CN109354309B - Heavy metal multiple composite treatment process for industrial wastewater - Google Patents

Heavy metal multiple composite treatment process for industrial wastewater Download PDF

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CN109354309B
CN109354309B CN201811320912.1A CN201811320912A CN109354309B CN 109354309 B CN109354309 B CN 109354309B CN 201811320912 A CN201811320912 A CN 201811320912A CN 109354309 B CN109354309 B CN 109354309B
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wastewater
sedimentation tank
heavy metal
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CN109354309A (en
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关伟
李铭珊
贾燕
胡小英
李开明
张明杨
温勇
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South China Institute of Environmental Science of Ministry of Ecology and Environment
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used

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  • Hydrology & Water Resources (AREA)
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Abstract

The invention discloses a heavy metal multiple composite treatment process for industrial wastewater, which comprises the following steps of A1, removing large solid matters from the industrial wastewater through a grid, then discharging the wastewater into a sedimentation tank I, and standing for 24-48 hours; the bottom of the sedimentation tank I is filled with river sand with the thickness of 20-40 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 20-40 cm; B1. 1kg of composite treating agent: adding a composite treating agent into the wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 200-300 revolutions/min for 20-40min, and standing for 2-4 hours; can accelerate the settling velocity of heavy metal ions, the heavy metal in the absorption waste water that can be better improves the contact probability of reaction to increase the contact effect of heavy metal trapping agent and heavy metal, improve the validity of chelation reaction, effectively get rid of multiple heavy metal in the system, make the total clearance of synthesizing waste water heavy metal can reach more than 99%.

Description

Heavy metal multiple composite treatment process for industrial wastewater
Technical Field
The invention relates to wastewater treatment, in particular to a heavy metal multiple compound treatment process for industrial wastewater.
Background
Electroplating is a process for decorating and protecting metal and non-metal surfaces and obtaining certain new properties by using an electrochemical method. In the electroplating industry, the common plating species include nickel plating, copper plating, chromium plating, zinc plating and the like. In the electroplating process, in order to ensure the quality of the electroplated product, ensure that the metal coating has a smooth and good appearance and is firmly combined with the plated part, dirt (oil, rust, oxide scale and the like) on the surface of the plated part must be thoroughly cleaned before plating, and the adhering liquid on the surface of the plated part must be cleaned after plating. Therefore, a large amount of waste water is inevitably discharged during the electroplating production. The sources of the electroplating wastewater are wide, and generally comprise the following steps: firstly, plating part cleaning wastewater; ② electroplating waste liquid; thirdly, other waste water comprises condensed water for scouring the floor of a workshop, scrubbing the floor and ventilating equipment and various bath solutions and drainage caused by leakage of a plating bath or improper operation management; and fourthly, the equipment cooling water is not polluted by heavy metal except for temperature reduction in the using process. Wherein, the cleaning water of the plating part is the main source of electroplating wastewater, and almost accounts for more than 80 percent of the discharge amount of the wastewater in a workshop. Because the function requirements of plated parts are different, and plating seeds, plating solution components, operation modes, process conditions and the like are also different, pollutants of electroplating wastewater are very complex and mainly contain metal ions such as chromium, copper, nickel, lead, gold, silver, cadmium and the like, wherein the contained heavy metal ions such as chromium, copper, nickel, zinc and the like and cyanide and the like have high toxicity, and some of the heavy toxic substances belong to carcinogenic, teratogenic and mutagenic substances and are extremely harmful to human beings.
Disclosure of Invention
In view of the above, the present invention provides a heavy metal multiple-compound treatment process for industrial wastewater, which can accelerate the settling velocity of heavy metal ions, better adsorb heavy metals in wastewater, and improve the contact probability of reaction, thereby increasing the contact effect of heavy metal trapping agent and heavy metals, improving the effectiveness of chelation reaction, effectively removing various heavy metals in the system, and enabling the total removal rate of heavy metals in comprehensive wastewater to reach more than 99%.
The heavy metal multiple composite treatment process for industrial wastewater comprises the following steps:
A1. removing large solid matters from the industrial wastewater through a grid, then discharging the wastewater into a sedimentation tank I, and standing for 24-48 hours; wherein, the bottom filler of the sedimentation tank I is river sand with the thickness of 20-40 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 20-40 cm;
B1. 1kg of composite treating agent: adding a composite treating agent into the wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 200 plus materials and 300 revolutions per minute for 20-40min, and standing for 2-4 h;
C1. discharging the wastewater treated in the step bIn a microbial reaction tank, firstly adjusting the pH value of the wastewater to 7-8, then adding 6 g of the complex microbial inoculum per cubic meter of liquid every time, adding for 1 time every day, continuously adding for two days, standing for five days, filtering the liquid through a plate-and-frame filter, and finally discharging; the compound microbial inoculum is prepared by the following method: culturing Thiobacillus denitrificans, Pseudomonas stutzeri, Pseudomonas aeruginosa and Bacillus cereus to concentration of 1 × 108Bacterial solution per ml, according to the ratio of 1: 1: 2: 2, and then mixing with sawdust according to a volume ratio of 1: 3, mixing and stirring uniformly, and finally drying at low temperature to obtain the product;
the composite treating agent comprises the following raw materials in parts by weight:
10-20 parts of sodium persulfate, 5-10 parts of polyepoxysuccinic acid sodium, 1-5 parts of tetraethylenepentamine dithiocarbamate, 1-3 parts of expanded rice hull powder, 1-5 parts of cross-linked rectorite, 5-10 parts of shell powder, 1-3 parts of flocculant, 4-8 parts of calcium dioxide, 4-8 parts of modified traditional Chinese medicine residues, 1-3 parts of potassium permanganate, 1-5 parts of dithiocarbamate chitosan and 1-3 parts of methacryloyloxyethyl trimethyl ammonium chloride, wherein the modified traditional Chinese medicine residues are prepared by the following method:
the modified traditional Chinese medicine residues are prepared in the following way:
a. preparing a liquid matrix: mixing 0.05 part of vitamin B1, 1-5 parts of Tween, 25-35 parts of monopotassium phosphate, 5-15 parts of magnesium sulfate heptahydrate, 0.1-1 part of calcium chloride dihydrate, 1-5 parts of ammonium tartrate and 200 parts of 100-fold trace element mixed solution in parts by weight;
b. adding liquid matrix into the dried and pulverized Chinese medicinal residue, sterilizing, inoculating 5.0% Phanerochaete chrysosporium suspension, sealing, culturing at 37 deg.C for 7-10 days, and drying the Chinese medicinal residue at 60-70 deg.C;
the crosslinked rectorite is treated by:
c. crushing the crosslinked rectorite to 60-80 meshes, calcining at the temperature of 350-400 ℃ for 1-2 hours, cooling, adding 15% citric acid aqueous solution with the same weight, performing ball milling for 2-4 hours, and collecting slurry;
d. dropwise adding a sodium hydroxide aqueous solution into the slurry, adjusting the pH value to 7-8, carrying out ultrasonic treatment for 40-50 minutes, standing for 3-5 hours, collecting precipitates, calcining at the temperature of 600-700 ℃ for 1-2 hours, and cooling;
further, the composite treating agent comprises the following raw materials in parts by weight:
15 parts of sodium persulfate, 7 parts of polyepoxysuccinic acid sodium, 3 parts of tetraethylenepentamine dithiocarbamate, 2 parts of puffed rice hull powder, 3 parts of crosslinked rectorite, 7 parts of shell powder, 2 parts of flocculant, 6 parts of calcium dioxide, 6 parts of modified traditional Chinese medicine residues, 2 parts of potassium permanganate, 3 parts of dithiocarbamate chitosan and 2 parts of methacryloyloxyethyl trimethyl ammonium chloride;
further, the flocculating agent is a mixture of polyacrylamide, dehydrated polymeric ferric sulfate and polyglutamic acid, and the mass ratio of the polyacrylamide: and (3) dehydrating polymeric ferric sulfate: polyglutamic acid 2: 3: 1;
further, the modified traditional Chinese medicine residue is a mixture of radix isatidis and fructus gardeniae;
further, the Phanerochaete chrysosporium content of the Phanerochaete chrysosporium suspension is 1.0 × 106Per mL;
further, in the step b, the dried traditional Chinese medicine residues are crushed to 40-60 meshes.
The invention has the beneficial effects that: the heavy metal multiple composite treatment process for industrial wastewater can accelerate the settling velocity of heavy metal ions, better adsorb heavy metals in wastewater and improve the contact probability of reaction, thereby increasing the contact effect of a heavy metal trapping agent and the heavy metals, improving the effectiveness of chelation reaction, effectively removing various heavy metals in a system and ensuring that the total removal rate of the heavy metals in the comprehensive wastewater can reach more than 99%. Heavy metals are effectively fixed through dithiocarbamic acid chitosan and other components, such as puffed rice hull powder, cross-linked rectorite, shell powder, modified traditional Chinese medicine residues and the like, and directly generate chemical, physical adsorption and ion exchange adsorption with heavy metal ions such as lead, cadmium and the like, wherein the modified traditional Chinese medicine residues have larger and more adsorption pores and large specific surface area, can provide more adsorption sites, and achieve the effect of multiple adsorption.
Detailed Description
Example one
The heavy metal multiple composite treatment process for industrial wastewater comprises the following steps:
A1. removing large solid matters from the industrial wastewater through a grating, then discharging the wastewater into a sedimentation tank I, and standing for 24 hours; wherein, the bottom filler of the sedimentation tank I is river sand with the thickness of 20 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 20 cm;
B1. 1kg of composite treating agent: adding a composite treating agent into wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 200 revolutions per minute for 20min, and standing for 2 hours;
C1. discharging the wastewater treated in the step b into a microbial reaction tank, firstly adjusting the pH of the wastewater to 7-8, then adding 6 g of the compound microbial inoculum into each cubic meter of the liquid every time, adding the compound microbial inoculum for 1 time every day, continuously adding the compound microbial inoculum for two days, standing for five days, filtering the liquid through a plate-and-frame filter, and finally discharging; the compound microbial inoculum is prepared by the following method: culturing Thiobacillus denitrificans, Pseudomonas stutzeri, Pseudomonas aeruginosa and Bacillus cereus to concentration of 1 × 108Bacterial solution per ml, according to the ratio of 1: 1: 2: 2, and then mixing with sawdust according to a volume ratio of 1: 3, mixing and stirring uniformly, and finally drying at low temperature to obtain the product;
the composite treating agent comprises the following raw materials in parts by weight:
10 parts of sodium persulfate, 5 parts of polyepoxysuccinic acid sodium, 1 part of tetraethylenepentamine dithiocarbamate, 1 part of puffed rice hull powder, 1 part of crosslinked rectorite, 5 parts of shell powder, 1 part of flocculant, 4 parts of calcium dioxide, 4 parts of modified traditional Chinese medicine residues, 1 part of potassium permanganate, 1 part of dithiocarbamate chitosan and 1 part of methacryloyloxyethyl trimethyl ammonium chloride, wherein the modified traditional Chinese medicine residues are prepared by the following method:
a. preparing a liquid matrix: mixing 0.05 part of vitamin B1, 3 parts of Tween, 30 parts of monopotassium phosphate, 5 parts of magnesium sulfate heptahydrate, 1 part of calcium chloride dihydrate, 4 parts of ammonium tartrate and 180 parts of mixed solution of trace elements in parts by weight;
b. adding dried and pulverized fructus Gardeniae and radix Isatidis residue into liquid matrix, sterilizing, and adding 5.0%
Figure BDA0001857478510000051
Phanerochaete chrysosporium suspension (content 1.0X 10)6one/mL), culturing at 37 deg.C for 7 days, and oven drying the residue at 64 deg.C;
the crosslinked rectorite is treated by:
c. crushing the crosslinked rectorite to 60 meshes, calcining for 1 hour at the temperature of 350 ℃, cooling, adding 15 percent citric acid aqueous solution with the same weight and concentration, performing ball milling for 2 hours, and collecting slurry;
d. and dropwise adding a sodium hydroxide aqueous solution into the slurry, adjusting the pH to 7, carrying out ultrasonic treatment for 40 minutes, standing for 3 hours, collecting precipitate, calcining at the temperature of 600 ℃ for 1 hour, and cooling.
Example two
The heavy metal multiple composite treatment process for industrial wastewater comprises the following steps:
A1. removing large solid matters from the industrial wastewater through a grating, then discharging the wastewater into a sedimentation tank I, and standing for 48 hours; wherein, the bottom filler of the sedimentation tank I is river sand with the thickness of 40 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 40 cm;
B1. 1kg of composite treating agent: adding a composite treating agent into wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 300 revolutions per minute for 40 minutes, and standing for 4 hours;
C1. discharging the wastewater treated in the step b into a microbial reaction tank, firstly adjusting the pH of the wastewater to 7-8, then adding 6 g of the compound microbial inoculum into each cubic meter of the liquid every time, adding the compound microbial inoculum for 1 time every day, continuously adding the compound microbial inoculum for two days, standing for five days, filtering the liquid through a plate-and-frame filter, and finally discharging; the compound microbial inoculum is prepared by the following method: thiobacillus denitrificans, pseudomonas stutzeri and pseudomonas aeruginosaFour kinds of bacteria, Bacillus cereus and Bacillus cereus, are cultured to concentration of 1 × 108Bacterial solution per ml, according to the ratio of 1: 1: 2: 2, and then mixing with sawdust according to a volume ratio of 1: 3, mixing and stirring uniformly, and finally drying at low temperature to obtain the product;
the composite treating agent comprises the following raw materials in parts by weight:
20 parts of sodium persulfate, 10 parts of polyepoxysuccinic acid sodium, 5 parts of tetraethylenepentamine dithiocarbamate, 3 parts of expanded rice hull powder, 5 parts of crosslinked rectorite, 10 parts of shell powder, 3 parts of flocculant, 8 parts of calcium dioxide, 8 parts of modified traditional Chinese medicine residues, 3 parts of potassium permanganate, 5 parts of dithiocarbamate chitosan and 3 parts of methacryloyloxyethyl trimethyl ammonium chloride, wherein the modified traditional Chinese medicine residues are prepared by the following method:
a. preparing a liquid matrix: mixing 0.08 part of vitamin B1, 1 part of Tween, 35 parts of monopotassium phosphate, 5 parts of magnesium sulfate heptahydrate, 1 part of calcium chloride dihydrate, 1 part of ammonium tartrate and 200 parts of mixed solution of trace elements according to parts by weight;
b. adding the dried and crushed gardenia and the isatis root dregs with 40 meshes into a liquid matrix, sterilizing and inoculating 5.0 percent
Figure BDA0001857478510000061
Phanerochaete chrysosporium suspension (content 1.0X 10)6one/mL), culturing at 37 deg.C for 10 days, and oven drying the residue at 60 deg.C.
The crosslinked rectorite is treated by:
c. crushing the crosslinked rectorite to 80 meshes, calcining at 400 ℃ for 2 hours, cooling, adding 15% citric acid aqueous solution with the same weight, performing ball milling for 4 hours, and collecting slurry;
d. and dropwise adding a sodium hydroxide aqueous solution into the slurry, adjusting the pH to 8, carrying out ultrasonic treatment for 50 minutes, standing for 5 hours, collecting precipitates, calcining at the temperature of 700 ℃ for 2 hours, and cooling.
EXAMPLE III
The heavy metal multiple composite treatment process for industrial wastewater comprises the following steps:
A1. removing large solid matters from the industrial wastewater through a grating, then discharging the wastewater into a sedimentation tank I, and standing for 24 hours; wherein, the bottom filler of the sedimentation tank I is river sand with the thickness of 20 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 40 cm;
B1. 1kg of composite treating agent: adding a composite treating agent into wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 200 revolutions per minute for 40 minutes, and standing for 2 hours;
C1. discharging the wastewater treated in the step b into a microbial reaction tank, firstly adjusting the pH of the wastewater to 7-8, then adding 6 g of the compound microbial inoculum into each cubic meter of the liquid every time, adding the compound microbial inoculum for 1 time every day, continuously adding the compound microbial inoculum for two days, standing for five days, filtering the liquid through a plate-and-frame filter, and finally discharging; the compound microbial inoculum is prepared by the following method: culturing Thiobacillus denitrificans, Pseudomonas stutzeri, Pseudomonas aeruginosa and Bacillus cereus to concentration of 1 × 108Bacterial solution per ml, according to the ratio of 1: 1: 2: 2, and then mixing with sawdust according to a volume ratio of 1: 3, mixing and stirring uniformly, and finally drying at low temperature to obtain the product;
the composite treating agent comprises the following raw materials in parts by weight:
10 parts of sodium persulfate, 10 parts of polyepoxysuccinic acid sodium, 1 part of tetraethylenepentamine dithiocarbamate, 3 parts of expanded rice hull powder, 1 part of crosslinked rectorite, 10 parts of shell powder, 1 part of flocculant, 8 parts of calcium dioxide, 4 parts of modified traditional Chinese medicine residues, 3 parts of potassium permanganate, 5 parts of dithiocarbamate chitosan and 1 part of methacryloyloxyethyl trimethyl ammonium chloride, wherein the modified traditional Chinese medicine residues are prepared by the following method:
a. preparing a liquid matrix: mixing 0.05 part of vitamin B1, 1 part of Tween, 35 parts of monopotassium phosphate, 5 parts of magnesium sulfate heptahydrate, 1 part of calcium chloride dihydrate, 1 part of ammonium tartrate and 200 parts of trace element mixed solution according to parts by weight;
b. adding the dried and crushed gardenia and the isatis root dregs with 40 meshes into a liquid matrix, sterilizing and inoculating 5.0 percent
Figure BDA0001857478510000071
Phanerochaete chrysosporium suspension (content 1.0X 10)6one/mL), culturing at 37 deg.C for 10 days, and oven drying the residue at 60 deg.C.
The crosslinked rectorite is treated by:
c. crushing the crosslinked rectorite to 60 meshes, calcining for 1 hour at the temperature of 400 ℃, cooling, adding 15 percent citric acid aqueous solution with the same weight, performing ball milling for 4 hours, and collecting slurry;
d. and dropwise adding a sodium hydroxide aqueous solution into the slurry, adjusting the pH to 7, carrying out ultrasonic treatment for 50 minutes, standing for 3 hours, collecting precipitates, calcining at the temperature of 700 ℃ for 1 hour, and cooling.
Example four
The heavy metal multiple composite treatment process for industrial wastewater comprises the following steps:
A1. removing large solid matters from the industrial wastewater through a grating, then discharging the wastewater into a sedimentation tank I, and standing for 40 hours; wherein, the bottom filler of the sedimentation tank I is river sand with the thickness of 30 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 30 cm;
B1. 1kg of composite treating agent: adding a composite treating agent into wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 200 revolutions per minute for 40min, and standing for 3 hours;
C1. discharging the wastewater treated in the step b into a microbial reaction tank, firstly adjusting the pH of the wastewater to 7-8, then adding 6 g of the compound microbial inoculum into each cubic meter of the liquid every time, adding the compound microbial inoculum for 1 time every day, continuously adding the compound microbial inoculum for two days, standing for five days, filtering the liquid through a plate-and-frame filter, and finally discharging; the compound microbial inoculum is prepared by the following method: culturing Thiobacillus denitrificans, Pseudomonas stutzeri, Pseudomonas aeruginosa and Bacillus cereus to concentration of 1 × 108Bacterial solution per ml, according to the ratio of 1: 1: 2: 2, and then mixing with sawdust according to a volume ratio of 1: 3 mass ratioMixing and stirring uniformly, and finally drying at low temperature to obtain the product;
the composite treating agent comprises the following raw materials in parts by weight:
20 parts of sodium persulfate, 5 parts of polyepoxysuccinic acid sodium, 5 parts of tetraethylenepentamine dithiocarbamate, 1 part of puffed rice hull powder, 5 parts of crosslinked rectorite, 5 parts of shell powder, 3 parts of flocculant, 4 parts of calcium dioxide, 8 parts of modified traditional Chinese medicine residues, 1 part of potassium permanganate, 5 parts of red mud particles, 1 part of dithiocarbamate and 3 parts of methacryloyloxyethyl trimethyl ammonium chloride, wherein the modified traditional Chinese medicine residues are prepared by the following method:
a. preparing a liquid matrix: mixing 0.08 part of vitamin B1, 5 parts of Tween, 35 parts of monopotassium phosphate, 15 parts of magnesium sulfate heptahydrate, 1 part of calcium chloride dihydrate, 5 parts of ammonium tartrate and 200 parts of trace element mixed solution according to parts by weight;
b. adding the dried and crushed medicinal residues of gardenia and isatis root into a liquid matrix, sterilizing and inoculating 5.0 percent
Figure BDA0001857478510000081
Phanerochaete chrysosporium suspension (content 1.0X 10)6one/mL), culturing at 37 deg.C for 10 days, and oven drying the residue at 70 deg.C.
The crosslinked rectorite is treated by:
c. crushing the crosslinked rectorite to 80 meshes, calcining at 350 ℃ for 2 hours, cooling, adding 15% citric acid aqueous solution with the same weight, performing ball milling for 2 hours, and collecting slurry;
d. and dropwise adding a sodium hydroxide aqueous solution into the slurry, adjusting the pH to 8, carrying out ultrasonic treatment for 40 minutes, standing for 5 hours, collecting precipitates, calcining at the temperature of 600 ℃ for 2 hours, and cooling.
EXAMPLE five
The heavy metal multiple composite treatment process for industrial wastewater comprises the following steps:
A1. removing large solid matters from the industrial wastewater through a grating, then discharging the wastewater into a sedimentation tank I, and standing for 30 hours; wherein, the bottom filler of the sedimentation tank I is river sand with the thickness of 30 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 30 cm;
B1. 1kg of composite treating agent: adding a composite treating agent into wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 250 revolutions per minute for 30 minutes, and standing for 3 hours;
C1. discharging the wastewater treated in the step b into a microbial reaction tank, firstly adjusting the pH of the wastewater to 7-8, then adding 6 g of the compound microbial inoculum into each cubic meter of the liquid every time, adding the compound microbial inoculum for 1 time every day, continuously adding the compound microbial inoculum for two days, standing for five days, filtering the liquid through a plate-and-frame filter, and finally discharging; the compound microbial inoculum is prepared by the following method: culturing Thiobacillus denitrificans, Pseudomonas stutzeri, Pseudomonas aeruginosa and Bacillus cereus to concentration of 1 × 108Bacterial solution per ml, according to the ratio of 1: 1: 2: 2, and then mixing with sawdust according to a volume ratio of 1: 3, mixing and stirring uniformly, and finally drying at low temperature to obtain the product;
the composite treating agent comprises the following raw materials in parts by weight:
15 parts of sodium persulfate, 5 parts of polyepoxysuccinic acid sodium, 5 parts of tetraethylenepentamine dithiocarbamate, 2 parts of puffed rice hull powder, 1 part of crosslinked rectorite, 10 parts of shell powder, 2 parts of flocculant, 6 parts of calcium dioxide, 4 parts of modified traditional Chinese medicine residues, 3 parts of potassium permanganate, 2 parts of dithiocarbamate chitosan and 1 part of methacryloyloxyethyl trimethyl ammonium chloride, wherein the modified traditional Chinese medicine residues are prepared by the following method:
a. preparing a liquid matrix: mixing 0.05 part of vitamin B1, 1 part of Tween, 25 parts of monopotassium phosphate, 5 parts of magnesium sulfate heptahydrate, 0.1 part of calcium chloride dihydrate, 1 part of ammonium tartrate and 100 parts of mixed solution of trace elements according to parts by weight;
b. adding the dried and crushed gardenia and the isatis root dregs with 40 meshes into a liquid matrix, sterilizing and inoculating 5.0 percent
Figure BDA0001857478510000091
Phanerochaete chrysosporium suspension (containing)The amount is 1.0X 106one/mL), culturing at 37 deg.C for 7 days, and oven drying the residue at 60 deg.C.
The crosslinked rectorite is treated by:
c. crushing the crosslinked rectorite to 70 meshes, calcining at 380 ℃ for 1.5 hours, cooling, adding 15% citric acid aqueous solution with the same weight, performing ball milling for 2.5 hours, and collecting slurry;
d. and dropwise adding a sodium hydroxide aqueous solution into the slurry, adjusting the pH to 7, carrying out ultrasonic treatment for 45 minutes, standing for 4 hours, collecting precipitate, calcining at the temperature of 620 ℃ for 1.5 hours, and cooling.
EXAMPLE six
The heavy metal multiple composite treatment process for industrial wastewater comprises the following steps:
A1. removing large solid matters from the industrial wastewater through a grating, then discharging the wastewater into a sedimentation tank I, and standing for 24 hours; wherein, the bottom filler of the sedimentation tank I is river sand with the thickness of 40 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 40 cm;
B1. 1kg of composite treating agent: adding a composite treating agent into wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 200 revolutions per minute for 40min, and standing for 3 hours;
C1. discharging the wastewater treated in the step b into a microbial reaction tank, firstly adjusting the pH of the wastewater to 7-8, then adding 6 g of the compound microbial inoculum into each cubic meter of the liquid every time, adding the compound microbial inoculum for 1 time every day, continuously adding the compound microbial inoculum for two days, standing for five days, filtering the liquid through a plate-and-frame filter, and finally discharging; the compound microbial inoculum is prepared by the following method: culturing Thiobacillus denitrificans, Pseudomonas stutzeri, Pseudomonas aeruginosa and Bacillus cereus to concentration of 1 × 108Bacterial solution per ml, according to the ratio of 1: 1: 2: 2, and then mixing with sawdust according to a volume ratio of 1: 3, mixing and stirring uniformly, and finally drying at low temperature to obtain the product;
the composite treating agent comprises the following raw materials in parts by weight:
15 parts of sodium persulfate, 7 parts of polyepoxysuccinic acid sodium, 3 parts of tetraethylenepentamine dithiocarbamate, 2 parts of puffed rice hull powder, 3 parts of crosslinked rectorite, 7 parts of shell powder, 2 parts of flocculant, 6 parts of calcium dioxide, 6 parts of modified traditional Chinese medicine residues, 2 parts of potassium permanganate, 3 parts of dithiocarbamate chitosan and 2 parts of methacryloyloxyethyl trimethyl ammonium chloride; the modified traditional Chinese medicine residues are prepared in the following way:
a. preparing a liquid matrix: mixing 0.06 part of vitamin B1, tween 3, 30 parts of monopotassium phosphate, 10 parts of magnesium sulfate heptahydrate, 0.61 part of calcium chloride dihydrate, 3 parts of ammonium tartrate and 150 parts of mixed solution of trace elements according to parts by weight;
b. adding the dried and crushed fructus Gardeniae and radix Isatidis dregs with 50 meshes into liquid matrix, sterilizing, and adding 5.0%
Figure BDA0001857478510000101
Phanerochaete chrysosporium suspension (content 1.0X 10)6one/mL), culturing at 37 deg.C for 8 days, and oven drying the residue at 65 deg.C;
the crosslinked rectorite is treated by:
c. crushing the crosslinked rectorite to 75 meshes, calcining at 360 ℃ for 1.8 hours, cooling, adding 15% citric acid aqueous solution with the same weight, performing ball milling for 2.5 hours, and collecting slurry;
d. and dropwise adding a sodium hydroxide aqueous solution into the slurry, adjusting the pH to 8, carrying out ultrasonic treatment for 48 minutes, standing for 3.8 hours, collecting precipitates, calcining at the temperature of 680 ℃ for 1.8 hours, and cooling.
In the above embodiment, the flocculant is a mixture of polyacrylamide, dehydrated polymeric ferric sulfate and polyglutamic acid, and the mass ratio of polyacrylamide: and (3) dehydrating polymeric ferric sulfate: polyglutamic acid 2: 3: 1; the molecular weight of the polyacrylamide is 400 ten thousand, and the modified traditional Chinese medicine residue is a mixture of isatis root and gardenia; the Phanerochaete chrysosporium suspension has Phanerochaete chrysosporium content of 1.0 × 106one/mL.
The heavy metal multiple composite treatment process for industrial wastewater compounded by the method is applied to electroplating wastewater treatment, and the treatment effect is as follows, wherein the unit mg/L is as follows:
item COD SS Zn2+ Pb2+ Ni2+ Cr6+ Mn Hg
Electroplating wastewater sample 200 145 165 220 10 110 8 5
Example 1 17 5.4 0.16 0.11 0.013 0.02 0.0005 0.0005
Example 2 14 4.6 0.2 0.16 0.011 0.03 0.0005 0.0006
Example 3 16 5.8 0.16 0.20 0.012 0.012 0.0003 0.0007
Example 4 17 6.1 0.13 0.15 0.009 0.022 0.0006 0.0005
Example 5 14 6.1 0.20 0.17 0.007 0.02 0.0003 0.0006
Example 6 15 4.6 0.16 0.12 0.014 0.01 0.0005 0.0004
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (2)

1. A heavy metal multiple composite treatment process for industrial wastewater is characterized in that: the method comprises the following steps:
A1. removing large solid matters from the industrial wastewater through a grid, then discharging the wastewater into a sedimentation tank I, and standing for 24-48 hours; wherein, the bottom filler of the sedimentation tank I is river sand with the thickness of 20-40 cm; the wastewater flowing out of the sedimentation tank I flows through a sedimentation tank II; wherein the bottom filler of the sedimentation tank II is red mud particles with the thickness of 20-40 cm;
B1. 1kg of composite treating agent: adding a composite treating agent into the wastewater discharged after precipitation treatment according to the proportion of 5 tons of wastewater, stirring at the speed of 200 plus materials and 300 revolutions per minute for 20-40min, and standing for 2-4 h;
C1. discharging the wastewater treated in the step b into a microbial reaction tank, firstly adjusting the pH of the wastewater to 7-8, then adding 6 g of the compound microbial inoculum into each cubic meter of the liquid every time, adding the compound microbial inoculum for 1 time every day, continuously adding the compound microbial inoculum for two days, standing for five days, filtering the liquid through a plate-and-frame filter, and finally discharging; the compound microbial inoculum is prepared by the following method: culturing Thiobacillus denitrificans, Pseudomonas stutzeri, Pseudomonas aeruginosa and Bacillus cereus to concentration of 1 × 108Bacterial solution per ml, according to the ratio of 1: 1: 2: 2, and then mixing with sawdust according to a volume ratio of 1: 3, mixing and stirring uniformly, and finally drying at low temperature to obtain the product;
the composite treating agent comprises the following raw materials in parts by weight:
10-20 parts of sodium persulfate, 5-10 parts of polyepoxysuccinic acid sodium, 1-5 parts of tetraethylenepentamine dithiocarbamate, 1-3 parts of expanded rice hull powder, 1-5 parts of cross-linked rectorite, 5-10 parts of shell powder, 1-3 parts of flocculant, 4-8 parts of calcium dioxide, 4-8 parts of modified traditional Chinese medicine residue, 1-3 parts of potassium permanganate, 1-5 parts of dithiocarbamate chitosan and 1-3 parts of methacryloyloxyethyl trimethyl ammonium chloride;
the modified traditional Chinese medicine residues are prepared in the following way:
a. preparing a liquid matrix: mixing 0.05 part of vitamin B1, 1-5 parts of Tween, 25-35 parts of monopotassium phosphate, 5-15 parts of magnesium sulfate heptahydrate, 0.1-1 part of calcium chloride dihydrate, 1-5 parts of ammonium tartrate and 200 parts of 100-fold trace element mixed solution in parts by weight;
b. adding liquid matrix into the dried and pulverized Chinese medicinal residue, sterilizing, inoculating 5.0% Phanerochaete chrysosporium suspension, sealing, culturing at 37 deg.C for 7-10 days, and drying the Chinese medicinal residue at 60-70 deg.C;
the crosslinked rectorite is treated by:
c. crushing the crosslinked rectorite to 60-80 meshes, calcining at the temperature of 350-400 ℃ for 1-2 hours, cooling, adding 15% citric acid aqueous solution with the same weight, performing ball milling for 2-4 hours, and collecting slurry;
d. dropwise adding a sodium hydroxide aqueous solution into the slurry, adjusting the pH value to 7-8, carrying out ultrasonic treatment for 40-50 minutes, standing for 3-5 hours, collecting precipitates, calcining at the temperature of 600-700 ℃ for 1-2 hours, and cooling;
the flocculant is a mixture of polyacrylamide, dehydrated polymeric ferric sulfate and polyglutamic acid, and the mass ratio of the polyacrylamide: and (3) dehydrating polymeric ferric sulfate: polyglutamic acid 2: 3: 1;
the modified traditional Chinese medicine residue is a mixture of radix isatidis and fructus gardeniae; the Phanerochaete chrysosporium suspension has Phanerochaete chrysosporium content of 1.0 × 106Per mL;
in the step b, the dried traditional Chinese medicine residues are crushed to 40-60 meshes.
2. The heavy metal multiple complex treatment process for industrial wastewater according to claim 1, characterized in that: the composite treating agent comprises the following raw materials in parts by weight:
15 parts of sodium persulfate, 7 parts of polyepoxysuccinic acid sodium, 3 parts of tetraethylenepentamine dithiocarbamate, 2 parts of expanded rice hull powder, 3 parts of crosslinked rectorite, 7 parts of shell powder, 2 parts of flocculant, 6 parts of calcium dioxide, 6 parts of modified traditional Chinese medicine residues, 2 parts of potassium permanganate, 3 parts of dithiocarbamate chitosan and 2 parts of methacryloyloxyethyl trimethyl ammonium chloride.
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