CN111646659A - Heavy metal polluted bottom mud curing agent and curing method thereof - Google Patents
Heavy metal polluted bottom mud curing agent and curing method thereof Download PDFInfo
- Publication number
- CN111646659A CN111646659A CN202010367544.7A CN202010367544A CN111646659A CN 111646659 A CN111646659 A CN 111646659A CN 202010367544 A CN202010367544 A CN 202010367544A CN 111646659 A CN111646659 A CN 111646659A
- Authority
- CN
- China
- Prior art keywords
- parts
- heavy metal
- curing
- curing agent
- bottom mud
- 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.)
- Granted
Links
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
- C02F11/008—Sludge treatment by fixation or solidification
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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)
Abstract
The invention discloses a heavy metal polluted bottom mud curing agent and a curing method thereof, and relates to the technical field of bottom mud treatment. The invention relates to a heavy metal polluted bottom sediment curing agent which comprises curing powder and curing liquid used in a matching way, wherein the curing powder comprises the following raw materials in parts by weight: 25-35 parts of heavy metal stabilizer, 1-5 parts of water glass, 2-4 parts of modified chitosan, 1.5-2 parts of ammonium persulfate and 1-2 parts of polyaluminium chloride, wherein the curing liquid comprises the following raw materials in parts by weight: 10-15 parts of polyacrylamide, 5-10 parts of sodium polystyrene sulfonate and 0.5-1.5 parts of glutaraldehyde. The invention discloses a heavy metal pollution bottom sediment curing agent and a curing method thereof, wherein the pH value of the cured bottom sediment is neutral, the subsequent resource utilization is more facilitated, the stability of the heavy metal in the bottom sediment is better, the heavy metal in the cured bottom sediment is re-dissolved and released, and the probability of secondary pollution is relatively lower.
Description
Technical Field
The invention relates to the technical field of bottom mud treatment, in particular to a heavy metal polluted bottom mud curing agent and a curing method thereof.
Background
Heavy metals, particularly lead, chromium and the like have obvious biotoxicity, can generate toxicity at trace concentration and can be converted into organic metal compounds (such as dimethyl mercuric) with stronger toxicity under the action of microorganisms; can be bio-enriched and enter the body through the food chain, resulting in a chronic route. With the rapid development of industrial and agricultural, a large amount of industrial and agricultural wastewater enters a river water body, after the industrial and agricultural wastewater carrying heavy metals enters the water body, the heavy metals cannot be degraded by microorganisms in the water body, and only can be subjected to various forms of mutual transformation, dispersion and enrichment processes (namely migration), and besides being taken away by suspended matters, the heavy metals are finally enriched in bottom mud due to adsorption and precipitation effects due to insufficient hydrodynamic force, so that the heavy metals become a long-term secondary pollution source and seriously threaten the living environment and health of human beings.
At present, most of researches on the treatment of the heavy metal polluted bottom sediment focus on the release of heavy metals in the bottom sediment and the direction of restoration by plants or microorganisms, and the solidification/stabilization technology is considered to be one of the best practical technologies for the heavy metal polluted bottom sediment. Most of the traditional bottom mud heavy metal immobilization technologies use experience and technologies in sludge disposal or soil remediation, such as cement solidification technology and lime solidification technology, because most heavy metal ions can react with OH-And the water-insoluble salts are generated, so that the pH value of the bottom mud polluted by the heavy metals is improved through solidification treatment, the heavy metals in the bottom mud are converted to stable state and are converted into substances with low solubility, low mobility and low toxicity, and the stable effect is achieved.
However, the sediment solidified by the method has the disadvantages that the pH value of the generated sediment condensate is high, which is not beneficial to resource utilization, and the heavy metal is easy to dissolve and release again along with the change of environment in the subsequent utilization process due to the transformation of the form of the heavy metal along with the pH value and the oxidation-reduction condition, so that secondary pollution is generated.
Disclosure of Invention
Aiming at the problems, the invention aims to disclose a heavy metal pollution bottom sediment curing agent and a curing method thereof, wherein the pH value of the cured bottom sediment is neutral, so that the subsequent resource utilization is more facilitated, the stability of the heavy metal in the bottom sediment is better, the heavy metal in the cured bottom sediment is re-dissolved and released, and the probability of secondary pollution is relatively low.
Specifically, the heavy metal polluted bottom sediment curing agent comprises curing powder and curing liquid which are matched, wherein the curing powder comprises the following raw materials in parts by weight: 25-35 parts of heavy metal stabilizer, 1-5 parts of water glass, 2-4 parts of modified chitosan, 1.5-2 parts of ammonium persulfate and 1-2 parts of polyaluminium chloride, wherein the curing liquid comprises the following raw materials in parts by weight: 10-15 parts of polyacrylamide, 5-10 parts of sodium polystyrene sulfonate and 0.5-1.5 parts of glutaraldehyde.
According to the bottom mud curing agent, the dehydration property of the bottom mud is improved by utilizing the curing powder, heavy metal ions are primarily stabilized, then the curing liquid is used, and the curing powder and the curing liquid interact and crosslink to form a skeleton with a three-dimensional network structure, so that the effect of curing the polluted bottom mud is achieved, the existing cement or lime curing materials are abandoned in the raw materials, the pH value of the obtained bottom mud cured substance is neutral, the application range is wider, the bottom mud curing agent can be used as greening nutrient soil, building material soil and the like, can be used as greening nutrient soil, and is less prone to hardening in the planting process. The heavy metal stabilizer in the invention stabilizes heavy metal ions in the bottom sediment in irreversible adsorption, ion exchange and other modes, and then is wrapped in the formed framework, so that on one hand, the leaching rate of heavy metal is reduced, the probability of secondary pollution caused by re-dissolution and release of heavy metal in the solidified bottom sediment is reduced, and on the other hand, the heavy metal stabilizer also plays a role in supporting and reinforcing the framework, thereby increasing the unconfined compressive strength of the solidified bottom sediment.
Further, the curing powder comprises the following raw materials in parts by weight: 30 parts of heavy metal stabilizer, 3 parts of water glass, 4 parts of modified chitosan, 1.7 parts of ammonium persulfate and 1.5 parts of polyaluminium chloride, wherein the curing liquid comprises the following raw materials in parts by weight: 12 parts of polyacrylamide, 8 parts of sodium polystyrene sulfonate and 1.3 parts of glutaraldehyde.
Furthermore, the heavy metal stabilizer is prepared by taking modified zeolite as a carrier, loading proline modified carbon quantum dots and then grafting polyethyleneimine.
The zeolite has a plurality of pore structures and good adsorption performance, and is modified to be used as a carrier to be compounded with carbon quantum dots, so that the specific surface area of the modified zeolite can be increased, and the contact active sites of the modified zeolite can be increased, thereby increasing the adsorption performance of the modified zeolite; the polyethyleneimine grafted on the surface can be crosslinked with sodium polystyrene sulfonate, the sodium polystyrene sulfonate can improve the dehydration performance of the sediment, and the grafting of the polyethyleneimine can promote the crosslinking of organic polymers on the surface of the heavy metal stabilizer, so that the heavy metal stabilizer is wrapped in a framework formed by crosslinking, and the probability of heavy metal dissolution is reduced.
Further, the modified chitosan is prepared by acidifying and modifying chitosan with hydrochloric acid.
The organic matter content of the sediment condensate can be increased by the chitosan, meanwhile, the sodium silicate is alkaline, the acidification modified chitosan is added, the pH value of the sediment can not be greatly changed by the addition of the curing agent to a certain extent, and the acidification chitosan can promote the curing to a certain extent.
Further, the preparation method of the heavy metal stabilizer comprises the following steps:
s1: dissolving aminoundecanoic acid in water, stirring at the speed of 1000r/min of 800-;
s2: dispersing the prepared proline modified carbon quantum dots in deionized water to obtain a proline modified carbon quantum dot solution, weighing modified zeolite, stirring and dispersing in a phosphate buffer solution, adding the proline modified carbon quantum dot solution, heating to 60-70 ℃, carrying out heat preservation and reflux for 24 hours, cooling to room temperature after the reaction is finished, filtering and drying;
s3: and (3) adding a product obtained by drying in the step S2 into a polyethyleneimine water solution, placing the polyethyleneimine water solution into a magnetic stirrer, reacting for 3 hours at the temperature of 40-45 ℃, and filtering and drying after the reaction is finished to obtain the heavy metal stabilizer.
Further, the preparation method of the modified zeolite specifically comprises the following steps: cleaning chabazite, placing in a muffle furnace, heating to 100 ℃, preserving heat for 1h, heating to 300 ℃, preserving heat for baking for 1h, finally heating to 500 ℃, preserving heat for baking for 2h, cooling to room temperature along with the furnace, taking out, soaking in a sodium hydroxide solution, heating in an oil bath for 3h, shaking for 10h, filtering, washing the solid to be neutral by deionized water, drying, and performing low-temperature plasma treatment to obtain the modified zeolite.
The chabazite contains sodium ions and has certain ion exchange capacity, partial impurities in the chabazite structure can be removed through roasting, and part of bound water is volatilized and separated, so that the specific surface area and the pore volume of the chabazite are improved, the adsorption capacity of the heavy metal stabilizer is finally improved, and the sodium ions in the chabazite are modified by utilizing sodium hydroxide, so that the capacity of ion exchange binding between the modified zeolite and the heavy metal ions is improved.
Further, the low-temperature plasma treatment takes the mixed gas of oxygen and nitrogen as the working gas, the pressure is 10-15Pa, the discharge power is 250-300W, and the treatment time is 5-8 min.
Through low temperature plasma processing, on the one hand, the surface of the chabazite is bombarded through the plasma, so that the chabazite becomes rougher and is more beneficial to the load of subsequent carbon quantum dots, and secondly, because the carbon quantum dots have stronger reduction performance, oxygen-containing groups are introduced to the surface of the chabazite by taking oxygen as working gas, the oxidation performance of the chabazite is increased to a certain extent, so that the carbon quantum dots are more easily combined with the chabazite, the binding force is stronger, and the loading capacity is more.
Further, the preparation method of the modified chitosan specifically comprises the following steps: adding chitosan into 0.1mol/L hydrochloric acid solution, soaking for 1h, adjusting pH to 4.5-5.5 with 1mol/L hydrochloric acid solution in the soaking process, drying at a constant temperature of 105 ℃ for 24h, grinding and sieving with a 100-mesh sieve to obtain the modified chitosan.
In addition, the invention also discloses a method for curing the heavy metal polluted bottom mud, which uses the curing agent and specifically comprises the following steps: uniformly stirring and mixing the curing powder and the polluted bottom mud according to the mass ratio of (0.75-1.5) to 10, standing for 4-6h, adding the curing liquid, continuously stirring and uniformly mixing, heating to 40-50 ℃, preserving heat for curing for 1d, and curing for 5d at normal temperature.
The invention has the beneficial effects that:
the invention discloses a heavy metal polluted bottom mud curing agent, which is characterized in that a raw material formula is designed, and a skeleton with a three-dimensional network structure is formed by cross-linking through interaction among raw materials, so that the polluted bottom mud is cured.
Detailed Description
The present invention will be described in detail with reference to specific examples below:
according to the heavy metal pollution bottom sediment curing agent and the curing method thereof, the raw material formula of the curing agent is designed, the cured bottom sediment is neutral, particularly, the heavy metal stabilizer is added into the formula, the curing agent is prepared by taking modified zeolite as a carrier, loading proline to modify carbon quantum dots and then grafting polyethyleneimine, the heavy metal ion stabilizing effect is good, the probability of dissolution and secondary pollution is low, and the curing agent is specifically as follows:
example one
Preparing modified chitosan: adding chitosan into 0.1mol/L hydrochloric acid solution, soaking for 1h, adjusting pH to 4.5-5.5 with 1mol/L hydrochloric acid solution in the soaking process, drying at a constant temperature of 105 ℃ for 24h, grinding and sieving with a 100-mesh sieve to obtain the modified chitosan.
Preparation of modified zeolite: cleaning 15g of chabazite, placing the chabazite in a muffle furnace, heating to 100 ℃, preserving heat for 1h, heating to 300 ℃, preserving heat for 1h, finally heating to 500 ℃, preserving heat for 2h, cooling to room temperature along with the furnace, taking out, soaking in 250ml of 1.5mol/L sodium hydroxide solution, heating in a 95 ℃ oil bath for 3h, shaking for 10h, filtering, washing the solid to be neutral by deionized water, drying, mixing oxygen and nitrogen in a volume ratio of 1:2 under the conditions that the pressure is 15Pa and the discharge power is 300W to obtain a mixed gas serving as a working gas, and carrying out low-temperature plasma treatment for 5min to obtain the modified zeolite.
Preparation of heavy metal stabilizers
S1: weighing 2.0g of aminoundecanoic acid, adding 25ml of water for dissolving, stirring at the speed of 800r/min, adding 25ml of 8% citric acid solution at the speed of 1d/s, then adding 0.25g of proline, placing in a 200 ℃ oven for reacting for 2.5 hours after ultrasonic dispersion is uniform, naturally cooling to room temperature, adjusting the pH value to be neutral by using 1mol/L of sodium hydroxide solution, filtering by using a 0.22 mu m microfiltration membrane, dialyzing the solid by using deionized water for 24 hours through a dialysis bag, and freeze-drying to obtain the proline modified carbon quantum dot.
S2: dispersing the prepared proline modified carbon quantum dots in deionized water according to a solid-to-liquid ratio of 50mg/L to obtain a proline modified carbon quantum dot solution, weighing 10g of modified zeolite, stirring and dispersing in 2L of phosphate buffer solution with the pH value of 7.4, adding 4L of proline modified carbon quantum dot solution, heating to 60 ℃, carrying out heat preservation and reflux for 24h, cooling to room temperature after the reaction is finished, filtering and drying.
S3: weighing the product obtained by drying in the step 5g S2, adding 200ml of 20% polyethyleneimine aqueous solution, adding 0.05g of gamma-aminopropyltriethoxysilane, placing in a magnetic stirrer, reacting for 3 hours at the temperature of 40 ℃ at the stirring speed of 20r/min, and filtering and drying after the reaction is finished to obtain the heavy metal stabilizer.
Preparation of the curing agent
A1: 5 parts of sodium polystyrene sulfonate, 35 parts of heavy metal stabilizer, 15 parts of polyacrylamide, 1 part of water glass, 2 parts of modified chitosan, 1.5 parts of ammonium persulfate, 1 part of polyaluminum chloride and 0.5 part of glutaraldehyde are respectively weighed.
A2: stirring and mixing water glass, modified chitosan and polyaluminium chloride uniformly, drying, grinding, sieving with a 100-mesh sieve to obtain mixed powder, and adding ammonium persulfate and a heavy metal stabilizer to obtain solidified powder; and uniformly stirring and mixing polyacrylamide, sodium polystyrene sulfonate and glutaraldehyde to obtain the curing liquid.
The curing agent is used for curing heavy metal polluted bottom mud of a river in Zhejiang province, and through detection, the pH value of the bottom mud is 7.12, and the contents of heavy metals in the bottom mud are as follows: cr 142.33mg/Kg, Ni 25.68mg/Kg, Cu 45.82mg/Kg, Pb 116.31mg/Kg and Zn 267.86mg/Kg, and the curing method comprises the following steps: uniformly stirring and mixing the curing powder and the polluted bottom mud according to the mass ratio of 0.75:10, standing for 6h, adding the curing liquid, continuously stirring and uniformly mixing, heating to 50 ℃, preserving heat and curing for 1d, and curing for 5d at normal temperature.
Example two
The modified chitosan was prepared as in example one.
Preparation of modified zeolite: cleaning 15g of chabazite, placing the chabazite in a muffle furnace, heating to 100 ℃, preserving heat for 1h, heating to 300 ℃, preserving heat for 1h, finally heating to 500 ℃, preserving heat for 2h, cooling to room temperature along with the furnace, taking out, soaking in 250ml of 1.5mol/L sodium hydroxide solution, heating in a 90 ℃ oil bath for 3h, shaking for 10h, filtering, washing the solid to be neutral by deionized water, drying, mixing oxygen and nitrogen in a volume ratio of 2:3 under the conditions that the pressure is 12Pa and the discharge power is 250W to obtain a mixed gas serving as a working gas, and carrying out low-temperature plasma treatment for 6min to obtain the modified zeolite.
Preparation of heavy metal stabilizers
S1: weighing 2.5g of aminoundecanoic acid, adding 40ml of water for dissolving, stirring at the speed of 1000r/min, adding 35ml of 10% citric acid solution at the speed of 1d/s, then adding 0.4g of proline, placing in a 200 ℃ oven for reacting for 2h after ultrasonic dispersion, naturally cooling to room temperature, adjusting the pH value to be neutral by using 1mol/L sodium hydroxide solution, filtering by using a 0.22 mu m microfiltration membrane, dialyzing the solid by using deionized water for 24h through a dialysis bag, and freeze-drying to obtain the proline modified carbon quantum dot.
S2: dispersing the prepared proline modified carbon quantum dots in deionized water according to a solid-to-liquid ratio of 50mg/L to obtain a proline modified carbon quantum dot solution, weighing 10g of modified zeolite, stirring and dispersing in 2L of phosphate buffer solution with the pH value of 7.4, adding 4L of proline modified carbon quantum dot solution, heating to 65 ℃, carrying out heat preservation and reflux for 24h, cooling to room temperature after the reaction is finished, filtering and drying.
S3: weighing a product obtained by drying in the step 7.32g S2, adding 250ml of 25% polyethyleneimine water solution, adding 0.08g of gamma-aminopropyltriethoxysilane, placing in a magnetic stirrer, reacting for 3h at the temperature of 40 ℃ at the stirring speed of 25r/min, and filtering and drying after the reaction is finished to obtain the heavy metal stabilizer.
The curing agent of the embodiment comprises the following raw materials in parts by weight: 10 parts of sodium polystyrene sulfonate, 10 parts of polyacrylamide, 25 parts of heavy metal stabilizer, 5 parts of water glass, 4 parts of modified chitosan, 2 parts of ammonium persulfate and 1 part of glutaraldehyde.
Preparation of the curing agent
A1: respectively weighing 10 parts of sodium polystyrene sulfonate, 25 parts of heavy metal stabilizer, 10 parts of polyacrylamide, 5 parts of water glass, 4 parts of modified chitosan, 2 parts of ammonium persulfate, 1.5 parts of polyaluminum chloride and 1 part of glutaraldehyde.
A2: stirring and mixing water glass, modified chitosan and polyaluminium chloride uniformly, drying, grinding, sieving with a 100-mesh sieve to obtain mixed powder, and adding ammonium persulfate and a heavy metal stabilizer to obtain solidified powder; and uniformly stirring and mixing polyacrylamide, sodium polystyrene sulfonate and glutaraldehyde to obtain the curing liquid.
The curing agent in the embodiment is used for curing the heavy metal polluted bottom mud which is the same as that in the embodiment I, and the curing method specifically comprises the following steps: uniformly stirring and mixing the curing powder and the polluted bottom mud according to the mass ratio of 1:10, standing for 5h, adding the curing liquid, continuously stirring and uniformly mixing, heating to 40 ℃, preserving heat for curing for 1d, and curing for 5d at normal temperature.
EXAMPLE III
The modified chitosan was prepared as in example one.
Preparation of modified zeolite: cleaning 15g of chabazite, placing the chabazite in a muffle furnace, heating to 100 ℃, preserving heat for 1h, heating to 300 ℃, preserving heat for 1h, finally heating to 500 ℃, preserving heat for 2h, cooling to room temperature along with the furnace, taking out, soaking in 250ml of 1.5mol/L sodium hydroxide solution, heating in a 95 ℃ oil bath for 3h, shaking for 10h, filtering, washing the solid to be neutral by deionized water, drying, mixing oxygen and nitrogen in a volume ratio of 1:1 under the conditions that the pressure is 10Pa and the discharge power is 280W to obtain a mixed gas serving as a working gas, and carrying out low-temperature plasma treatment for 8min to obtain the modified zeolite.
Preparation of heavy metal stabilizers
S1: weighing 2.0g of aminoundecanoic acid, dissolving in 40ml of water, stirring at 900r/min, adding 25ml of 10% citric acid solution at 1d/s, adding 0.3g of proline, ultrasonically dispersing uniformly, placing in a 200 ℃ oven for reaction for 3h, naturally cooling to room temperature, adjusting the pH value to be neutral by using 1mol/L sodium hydroxide solution, filtering by using a 0.22 mu m microfiltration membrane, dialyzing the solid by using deionized water for 24h through a dialysis bag, and freeze-drying to obtain the proline modified carbon quantum dot.
S2: dispersing the prepared proline modified carbon quantum dots in deionized water according to a solid-to-liquid ratio of 50mg/L to obtain a proline modified carbon quantum dot solution, weighing 10g of modified zeolite, stirring and dispersing in 2L of phosphate buffer solution with the pH value of 7.4, adding 4L of proline modified carbon quantum dot solution, heating to 70 ℃, carrying out heat preservation and reflux for 24h, cooling to room temperature after the reaction is finished, filtering and drying.
S3: weighing the product obtained by drying in the step 4.94g S2, adding 300ml of 20% polyethyleneimine water solution, adding 0.05g of gamma-aminopropyltriethoxysilane, placing in a magnetic stirrer, reacting for 3h at the temperature of 45 ℃ at the stirring speed of 20r/min, and filtering and drying after the reaction is finished to obtain the heavy metal stabilizer.
The curing agent of the embodiment comprises the following raw materials in parts by weight: 8 parts of sodium polystyrene sulfonate, 12 parts of polyacrylamide, 30 parts of heavy metal stabilizer, 3 parts of water glass, 4 parts of modified chitosan, 2 parts of coagulant, 1.7 parts of ammonium persulfate and 1.3 parts of glutaraldehyde.
Preparation of the curing agent
A1: 8 parts of sodium polystyrene sulfonate, 30 parts of heavy metal stabilizer, 12 parts of polyacrylamide, 3 parts of water glass, 4 parts of modified chitosan, 1.7 parts of ammonium persulfate, 5 parts of polyaluminum chloride and 1.5 parts of glutaraldehyde are respectively weighed.
A2: stirring and mixing water glass, modified chitosan and polyaluminium chloride uniformly, drying, grinding, sieving with a 100-mesh sieve to obtain mixed powder, and adding ammonium persulfate and a heavy metal stabilizer to obtain solidified powder; and uniformly stirring and mixing polyacrylamide, sodium polystyrene sulfonate and glutaraldehyde to obtain the curing liquid.
The curing agent in the embodiment is used for curing the heavy metal polluted bottom mud which is the same as that in the embodiment I, and the curing method specifically comprises the following steps: uniformly stirring and mixing the curing powder and the polluted bottom mud according to the mass ratio of 1.5:10, standing for 6h, adding the curing liquid, continuously stirring and uniformly mixing, heating to 45 ℃, preserving heat for curing for 1d, and curing for 5d at normal temperature.
Comparative example: the same bottom mud is solidified by the existing cement curing agent, and the concrete operation is as follows: and uniformly stirring and mixing the cement and the bottom mud according to the mass ratio of 6:10, and then placing the mixture in a constant-temperature constant-humidity curing box for curing for 7 d.
The water content, pH value and unconfined compressive strength of the sediment condensate obtained by curing the curing agents of the first to third examples and the curing agent of the comparative example are detected, and the detection results are shown in Table 1:
TABLE 1
The curing agent prepared by the invention has the advantages that the water content of the cured bottom mud is obviously smaller than that of the existing curing agent, the pH value of the cured bottom mud is close to neutral and is far smaller than that of the existing cement curing agent, the strength of the cured bottom mud is obviously higher than that of the cured bottom mud of the existing curing agent, and the curing effect is better.
Heavy metal leaching experiment: all the cured sediment cured materials obtained by curing are dried for 8 hours at the temperature of 105 ℃, and the water content of the cured sediment cured materials is calculated. According to the water content, a sample with 5g of dry mud is measured, and is added into a beaker for a neutral dissolution experiment according to the water-solid ratio of 10 g/L. The heavy metal content of the supernatant was measured using an inductively coupled plasma emission spectrometer (ICP, Prodigy, usa).
The results are shown in table 2:
TABLE 2
| Detecting items | Cr/(mg/L) | Ni/(mg/L) | Cu/(mg/L) | Pb/(mg/L) | Zn/(mg/L) |
| Example one | 0.04 | 0.64 | 0.56 | 0.03 | 1.02 |
| Example two | 0.03 | 0.61 | 0.64 | 0.02 | 0.89 |
| EXAMPLE III | 0.03 | 0.63 | 0.59 | 0.04 | 0.94 |
| Comparative example | 3.86 | 15.49 | 16.38 | 0.67 | 37.94 |
As can be seen from the above table, after the curing agent disclosed by the invention is used for curing the heavy metal polluted bottom sediment, the leaching concentration value of the heavy metal of a cured substance of the bottom sediment can meet the requirements of Integrated wastewater discharge Standard (GB8978-1996) and can basically meet the requirements of III-class concentration limit of surface Water environmental quality Standard (GB3838-2002), and the heavy metal ions in the bottom sediment are basically stabilized after being cured and the risk to the environment is within an acceptable level.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims. The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.
Claims (9)
1. The heavy metal polluted bottom sediment curing agent is characterized by comprising curing powder and curing liquid which are matched for use, wherein the curing powder comprises the following raw materials in parts by weight: 25-35 parts of heavy metal stabilizer, 1-5 parts of water glass, 2-4 parts of modified chitosan, 1.5-2 parts of ammonium persulfate and 1-2 parts of polyaluminium chloride, wherein the curing liquid comprises the following raw materials in parts by weight: 10-15 parts of polyacrylamide, 5-10 parts of sodium polystyrene sulfonate and 0.5-1.5 parts of glutaraldehyde.
2. The curing agent for heavy metal polluted bottom mud according to claim 1, wherein the curing powder comprises the following raw materials in parts by weight: 30 parts of heavy metal stabilizer, 3 parts of water glass, 4 parts of modified chitosan, 1.7 parts of ammonium persulfate and 1.5 parts of polyaluminium chloride, wherein the curing liquid comprises the following raw materials in parts by weight: 12 parts of polyacrylamide, 8 parts of sodium polystyrene sulfonate and 1.3 parts of glutaraldehyde.
3. The heavy metal contaminated bottom mud curing agent as claimed in claim 2, wherein the heavy metal stabilizer is prepared by taking modified zeolite as a carrier, loading proline modified carbon quantum dots, and then grafting polyethyleneimine.
4. The curing agent for heavy metal contaminated bottom mud according to claim 3, wherein the modified chitosan is prepared by acidifying and modifying chitosan with hydrochloric acid.
5. The curing agent for heavy metal contaminated bottom mud according to claim 4, wherein the preparation method for the heavy metal stabilizer comprises the following steps:
s1: dissolving aminoundecanoic acid in water, stirring at the speed of 1000r/min of 800-;
s2: dispersing the prepared proline modified carbon quantum dots in deionized water to obtain a proline modified carbon quantum dot solution, weighing modified zeolite, stirring and dispersing in a phosphate buffer solution, adding the proline modified carbon quantum dot solution, heating to 60-70 ℃, carrying out heat preservation and reflux for 24 hours, cooling to room temperature after the reaction is finished, filtering and drying;
s3: and (3) adding a product obtained by drying in the step S2 into a polyethyleneimine water solution, placing the polyethyleneimine water solution into a magnetic stirrer, reacting for 3 hours at the temperature of 40-45 ℃, and filtering and drying after the reaction is finished to obtain the heavy metal stabilizer.
6. The heavy metal polluted bottom mud curing agent as claimed in claim 5, wherein the preparation method of the modified zeolite specifically comprises the following steps: cleaning chabazite, placing in a muffle furnace, heating to 100 ℃, preserving heat for 1h, heating to 300 ℃, preserving heat for 1h, finally heating to 500 ℃, preserving heat for 2h, cooling to room temperature along with the furnace, taking out, soaking in a sodium hydroxide solution, heating in an oil bath for 3h, shaking for 10h, filtering, washing the solid to be neutral by deionized water, drying, and carrying out low-temperature plasma treatment to obtain the modified zeolite.
7. The curing agent for heavy metal contaminated bottom mud as claimed in claim 6, wherein the low temperature plasma treatment is performed by using a mixed gas of oxygen and nitrogen as a working gas, the pressure is 10-15Pa, the discharge power is 250-300W, and the treatment time is 5-8 min.
8. The heavy metal polluted bottom mud curing agent as claimed in claim 7, wherein the preparation method of the modified chitosan comprises the following specific steps: adding chitosan into 0.1mol/L hydrochloric acid solution, soaking for 1h, adjusting pH to 4.5-5.5 with 1mol/L hydrochloric acid solution in the soaking process, drying at a constant temperature of 105 ℃ for 24h, grinding and sieving with a 100-mesh sieve to obtain the modified chitosan.
9. A method for solidifying heavy metal contaminated substrate sludge, characterized in that the method uses the solidifying agent according to any one of claims 1 to 8, and the method comprises the following steps: uniformly stirring and mixing the curing powder and the polluted bottom mud according to the mass ratio of (0.75-1.5) to 10, standing for 4-6h, adding the curing liquid, continuously stirring and uniformly mixing, heating to 40-50 ℃, preserving heat for curing for 1d, and curing for 5d at normal temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010367544.7A CN111646659B (en) | 2020-04-30 | 2020-04-30 | Heavy metal polluted bottom mud curing agent and curing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010367544.7A CN111646659B (en) | 2020-04-30 | 2020-04-30 | Heavy metal polluted bottom mud curing agent and curing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111646659A true CN111646659A (en) | 2020-09-11 |
| CN111646659B CN111646659B (en) | 2022-08-16 |
Family
ID=72345987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010367544.7A Active CN111646659B (en) | 2020-04-30 | 2020-04-30 | Heavy metal polluted bottom mud curing agent and curing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111646659B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398888A (en) * | 2021-07-13 | 2021-09-17 | 江苏建霖环保科技有限公司 | Composite water purifying agent and preparation method thereof |
| CN113600233A (en) * | 2021-08-31 | 2021-11-05 | 东风商用车有限公司 | Metal-doped palladium molecular sieve catalyst, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01176499A (en) * | 1987-12-28 | 1989-07-12 | Terunaito:Kk | Treatment of sludge |
| CN106007290A (en) * | 2016-07-14 | 2016-10-12 | 慎叶 | Novel environment-friendly sludge heavy metal remover and preparation method thereof |
| CN106865952A (en) * | 2017-03-20 | 2017-06-20 | 北京君联合环境科技有限公司 | A kind of method of sludge adjusting material and its application and quenched sludge |
| CN108862958A (en) * | 2018-07-24 | 2018-11-23 | 四川大航建设工程有限公司 | A kind of sludge heavy-metal curing agent and its preparation method and application |
| CN110577350A (en) * | 2019-10-17 | 2019-12-17 | 四川公路桥梁建设集团有限公司 | Harmless treatment method for engineering waste slurry |
-
2020
- 2020-04-30 CN CN202010367544.7A patent/CN111646659B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01176499A (en) * | 1987-12-28 | 1989-07-12 | Terunaito:Kk | Treatment of sludge |
| CN106007290A (en) * | 2016-07-14 | 2016-10-12 | 慎叶 | Novel environment-friendly sludge heavy metal remover and preparation method thereof |
| CN106865952A (en) * | 2017-03-20 | 2017-06-20 | 北京君联合环境科技有限公司 | A kind of method of sludge adjusting material and its application and quenched sludge |
| CN108862958A (en) * | 2018-07-24 | 2018-11-23 | 四川大航建设工程有限公司 | A kind of sludge heavy-metal curing agent and its preparation method and application |
| CN110577350A (en) * | 2019-10-17 | 2019-12-17 | 四川公路桥梁建设集团有限公司 | Harmless treatment method for engineering waste slurry |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398888A (en) * | 2021-07-13 | 2021-09-17 | 江苏建霖环保科技有限公司 | Composite water purifying agent and preparation method thereof |
| CN113600233A (en) * | 2021-08-31 | 2021-11-05 | 东风商用车有限公司 | Metal-doped palladium molecular sieve catalyst, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111646659B (en) | 2022-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107522436B (en) | Sludge curing agent and preparation method and application method thereof | |
| Dubey et al. | Adsorption of chromium (VI) on low cost adsorbents derived from agricultural waste material: a comparative study | |
| Kaewsarn et al. | Cadmium (II) removal from aqueous solutions by pre-treated biomass of marine alga Padina sp. | |
| CN102527347B (en) | Magnetic chitosan/cationic surface active agent modified zeolite adsorbent and preparation method and application thereof | |
| Rakhshaee et al. | Kinetic modeling and thermodynamic study to remove Pb (II), Cd (II), Ni (II) and Zn (II) from aqueous solution using dead and living Azolla filiculoides | |
| CN111646659B (en) | Heavy metal polluted bottom mud curing agent and curing method thereof | |
| CN101811021B (en) | Amphiphilic adsorbent capable of adsorbing both organic matter and heavy metal cation and preparation method thereof | |
| CN107185503B (en) | The preparation method of the charcoal of immobilized beta-cyclodextrin for sticking cadmium ion | |
| CN1644495A (en) | Method for preparing active carbon from urban sewage treatment plant mud | |
| CN111234827B (en) | Heavy metal contaminated soil remediation agent and preparation method and application thereof | |
| CN110078045B (en) | Biochar and soil mercury stabilizing agent based on straw and preparation method thereof | |
| CN106378094A (en) | Preparation method of amino iron-carrying composite modified biochar | |
| CN106607006A (en) | Preparation method for adsorbent capable of removing nitrogen and phosphorus simultaneously | |
| CN104289181A (en) | Preparation and application of magnetic hydroxyapatite/graphene oxide adsorbent | |
| CN106830621B (en) | Composite sludge dehydrating agent and preparation method and application thereof | |
| CN109608021A (en) | Deep dehydration method for sludge | |
| Su et al. | Preparation of a surface molecular‐imprinted adsorbent for Ni2+ based on Penicillium chrysogenum | |
| CN109126697A (en) | A kind of natural material compound adsorbent and preparation method thereof, application | |
| CN111499000B (en) | Constructed wetland filler and preparation method thereof | |
| CN109467145A (en) | A kind of organic waste water treatment agent containing porous sepiolite | |
| CN109401757A (en) | A kind of modified biomass charcoal, preparation method and application for reducing soil available chromium | |
| CN110791292A (en) | Repairing agent suitable for lead-polluted soil and preparation method thereof | |
| CN110606792A (en) | Preparation method of soil conditioner based on paper mill sludge and vermiculite powder | |
| CN115646458A (en) | Phosphorus adsorption hydrogel and preparation method and application thereof | |
| CN108423955B (en) | Process for removing heavy metal copper in municipal sludge |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |