CN108128834B - Chromium adsorbent and preparation method and application thereof - Google Patents
Chromium adsorbent and preparation method and application thereof Download PDFInfo
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- CN108128834B CN108128834B CN201711266273.0A CN201711266273A CN108128834B CN 108128834 B CN108128834 B CN 108128834B CN 201711266273 A CN201711266273 A CN 201711266273A CN 108128834 B CN108128834 B CN 108128834B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/0072—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention relates to a chromium adsorbent and a preparation method and application thereof, belonging to the technical field of water treatment. The adsorbent is prepared by modifying a ceramsite material by adopting different acids and bases, can be fully contacted with a reaction liquid, has higher adsorption performance, can effectively remove low-concentration hexavalent chromium in wastewater, and is low in cost, simple in modification method, low in price and easy to obtain, and suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a chromium adsorbent and a preparation method and application thereof.
Background
Chromium occurs in nature in mainly trivalent and hexavalent forms. Among them, Cr (VI) has high oxidizing property and carcinogenicity, its compound can not be naturally degraded, and can be accumulated in the organism, and its toxicity is 100 times that of Cr (III). The migration and transformation modes of chromium in the water body mainly comprise hydrolysis, adsorption, precipitation, oxidation reduction and complexation. There are many methods for removing Cr (VI), including adsorption, chemical precipitation, ion exchange, biological methods, etc.
The adsorption method mainly utilizes insoluble solid materials with high specific surface area as an adsorbent, and utilizes the mechanisms of chemical adsorption, physical adsorption and the like to adsorb heavy metals in water on the surface of the adsorbent so as to achieve the aim of removing the heavy metals. The adsorption method is simple to operate, has little pollution, and most of the adsorbent can be reused. The adsorbents commonly used are mainly: activated carbon, sepiolite, alumina, some biological adsorbents and the like, but the concentration requirement of the activated carbon on Cr (VI) is usually more than 10mg/L, and the adsorption effect on low-concentration chromium is poor.
The inside structure of the ceramsite material is characterized by fine honeycomb micropores which are closed but not communicated. The ceramsite is formed by wrapping gas into the shell, so that the ceramsite has the characteristic of light weight. In addition, the ceramsite has huge specific surface area and good chemical and thermal stability. However, the production process of the ceramsite material is rough, and the pore channels contain a large amount of impurities, so that the combination of heavy metal ions and the ceramsite material is limited. In recent years, the research on ceramsite materials has attracted general attention, but the research on the application of ceramsite to adsorb heavy metal Cr is less.
Disclosure of Invention
The invention aims to provide a chromium adsorbent, a preparation method and application thereof. In addition, the modification method is simple, the ceramsite is cheap and easy to obtain, and the method is suitable for large-scale industrial production.
The invention adopts the following technical scheme:
a chromium adsorbent is a modified ceramsite.
The preparation method of the chromium adsorbent comprises the following steps:
(1) crushing ceramsite to 40-120 meshes, adding methanol, performing ultrasonic treatment for 5-15 min, standing, performing vacuum filtration, and drying at 60-120 ℃ for 2-3 h;
(2) adding an eluent with the concentration of 0.5-2 mol/L into the dried sample, carrying out ultrasonic treatment for 5-15 min, carrying out vacuum filtration after elution, and drying for 2-3h at the temperature of 60-120 ℃;
(3) and (3) placing the ceramsite treated in the step (2) into a muffle furnace, roasting for 2-3h at 400-600 ℃, taking out, and grinding to 40-120 meshes to obtain the modified ceramsite.
In the preparation method, the ceramsite in the step (1) is more than one of fly ash ceramsite, clay ceramsite, biological sludge ceramsite and garbage ceramsite.
In the preparation method, in the step (1), the mass-to-volume ratio of the ceramsite to the methanol is 1-5 g:10 mL.
In the preparation method, the eluent in the step (2) is HCl and HNO3Or H2SO4。
In the preparation method, the eluent in the step (2) is NaOH or Ca (OH)2Or Ba (OH)2。
In the preparation method, the mass-volume ratio of the ceramsite in the step (2) to the eluent is 1-5 g:5 mL.
An application of the chromium adsorbent in removing low-concentration Cr in wastewater.
Further, the concentration of Cr in the wastewater is 0.1-1 mg/L.
Further, Cr in the wastewater is hexavalent.
The invention has the beneficial effects that: the invention uses the eluant to process the ceramsite material, because the ceramsite material has rough production process and contains a large amount of impurities in the pore channel, the combination of heavy metal ions and the ceramsite material is limited, and after the ceramsite material is processed by the eluant, the impurities blocking the pore channel are removed, thereby greatly improving the adsorption capacity of the ceramsite to chromium ions; the methanol is mainly used for removing other metal salt impurities in the ceramsite; the baking is to make the porcelain granule treated by the eluent have stable adsorption effect, remove volatile components and improve the mechanical strength of the porcelain granule.
The modified ceramsite prepared by the method has good adsorption performance, and can effectively remove Cr, especially Cr (VI), in wastewater. In addition, the preparation method is simple, the conditions are easy to obtain, the time consumption is short, the cost is low, the preparation method is suitable for large-scale industrial production, and the preparation method has a good application prospect in the technical field of water treatment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to examples. The following examples are only some examples of the present invention and are not intended to be exhaustive. Other embodiments, which can be obtained by others skilled in the art without any inventive step, are within the scope of the present invention.
Example 1
Preparation of chromium adsorbent:
the fly ash ceramsite is crushed to 40 meshes, and methanol is added, wherein the solid-to-liquid ratio is 1g:10 mL. Carrying out ultrasonic treatment for 5min under the ultrasonic condition, standing, carrying out vacuum filtration and drying, placing a dried sample in a beaker, adding HCl with the concentration of 1mol/L, wherein the solid-to-liquid ratio is 1g:5mL, eluting, carrying out vacuum filtration, drying at 110 ℃ for 2h, roasting in a muffle furnace at 500 ℃ for 3h, and grinding to 40 meshes to obtain the modified ceramsite.
Application of the chromium adsorbent:
the adsorbent is added into chromium-containing wastewater with the initial concentration of 0.6mg/L, the concentration of chromium in the adsorbed wastewater is measured by a heavy metal multi-parameter measuring instrument, and the removal efficiency of the chromium is calculated to be 94.34%.
Example 2
Preparation of chromium adsorbent:
the fly ash ceramsite is crushed to 60 meshes, and methanol is added, wherein the solid-to-liquid ratio is 1g:5 mL. Performing ultrasonic treatment for 10min under ultrasonic condition, standing, vacuum filtering and drying, placing the dried sample in a beaker, adding 0.5mol/L Ba (OH)2And (3) eluting, then carrying out vacuum filtration, drying at 60 ℃ for 2h, then placing in a muffle furnace, roasting at 550 ℃ for 3h, and grinding to 60 meshes to obtain the modified ceramsite.
Application of the chromium adsorbent:
the adsorbent is added into chromium-containing wastewater with the initial concentration of 0.6mg/L, the concentration of chromium in the adsorbed wastewater is measured by a heavy metal multi-parameter measuring instrument, and the removal efficiency of chromium is calculated to be 96.42%.
Example 3
Preparation of chromium adsorbent:
the clay ceramsite is crushed to 100 meshes, and methanol is added, wherein the solid-to-liquid ratio is 3g:10 mL. Performing ultrasonic treatment for 5min under the ultrasonic condition, standing, performing vacuum filtration and drying, placing a dried sample in a beaker, adding NaOH with the concentration of 0.5mol/L, wherein the solid-to-liquid ratio is 1g:5mL, performing vacuum filtration after elution, drying at 110 ℃ for 2h, placing in a muffle furnace, roasting at 500 ℃ for 2h, and grinding to 100 meshes to obtain the modified ceramsite.
Application of the chromium adsorbent:
the adsorbent is added into chromium-containing wastewater with the initial concentration of 1mg/L, the concentration of chromium in the adsorbed wastewater is measured by a heavy metal multi-parameter measuring instrument, and the removal efficiency of the chromium is calculated to be 92.24%.
Example 4
Preparation of chromium adsorbent:
the biological sludge ceramsite is crushed into 120 meshes, and methanol is added, wherein the solid-to-liquid ratio is 2g:5 mL. Performing ultrasonic treatment for 10min under ultrasonic condition, standing, vacuum filtering and drying, placing the dried sample in a beaker, adding HNO with concentration of 2mol/L3And (3) eluting, then carrying out vacuum filtration, drying at 90 ℃ for 2h, then placing in a muffle furnace, roasting at 600 ℃ for 2h, and grinding to 120 meshes to obtain the modified ceramsite.
Application of the chromium adsorbent:
the adsorbent is added into chromium-containing wastewater with the initial concentration of 1mg/L, the concentration of chromium in the adsorbed wastewater is measured by a heavy metal multi-parameter measuring instrument, and the removal efficiency of chromium is calculated to be 87.62%.
Example 5
Preparation of chromium adsorbent:
the garbage ceramsite is crushed to 60 meshes, and methanol is added, wherein the solid-to-liquid ratio is 1g:2 mL. Performing ultrasonic treatment for 15min under ultrasonic condition, standing, vacuum filtering, drying, placing the dried sample in a beaker, adding Ca (OH) with concentration of 1mol/L2And the solid-liquid ratio is 1g:5mL, after elution, vacuum filtration is carried out, drying is carried out for 2h at the temperature of 100 ℃, then the obtained product is placed into a muffle furnace to be roasted for 2.5h at the temperature of 500 ℃, and the obtained product is ground to 60 meshes, thus obtaining the modified ceramsite.
Application of the chromium adsorbent:
the adsorbent is added into chromium-containing wastewater with the initial concentration of 0.5mg/L, the concentration of chromium in the adsorbed wastewater is measured by a heavy metal multi-parameter measuring instrument, and the removal efficiency of the chromium is calculated to be 85.17%.
Example 6
Preparation of chromium adsorbent:
pulverizing garbage ceramsite to 100 meshes, adding methanol, and adding solid-to-liquid ratio1g:2 mL. Performing ultrasonic treatment for 10min under ultrasonic condition, standing, vacuum filtering and drying, placing the dried sample in a beaker, adding 0.5mol/L H2SO4And the solid-liquid ratio is 1g:5mL, after elution, vacuum filtration is carried out, drying is carried out for 3h at the temperature of 110 ℃, then the obtained product is placed into a muffle furnace to be roasted for 2.5h at the temperature of 550 ℃, and the obtained product is ground to 100 meshes, thus obtaining the modified ceramsite.
Application of the chromium adsorbent:
the adsorbent is added into chromium-containing wastewater with the initial concentration of 0.5mg/L, the concentration of chromium in the adsorbed wastewater is measured by a heavy metal multi-parameter measuring instrument, and the removal efficiency of the chromium is calculated to be 86.23%.
Comparative example 1
And (3) ceramsite pretreatment: respectively crushing commercially available fly ash ceramsite, clay ceramsite, biological sludge ceramsite and garbage ceramsite into 60 meshes, and drying at 100 ℃ for 2h to obtain the pretreated ceramsite.
Application of the chromium adsorbent:
adding 1g of each of the four pretreated ceramsite into chromium-containing wastewater with the initial concentration of 0.6mg/L, respectively, measuring the chromium concentration in the adsorbed wastewater by using a heavy metal multi-parameter tester, and calculating to obtain the chromium removal efficiency of 32.2%, 30.5%, 27.0% and 33.5%.
Comparative example 2
And (3) ceramsite pretreatment: respectively crushing commercially available fly ash ceramsite, clay ceramsite, biological sludge ceramsite and garbage ceramsite into 60 meshes, dissolving various metal salt impurities in the ceramsite according to the solid-to-liquid ratio of 1:10(g: mL) of the ceramsite to methanol, carrying out ultrasonic treatment for 10min under the ultrasonic condition, standing, carrying out vacuum filtration, and drying at 100 ℃ for 2 h. Then placing the mixture into a muffle furnace to be roasted for 3h at the temperature of 500 ℃, and grinding the mixture to 60 meshes to obtain the pretreated ceramsite.
Application of the chromium adsorbent:
adding 1g of each of the four pretreated ceramsite into chromium-containing wastewater with the initial concentration of 0.6mg/L, respectively, measuring the chromium concentration in the adsorbed wastewater by using a heavy metal multi-parameter tester, and calculating to obtain the chromium removal efficiencies of 57.2%, 53.4%, 55.1% and 50.3%.
Comparative example 3
And (3) ceramsite pretreatment: respectively crushing commercially available fly ash ceramsite, clay ceramsite, biological sludge ceramsite and garbage ceramsite into 60 meshes, and drying at 100 ℃ for 2 h. And (3) placing the dried sample in a beaker, adding 1mol/L HCl to ensure that the solid-to-liquid ratio of the ceramsite to the HCl is 1:5(g: mL), placing the sample in a muffle furnace, roasting the sample for 3 hours at 500 ℃, and grinding the sample to 60 meshes to obtain the pretreated ceramsite.
Application of the chromium adsorbent:
adding 1g of each of the four pretreated ceramsite into chromium-containing wastewater with the initial concentration of 0.6mg/L, respectively, measuring the chromium concentration in the adsorbed wastewater by using a heavy metal multi-parameter tester, and calculating to obtain the chromium removal efficiencies of 52.2%, 59.5%, 61.1% and 53.8%.
Comparative example 4
And (3) ceramsite pretreatment: respectively crushing commercially available fly ash ceramsite, clay ceramsite, biological sludge ceramsite and garbage ceramsite into 20 meshes, dissolving various metal salt impurities in the ceramsite according to the solid-to-liquid ratio of 1:10(g: mL) of the ceramsite to methanol, carrying out ultrasonic treatment for 10min under the ultrasonic condition, standing, carrying out vacuum filtration, and drying at 100 ℃ for 2 h. And (3) placing the dried sample in a beaker, adding 1mol/L HCl to ensure that the solid-to-liquid ratio of the ceramsite to the HCl is 1:5(g: mL), placing the sample in a muffle furnace, roasting the sample for 3 hours at 500 ℃, and grinding the sample to 20 meshes to obtain the pretreated ceramsite.
Application of the chromium adsorbent:
adding 1g of each of the four pretreated ceramsite into chromium-containing wastewater with the initial concentration of 0.6mg/L, respectively, measuring the chromium concentration in the adsorbed wastewater by using a heavy metal multi-parameter tester, and calculating to obtain the chromium removal efficiency of 72.2%, 67.5%, 63.8% and 72.9%.
Claims (9)
1. The chromium adsorbent is characterized by being modified ceramsite and used for adsorbing hexavalent chromium with the concentration of 0.1-1 mg/L in wastewater, and is prepared by the following method:
(1) crushing ceramsite to 40-120 meshes, adding methanol, performing ultrasonic treatment for 5-15 min, standing, performing vacuum filtration, and drying at 60-120 ℃ for 2-3 h;
(2) adding an eluent with the concentration of 0.5-2 mol/L into the dried sample, carrying out ultrasonic treatment for 5-15 min, carrying out vacuum filtration after elution, and drying for 2-3h at the temperature of 60-120 ℃;
(3) and (3) placing the ceramsite treated in the step (2) into a muffle furnace, roasting for 2-3h at 400-600 ℃, taking out, and grinding to 40-120 meshes to obtain the modified ceramsite.
2. The method according to claim 1, wherein the ceramsite in step (1) is one or more of fly ash ceramsite, clay ceramsite, biological sludge ceramsite and garbage ceramsite.
3. The preparation method according to claim 1, wherein in the step (1), the mass-to-volume ratio of the ceramsite to the methanol is 1-5 g:10 mL.
4. The method according to claim 1, wherein the eluent in step (2) is HCl, HNO3Or H2SO4。
5. The method according to claim 1, wherein the eluent in the step (2) is NaOH, Ca (OH)2Or Ba (OH)2。
6. The preparation method according to claim 1, wherein the mass-to-volume ratio of the ceramsite to the eluent in the step (2) is 1-5 g:5 mL.
7. Use of the chromium adsorbent of claim 1 for removing low concentrations of Cr from wastewater.
8. The use according to claim 7, wherein the concentration of Cr in the wastewater is 0.1-1 mg/L.
9. Use according to claim 8, wherein Cr in said wastewater is hexavalent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106915972A (en) * | 2017-03-13 | 2017-07-04 | 内蒙古科技大学 | A kind of modified coal ash haydite and its preparation method and application |
| CN107413314A (en) * | 2017-07-26 | 2017-12-01 | 河北科技大学 | The preparation method and application of the modified adsorbents of PEI/ZSM 5 of chromium in a kind of removal waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106915972A (en) * | 2017-03-13 | 2017-07-04 | 内蒙古科技大学 | A kind of modified coal ash haydite and its preparation method and application |
| CN107413314A (en) * | 2017-07-26 | 2017-12-01 | 河北科技大学 | The preparation method and application of the modified adsorbents of PEI/ZSM 5 of chromium in a kind of removal waste water |
Non-Patent Citations (1)
| Title |
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| 自制污泥基陶粒的表面改性及其在含Cr(VI)废水生物净化方面的应用;孙浩;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150916(第10期);摘要，第35-37页的第4.3.5节 * |
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