CN111330536B - Preparation and use methods of anion and cation compound modified activated ore for repairing and treating heavy metal polluted site wastewater - Google Patents
Preparation and use methods of anion and cation compound modified activated ore for repairing and treating heavy metal polluted site wastewater Download PDFInfo
- Publication number
- CN111330536B CN111330536B CN202010164891.XA CN202010164891A CN111330536B CN 111330536 B CN111330536 B CN 111330536B CN 202010164891 A CN202010164891 A CN 202010164891A CN 111330536 B CN111330536 B CN 111330536B
- Authority
- CN
- China
- Prior art keywords
- heavy metal
- modified activated
- anion
- compound modified
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/008—Sludge treatment by fixation or solidification
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- C02F2101/20—Heavy metals or heavy metal 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The scheme discloses a preparation and use method of anion and cation compound modified activated ore for repairing and treating waste water in heavy metal pollution sites, which comprises the steps of taking natural clay ore as a raw material, crushing and screening the natural clay ore to form irregular particles, processing the irregular particles into amorphous particles with the size of 0.15-8mm, putting the amorphous particles into a filter tank, introducing a certain amount of activating agent solution, activating the particles for a certain time at a certain empty bed flow rate, taking the particles out, rinsing the particles with water, draining the particles, drying and crushing the particles. Heavy metal ions such as Pb in the polluted water are treated by anion-cation exchange, chemical adsorption and mineralization of the heavy metal ions by using the compound modified activated ore 2+ 、Cr 3+ 、Ni 2+ 、CrO 4 2‑ 、Cr 2 O 7 2‑ 、AsO 3 3‑ 、AsO 4 3‑ And filtering and removing after adsorption to achieve the aim of restoring the heavy metal polluted water. The raw material clay ore has low cost, simple processing technology, good effect of removing heavy metal by using the compound modified activated ore, quick response, no secondary pollution and stable sludge property, reduces the activity and the mobility of heavy metal ions, is solidified and stabilized with the site heavy metal polluted soil, and the leachate can reach the IV-type standard of underground water.
Description
Technical Field
The invention belongs to the field of environmental remediation and treatment, and relates to a preparation and application method of anion and cation compound modified activated ore for remediating and treating wastewater in heavy metal polluted sites.
Background
With the rapid development of economy, industrialization and urbanization, the problem of soil environment safety in China is increasingly severe, industrial wastewater, sludge and the like of various industries can become site heavy metal pollution sources, a large amount of wastewater generated by industrial and mining enterprises is discharged in an irregular manner due to historical reasons, heavy metal accumulation in water bodies around the enterprises is aggravated, heavy metal pollution in foundation pit wastewater generated in the site repairing process is serious, and therefore heavy metal wastewater treatment is an indispensable part in site repairing.
The treatment technology of heavy metal wastewater comprises a chemical precipitation method, an adsorption method, an ion exchange method, a membrane separation method and the like, the adsorption method is always researched as the most economic treatment technology of heavy metals in water, and the remediation goal can be economically and effectively achieved by selecting a proper adsorbent and a water treatment process with reasonable design. Common adsorbents comprise activated carbon, silicate ore adsorption materials, activated alumina, organic adsorption materials and the like, wherein the silicate ore adsorption materials are wide in raw materials and low in cost, and have high heavy metal removal efficiency after modification and activation, but the sludge generated by wastewater treatment is large in amount, contains heavy metals, belongs to solid waste, and needs to be subjected to compliance treatment.
The silicate ore adsorbing material is mainly clay minerals such as zeolite, attapulgite, kaolin and the like, and the clay generally has higher Cation Exchange Capacity (CEC), namely has stronger ion exchange and adsorption effects on cations. In the prior art research, the cation exchange capacity is generally improved by adopting an acid modification mode, namely, the clay mineral crystal is soaked in a hydrochloric acid solution with a certain concentration, high-valence cations in the clay mineral crystal are replaced by hydrogen ions, impurity ions are removed, the ore is purified, and the adsorption capacity of the clay to heavy metal cations is improved.
Disclosure of Invention
The invention aims to provide a preparation method of anion and cation compound modified activated ore for repairing and treating wastewater in a heavy metal pollution site, which comprises the following steps: taking natural zeolite and hydrotalcite as raw materials, crushing and screening the raw materials to form amorphous particles with the size of 0.15-8mm, mixing the amorphous particles according to a certain weight ratio, putting the amorphous particles into a filter tank, introducing an activating agent solution, activating for 0.1-2h at an empty bed flow rate (super stability) of 1-20 m/h, rinsing the amorphous particles with pure water, draining the activated particles, drying the rinsed activated particles to obtain a compound modified activated ore particle filter material, and crushing the compound modified activated ore particle filter material to be less than 0.075mm to obtain the compound modified activated ore powder adsorbent.
Wherein, the weight ratio of the natural zeolite to the hydrotalcite is 1-5: 1; the size of the amorphous particles is preferably 1-6 mm; the activator solution is an inorganic salt solution; the inorganic salt solution is 5 to 10 percent sodium chloride solution, and hydrochloric acid is used for adjusting the pH value to 3 to 4; the ratio of the filter sectional area of the filter to the filter depth is 1.2-4: 1, the flow rate of an empty bed is 2-8 m/h, and the activation time is 0.5-1 h.
The use method of the anion and cation compound modified activated ore for restoring and treating the wastewater of the heavy metal polluted site comprises the following steps: adding 0.5-5 g/L of compound modified activated ore powder adsorbent into the wastewater to be repaired, adding at least one of ferrous sulfate, ferric sulfate, quicklime and polymeric flocculant into the wastewater to be repaired, stirring for reaction for 5-60 min, and then precipitating and filtering.
Wherein, the sedimentation filtration adopts a pressure filter for filtration, the compound modified activated ore particle filter material as described in claim 1 is filled in the pressure filter, and the ratio of the filtration sectional area to the filtration depth of the pressure filter is 1.2-4: 1, the flow rate of an empty bed is 4-16 m/h, and the contact time of the empty bed is 0.1-0.5 h.
The dosage of the ferrous sulfate is 0.05-0.5 g/L, the dosage of the ferric sulfate is 0.05-0.5 g/L, the dosage of the quicklime is 0.1-2 g/L, and the dosage of the polymeric flocculant is 0.005-0.05 g/L; the polymeric flocculant is at least one of polyaluminium chloride, polyferric sulfate and polyacrylamide.
Sludge and filter materials generated by the treatment of waste water in a heavy metal pollution site are solidified and stabilized together with the heavy metal pollution soil in the site, and the solidification and stabilization treatment method comprises the following steps: firstly, adding 0.5-4% of ferrous sulfate into sludge, filter materials and site heavy metal polluted soil, fully and uniformly stirring the mixture, keeping 25-40% of water, curing the mixture for 3-7 days, crushing the sludge, the filter materials and the site heavy metal polluted soil into 5-50 mm after the sludge, the filter materials and the site heavy metal polluted soil are slightly dried in the air, adding 5-20% of cement into the sludge, the filter materials and the site heavy metal polluted soil, uniformly stirring the mixture, spraying 20-50% of clean water or site wastewater after repair treatment, and covering a PE film or geotextile for curing for 15-40 days to finish curing and stabilizing treatment.
The scheme is inspired by the ion exchange and regeneration principles of mixed bed resin, two natural ores respectively having anion and cation exchange capacity are selected for compounding, and the compounded ores are subjected to flow modification and activation, so that the operation is simple and easy to realize, the adsorption performance of the natural ores is greatly improved, and the using amount of the adsorbent can be reduced.
Compared with natural zeolite, the activated zeolite has increased calcium exchange amount, ammonia adsorption amount, inner surface area and total negative charge amount. The increase of the internal surface area shows that some original pore channels of the natural zeolite are blocked and can not be exchanged, impurities are removed after modification, the pore channels are unblocked, and the natural zeolite contains various ions which easily cause stacking defects and have a plurality of bottlenecks.
Zeolite is a tetrahedron composed of 3 elements Si, al, O, in which a three-dimensional framework of infinite extension is formed between the silicon-oxygen tetrahedron and the aluminum-oxygen tetrahedron. In the tetrahedral structure of the zeolite, negative charges caused by the replacement of silicon ions by aluminum ions are balanced by potassium, sodium, calcium, magnesium and other ions, so that the zeolite has stronger ion exchange and adsorption capacity, passivates heavy metal ions in soil, reduces the biological effectiveness of the heavy metal ions, and is widely applied in the fields of agricultural production and environmental protection.
The adsorption amount of the zeolite to the heavy metal cations is closely related to the valence number of the cations bound in the zeolite and the hydration radius of the cations. When the valence of the cation combined in the zeolite is high, the cation has strong binding force with the negative charge of the zeolite framework, is not easy to exchange with heavy metal cations, and has low heavy metal adsorption capacity. The smaller the radius of the hydrated ion, the stronger the binding force between the hydrated ion and the negative charge of the zeolite framework, and conversely, the larger the binding force, the weaker the binding force, and the hydrated ion is easy to exchange heavy metal cations. Of the monovalent ions, the radius of sodium hydrated ion is larger than that of potassium hydrated ion and larger than that of ammonium hydrated ion, and the binding force between the sodium hydrated ion and the negative charge of zeolite skeleton is weaker than that between the potassium hydrated ion and the ammonium hydrated ion, so that the heavy metal adsorption capacity of sodium zeolite is larger, and natural zeolite is Ca 2+ To bind mainly cations, ca 2+ The hydrated ions are divalent ions and have strong binding force, so the sodium type zeolite modified by the sodium ions can be used for treating high-valence heavy metal cations such as Pb 2+ 、Cr 3+ 、Ni 2+ The adsorption of (A) is obviously higher than that of natural zeolite.
The hydrotalcite material is a layered double hydroxide, and belongs to anionic layered compounds. The layered compound is a compound with a layered structure, interlayer ions and ion exchangeability, and is composed of a main body layer with positive chargesThe plates and interlayer anions are assembled into compounds by non-covalent interactions, mg being located on the layers 2+ Can be coated with Al within a certain range 3+ 、Fe 3+ By substitution, the laminate is positively charged and there is exchangeable CO between layers 3 2- Balancing with positive charges on the laminate, so that the overall structure of the LDHs is electrically neutral. Due to the fact that the laminated plates and the interlayer anions are connected through hydrogen bonds, the interlayer anions of the hydrotalcite have interchangeability. The interlayer anion can be exchanged with various anions including inorganic ions, organic ions, homoions, heteropoly acid ions, and anions of coordination compounds. Under normal conditions, the higher the ion valence number, the larger the atomic number, the smaller the ionic hydration radius and the stronger the binding force, and the natural hydrotalcite interlamination ions mainly contain CO 3 2- 、SO 4 2- The high-valence anions such as the LDHs interlayer anions after the chloride ion modification activation under the promotion of acid are replaced by monovalent chloride ions, and the high-valence heavy metal anions CrO are replaced by the monovalent chloride ions 4 2- 、Cr 2 O 7 2- And the adsorption effect is greatly enhanced. The acid is added for cation adjustment in order to make interlayer anions adsorbed in hydrotalcite easily desorbed in a solution or in order to make replacement anions easily adsorbed in hydrotalcite.
The scheme is that zeolite with cation exchange capacity and hydrotalcite with anion exchange capacity are compounded in certain proportion, and high concentration salt solution is used to modify and activate the flow of zeolite under acid condition to replace Na with cation in zeolite + And hydrotalcite interlayer anion is replaced by Cl - Impurity ions are removed, the microscopic pore structure of the ore is improved, and the synchronous adsorption effect on the heavy metal of the anions and the cations is obviously enhanced.
Detailed Description
The present invention is described in detail by the following specific examples, which are provided for the purpose of illustration and are not to be construed as limiting the invention.
Example 1
Natural zeolite and hydrotalcite are used as raw materials, and are processed into amorphous particles with the size of 3-6mm through crushing and screening, and the weight ratio of the amorphous particles to the zeolite is 2:1 weight ratio, placing the mixture into a filter, introducing a mixed solution of HCl and NaCl with the pH value of 3.0, activating the mixture for 0.5 hour at an empty bed flow rate of 6 m/hour, rinsing the mixture for 2 times by using pure water, draining the mixture, and finally drying and crushing the mixture to obtain a finished product with the particle size of less than 0.075 mm. The indexes for representing the cation exchange performance comprise calcium exchange amount, ammonia absorption amount and the like, and the indexes are respectively determined according to the method 1 part of YS/T1065.1-2015 zeolite physical property: EDTA titration method for measuring calcium exchange capacity and GB/T21695-2008 feed-grade zeolite powder. The hexavalent chromium adsorption method described in patent document 200510050873.4 is adopted to characterize the anion exchange performance, namely 0.5g/L of adsorbent is put into a hexavalent chromium solution with the pH value of 100mg/L and the solution is adsorbed for 2 hours at the temperature of 40 ℃. The ion exchange properties of the ore are shown in table 1.
TABLE 1 ion exchange Properties of the ores
Example 2
The concentration of heavy metals Pb, ni and Cr (VI) in pond water in a certain polluted site is 3-10.5 times of the IV standard of surface water, and the total amount is about 40000m 3 The method adopts integrated water treatment equipment for treatment, and the treatment process comprises the following steps: performing adsorption, coagulating sedimentation and filtering by using a compound modified activated ore powder adsorbent, and adding 0.1g/L FeSO 4 ·7H 2 O, 2.5g/L compound modified activated ore, 0.5g/LCaO and 0.008g/LPAM, the total hydraulic retention time is 40min, the empty bed flow rate of the filter is 10m/h, and the effluent reaches the repair target value, as shown in Table 2.
TABLE 2 site pond water contaminant index
| Pb(mg/L) | Ni(mg/L) | Cr(VI)(mg/L) | |
| Raw water | 0.29 | 0.32 | 0.52 |
| Discharging water | 0.022 | <0.03 | 0.016 |
| Repair target value | 0.05 | 0.1 | 0.05 |
After sludge dehydration, the sludge is solidified and stabilized with waste particle filter materials, the to-be-repaired contaminated soil of the site and bottom mud, and the specific scheme is that a certain amount of FeSO is respectively added 4 ·7H 2 O and cement, 1:4 water-soil ratio, maintaining for 28d, and preparing leachate according to the standard of HJT 299-2007 solid waste leaching toxicity leaching method sulfuric acid-nitric acid method to reach the repair target value, as shown in Table 3.
TABLE 3 leachate of sludge, filter material, contaminated soil and substrate sludge
| Pb(mg/L) | Ni(mg/L) | Cr(VI)(mg/L) | |
| Leach liquor | 0.072 | <0.03 | 0.036 |
| Repair target value | 0.1 | 0.1 | 0.1 |
Example 3
The concentration of heavy metals Pb and As in foundation pit wastewater of a certain polluted site is 5-8.5 times of the IV standard of surface water, and the wastewater is treated by adopting integrated water treatment equipment, wherein the treatment process comprises the following steps: carrying out adsorption, coagulating sedimentation and filtering on a compound modified activated ore powder adsorbent, and adding 0.05g/L Fe 2 (SO 4 ) 3 2g/L of compound modified activated ore, 0.5g/L of CaO and 0.008g/L of PAM, wherein the total hydraulic retention time is 40min, the empty bed flow rate of the filter is 10m/h, and the effluent reaches the repair target value, as shown in Table 4.
TABLE 4 Foundation pit Water contaminant index
| Pb(mg/L) | As(mg/L) | |
| Raw water | 0.25 | 0.85 |
| Discharging water | 0.023 | 0.089 |
| Repair target value | 0.05 | 0.1 |
The sludge is solidified and stably repaired together with the waste particle filter material and the polluted soil to be repaired in the field after being dehydrated, and the specific scheme is that a certain amount of FeSO is respectively added 4 ·7H 2 O and cement, 1:4 water-soil ratio, maintaining for 28d, and preparing leachate according to the standard of HJT 299-2007 solid waste leaching toxicity leaching method sulfuric acid-nitric acid method to reach the repair target value, as shown in Table 3.
TABLE 3 leachate of contaminated soil and sludge filter
| Pb(mg/L) | As(mg/L) | |
| Leach liquor | 0.062 | 0.026 |
| Target value of repair | 0.1 | 0.05 |
Claims (3)
1. The preparation method of the anion and cation compound modified activated ore for restoring and treating the wastewater of the heavy metal polluted site is characterized by comprising the following steps of: taking natural zeolite and hydrotalcite as raw materials, crushing and screening the raw materials to form amorphous particles with the size of 1-6 mm, mixing the amorphous particles according to a certain weight ratio, putting the amorphous particles into a filter tank, introducing an activator solution, activating for 0.1-2h at an empty bed flow rate of 1-20m/h, rinsing with pure water, draining, drying to obtain a cation and anion compound modified activated ore particle filter material, and crushing to the size of less than 0.075mm to obtain the cation and anion compound modified activated ore powder adsorbent; the weight ratio of the natural zeolite to the hydrotalcite is 1 to 5:1; the activator solution is an inorganic salt solution; the inorganic salt solution is a 5% -10% sodium chloride solution, and the pH value is adjusted to 3 to 4 by hydrochloric acid; the ratio of the filtering sectional area of the filter to the filtering depth is 1.2 to 4:1;
the application method of the anion and cation compound modified activated ore for repairing and treating the wastewater of the heavy metal pollution site comprises the following steps: adding 0.5-5g/L of compound modified activated ore powder adsorbent into the wastewater to be repaired, adding at least one of ferrous sulfate, ferric sulfate, quicklime and a polymeric flocculant into the wastewater to be repaired, stirring for reaction for 5-60min, and then precipitating and filtering;
and (2) filtering the sediment by using a pressure filter, filling the anion and cation compound modified activated ore particle filter material into the pressure filter, wherein the ratio of the filtering sectional area to the filtering depth of the pressure filter is 1.2 to 4:1, the air bed flow rate is 4 to 16m/h, and the air bed contact time is 0.1 to 0.5h;
the dosage of the ferrous sulfate is 0.05-0.5 g/L, the dosage of the ferric sulfate is 0.05-0.5 g/L, the dosage of the quicklime is 0.1-2g/L, and the dosage of the polymeric flocculant is 0.005-0.05g/L; the polymeric flocculant is at least one of polyaluminium chloride, polyferric sulfate and polyacrylamide;
the sludge and the filter material generated by the treatment of the waste water in the heavy metal polluted site are solidified and stabilized together with the heavy metal polluted soil in the site, and the solidification and stabilization treatment method comprises the following steps: firstly, adding 0.5-4% of ferrous sulfate into sludge, filter materials and site heavy metal polluted soil, fully stirring uniformly, keeping 25-40% of water, curing for 3-7 d, slightly airing, crushing the sludge, the filter materials and the site heavy metal polluted soil into 5-50mm, adding 5-20% of cement into the sludge, the filter materials and the site heavy metal polluted soil, uniformly stirring, spraying 20-50% of clean water or site wastewater after repair treatment, and covering PE (polyethylene) membranes or geotextiles for curing for 15-40d to finish curing and stabilizing treatment.
2. The method according to claim 1, wherein the heavy metal ion suitable for the anion-cation complex modified activated ore is Pb 2+ 、Cr 3+ 、Ni 2+ 、CrO4 2- 、Cr 2 O 7 2- 、AsO 3 3- 、AsO 4 3- At least one of (1).
3. The preparation method according to claim 1, wherein the flow rate of the activated air bed is 2 to 8m/h, and the activation time is 0.5 to 1h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010164891.XA CN111330536B (en) | 2020-03-11 | 2020-03-11 | Preparation and use methods of anion and cation compound modified activated ore for repairing and treating heavy metal polluted site wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010164891.XA CN111330536B (en) | 2020-03-11 | 2020-03-11 | Preparation and use methods of anion and cation compound modified activated ore for repairing and treating heavy metal polluted site wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111330536A CN111330536A (en) | 2020-06-26 |
| CN111330536B true CN111330536B (en) | 2023-03-28 |
Family
ID=71176248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010164891.XA Active CN111330536B (en) | 2020-03-11 | 2020-03-11 | Preparation and use methods of anion and cation compound modified activated ore for repairing and treating heavy metal polluted site wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111330536B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536221A (en) * | 2021-06-28 | 2022-12-30 | 无锡金鹏环保科技有限公司 | Method for purifying heavy metal sludge |
| CN113321351B (en) * | 2021-08-02 | 2021-11-12 | 清大国华环境集团股份有限公司 | Method for treating cadmium wastewater and solidifying cadmium slag |
| CN113877523A (en) * | 2021-11-02 | 2022-01-04 | 中国人民大学 | Modified vermiculite adsorbent and preparation method and application method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101797496A (en) * | 2010-01-07 | 2010-08-11 | 北京林业大学 | Preparation method of inorganic-organic compound-type adsorbent based on clinoptilolite and application for removing Cr(VI) in industrial waste water |
| CN104289185A (en) * | 2014-10-28 | 2015-01-21 | 北京林业大学 | Granular filtering material for adsorbing and removing heavy metals in water and preparation method thereof |
| CN106732343A (en) * | 2016-11-22 | 2017-05-31 | 衢州学院 | A kind of preparation method of modified zeolite and the modified zeolite for preparing |
| CN108726823A (en) * | 2017-12-19 | 2018-11-02 | 上海傲江生态环境科技有限公司 | The method that greasy filth stabilizes solidification medicament and repairs Heavy Metal Pollution in Sediments soil |
| CN110724401A (en) * | 2019-11-22 | 2020-01-24 | 浙江丰虹新材料股份有限公司 | Synergistic self-repairing corrosion-resistant additive and application thereof |
-
2020
- 2020-03-11 CN CN202010164891.XA patent/CN111330536B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101797496A (en) * | 2010-01-07 | 2010-08-11 | 北京林业大学 | Preparation method of inorganic-organic compound-type adsorbent based on clinoptilolite and application for removing Cr(VI) in industrial waste water |
| CN104289185A (en) * | 2014-10-28 | 2015-01-21 | 北京林业大学 | Granular filtering material for adsorbing and removing heavy metals in water and preparation method thereof |
| CN106732343A (en) * | 2016-11-22 | 2017-05-31 | 衢州学院 | A kind of preparation method of modified zeolite and the modified zeolite for preparing |
| CN108726823A (en) * | 2017-12-19 | 2018-11-02 | 上海傲江生态环境科技有限公司 | The method that greasy filth stabilizes solidification medicament and repairs Heavy Metal Pollution in Sediments soil |
| CN110724401A (en) * | 2019-11-22 | 2020-01-24 | 浙江丰虹新材料股份有限公司 | Synergistic self-repairing corrosion-resistant additive and application thereof |
Non-Patent Citations (9)
| Title |
|---|
| "Layered double hydroxide/eggshell membrane：An inorganic biocomposite membrane as an efficient adsorbent for Cr(VI) removal";Guo Xiaoxiao et al.;《Chemical Engineering Journal》;20111231;第166卷(第1期);第81-87页 * |
| "Removal of Mn(II), Fe(III) and Cr(III) from aqueous solutions using Bulgarian clinoptilolite";Vassileva P. S et al.;《BULGARIAN CHEMICAL COMMUNICATIONS》;20121231;第44卷(第2期);第180-187页 * |
| "Zn系LDHs负载改性石英砂和沸石对Cr( VI) 吸附效果对比及其作用机理研究";何春艳等;《环境科学学报》;20180910;第39卷(第2期);第399-409页 * |
| 天然沸石在水污染控制中的应用;柳萍，王建龙;《离子交换与吸附》;19960820(第04期);全文 * |
| 改性天然矿物吸附废水中重金属离子的研究进展;石太宏等;《水处理技术》;20090410(第04期);全文 * |
| 改性沸石制备及对其铬吸附特性的研究;黄玉梅;《硅酸盐通报》;20170115(第01期);全文 * |
| 改性硅酸盐矿物在修复土壤重金属污染中的应用;于勤勤等;《安徽农学通报》;20080510(第09期);全文 * |
| 柠檬酸三钠对Co~(2+)-Ni~(2+)-Fe~(3+)-CO_3~(2-) LDHs形貌及其离子交换性能的影响;马向荣等;《无机材料学报》;20141215(第12期);全文 * |
| 非金属矿物的改型改性及其在环境保护中的应用;潘忠华，潘兆橹;《地质科技情报》;19950930(第03期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111330536A (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111330536B (en) | Preparation and use methods of anion and cation compound modified activated ore for repairing and treating heavy metal polluted site wastewater | |
| Koshy et al. | Fly ash zeolites for water treatment applications | |
| Zhao et al. | Application of sodium titanate nanofibers as constructed wetland fillers for efficient removal of heavy metal ions from wastewater | |
| CN102190345B (en) | Method for enriching low-concentration heavy metal in water by recyclable magnesium hydroxide adsorbent | |
| CN103086460B (en) | Phosphorus-removing method based on nano-grade iron | |
| CN104136113A (en) | Porous composite media for removing phosphorus from water | |
| CN101920191B (en) | Application of activated carbon modified material and application in removing arsenic from water | |
| Gan et al. | Antimony (Sb) pollution control by coagulation and membrane filtration in water/wastewater treatment: A comprehensive review | |
| CN101920188B (en) | Method for modifying manganese ore and application thereof in removal of arsenic from groundwater permeable reactive wall | |
| Aneke et al. | Adsorption of heavy metals from contaminated water using leachate modular tower | |
| Sevgili et al. | An environmentally sustainable way for effective water purification by adsorptive red mud cementitious composite cubes modified with bentonite and activated carbon | |
| Saliu et al. | Assessing the suitability of solid aggregates for nutrient recovery from aqua systems | |
| CN102557367B (en) | Method for recycling and safely disposing aluminum-salt containing coagulated sludge | |
| CN104645932B (en) | A kind of composite modified zeolite of iron and manganese oxides and preparation method and application | |
| Anjali et al. | Experimental studies of slag filter for drinking water treatment | |
| CN109847704B (en) | Method for preparing heavy metal chromium adsorbent by utilizing Dian pond dredged sediment and application | |
| CN1321086C (en) | Modified bentonite chromium remover and its manufacturing method | |
| Chen et al. | Removal of phosphorus from water using scallop shell synthesized ceramic biomaterials | |
| El-Mahalaway et al. | Sorption characteristics of iron, fluoride and phosphate from wastewater of phosphate fertilizer plant using natural sodium bentonite | |
| Zhao et al. | Study on the feasibility and stability of drinking water treatment sludge (DWTS)@ zeolite to remove phosphorus from constructed wetlands | |
| Pająk | Alum sludge as an adsorbent for inorganic and organic pollutants removal from aqueous solutions: a review | |
| Ren et al. | Preparation of fluoride adsorbent by resource utilization of carbide slag from industrial waste | |
| Carleton et al. | Laboratory evaluation of alum, ferric and ferrous-water treatment residuals for removing phosphorous from surface water | |
| CN106621561A (en) | Sewage filter screen for adsorbing nitrogen and phosphorus elements in sewage | |
| CN101863545A (en) | Decolorizing agent for coked waste water and using method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 213100 No. 22, Lingxiang Road, Wujin economic development zone, Changzhou City, Jiangsu Province Applicant after: JIANGSU YANGTZE RIVER DELTA ENVIRONMENTAL SCIENCE AND TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. Address before: 213100 No. 22, Lingxiang Road, economic development zone, Wujin District, Changzhou City, Jiangsu Province Applicant before: JIANGSU YANGTZE RIVER DELTA ENVIRONMENTAL SCIENCE AND TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |