CN111620530A - Reducing iron-sulfur mixed colloid, preparation method and application thereof - Google Patents
Reducing iron-sulfur mixed colloid, preparation method and application thereof Download PDFInfo
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- CN111620530A CN111620530A CN202010527819.9A CN202010527819A CN111620530A CN 111620530 A CN111620530 A CN 111620530A CN 202010527819 A CN202010527819 A CN 202010527819A CN 111620530 A CN111620530 A CN 111620530A
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- reducing iron
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- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 title claims abstract description 42
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 10
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- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229920000193 polymethacrylate Polymers 0.000 claims abstract description 8
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- 239000000243 solution Substances 0.000 claims description 34
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- 239000003381 stabilizer Substances 0.000 claims description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 230000002829 reductive effect Effects 0.000 abstract description 19
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- 230000008569 process Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
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- 239000010865 sewage Substances 0.000 description 11
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- 229910052793 cadmium Inorganic materials 0.000 description 8
- 229910052745 lead Inorganic materials 0.000 description 8
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- 238000007605 air drying Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
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- 239000011790 ferrous sulphate Substances 0.000 description 3
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- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 240000006909 Tilia x europaea Species 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
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- 150000007522 mineralic acids Chemical class 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 231100000502 fertility decrease Toxicity 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 239000010841 municipal wastewater Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a reductive iron-sulfur mixed colloid, a preparation method and application thereof. The colloid comprises a water-soluble organic high molecular compound and a ferrous sulfide compound; the water-soluble organic high molecular compound is one or two of polyacrylate and polymethacrylate. The reductive iron-sulfur mixed colloid disclosed by the invention has a high passivation rate on heavy metals in sludge under different pH and organic matter conditions, and has an obvious and long-lasting passivation effect. The preparation method disclosed by the invention is simple, practical, convenient and easy to implement, simple in requirements on process equipment, green in process, free of secondary pollution, wide in raw material cost source, low in price, capable of efficiently passivating polluted heavy metal sludge and good in market application potential.
Description
Technical Field
The invention relates to a sludge repairing agent, in particular to a reductive iron-sulfur mixed colloid, a preparation method and application thereof.
Background
Sludge is a solid, semi-solid or liquid residue produced in the sewage treatment process, and is a heterogeneous body with extremely complex components, such as bacterial cells, organic debris, inorganic particles and the like. With the economic development and the improvement of urbanization level, 4500 ten thousand tons of sludge are produced in the whole world. Due to the drastically multiplied sludge yield and complex composition, effective sludge treatment and disposal techniques have become one of the current hotspots. Sludge treatment is an important link in the sewage treatment process. Because of the special method for treating the sludge at present, the treatment cost of the sludge accounts for more than 50 percent of the operation cost of sewage treatment, and because the municipal sludge has strong metal fixing capacity, the heavy metal content in the sludge is very high. Heavy metals in the sludge are extremely easy to volatilize, leach, run off from the surface and absorb by crops, and the like, so that the ecological safety and the human health of soil and underground water are threatened.
At present, the treatment of heavy metals in sludge in industry is mainly passivation. The passivation is a method for dissolving and separating heavy metals in sludge or sediments thereof into a liquid phase or solidifying the heavy metals into stable substances, thereby reducing the total content of harmful substances such as heavy metals and the like. The main passivation materials at present are of the following classes: acids: the acid comprises inorganic acid and organic acid, wherein the main types of the inorganic acid are as follows: nitric acid, sulfuric acid, hydrochloric acid, and the like; the main types of organic acids are: acetic acid, citric acid, oxalic acid, aspartic acid, and the like. The acid material has the problems of reduced fertility of the treated sludge, high treatment cost, secondary pollution and the like; chelating agent: the main types of the method are Ethylene Diamine Tetraacetic Acid (EDTA), nitrilotriacetic acid (NTA), S-ethylenediamine disuccinic acid (S, S-EDDS), glutamic acid, N-tetrasodium diacetate (GLDA), ammonia water and the like, the addition of a chelating agent can change the form proportion of heavy metals in the sludge, has a certain effect on treating the heavy metals in the sludge, and simultaneously has an enhanced effect on removing the heavy metals by an electrochemical method, but the method can generate secondary pollution, and the treatment of leachate becomes a new problem; passivating agent: common passivators mainly comprise phosphate fertilizers (ground phosphate rock, phosphate fertilizers and the like), limes (lime, fly ash, coal cinder, cement kiln ash, waste incineration ash and the like), aluminosilicate cement, bentonite, humus and the like, and the passivators mainly convert heavy metals from an unstable state to a stable state to reduce the activity, migration capacity, dissolution rate and the like of the heavy metals in sludge so as to control the damage of the heavy metals. Therefore, the selection of a sludge heavy metal treatment method with uniform treatment effect, strong mobility and high efficiency is one of the practical problems to be solved at present.
Ferrous sulfide is a material with low cost, no toxicity and wide sources, and is composed of secondary iron ions and divalent sulfur ions, so that the biological effectiveness of heavy metals in sludge and soil can be reduced by means of adsorption, chemical reduction, formation of heavy metal sulfides and the like. The ferrous sulfide colloid has larger specific surface area and reaction activity, has negative charges on the surface and stronger adsorption capacity, and can adsorb heavy metals with originally weaker mobility in the sludge on the surface of the ferrous sulfide colloid, and complete reduction and sulfide passivation. The ferrous sulfide colloid passivates heavy metals in the sludge by capturing, flocculating, blocking, depositing and the like, so that the reaction efficiency of ferrous sulfide and the sludge heavy metals is improved, the sludge treatment cost is reduced, and the problem of sludge heavy metal treatment can be well solved.
The ferrous sulfide reported in related documents and patents at present is mainly ferrous sulfide particles or nano ferrous sulfide. But ferrous sulfide minerals have larger grain size and low passivation efficiency on heavy metals; and due to van der waals force among nano particles, nano ferrous sulfide is easy to agglomerate among the particles to form large particle agglomerates, so that surface reaction sites are reduced, the reactivity and the migration capability of ferrous sulfide particles are obviously reduced, the reactivity can be lost in a short time, and the industrial application of the nano ferrous sulfide is obviously limited. The existing iron-based colloid is easy to oxidize, easy to agglomerate, short in reaction time and poor in passivation effect, and is a main problem in the treatment of sludge containing heavy metals by using the iron-based colloid at present. Therefore, the iron-based colloid has not been very effective in stabilizing heavy metals in sludge treatment.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a reductive iron-sulfur mixed colloid with smaller particle size, larger specific surface area and stronger reaction efficiency, which can remarkably improve the passivation capability on heavy metals in sludge. The invention also provides a preparation method and application of the reducing iron-sulfur mixed colloid.
The technical scheme is as follows: the reducing iron-sulfur mixed colloid comprises a water-soluble organic high molecular compound and a ferrous sulfide compound; the water-soluble organic high molecular compound is one or two of polyacrylate and polymethacrylate.
The colloid is prepared by the following method: adding FeSO into water-soluble organic high molecular compound solution under oxygen-free condition4Solution, followed by dropwise addition of Na2And (5) obtaining the reducing iron-sulfur mixed colloid after the reaction of the S solution is finished.
The mass percentage concentration of the water-soluble organic high molecular compound solution is 0.05-0.3%; the water-soluble organic high molecular compound and FeSO4The mass ratio of (A) to (B) is 1: 5-20.
The FeSO4Molar concentration of the solution and Na2The molar concentration ratio of S solution is 1:1.8-2.2, and the FeSO4With Na2The molar ratio of S addition is 0.8-1.2: 1.
The preparation method of the reducing iron-sulfur mixed colloid comprises the following steps:
(1) heating and stirring one or two of polyacrylate and polymethacrylate to dissolve in water to obtain water-soluble organic high molecular compound aqueous solution;
(2) adding FeSO into the water-soluble organic high molecular compound aqueous solution in the step (1) in a nitrogen atmosphere and in a stirring environment4Obtaining water-soluble organic high molecular ferrous mixed colloid;
(3) the water in the step (2)Adding Na into the mixed colloid of soluble organic high molecular ferrous under nitrogen atmosphere2And (5) uniformly stirring the S solution to obtain the reducing iron-sulfur mixed colloid.
In the step (1), the mass percentage concentration of the water-soluble organic high molecular compound aqueous solution is 0.05-0.3%.
In the step (1), the heating temperature range is 50-95 ℃, and the stirring speed is 250-450 r/min.
In the step (2), FeSO4The mass ratio of the water soluble organic polymer to the water soluble organic polymer is 5-20: 1.
In the step (3), Na is added2Continuously aerating the S solution for 0.2-1h in the nitrogen atmosphere; the stirring condition is magnetic stirring at 250-450 r/min; FeSO4With Na2The molar ratio of S is 0.8-1.2: 1.
The application of the reductive iron-sulfur mixed colloid in the sludge heavy metal stabilizer is specifically to the application of the sludge heavy metal stabilizer in the passivation of heavy metals in sludge.
Has the advantages that: (1) the reducing iron-sulfur mixed colloid disclosed by the invention has good stability, the pH value is 4.5-9.0, the average hydraulic diameter of the colloid is 50-95 nm, the colloid has very good stability and large specific surface area, and has good reaction activity with target pollutants and good sludge heavy metal passivation capability; (2) the method for preparing the reductive iron-sulfur mixed colloid has the advantages of wide raw material source, low cost, safe, green and energy-saving technical process, capability of treating heavy metal pollution in the sludge in situ, low cost, short treatment time and simple and easy operation, does not have high requirement on equipment in the synthesis process, and has higher economic utilization; (3) the reductive iron-sulfur mixed colloid has good practical application potential, achieves very good effect on the passivation rate of heavy metals in sludge under the conditions of different pH values and organic matters, has long passivation effect, and has good practical application potential.
Drawings
Fig. 1 is a hydraulic diameter distribution diagram of the reduced iron-sulfur mixed colloid particles prepared by the present invention, wherein, a is a hydraulic diameter distribution diagram of the colloid at a pH of 4.5, b is a hydraulic diameter distribution diagram of the colloid at a pH of 6.0, c is a hydraulic diameter distribution diagram of the colloid at a pH of 7.5, and d is a hydraulic diameter distribution diagram of the colloid at a pH of 9.0.
Detailed Description
Example 1: preparation and application of reductive iron-sulfur mixed colloid for stabilizing and repairing heavy metal in sludge
In the embodiment, the water-soluble organic high molecular compound is sodium Polyacrylate (PAAS), and is mechanically stirred for 1h at 400r/min under the water bath condition of 80 ℃, dissolved in water, and prepared into a sodium polyacrylate solution with the mass percentage of 0.1%; ferrous sulfate (FeSO)4) The concentration of the solution is 0.25 mol/L; sodium sulfide (Na)2S) the concentration of the solution is 0.5 mol/L.
Exposing the prepared water-soluble organic polymer solution to nitrogen for 0.5h, mechanically stirring at the speed of 400r/min under the condition of normal temperature and no oxygen, and slowly adding FeSO into the solution at the speed of less than 5mL/min4Dissolving to obtain water-soluble organic high-molecular ferrous mixed colloid, in which FeSO is contained4The mass ratio of the PAAS to the PAAS is 10: 1. after the completion of the dropwise addition, nitrogen gas was purged for 10 min.
Under the condition of normal temperature and no oxygen, mechanically stirring at 400r/min, and slowly dripping Na into the water-soluble organic polymer ferrous mixed colloid at the speed of less than 5mL/min2S solution of Na in2S and FeSO4The molar ratio is 1:1. reacting for 1h under an anaerobic condition to obtain a mixed reductive iron-sulfur mixed colloid, namely the sludge heavy metal stabilizer.
The sludge heavy metal stabilizer prepared in the embodiment 1 takes municipal sludge remediation of a sewage treatment plant A in Nanjing as an example, and the specific application steps are as follows:
collecting a municipal sludge sample of a sewage treatment plant A in Nanjing, naturally drying, and then using HF-HClO4-HNO3After digestion, the major heavy metals were Cd, Cr, Cu, Ni and Pb, as determined by ICP-MS. And adding 200mL of reducing iron-sulfur mixed colloid into 1kg of sludge with the water content of 40%, wherein the pH value of the added reducing iron-sulfur mixed colloid is 7.5. Use ofAnd mechanically stirring at 500r/min, sealing and stirring for 2 hours, covering a plastic film, allowing rainwater and external water to permeate, and maintaining at room temperature for 7 days, and reacting to obtain the repaired sludge. And (4) air-drying the sludge under the natural condition again, and evaluating the repairing effect by adopting an SPLP leaching experiment. The results show that the passivation rates of Cd, Cr, Cu, Ni and Pb in the active state in this example are 77.1%, 93.3%, 74.8%, 43.9% and 88.1%, respectively. The detailed parameters are shown in table 1.
Example 2: preparation and application of reductive iron-sulfur mixed colloid for stabilizing and repairing heavy metal in sludge
In the embodiment, the water-soluble organic high molecular compound is Sodium Polymethacrylate (SPMAA), and the water-soluble organic high molecular compound is mechanically stirred for 1 hour at 350r/min under the water bath condition at the temperature of 70 ℃, dissolved in water and prepared into a sodium polymethacrylate solution with the mass percentage of 0.15%; ferrous sulfate (FeSO)4) The concentration of the solution is 0.5 mol/L; sodium sulfide (Na)2S) the concentration of the solution is 1.0 mol/L.
The prepared water-soluble organic polymer solution is aerated with nitrogen for 0.5h, mechanically stirred at the speed of 400r/min under the condition of normal temperature and no oxygen, and FeSO is added into the solution at the speed of 50 drops/min4Dissolving to obtain water-soluble organic high-molecular ferrous mixed colloid, in which FeSO is contained4The mass ratio of the SPMAA to the SPMAA is 20:1, after the completion of the dropwise addition, nitrogen gas was purged for 10 min.
Slowly dripping Na into the water-soluble organic polymer ferrous mixed colloid at the speed of less than 5mL/min by mechanical stirring at the normal temperature and under the oxygen-free condition2S solution of Na in2S and FeSO4The molar ratio is 1.2: 1. reacting for 1h under an anaerobic condition to obtain a mixed reductive iron-sulfur mixed colloid, namely the sludge heavy metal stabilizer.
The sludge heavy metal stabilizer prepared in the embodiment 2 takes municipal sludge remediation of a B sewage treatment plant in Nanjing as an example, and the specific application steps are as follows:
collecting municipal sludge sample of Nanjing municipal wastewater treatment plant B, and using HF-HClO4-HNO3After digestion, the major heavy metals were Cd, Mn, Pb and Zn as determined by ICP-MS. Adding into 1kg of sludge with water content of 50%Adding 300mL of reducing iron-sulfur mixed colloid, wherein the pH value of the added reducing iron-sulfur mixed colloid is 7.5. And (3) mechanically stirring at 500r/min, sealing and stirring for 2 hours, covering a plastic film, allowing rainwater and external water to permeate, and maintaining at room temperature for 7d, and reacting to obtain the repaired sludge. And (4) air-drying the sludge under the natural condition again, and evaluating the repairing effect by adopting an SPLP leaching experiment. The results show that the passivation rates of Cd, Mn, Pb and Zn in the active states in the embodiment are 81.8%, 96.1%, 92.1% and 79.7%, respectively. The detailed parameters are shown in Table 2.
Example 3: preparation and application of original iron-sulfur mixed colloid for stabilizing and repairing heavy metal in sludge
In the embodiment, the water-soluble organic high molecular compound is sodium Polyacrylate (PAAS), and is mechanically stirred for 1h at 400r/min under the water bath condition of 75 ℃, dissolved in water, and prepared into a sodium polyacrylate solution with the mass percentage of 0.15%; ferrous sulfate (FeSO)4) The concentration of the solution is 0.5 mol/L; sodium sulfide (Na)2S) the concentration of the solution is 1.0 mol/L.
Exposing the prepared water-soluble organic polymer solution to nitrogen for 0.5h, mechanically stirring at the speed of 400r/min under the condition of normal temperature and no oxygen, and slowly adding FeSO into the solution at the speed of less than 5mL/min4Dissolving to obtain water-soluble organic high-molecular ferrous mixed colloid, in which FeSO is contained4The mass ratio of the PAAS to the PAAS is 12: 1. after the completion of the dropwise addition, nitrogen gas was purged for 10 min.
Under the condition of normal temperature and no oxygen, mechanically stirring at 400r/min, and slowly dripping Na into the water-soluble organic polymer ferrous mixed colloid at the speed of less than 5mL/min2S solution of Na in2S and FeSO4The molar ratio is 1:1. reacting for 1h under an anaerobic condition to obtain a mixed reductive iron-sulfur mixed colloid, namely the sludge heavy metal stabilizer.
The sludge heavy metal stabilizer prepared in the embodiment 3 takes municipal sludge remediation of a C sewage treatment plant in Nanjing as an example, and the specific application steps are as follows:
collecting municipal sludge samples of C sewage treatment plants in Nanjing, naturally drying, and then using HF-HClO4-HNO3After digestionThe major heavy metals were Cd, Cu and Pb, as determined by ICP-MS. Adding 250mL of reducing iron-sulfur mixed colloid into 1kg of sludge with the water content of 45%, wherein the pH value of the added reducing iron-sulfur mixed colloid is 7.5. And (3) mechanically stirring at 500r/min, sealing and stirring for 2 hours, covering a plastic film, allowing rainwater and external water to permeate, and maintaining at room temperature for 7d, and reacting to obtain the repaired sludge. And (4) air-drying the sludge under the natural condition again, and evaluating the repairing effect by adopting an SPLP leaching experiment. The results show that the passivation rates of Cd, Cu and Pb in the active state in this example are 80.65%, 91.54% and 94.77%, respectively. The detailed parameters are shown in Table 3.
TABLE 1A stabilization data sheet for heavy metal in sludge of sewage treatment plant
TABLE 2B stabilization data sheet for heavy metal in sludge from sewage treatment plant
TABLE 3C stabilization data sheet for sludge heavy metal of sewage treatment plant
Comparative example 1: the restoration effect was evaluated by the SPLP leaching test, following the procedure of example 1, replacing sodium Polyacrylate (PAAS) with pure water, and the remaining steps were the same as those of example 1. The results show that the passivation rates of Cd, Cr, Cu, Ni and Pb in the active states in the comparative example are 14.2%, 9.8%, 20.0%, 8.9% and 20.8%, respectively.
Table 4 table of stabilization data of heavy metal in sludge in comparative example 1
Comparative example 2: the restoration effect was evaluated by the SPLP leaching experiment according to the method of example 2, in which Sodium Polymethacrylate (SPMAA) was replaced with pure water, and the remaining steps were the same as those of example 1. The results show that the passivation rates of Cd, Mn, Pb and Zn in the active states in the comparative example are 14.7%, 21.0%, 14.0%, 8.9% and 26.9%, respectively.
TABLE 5 table of stabilization data of heavy metals in sludge in comparative example 2
Example 4: pH stability of sludge heavy metal stabilizer
In order to test the stability of the reducing iron-sulfur mixed colloid under different pH conditions, sludge heavy metal stabilizers, sample 1, sample 2, sample 3 and sample 4, were prepared by the method of example 1 under oxygen-free conditions. The prepared sludge heavy metal stabilizer is prepared by respectively adjusting reductive iron-sulfur mixed colloid (the pH value of a sample 1 is 4.5, the pH value of a sample 2 is 6.0, the pH value of a sample 3 is 7.5 and the pH value of a sample 4 is 9.0) by using 0.01M HCl and 0.01M NaOH under an anaerobic condition, the prepared sample 1-4 is placed for 24 hours under the anaerobic condition, the particle size of the prepared sample is measured by using Zetasizer, the result is shown in figure 1, and the results show that the prepared reductive iron-sulfur mixed colloid has the hydraulic diameter of 50-95 nm under the condition that the pH value is 4.5-9.0, is uniformly dispersed, can be better combined with heavy metals in sludge and has an excellent effect of removing the heavy metals in sludge.
The heavy metal passivator is applied to ex-situ remediation of sludge polluted by heavy metals, has the advantages of short remediation period, good effect of stabilizing the heavy metals, high heavy metal passivation rate after 7 days, and good practical application potential.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof.
Claims (10)
1. A reducing iron-sulfur mixed colloid is characterized in that the colloid comprises a water-soluble organic high molecular compound and a ferrous sulfide compound; the water-soluble organic high molecular compound is one or two of polyacrylate and polymethacrylate.
2. The reducing iron sulfur mixed colloid of claim 1, wherein the colloid is prepared by the following method: adding FeSO into water-soluble organic high molecular compound solution under oxygen-free condition4Solution, followed by dropwise addition of Na2And (5) obtaining the reducing iron-sulfur mixed colloid after the reaction of the S solution is finished.
3. The reducing iron-sulfur mixed colloid as claimed in claim 2, wherein the water-soluble organic high molecular compound solution has a mass percentage concentration of 0.05-0.3%; the water-soluble organic high molecular compound and FeSO4The mass ratio of (A) to (B) is 1: 5-20.
4. The reducing iron sulfur mixed colloid of claim 3, wherein the FeSO is4Molar concentration of the solution and Na2The molar concentration ratio of S solution is 1:1.8-2.2, and the FeSO4With Na2The molar ratio of S addition is 0.8-1.2: 1.
5. The method for preparing the reducing iron-sulfur mixed colloid according to claim 1, comprising the steps of:
(1) heating and stirring one or two of polyacrylate and polymethacrylate to dissolve in water to obtain water-soluble organic high molecular compound aqueous solution;
(2) adding FeSO into the water-soluble organic high molecular compound aqueous solution in the step (1) in a nitrogen atmosphere and in a stirring environment4Obtaining water-soluble organic high molecular ferrous mixed colloid;
(3) mixing the water-soluble organic polymer ferrous mixed colloid in the step (2) inAdding Na under nitrogen atmosphere2And (5) uniformly stirring the S solution to obtain the reducing iron-sulfur mixed colloid.
6. The method for preparing a reducing iron-sulfur mixed colloid according to claim 5, wherein in the step (1), the mass percentage concentration of the water-soluble organic high molecular compound aqueous solution is 0.05-0.3%.
7. The method as claimed in claim 5, wherein the heating temperature in step (1) is 50-95 ℃ and the stirring rate is 250-450 r/min.
8. The method for preparing a reducing iron-sulfur mixed colloid according to claim 5, wherein in the step (2), FeSO is added4The mass ratio of the water soluble organic polymer to the water soluble organic polymer is 5-20: 1.
9. The method for preparing a reducing iron-sulfur mixed colloid according to claim 5, wherein in the step (3), Na is added2Continuously aerating the S solution for 0.2-1h in the nitrogen atmosphere; the stirring condition is magnetic stirring at 250-450 r/min; FeSO4With Na2The molar ratio of S is 0.8-1.2: 1.
10. The use of the reducing iron-sulfur mixed colloid of any one of claims 1-4 as a stabilizer for heavy metals in sludge.
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