay mineral is calcium-base bentonite, and smectite content is 60 ~ 95%, and cation exchange capacity is 40 ~ 120meq/100g;
2) stirring that added water by said mixture forms half-dried raw material, and wherein water and bentonitic mass ratio are 0.3 ~ 0.7:1;
3) by half-dried raw material by extruded formation strip-shaped materials, at 40 ~ 100 DEG C, predrying 2 ~ 48h is 2 ~ 30% to its moisture content;
4) in 400 ~ 800 DEG C of roasting 1 ~ 6h after the strip-shaped materials granulation after predrying, obtained inorganic adsorbing material.
Preferably, described binding agent is sodium metasilicate, and its modulus is 2.0 ~ 2.5.
Preferably, described pore former is the Organic Sodium Salt that molecular weight is greater than 300, such as odium stearate, enuatrol etc.
Preferably, the mass ratio of described calcium-base bentonite, binding agent and pore former is 10:0.5 ~ 2:0.1 ~ 5.
Preferably, step 2) in, described water and bentonitic mass ratio are 0.4 ~ 0.6:1.
Preferably, step 4) in, described roasting is at 400 ~ 800 DEG C of roasting 1 ~ 6h.
The heavy metal inorganic adsorbing material prepared by said method, described inorganic adsorbing material is spherical or column.Preferably, the particle diameter of described inorganic adsorbing material is 3 ~ 5mm, pore volume 0.2 ~ 0.4cm
3/ g, aperture 50 ~ 80nm.
The application of above-mentioned heavy metal inorganic adsorbing material in heavy metal containing wastewater treatment.Preferably, described heavy metal wastewater thereby is Mn-bearing waste water, and described heavy metal inorganic adsorbing material is for adsorbing manganese ion.
Compared to prior art, the present invention has following beneficial effect:
1. be primary raw material with calcium-base bentonite, add binding agent and pore former and make granular adsorption material by sintering, this sorbing material mechanical strength is high, acid and alkali-resistance, pore sphere or the cylindrical particle with certain pore volume is formed after adding pore former, specific area is large, can realize the efficient adsorption to manganese ion.
2. preparation process is simple, and with low cost, treatment effect is good, and treating capacity is large, and reusable edible, can not cause secondary pollution, be suitable for commercial Application.
Below in conjunction with drawings and Examples, the present invention is described in further detail; But heavy metal species inorganic adsorbing material of the present invention and its preparation method and application is not limited to embodiment.
Accompanying drawing explanation
Fig. 1 is the adsorption effect schematic diagram of inorganic adsorbing material to manganese ion in manganese sulfate solution of embodiment 1;
Fig. 2 is the adsorption effect schematic diagram of inorganic adsorbing material to manganese ion in manganese sulfate solution of embodiment 2;
Fig. 3 is the adsorption effect schematic diagram of inorganic adsorbing material to certain mine Mn-bearing waste water of embodiment 3.
Detailed description of the invention
Embodiment 1
1000g calcium-base bentonite, 100g sodium metasilicate (modulus 2.0) and 50g odium stearate are mixed into homogeneous mixed-powder; In above mixed-powder, add 500g running water and stir, until moisture distribution evenly forms half-dried raw material; Again the raw material obtained are joined forming machine and carry out extruded moulding, be then placed in baking oven inner drying, 50 ~ 60 DEG C of predrying 24h; The predrying strip-shaped materials obtained is carried out disconnected grain; Roasting 2h in the Muffle furnace finally particle being placed in 600 DEG C, obtained heavy metal goal orientation type inorganic adsorbing material, particle diameter is 4mm, and pore volume is 0.26cm
3/ g, average pore size is 58nm.
Above-mentioned sorbing material is used for the absorption of manganese ion in autogamy manganese sulfate solution, specific as follows:
Preparation 2L, initial concentration are the manganese ion solution of 5.0mg/L, are loaded by 50g adsorption particle in resin column, regulate peristaltic pump flow velocity to be 5BV/h, carry out circulation absorption.
Adsorption particle to the manganese ion concentration situation of liquid after the Dynamic Adsorption effect of manganese ion and process as shown in Figure 1.As shown in Figure 1, be that in the Dynamic Adsorption process of the manganese ion of 5.0mg/L, clearance raises along with time lengthening to initial concentration, and when treated between reach 12h after, after process, in liquid, the concentration of manganese ion is down to below 0.01mg/L, and clearance reaches more than 99%.
Embodiment 2
1000g calcium-base bentonite, 50g sodium metasilicate (modulus 2.5) and 100g odium stearate are mixed into homogeneous mixed-powder; In above mixed-powder, add 400g running water and stir, until moisture distribution evenly forms half-dried raw material; Again the raw material obtained are joined forming machine and carry out extruded moulding, be then placed in baking oven inner drying, 80 ~ 100 DEG C of predrying 6h; The predrying strip-shaped materials obtained is carried out disconnected grain; Roasting 1h in the Muffle furnace finally particle being placed in 800 DEG C, obtained heavy metal goal orientation type inorganic adsorbing material, particle diameter is 3mm, pore volume 0.3cm
3/ g, average pore size 55nm.
Above-mentioned sorbing material is used for the absorption of manganese ion in autogamy manganese sulfate solution, specific as follows:
Preparation 2L, initial concentration are the manganese ion solution of 1.0mg/L, are loaded by 50g adsorption particle in resin column, regulate peristaltic pump flow velocity to be 5BV/h, carry out circulation absorption.
Adsorption particle to the manganese ion concentration situation of liquid after the Dynamic Adsorption effect of manganese ion and process as shown in Figure 2.As shown in Figure 2, be that in the Dynamic Adsorption process of the manganese ion of 1.0mg/L, clearance raises along with time lengthening to initial concentration, and when treated between reach 12h after, after process, in liquid, the concentration of manganese ion is down to below 0.01mg/L, and clearance reaches more than 99%.
Embodiment 3
1000g calcium-base bentonite, 300g sodium metasilicate (modulus 2.2) and 500g odium stearate are mixed into homogeneous mixed-powder; In above mixed-powder, add 700g running water and stir, until moisture distribution evenly forms half-dried raw material; Again the raw material obtained are joined forming machine and carry out extruded moulding, be then placed in large-scale baking oven inner drying, 40 ~ 50 DEG C of predrying 48h; The predrying strip-shaped materials obtained is carried out disconnected grain; Roasting 6h in the Muffle furnace finally particle being placed in 400 DEG C, obtained heavy metal goal orientation type inorganic adsorbing material, particle diameter is 4mm, pore volume 0.32cm
3/ g, average pore size 68nm.
Above-mentioned sorbing material is used for the purification absorption of certain ore Mn-bearing waste water, specific as follows:
Get 2L mine Mn-bearing waste water, manganese ion concentration is 4.85mg/L, is loaded by 50g adsorption particle in resin column, regulates peristaltic pump flow velocity to be 5BV/h, carry out circulation absorption.
Adsorption particle to the manganese ion concentration situation of liquid after the Dynamic Adsorption effect of manganese ion and process as shown in Figure 3.As shown in Figure 3, in the Dynamic Adsorption process of the manganese ion in mine wastewater, clearance raises along with time lengthening, and when treated between reach 12h after, after process, the concentration of manganese ion is down to below 0.01mg/L in liquid, and clearance reaches more than 99%.
Embodiment 4
1000g calcium-base bentonite, 200g sodium metasilicate (modulus 2.3) and 1000g odium stearate are mixed into homogeneous mixed-powder; In above mixed-powder, add 600g running water and stir, until moisture distribution evenly forms half-dried raw material; Again the raw material obtained are joined forming machine and carry out extruded moulding, be then placed in baking oven inner drying, 60 ~ 80 DEG C of predrying 12h; The predrying strip-shaped materials obtained is carried out disconnected grain; Roasting 3h in the Muffle furnace finally particle being placed in 700 DEG C, obtained heavy metal goal orientation type inorganic adsorbing material, particle diameter is 4.6mm, pore volume 0.38cm
3/ g, average pore size 70nm.
Above-described embodiment is only used for further illustrating heavy metal species inorganic adsorbing material of the present invention and its preparation method and application; but the present invention is not limited to embodiment; every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all fall in the protection domain of technical solution of the present invention.
Claims (10)
1. the preparation method of a heavy metal species inorganic adsorbing material, is characterized in that comprising the following steps:
1) natural clay mineral, binding agent and pore former are mixed with the ratio of mass ratio 10:0.5 ~ 3:0.1 ~ 10, wherein natural clay mineral is calcium-base bentonite, and smectite content is 60 ~ 95%, and cation exchange capacity is 40 ~ 120meq/100g;
2) stirring that added water by said mixture forms half-dried raw material, and wherein water and bentonitic mass ratio are 0.3 ~ 0.7:1;
3) by half-dried raw material by extruded formation strip-shaped materials, at 40 ~ 100 DEG C, predrying 2 ~ 48h is 2 ~ 30% to its moisture content;
4) in 400 ~ 800 DEG C of roasting 1 ~ 6h after the strip-shaped materials granulation after predrying, obtained inorganic adsorbing material.
2. preparation method according to claim 1, is characterized in that: described binding agent is sodium metasilicate, and its modulus is 2.0 ~ 2.5.
3. preparation method according to claim 1, is characterized in that: described pore former is the Organic Sodium Salt that molecular weight is greater than 300.
4. preparation method according to claim 1, is characterized in that: the mass ratio of described calcium-base bentonite, binding agent and pore former is 10:0.5 ~ 2:0.1 ~ 5.
5. preparation method according to claim 1, is characterized in that: step 2) in, described water and bentonitic mass ratio are 0.4 ~ 0.6:1.
6. preparation method according to claim 1, is characterized in that: step 4) in, described roasting is at 400 ~ 800 DEG C of roasting 1 ~ 6h.
7. the heavy metal inorganic adsorbing material prepared by the method described in any one of claim 1 ~ 6, is characterized in that: described inorganic adsorbing material is spherical or column.
8. heavy metal inorganic adsorbing material according to claim 7, is characterized in that: the particle diameter of described inorganic adsorbing material is 3 ~ 5mm, pore volume 0.2 ~ 0.4cm
3/ g, aperture 50 ~ 80nm.
9. the application of heavy metal inorganic adsorbing material according to claim 7 in heavy metal containing wastewater treatment.
10. application according to claim 9, is characterized in that: described heavy metal wastewater thereby is Mn-bearing waste water, and described heavy metal inorganic adsorbing material is for adsorbing manganese ion.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106362675A (en) * | 2016-10-10 | 2017-02-01 | 四川奎能环保科技有限公司 | Resource utilization method of water-based rock debris |
| CN107175067A (en) * | 2017-06-09 | 2017-09-19 | 信阳师范学院 | MnO2NaCl/ bentone adsorbents and preparation method and application |
| CN108114694A (en) * | 2017-11-30 | 2018-06-05 | 广西大学 | A kind of organic decoration magnetism alkaline calcium bentonite and preparation method thereof |
| CN108658592A (en) * | 2018-05-30 | 2018-10-16 | 佛山市航祥千安科技有限公司 | A kind of water purification porous ceramic film material |
| CN112221462A (en) * | 2020-10-19 | 2021-01-15 | 索通发展股份有限公司 | Preparation method and application of porous spherical particles |
| CN112371080A (en) * | 2020-10-26 | 2021-02-19 | 松山湖材料实验室 | Mesoporous adsorption material and preparation method and application thereof |
| CN116688937A (en) * | 2023-07-18 | 2023-09-05 | 青岛理工大学 | Composite mineral particles, preparation method and application thereof, and method for treating acidic manganese-containing wastewater to recover manganese oxide |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106362675A (en) * | 2016-10-10 | 2017-02-01 | 四川奎能环保科技有限公司 | Resource utilization method of water-based rock debris |
| CN107175067A (en) * | 2017-06-09 | 2017-09-19 | 信阳师范学院 | MnO2NaCl/ bentone adsorbents and preparation method and application |
| CN108114694A (en) * | 2017-11-30 | 2018-06-05 | 广西大学 | A kind of organic decoration magnetism alkaline calcium bentonite and preparation method thereof |
| CN108114694B (en) * | 2017-11-30 | 2020-12-25 | 广西大学 | Organic modified magnetic alkaline calcium bentonite and preparation method thereof |
| CN108658592A (en) * | 2018-05-30 | 2018-10-16 | 佛山市航祥千安科技有限公司 | A kind of water purification porous ceramic film material |
| CN112221462A (en) * | 2020-10-19 | 2021-01-15 | 索通发展股份有限公司 | Preparation method and application of porous spherical particles |
| CN112371080A (en) * | 2020-10-26 | 2021-02-19 | 松山湖材料实验室 | Mesoporous adsorption material and preparation method and application thereof |
| CN112371080B (en) * | 2020-10-26 | 2023-03-28 | 松山湖材料实验室 | Mesoporous adsorption material and preparation method and application thereof |
| CN116688937A (en) * | 2023-07-18 | 2023-09-05 | 青岛理工大学 | Composite mineral particles, preparation method and application thereof, and method for treating acidic manganese-containing wastewater to recover manganese oxide |
| CN116688937B (en) * | 2023-07-18 | 2024-04-16 | 青岛理工大学 | Composite mineral particles, preparation method and application thereof, and method for treating acidic manganese-containing wastewater to recover manganese oxide |
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Application publication date: 20151209 |