CN110860278A - Adsorbent for underground water and preparation method thereof - Google Patents
Adsorbent for underground water and preparation method thereof Download PDFInfo
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- CN110860278A CN110860278A CN201911345539.XA CN201911345539A CN110860278A CN 110860278 A CN110860278 A CN 110860278A CN 201911345539 A CN201911345539 A CN 201911345539A CN 110860278 A CN110860278 A CN 110860278A
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2101/103—Arsenic compounds
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
Abstract
The invention provides an adsorbent for underground water, which comprises the following raw materials: bagasse, tea seed shells, red mud, fly ash, an activating agent, ferric chloride, aluminum chloride, potassium hydroxide, a foaming agent, a binder and epoxidized soybean oil. The preparation method comprises the steps of drying bagasse and tea seed shells in the sun, crushing, pretreating, mixing with an activating agent, and carbonizing; then mixing and calcining the red mud, the fly ash, the foaming agent and the binder; then reacting aluminum chloride, ferric chloride and potassium hydroxide to prepare the iron-aluminum composite adsorbent; and finally, mixing the soybean oil with the epoxidized soybean oil, and grinding to obtain the soybean oil. The adsorbent has obvious advantages in synchronous arsenic and fluorine removal, and shows good adsorption effect.
Description
Technical Field
The invention belongs to the technical field of underground water treatment, and particularly relates to an adsorbent for underground water and a preparation method thereof.
Background
The hazards of arsenic and fluorine in groundwater have recently attracted considerable worldwide attention. Recent studies have found that there are many countries and regions around the world where the pollution of arsenic and fluorine is a problem, such as china, mexico, argentina, and pakistan. As arsenic and fluorine in the groundwater have high toxicity and harm, the standards of arsenic and fluorine in the drinking water standard of China are respectively improved to 0.01mg/L and 1.0 mg/L.
The toxicity and contamination of arsenic and fluorine are a worldwide problem and are of widespread concern. In many areas, the phenomenon of coexistence of arsenic and fluorine is reported, and particularly, the phenomenon is most serious in pakistan, argentina, mexico, inner Mongolia of China, Shanxi and Shaanxi, so that the development of a method for removing arsenic and fluorine is urgently needed at the present stage.
At present, a nanofiltration and reverse osmosis combined method, a coagulation method, an adsorbent method and the like are used for removing arsenic and fluorine together. However, these methods have drawbacks: 1. the membrane treatment method has high cost, has the problems of membrane pollution and high energy consumption, and is not suitable for developing countries at present; 2. the coagulated sludge produced by the coagulation method is not easy to be treated, which causes secondary pollution, and the cooperation of a filtering process is needed after coagulation, so that the treatment cost is increased. Aiming at the existing dispersion in China, the water supply mode is adopted, and the adsorption method has the advantages of low cost, simple operation, good removal effect, no secondary pollution and the like, and has high applicability, so that the development of a novel effective adsorbent becomes a key for solving the problem of coexisting arsenic and fluorine in water.
Disclosure of Invention
The invention aims to provide an adsorbent for underground water and a preparation method thereof.
The adsorbent for the underground water comprises the following raw materials in parts by weight: 30-50 parts of bagasse, 20-30 parts of tea seed shells, 10-20 parts of red mud, 2-4 parts of fly ash, 3-5 parts of an activating agent, 5-10 parts of ferric chloride, 5-10 parts of aluminum chloride, 20-30 parts of potassium hydroxide, 2-4 parts of a foaming agent, 1-2 parts of a binder and 0.8-1.5 parts of epoxidized soybean oil.
Further, the activating agent is a mixture of zinc chloride and citric acid, and the weight ratio of the zinc chloride to the citric acid is 10: 1.
further, the foaming agent is one selected from sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate or rosin soap foaming agents.
Further, the adhesive is ethylene-vinyl acetate copolymer.
The preparation method of the adsorbent for the underground water comprises the following steps:
step 1, drying bagasse and tea seed shells in the sun, and crushing the bagasse and tea seed shells until the bagasse and tea seed shells can pass through a 20-mesh sieve to obtain dry powder;
step 2, adding the dry powder obtained in the step 1 into a 5wt% sodium hydroxide solution with the weight being 10 times that of the dry powder, heating to 60-70 ℃, preserving heat for 2-3h, cooling and filtering to obtain wet powder;
step 3, mixing the wet powder obtained in the step 2 with an activating agent, and carbonizing to obtain a mixture 1;
step 4, mixing and calcining the red mud, the fly ash, the foaming agent and the binder to obtain a mixture 2;
step 5, adding aluminum chloride and ferric chloride into water of which the weight is 10 times that of the aluminum chloride and the ferric chloride, adding potassium hydroxide under the stirring condition, dispersing, standing, taking the lower-layer precipitate, and drying to obtain mixed powder;
and 6, mixing the mixture 1, the mixture 2, the mixed powder and the epoxidized soybean oil, and grinding to obtain the epoxy soybean oil.
Further, the carbonization condition in the step 3 is 500-600 ℃ and 1-2 h.
Further, the calcination condition in the step 4 is 200-300 ℃ for 1-2 h.
According to the invention, bagasse and tea seed shell carbide, red mud and fly ash are calcined and granulated to be compounded to be used as a mixed carrier, the mixed carrier is used for loading an iron-aluminum adsorbent, the adsorbent for removing arsenic and fluorine together for underground water is prepared, and the adsorbent has a remarkable adsorption removal effect on arsenic and fluorine under the condition of pH 6. The bagasse and the tea seed shells are carbonized to form a sparse matrix, and the granulated red mud is filled into the matrix to form a dense mixed carrier, so that on one hand, the uniformity of compounding the carrier and the iron-aluminum adsorbent can be improved, and the specific surface area and the adsorption performance of the material are effectively improved; on the other hand, the adsorbent has a compact structure, good formability, high strength and strong water resistance, and can meet the requirements of the fixed bed adsorbent. The addition of the epoxidized soybean oil increases the combination degree of the mixed carrier and the iron-aluminum adsorbent, thereby effectively improving the efficiency of the iron-aluminum adsorbent.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
The adsorbent for the underground water comprises the following raw materials in parts by weight: 30 parts of bagasse, 20 parts of tea seed shells, 10 parts of red mud, 2 parts of fly ash, 3 parts of an activating agent, 5 parts of ferric chloride, 5 parts of aluminum chloride, 20 parts of potassium hydroxide, 2 parts of a foaming agent, 1 part of a binder and 0.8 part of epoxidized soybean oil.
The activating agent is a mixture of zinc chloride and citric acid, and the weight ratio of the zinc chloride to the citric acid is 10: 1.
the foaming agent is sodium dodecyl benzene sulfonate. The binder is ethylene-vinyl acetate copolymer.
The preparation method of the adsorbent for the underground water comprises the following steps:
step 1, drying bagasse and tea seed shells in the sun, and crushing the bagasse and tea seed shells until the bagasse and tea seed shells can pass through a 20-mesh sieve to obtain dry powder;
step 2, adding the dry powder obtained in the step 1 into a 5wt% sodium hydroxide solution with the weight being 10 times that of the dry powder, heating to 60-70 ℃, preserving heat for 2-3h, cooling and filtering to obtain wet powder;
step 3, mixing the wet powder obtained in the step 2 with an activating agent, and carbonizing for 2 hours at 500 ℃ to obtain a mixture 1;
step 4, mixing the red mud, the fly ash, the foaming agent and the binder, and calcining for 2 hours at 200 ℃ to obtain a mixture 2;
step 5, adding aluminum chloride and ferric chloride into water of which the weight is 10 times that of the aluminum chloride and the ferric chloride, adding potassium hydroxide under the stirring condition, dispersing, standing, taking the lower-layer precipitate, and drying to obtain mixed powder;
and 6, mixing the mixture 1, the mixture 2, the mixed powder and the epoxidized soybean oil, and grinding to obtain the epoxy soybean oil.
0.1g of the obtained adsorbent is added into 1L of aqueous solution containing 20mg/L fluorine and 5mg/L arsenic, the mixture is kept stand for 24h at 25 ℃ under the condition of pH 6, the solution is filtered and sampled by a 0.22 mu m acetate fiber membrane, the fluorine concentration in the solution is less than 1.0mg/L, the arsenic concentration in the solution is less than 0.01mg/L, and the requirement of drinking water is met.
Through detection, the Langmuir theoretical maximum adsorption capacities for arsenic and fluorine can reach 82.15mg/g and 53.42mg/g respectively.
Example 2
The adsorbent for the underground water comprises the following raw materials in parts by weight: 40 parts of bagasse, 24 parts of tea seed shells, 12 parts of red mud, 3 parts of fly ash, 4 parts of an activating agent, 7 parts of ferric chloride, 8 parts of aluminum chloride, 23 parts of potassium hydroxide, 3 parts of a foaming agent, 2 parts of a binder and 1.1 parts of epoxidized soybean oil.
The activating agent is a mixture of zinc chloride and citric acid, and the weight ratio of the zinc chloride to the citric acid is 10: 1.
the foaming agent is fatty alcohol-polyoxyethylene ether sodium sulfate. The binder is ethylene-vinyl acetate copolymer.
The preparation method of the adsorbent for the underground water comprises the following steps:
step 1, drying bagasse and tea seed shells in the sun, and crushing the bagasse and tea seed shells until the bagasse and tea seed shells can pass through a 20-mesh sieve to obtain dry powder;
step 2, adding the dry powder obtained in the step 1 into a 5wt% sodium hydroxide solution with the weight being 10 times that of the dry powder, heating to 60-70 ℃, preserving heat for 2-3h, cooling and filtering to obtain wet powder;
step 3, mixing the wet powder obtained in the step 2 with an activating agent, and carbonizing for 2 hours at 600 ℃ to obtain a mixture 1;
step 4, mixing the red mud, the fly ash, the foaming agent and the binder, and calcining for 2 hours at 300 ℃ to obtain a mixture 2;
step 5, adding aluminum chloride and ferric chloride into water of which the weight is 10 times that of the aluminum chloride and the ferric chloride, adding potassium hydroxide under the stirring condition, dispersing, standing, taking the lower-layer precipitate, and drying to obtain mixed powder;
and 6, mixing the mixture 1, the mixture 2, the mixed powder and the epoxidized soybean oil, and grinding to obtain the epoxy soybean oil.
0.1g of the obtained adsorbent is added into 1L of aqueous solution containing 20mg/L fluorine and 5mg/L arsenic, the mixture is kept stand for 24h at 25 ℃ under the condition of pH 6, the solution is filtered and sampled by a 0.22 mu m acetate fiber membrane, the fluorine concentration in the solution is less than 1.0mg/L, the arsenic concentration in the solution is less than 0.01mg/L, and the requirement of drinking water is met.
Through detection, the Langmuir theoretical maximum adsorption capacities for arsenic and fluorine can reach 79.87mg/g and 52.06mg/g respectively.
Example 3
The adsorbent for the underground water comprises the following raw materials in parts by weight: 50 parts of bagasse, 30 parts of tea seed shells, 20 parts of red mud, 4 parts of fly ash, 5 parts of an activating agent, 10 parts of ferric chloride, 10 parts of aluminum chloride, 30 parts of potassium hydroxide, 4 parts of a foaming agent, 2 parts of a binder and 1.5 parts of epoxidized soybean oil.
The activating agent is a mixture of zinc chloride and citric acid, and the weight ratio of the zinc chloride to the citric acid is 10: 1.
the foaming agent is a rosin soap foaming agent. The binder is ethylene-vinyl acetate copolymer.
The preparation method of the adsorbent for the underground water comprises the following steps:
step 1, drying bagasse and tea seed shells in the sun, and crushing the bagasse and tea seed shells until the bagasse and tea seed shells can pass through a 20-mesh sieve to obtain dry powder;
step 2, adding the dry powder obtained in the step 1 into a 5wt% sodium hydroxide solution with the weight being 10 times that of the dry powder, heating to 60-70 ℃, preserving heat for 2-3h, cooling and filtering to obtain wet powder;
step 3, mixing the wet powder obtained in the step 2 with an activating agent, and carbonizing for 2 hours at 500 ℃ to obtain a mixture 1;
step 4, mixing the red mud, the fly ash, the foaming agent and the binder, and calcining for 2 hours at 200 ℃ to obtain a mixture 2;
step 5, adding aluminum chloride and ferric chloride into water of which the weight is 10 times that of the aluminum chloride and the ferric chloride, adding potassium hydroxide under the stirring condition, dispersing, standing, taking the lower-layer precipitate, and drying to obtain mixed powder;
and 6, mixing the mixture 1, the mixture 2, the mixed powder and the epoxidized soybean oil, and grinding to obtain the epoxy soybean oil.
0.1g of the obtained adsorbent is added into 1L of aqueous solution containing 20mg/L fluorine and 5mg/L arsenic, the mixture is kept stand for 24h at 25 ℃ under the condition of pH 6, the solution is filtered and sampled by a 0.22 mu m acetate fiber membrane, the fluorine concentration in the solution is less than 1.0mg/L, the arsenic concentration in the solution is less than 0.01mg/L, and the requirement of drinking water is met.
Through detection, the Langmuir theoretical maximum adsorption capacities for arsenic and fluorine can reach 80.52mg/g and 51.76mg/g respectively.
Example 4
This example differs from example 2 in that: epoxidized soybean oil was not added.
The adsorbent for the underground water comprises the following raw materials in parts by weight: 40 parts of bagasse, 24 parts of tea seed shells, 12 parts of red mud, 3 parts of fly ash, 4 parts of an activating agent, 7 parts of ferric chloride, 8 parts of aluminum chloride, 23 parts of potassium hydroxide, 3 parts of a foaming agent and 2 parts of a binder.
The activating agent is a mixture of zinc chloride and citric acid, and the weight ratio of the zinc chloride to the citric acid is 10: 1.
the foaming agent is fatty alcohol-polyoxyethylene ether sodium sulfate. The binder is ethylene-vinyl acetate copolymer.
The preparation method of the adsorbent for the underground water comprises the following steps:
step 1, drying bagasse and tea seed shells in the sun, and crushing the bagasse and tea seed shells until the bagasse and tea seed shells can pass through a 20-mesh sieve to obtain dry powder;
step 2, adding the dry powder obtained in the step 1 into a 5wt% sodium hydroxide solution with the weight being 10 times that of the dry powder, heating to 60-70 ℃, preserving heat for 2-3h, cooling and filtering to obtain wet powder;
step 3, mixing the wet powder obtained in the step 2 with an activating agent, and carbonizing for 2 hours at 600 ℃ to obtain a mixture 1;
step 4, mixing the red mud, the fly ash, the foaming agent and the binder, and calcining for 2 hours at 300 ℃ to obtain a mixture 2;
step 5, adding aluminum chloride and ferric chloride into water of which the weight is 10 times that of the aluminum chloride and the ferric chloride, adding potassium hydroxide under the stirring condition, dispersing, standing, taking the lower-layer precipitate, and drying to obtain mixed powder;
and 6, mixing the mixture 1, the mixture 2 and the mixed powder, and grinding to obtain the material.
0.1g of the obtained adsorbent is added into 1L of aqueous solution containing 20mg/L fluorine and 5mg/L arsenic, the mixture is kept stand for 24h at 25 ℃ under the condition of pH 6, the solution is filtered and sampled by a 0.22 mu m acetate fiber membrane, the fluorine concentration in the solution is less than 1.0mg/L, the arsenic concentration in the solution is less than 0.01mg/L, and the requirement of drinking water is met.
Through detection, the Langmuir theoretical maximum adsorption capacities for arsenic and fluorine can reach 63.15mg/g and 37.81mg/g respectively.
Claims (7)
1. An adsorbent for underground water, characterized in that: the raw materials comprise the following components in parts by weight: 30-50 parts of bagasse, 20-30 parts of tea seed shells, 10-20 parts of red mud, 2-4 parts of fly ash, 3-5 parts of an activating agent, 5-10 parts of ferric chloride, 5-10 parts of aluminum chloride, 20-30 parts of potassium hydroxide, 2-4 parts of a foaming agent, 1-2 parts of a binder and 0.8-1.5 parts of epoxidized soybean oil.
2. An adsorbent for groundwater according to claim 1, characterized in that: the activating agent is a mixture of zinc chloride and citric acid, and the weight ratio of the zinc chloride to the citric acid is 10: 1.
3. an adsorbent for groundwater according to claim 1, characterized in that: the foaming agent is selected from one of sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether sodium sulfate or rosin soap foaming agents.
4. An adsorbent for groundwater according to claim 1, characterized in that: the binder is ethylene-vinyl acetate copolymer.
5. The method of preparing an adsorbent for groundwater as claimed in claim 1, wherein: the method comprises the following steps:
step 1, drying bagasse and tea seed shells in the sun, and crushing the bagasse and tea seed shells until the bagasse and tea seed shells can pass through a 20-mesh sieve to obtain dry powder;
step 2, adding the dry powder obtained in the step 1 into a 5wt% sodium hydroxide solution with the weight being 10 times that of the dry powder, heating to 60-70 ℃, preserving heat for 2-3h, cooling and filtering to obtain wet powder;
step 3, mixing the wet powder obtained in the step 2 with an activating agent, and carbonizing to obtain a mixture 1;
step 4, mixing and calcining the red mud, the fly ash, the foaming agent and the binder to obtain a mixture 2;
step 5, adding aluminum chloride and ferric chloride into water of which the weight is 10 times that of the aluminum chloride and the ferric chloride, adding potassium hydroxide under the stirring condition, dispersing, standing, taking the lower-layer precipitate, and drying to obtain mixed powder;
and 6, mixing the mixture 1, the mixture 2, the mixed powder and the epoxidized soybean oil, and grinding to obtain the epoxy soybean oil.
6. A method of producing an adsorbent for groundwater according to claim 5, characterized in that: the carbonization condition in the step 3 is 500-.
7. A method of producing an adsorbent for groundwater according to claim 5, characterized in that: the calcination condition in the step 4 is 200-300 ℃ and 1-2 h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117486438A (en) * | 2024-01-03 | 2024-02-02 | 北京哈泰克工程技术有限公司 | Treatment method of desulfurization wastewater of power plant |
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| CN117486438B (en) * | 2024-01-03 | 2024-04-02 | 北京哈泰克工程技术有限公司 | Treatment method of desulfurization wastewater of power plant |
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Application publication date: 20200306 |