CN110240456B - Treatment method of industrial wastewater containing heavy metal ions and heavy metal ion-sulphoaluminate cement-bentonite composite material - Google Patents
Treatment method of industrial wastewater containing heavy metal ions and heavy metal ion-sulphoaluminate cement-bentonite composite material Download PDFInfo
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- CN110240456B CN110240456B CN201910672951.6A CN201910672951A CN110240456B CN 110240456 B CN110240456 B CN 110240456B CN 201910672951 A CN201910672951 A CN 201910672951A CN 110240456 B CN110240456 B CN 110240456B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
- C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
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Abstract
The invention belongs to the technical field of heavy metal wastewater treatment, and particularly relates to a treatment method of heavy metal ion-containing industrial wastewater and a heavy metal ion-sulphoaluminate cement-bentonite composite material. Firstly, detecting the type and concentration of heavy metal ions in industrial wastewater; then mixing sulphoaluminate cement, bentonite, water reducing agent and medium-grade sand uniformly according to a certain proportion, adding heavy metal solution in the form of mixing water and uniformly stirring to obtain the composite material, wherein the Cr is mixed with the material3+、Pb2+The curing rate of the resin reaches 99 percent. The method has the advantages of good curing effect and curing stability on heavy metal ions, low raw material cost, simple treatment process, reduction of sludge accumulation, repeated utilization in building base materials or roadbed materials after heavy metal curing, and suitability for popularization and application.
Description
Technical Field
The invention belongs to the technical field of heavy metal wastewater treatment, and particularly relates to a treatment method of heavy metal ion-containing industrial wastewater and a heavy metal ion-sulphoaluminate cement-bentonite composite material.
Background
The heavy metal wastewater has wide sources and large water quantity, and mainly comes from mine drainage, waste stone field leaching water, tailing drainage of a mineral processing field, dust removal drainage of a nonferrous metal smelting plant, pickling wastewater of a nonferrous metal processing plant, plated part washing water of an electroplating plant, pickling drainage of a steel plant, electrolysis, pesticide, medicine, paint, dye and other industrial wastewater. The heavy metal has the characteristics of long-term and continuous toxic effect and no biological degradation, and even if the concentration of the heavy metal in the industrial wastewater is small, the heavy metal can be absorbed and enriched by plants and other organisms and then is accumulated in human bodies and livestock bodies through a food chain, so that the health of the plants, the animals and even the human bodies is directly influenced. The increasing heavy metal pollution has made a significant threat to human survival safety. The pollution of water body which is difficult to control and has very strong diffusivity also becomes a great obstacle to the sustainable development of human health, economy and society. Therefore, the problem of disposing industrial wastewater containing heavy metal ions has become a great problem to be solved urgently.
At present, heavy metal wastewater treatment methods can be divided into three categories: (1) chemical treatment; (2) a physical treatment method; (3) a biological treatment method. The chemical treatment method mainly refers to a method for removing heavy metal ions in wastewater through chemical reaction by adding a chemical reagent, and specifically can be divided into a neutralization precipitation method, a sulfide precipitation method, a ferrite coprecipitation method, a chemical reduction method and the like, and is suitable for treating wastewater containing heavy metal ions with high concentration, but the chemical treatment of the heavy metal wastewater is generally carried out in a precipitation mode, so that new pollutants are easily generated, and secondary pollution is caused; the physical treatment method is a method for adsorbing, concentrating and separating heavy metals in wastewater under the condition of not changing the chemical forms of the heavy metals, and comprises an adsorption method, an ion exchange method, a membrane separation method and the like, wherein the physical treatment method has a good effect of removing the heavy metals and does not produce secondary pollution, but has a complex treatment process and high treatment cost; the biological treatment method is a method for removing heavy metals in wastewater by virtue of flocculation, absorption, accumulation, enrichment and other effects of plants, microorganisms or derivatives thereof, and specifically comprises biological flocculation, biological adsorption, phytoremediation and the like.
Patent CN108911136A discloses a heavy metal wastewater treatment method, which comprises the steps of firstly carrying out homogenization treatment on heavy metal wastewater to balance the quality of heavy metal wastewater from different processes, then carrying out anaerobic # aerobic cycle treatment on the heavy metal wastewater after the anaerobic treatment in a membrane bioreactor, wherein heavy metal ions are reduced under the action of microorganisms in the anaerobic treatment process, a hollow fiber membrane containing quinone groups is filled in the membrane bioreactor, and the quinone groups in the fiber membrane can be used as an electronic mediator to accelerate the enzymatic reduction reaction of the heavy metal ions in the anaerobic process, so that the purpose of efficiently removing the heavy metal ions is achieved. However, the treatment process is complicated, the treatment period is long, and the cost of the fiber membrane is high.
Patent CN109553215A discloses a method for treating electroplating wastewater, which comprises the steps of reduction, alkali precipitation, oxidation, flocculation and sedimentation, and discharge regulation, wherein a flocculating agent for flocculation and sedimentation comprises an amphoteric polymer chelating flocculating agent PDMAMDTC; the amphoteric polymeric chelate flocculant PDMAMDTC is prepared by initiating dimethyl diallyl ammonium chloride and acrylamide by ammonium persulfate, copolymerizing to form a basic skeleton, linking formaldehyde and triethylene tetramine, initiating by acryloyl morpholine and imidazoline, and reacting with carbon disulfide in an alkaline environment. The treatment method for the electroplating wastewater provided by the application has the advantages of excellent treatment effect and low treatment cost, but the preparation process of the flocculating agent is complicated, and the used formaldehyde is harmful to human bodies.
Patent CN108101253A discloses a method for treating heavy metal wastewater, comprising the following steps: (1) iron removal operation, namely adjusting the pH value of the wastewater to 4-5, adding a flocculating agent, and settling to remove iron ions in the wastewater; (2) copper deposition, namely adding sodium sulfide and a flocculating agent into the supernatant treated in the step (1), and removing copper ions in the wastewater through deposition; (3) and (3) neutralizing, namely adjusting the pH value of the supernatant treated in the step (2) to 6-7, adding a flocculating agent, and settling to remove heavy metal ions in the wastewater to obtain clear water which reaches the discharge standard. However, sodium sulfide used in the method is toxic, and if the sodium sulfide is excessive, H is easily generated in acid wastewater2S, causing secondary pollution.
Patent CN108975566A discloses a method for treating electroplating wastewater, which comprises using an electrolysis device equipped with an iron plate electrode, injecting clear water added with electrolyte into an electrolysis box, electrifying to electrolyze water to generate water rich in ferrous ions, discharging the water rich in ferrous ions into a storage tank for storage, and proportionally filling the water solution rich in ferrous ions into the electroplating wastewater in a treatment tank to reduce heavy metals in the wastewater; and adjusting the pH of the mixed liquid in the treatment tank, adding a flocculating agent PAM, sampling to detect the content of heavy metal, and discharging into a sedimentation tank for sedimentation after the heavy metal is qualified. However, the method consumes electric energy, is high in operation and maintenance cost, and the precipitate needs to be further treated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for treating industrial wastewater containing heavy metal ions and a heavy metal ion-sulphoaluminate cement-bentonite composite material, wherein the method has the characteristics of excellent heavy metal ion curing effect, low treatment cost, simple treatment process, short flow and no secondary pollution.
The technical scheme adopted by the invention is as follows:
a treatment method of industrial wastewater containing heavy metal ions comprises the following steps:
step one, mixing and uniformly stirring sulphoaluminate cement, bentonite, a water reducing agent and quartz sand to prepare a sulphoaluminate cement-bentonite composite material;
adding industrial wastewater containing heavy metal ions into the sulphoaluminate cement-bentonite composite material, and uniformly stirring to obtain a mixture;
and step three, pouring, molding and curing the mixture obtained in the step two in a mold, so that the heavy metal ions in the industrial wastewater containing the heavy metal ions are cured.
In the first step, 50-100 parts by mass of sulphoaluminate cement, 10-50 parts by mass of bentonite, 0.8-1.2 parts by mass of a water reducing agent and 150-200 parts by mass of medium-grade sand are mixed and uniformly stirred to prepare the sulphoaluminate cement-bentonite composite material.
In the first step, the stirring speed is 300-600 rpm, and the stirring time is 5-10 min.
In the second step, the stirring speed is 1000-1500 rpm, and the stirring time is 3-5 min.
The sulphoaluminate cement in the first step is low-alkalinity sulphoaluminate cement with the strength grade of 42.5.
The bentonite in the first step is one or the combination of sodium bentonite and calcium bentonite.
The water reducing agent in the first step is a naphthalene water reducing agent, a sulfamate water reducing agent or a polycarboxylic acid water reducing agent, and the water reducing rate is 15-35%.
The medium-grade sand in the step one is medium-grade sand meeting the ISO standard requirement.
In the second step, 465-925 parts of heavy metal ion-containing industrial wastewater is added into each 1000 parts of sulphoaluminate cement-bentonite composite material by mass percent.
And in the third step, the mixture obtained in the second step is cast, molded and placed into a mold for maintenance to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material.
Compared with the prior art, the invention has the following beneficial effects:
adding the industrial wastewater containing the heavy metal into a sulphoaluminate cement-bentonite composite material in a form of mixing water, uniformly stirring to obtain a mixture, casting and molding the obtained mixture, filling the mixture into a mold for curing, and solidifying the heavy metal ions in the industrial wastewater containing the heavy metal ions; the material which has the function of solidifying the heavy metal is sulphoaluminate cement-bentonite composite material, wherein the main hydration products of the sulphoaluminate cement are ettringite and aluminum hydroxide gel, wherein the basic structural unit of the ettringite is [ Ca3Al(OH)6·12H2O]It is composed of Al (OH)6Octahedral chain, which is surrounded by three calcium polyhedrons, each calcium polyhedron is matched with OH-and four water molecules to form crystal column parallel to the needle axis, and SO4 2-And H2O is contained in the channel between them, and the channel structure can relatively easily replace SO with oxyanions of similar structure and radius4 2-E.g. AsO4 3-、CO3 2-、NO3 -、SeO4 2-、CrO4 2-Or B (OH)4 -Moreover, through chemical replacement and surface electronegativity, ettringite can hold many foreign ions such as Al among crystal columns3+Can be made of Fe3+、Cr3+、Mn3+Isosubstitution of, Ca2+Can be coated with Mg2+、Zn2+、Mn2+、Fe2+、Co2+Or Ni2+And (4) substitution. In addition, the aluminum hydroxide gel also has strong adsorption capacity and can adsorb heavy metal ions. The crystal structure of the incorporated bentonite is similar to that of silicate minerals, wherein Si is4+Is covered with Al3+Is substituted, and K+、Na+、Ca2+、Mg2+When the cation compensates the excess charge, the heavy metal ion can replace the cation in the water solution through ion exchange; the surface of the bentonite particles can also form a hydrated oxide covering layer, so that the surface of the bentonite particles is electronegative, and the heavy metal ions can be favorably complexed and adsorbed. In addition, the bentonite has fine particles, large specific surface area and certain physical adsorption effect on heavy metal ions. In conclusion, the method is simple and easy to operate and short in flow. No harm to human body, high solidifying rate of heavy metal ions, low price and rich sources of raw materials, no secondary pollution and great reduction of sludge accumulation.
The heavy metal ion-sulphoaluminate cement-bentonite composite material has the advantages that the initial setting time is 33-158 min, the final setting time is 39-188 min, the 1d compressive strength is 1.05-26.83 MPa, the 7d compressive strength is 1.58-33.59 MPa, and the 28d compressive strength is 1.78-42.28 MPa, has good construction performance, and can be used in building basic materials or roadbed materials; and the heavy metal content is low, and can meet the regulations in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
Detailed Description
The present invention will be further described with reference to the following examples.
The invention provides a method for treating industrial wastewater containing heavy metal ions, which comprises the following steps:
detecting the type and concentration of heavy metal ions in the industrial wastewater by adopting an inductively coupled plasma emission spectrometry;
step two, mixing the sulphoaluminate cement, the bentonite, the water reducing agent and the quartz sand uniformly in a stirrer to prepare the sulphoaluminate cement-bentonite composite material, wherein the stirring speed is 300-600 rpm, and the stirring time is 5-10 min; then adding the industrial wastewater with the known heavy metal concentration in the step one into the sulphoaluminate cement-bentonite composite material, and uniformly stirring at 1000-1500 rpm to obtain a mixture, wherein the stirring time is 3-5 min;
and step three, pouring and molding the mixture, filling the mixture into a mold for curing, so that the heavy metal ions in the industrial wastewater containing the heavy metal ions are cured, and the material obtained by curing is the heavy metal ion-sulphoaluminate cement-bentonite composite material.
In the method for treating the industrial wastewater containing the heavy metal ions, the raw materials comprise sulphoaluminate cement, bentonite, a water reducing agent and medium-grade sand, and the method comprises the following steps of: 50-100 parts of sulphoaluminate cement, 10-50 parts of bentonite, 0.8-1.2 parts of water reducing agent and 150-200 parts of medium-grade sand. The sulphoaluminate cement adopts low-alkalinity sulphoaluminate cement with 42.5 strength grade; the bentonite is one or the combination of two of sodium bentonite and calcium bentonite; the water reducing agent is a naphthalene water reducing agent, a sulfamate water reducing agent or a polycarboxylic acid water reducing agent, and the water reducing rate is 15-35%; the medium-grade sand meets the requirements of ISO standard. According to the mass percentage, 465-925 parts of industrial wastewater containing heavy metal ions are added into each 1000 parts of sulphoaluminate cement-bentonite composite material. The obtained heavy metal ion-sulphoaluminate cement-bentonite composite material can be applied to building base materials or roadbed materials.
Example 1
Adding 2g of chromium nitrate into 465g of water, and uniformly stirring until the chromium nitrate is completely dissolved; uniformly mixing 900g of sulphoaluminate cement, 100g of calcium bentonite, 12g of sulfamate water reducing agent and 2000g of medium-grade sand in a stirrer to prepare a dry powder material, wherein the stirring speed is 300rpm, and the stirring time is 5 min; then adding a chromium nitrate solution into the mixture, and uniformly stirring at 1000rpm for 3 min; then the mixture is cast, molded, filled into a mold and maintained, so that the heavy metal ion-sulphoaluminate cement-bentonite with the curing rate of 99.967 percent, the initial setting time of 33min, the final setting time of 43min, the 1d compressive strength of 22.96MPa, the 7d compressive strength of 32.43MPa and the 28d compressive strength of 40.82MPa is obtainedThe composite material is subjected to a leaching toxicity test according to a horizontal oscillation method, and 100g of Cr in 1L of deionized water of the heavy metal ion-sulphoaluminate cement-bentonite composite material is measured by adopting an inductively coupled plasma emission spectrometer3+The leaching concentration of the chromium-free chromium leaching solution is 0.669mg/L, which is far lower than the limit value of the total Cr leaching concentration specified in the identification standard for hazardous wastes and the identification standard for leaching toxicity (GB 5085.3-2007).
Example 2
Adding 6g of chromium nitrate into 465g of water, and uniformly stirring until the chromium nitrate is completely dissolved; uniformly mixing 900g of sulphoaluminate cement, 100g of calcium bentonite, 10g of naphthalene water reducer and 2000g of medium-grade sand in a stirrer to prepare a dry powder material, wherein the stirring speed is 300rpm, and the stirring time is 5 min; then adding a chromium nitrate solution into the mixture, and uniformly stirring at 1200rpm for 3 min; then pouring and molding the mixture, filling the mixture into a mold for curing to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.992 percent, the initial setting time of 59min, the final setting time of 66min, the 1d compressive strength of 26.83MPa, the 7d compressive strength of 30.29MPa and the 28d compressive strength of 33.88MPa, carrying out leaching toxicity test according to a horizontal oscillation method, and measuring 100g of the heavy metal ion-sulphoaluminate cement-bentonite composite material in 1L of deionized water by adopting an inductive coupling plasma emission spectrometer3+The leaching concentration of (A) is 0.491mg/L, which is far lower than the limit value of the total Cr leaching concentration of 15mg/L specified in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
Example 3
Adding 10g of chromium nitrate into 465g of water, and uniformly stirring until the chromium nitrate is completely dissolved; uniformly mixing 900g of sulphoaluminate cement, 100g of sodium bentonite, 8g of polycarboxylic acid water reducing agent and 2000g of medium-grade sand in a stirrer to prepare dry powder, wherein the stirring speed is 300rpm, and the stirring time is 5 min; then adding a chromium nitrate solution into the mixture, and uniformly stirring at 1500rpm for 3 min; then pouring and molding the mixture, filling the mixture into a mold for curing to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.998 percent, the initial setting time of 79min, the final setting time of 89min, the 1d compressive strength of 21.80MPa, the 7d compressive strength of 29.19MPa and the 28d compressive strength of 32.13MPaThe material is subjected to a leaching toxicity test according to a horizontal oscillation method, and 100g of Cr in 1L of deionized water of the heavy metal ion-sulphoaluminate cement-bentonite composite material is measured by adopting an inductively coupled plasma emission spectrometer3+The leaching concentration of (A) is 0.246mg/L, which is far lower than the limit value of 15mg/L of the total Cr leaching concentration specified in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
Example 4
Adding 2g of lead nitrate into 465g of water, and uniformly stirring until the lead nitrate is completely dissolved; uniformly mixing 900g of sulphoaluminate cement, 100g of calcium bentonite, 12g of sulfamate water reducing agent and 2000g of medium-grade sand in a stirrer to prepare a dry powder material, wherein the stirring speed is 300rpm, and the stirring time is 5 min; then adding a lead nitrate solution into the mixture, and uniformly stirring at 1000rpm for 3 min; then pouring and molding the mixture, filling the mixture into a mold for curing to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.997 percent, the initial setting time of 34min, the final setting time of 39min, the 1d compressive strength of 18.34MPa, the 7d compressive strength of 30.31MPa and the 28d compressive strength of 36.42MPa, carrying out a leaching toxicity test according to a horizontal oscillation method, and measuring 100g of the heavy metal ion-sulphoaluminate cement-bentonite composite material by adopting an inductive coupling plasma emission spectrometer to obtain Pb in 1L of deionized water2+The leaching concentration of (2) is 0.047mg/L, which is far lower than the limit value of the total Pb leaching concentration of 5mg/L specified in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
Example 5
Adding 6g of lead nitrate into 465g of water, and uniformly stirring until the lead nitrate is completely dissolved; uniformly mixing 900g of sulphoaluminate cement, 100g of sodium bentonite, 8g of naphthalene water reducer and 2000g of medium-grade sand in a stirrer to prepare a dry powder material, wherein the stirring speed is 300rpm, and the stirring time is 5 min; then adding a lead nitrate solution into the mixture, and uniformly stirring at 1200rpm for 3 min; then pouring and molding the mixture, filling the mixture into a mold and curing the mixture to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.998 percent, the initial setting time of 52min, the final setting time of 58min, the 1d compressive strength of 19.74MPa, the 7d compressive strength of 33.59MPa and the 28d compressive strength of 42.28MPaThe material is subjected to a leaching toxicity test according to a horizontal oscillation method, and 100g of Pb of the heavy metal ion-sulphoaluminate cement-bentonite composite material in 1L of deionized water is measured by adopting an inductive coupling plasma emission spectrometer2+The leaching concentration of (2) is 0.097mg/L, which is far lower than the limit value of the total Pb leaching concentration of 5mg/L specified in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
Example 6
Adding 10g of lead nitrate into 465g of water, and uniformly stirring until the lead nitrate is completely dissolved; uniformly mixing 900g of sulphoaluminate cement, 100g of sodium bentonite, 10g of naphthalene water reducer and 2000g of medium-grade sand in a stirrer to prepare a dry powder material, wherein the stirring speed is 300rpm, and the stirring time is 5 min; then adding a lead nitrate solution into the mixture, and uniformly stirring at 1500rpm for 3 min; then pouring and molding the mixture, filling the mixture into a mold for curing to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.997 percent, the initial setting time of 66min, the final setting time of 71min, the 1d compressive strength of 18.83MPa, the 7d compressive strength of 30.40MPa and the 28d compressive strength of 33.67MPa, carrying out a leaching toxicity test according to a horizontal oscillation method, and measuring 100g of the heavy metal ion-sulphoaluminate cement-bentonite composite material by adopting an inductive coupling plasma emission spectrometer to obtain Pb in 1L of deionized water2+The leaching concentration of (2) is 0.275mg/L, which is far lower than the limit value of the total Pb leaching concentration of 5mg/L specified in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
Example 7
Adding 10g of chromium nitrate into 580g of water, and uniformly stirring until the chromium nitrate is completely dissolved; uniformly mixing 800g of sulphoaluminate cement, 200g of calcium bentonite, 10g of naphthalene water reducer and 2000g of medium-grade sand in a stirrer to prepare a dry powder material, wherein the stirring speed is 450rpm, and the stirring time is 8 min; then adding a chromium nitrate solution into the mixture, and uniformly stirring at 1500rpm for 4 min; then the mixture is cast, molded and cured in a mold, so that the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.997 percent, the initial setting time of 87min, the final setting time of 96min, the 1d compressive strength of 11.05MPa, the 7d compressive strength of 15.08MPa and the 28d compressive strength of 17.33MPa is obtainedPerforming leaching toxicity test according to horizontal oscillation method, and measuring 100g of Cr in 1L of deionized water by using inductively coupled plasma emission spectrometer3+The leaching concentration of (A) is 0.327mg/L, which is far lower than the limit value of 15mg/L of the total Cr leaching concentration specified in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
Example 8
Adding 10g of lead nitrate into 580g of water, and uniformly stirring until the lead nitrate is completely dissolved; uniformly mixing 800g of sulphoaluminate cement, 200g of sodium bentonite, 8g of polycarboxylic acid water reducing agent and 2000g of medium-grade sand in a stirrer to prepare dry powder, wherein the stirring speed is 450rpm, and the stirring time is 8 min; then adding a lead nitrate solution into the mixture, and uniformly stirring at 1500rpm for 4 min; then pouring and molding the mixture, filling the mixture into a mold for curing to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.995 percent, the initial setting time of 80min, the final setting time of 85min, the 1d compressive strength of 10.81MPa, the 7d compressive strength of 18.60MPa and the 28d compressive strength of 22.72MPa, carrying out a leaching toxicity test according to a horizontal oscillation method, and measuring 100g of the heavy metal ion-sulphoaluminate cement-bentonite composite material by adopting an inductive coupling plasma emission spectrometer to obtain Pb in 1L of deionized water2+The leaching concentration of the lead-free acid is 0.498mg/L which is far lower than the limit value of the total Pb leaching concentration specified in a hazardous waste identification standard and a leaching toxicity identification standard (GB5085.3-2007) by 5 mg/L.
Example 9
Adding 6g of chromium nitrate into 925g of water, and uniformly stirring until the chromium nitrate is completely dissolved; uniformly mixing 500g of sulphoaluminate cement, 500g of calcium bentonite, 10g of naphthalene water reducer and 2000g of medium-grade sand in a stirrer to prepare a dry powder material, wherein the stirring speed is 600rpm, and the stirring time is 10 min; then adding a chromium nitrate solution into the mixture, and uniformly stirring at 1200rpm for 5 min; then pouring and molding the mixture, filling the mixture into a mold for curing to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.991 percent, the initial setting time of 158min, the final setting time of 188min, the 1d compressive strength of 1.05MPa, the 7d compressive strength of 1.58MPa and the 28d compressive strength of 1.78MPaPerforming leaching toxicity test by horizontal oscillation method, and measuring 100g of Cr in 1L of deionized water by using inductively coupled plasma emission spectrometer3+The leaching concentration of (A) is 0.570mg/L, which is far lower than the limit value of the total Cr leaching concentration of 15mg/L specified in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
Example 10
Adding 10g of lead nitrate into 580g of water, and uniformly stirring until the lead nitrate is completely dissolved; uniformly mixing 500g of sulphoaluminate cement, 500g of sodium bentonite, 8g of polycarboxylic acid water reducing agent and 2000g of medium-grade sand in a stirrer to prepare dry powder, wherein the stirring speed is 600rpm, and the stirring time is 10 min; then adding a lead nitrate solution into the mixture, and uniformly stirring at 1500rpm for 5 min; then pouring and molding the mixture, filling the mixture into a mold for curing to obtain the heavy metal ion-sulphoaluminate cement-bentonite composite material with the curing rate of 99.996 percent, the initial setting time of 148min, the final setting time of 178min, the 1d compressive strength of 1.49MPa, the 7d compressive strength of 1.85MPa and the 28d compressive strength of 2.21MPa, carrying out a leaching toxicity test according to a horizontal oscillation method, and measuring 100g of the heavy metal ion-sulphoaluminate cement-bentonite composite material by adopting an inductive coupling plasma emission spectrometer to obtain Pb in 1L of deionized water2+The leaching concentration of (2) is 0.447mg/L, which is far lower than the limit value of the total Pb leaching concentration of 5mg/L specified in the identification standard of hazardous wastes and the identification standard of leaching toxicity (GB 5085.3-2007).
In conclusion, the invention has the advantages of good curing effect and curing stability on heavy metal ions, low raw material cost, simple treatment process, reduction of sludge accumulation, reusability in building basic materials or roadbed materials after heavy metal curing, and suitability for popularization and application.
Claims (5)
1. A treatment method of industrial wastewater containing heavy metal ions is characterized by comprising the following steps:
step one, mixing and uniformly stirring sulphoaluminate cement, bentonite, a water reducing agent and quartz sand to prepare a sulphoaluminate cement-bentonite composite material;
adding industrial wastewater containing heavy metal ions into the sulphoaluminate cement-bentonite composite material, and uniformly stirring to obtain a mixture;
step three, pouring, molding and curing the mixture obtained in the step two in a mold to enable heavy metal ions in the industrial wastewater containing the heavy metal ions to be cured;
in the first step, 50-100 parts by mass of sulphoaluminate cement, 10-50 parts by mass of bentonite, 0.8-1.2 parts by mass of a water reducing agent and 150-200 parts by mass of medium-grade sand are mixed and uniformly stirred to prepare a sulphoaluminate cement-bentonite composite material;
the sulphoaluminate cement in the first step is low-alkalinity sulphoaluminate cement with the strength grade of 42.5;
the bentonite in the first step is one or the combination of sodium bentonite and calcium bentonite;
the water reducing agent in the first step is a naphthalene water reducing agent, an aminosulfonate water reducing agent or a polycarboxylic acid water reducing agent, and the water reducing rate is 15-35%;
in the second step, 465-925 parts of heavy metal ion-containing industrial wastewater is added into each 1000 parts of sulphoaluminate cement-bentonite composite material by mass percent.
2. The method for treating industrial wastewater containing heavy metal ions according to claim 1, wherein in the first step, the stirring speed is 300-600 rpm, and the stirring time is 5-10 min.
3. The method for treating industrial wastewater containing heavy metal ions according to claim 1, wherein in the second step, the stirring speed is 1000-1500 rpm, and the stirring time is 3-5 min.
4. The method for treating industrial wastewater containing heavy metal ions according to claim 1, wherein the medium-grade sand in the first step is medium-grade sand meeting ISO standard requirements.
5. A heavy metal ion-sulphoaluminate cement-bentonite composite material, which is characterized in that the heavy metal ion-sulphoaluminate cement-bentonite composite material is obtained by the method for treating the industrial wastewater containing the heavy metal ions according to any one of claims 1 to 4.
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