CN109384277A - The composite treating agent of comprehensive removal heavy metal out of electroplating wastewater - Google Patents

The composite treating agent of comprehensive removal heavy metal out of electroplating wastewater Download PDF

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Publication number
CN109384277A
CN109384277A CN201811320911.7A CN201811320911A CN109384277A CN 109384277 A CN109384277 A CN 109384277A CN 201811320911 A CN201811320911 A CN 201811320911A CN 109384277 A CN109384277 A CN 109384277A
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parts
heavy metal
chinese medicine
medicine slag
bagasse
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Inventor
关伟
徐凤
李铭珊
唐娜
胡小英
贾燕
杜建伟
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CHONGQING MUNICIPAL SOLID WASTE MANAGEMENT CENTER
South China Institute of Environmental Science of Ministry of Ecology and Environment
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CHONGQING MUNICIPAL SOLID WASTE MANAGEMENT CENTER
South China Institute of Environmental Science of Ministry of Ecology and Environment
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Priority to CN201811320911.7A priority Critical patent/CN109384277A/en
Publication of CN109384277A publication Critical patent/CN109384277A/en
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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
    • 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
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention discloses a kind of composite treating agents of comprehensive removal heavy metal out of electroplating wastewater, including sodium pyrosulfite, polyepoxy sodium succinate, tetren dithiocar-bamate, Expanded rice husk powder, cross-linked rectorite, shell powder, flocculant, calcium hydroxide, modified Chinese medicine slag, ferric trichloride, bagasse, aminodithioformic acid chitosan, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride；Heavy metal is effectively fixed by components such as aminodithioformic acid chitosans, chemistry, physical absorption and ion exchange adsorption directly occurs with heavy metal ion such as lead, cadmiums by the other components such as Expanded rice husk powder, cross-linked rectorite and shell powder, modified Chinese medicine slag, wherein modified Chinese medicine slag has larger and more absorption hole, large specific surface area, more adsorption sites are capable of providing, achieve the effect that multiple absorption.

Description

The composite treating agent of comprehensive removal heavy metal out of electroplating wastewater
Technical field
The present invention relates to wastewater treatment, in particular to a kind of composite treating agent of comprehensive removal heavy metal out of electroplating wastewater.
Background technique
Plating is metal and nonmetallic surface to be decorated, protected and obtained certain new capabilities using the method for electrochemistry A kind of technical process.In electroplating industry, common plating has nickel plating, copper facing, chromium plating, zinc-plated etc..In the plating process, in order to The quality for guaranteeing electroplated product makes the coat of metal have flat and smooth good appearance and be firmly combined with plating piece, it is necessary to plate It is preceding that dirt (oil, rust, oxide skin etc.) thorough cleaning on plating piece surface is clean, and the attachment liquid after plating plating piece surface is clear Wash clean.Therefore, a large amount of waste water are necessarily discharged in plating production process.And the source of electroplating wastewater is generally comprised than wide Several below: 1. plating piece cleans waste water；2. electroplating effluent；3. other waste water, including wash away mill floor, scrub floor and lead to Wind devices condensed water and as coating bath leakage or operational administrative it is improper caused by run, drip, leak various tank liquors and draining；④ Component cooling water, component cooling water is in use in addition to cooling, the typically no pollution by heavy metal.Wherein, it plates Part ejected wash water is the main source of electroplating wastewater, almost accounts for 80% or more of plant effluent discharge amount.Due to plating piece functional requirement Difference, plating, bath composition, mode of operation, process conditions etc. are also different, and therefore, the pollutant of electroplating wastewater is very complicated, mainly Contain the metal ions such as chromium, copper, nickel, lead, gold, silver, cadmium, wherein the heavy metal ion such as chromium, copper, nickel, zinc for containing and cyanide Etc. being more toxic, some belong to carcinogenic, teratogenesis, mutagenic extremely toxic substance, do great harm to human beings.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of combined processings of comprehensive removal heavy metal out of electroplating wastewater Agent can accelerate the sinking speed of heavy metal ion, can preferably adsorb the heavy metal in waste water, improve the contact machine of reaction Rate improves chelatropic reaction, redox validity, effectively to increase contact effect of the heavy metal chelating agent with heavy metal Various heavy in removal system enables the total removal rate of comprehensive wastewater heavy metal to reach 99% or more.
The composite treating agent of comprehensive removal heavy metal out of electroplating wastewater of the invention, the compound formulation raw material is by weight Including following components:
10-20 parts of sodium pyrosulfites, 5-10 parts of polyepoxy sodium succinates, 1-5 parts of tetren dithiocarbamates first Hydrochlorate, 1-3 parts of Expanded rice husk powder, 1-5 parts of cross-linked rectorite, 5-10 parts of shell powder, 1-3 parts of flocculant, calcium hydroxide 4-8 Part, modified Chinese medicine slag 4-8 parts, 1-3 parts of ferric trichloride, 1-5 parts of bagasse, 1-5 parts of aminodithioformic acid chitosan, methyl-prop 1-3 parts of alkene acyloxyethyl trimethyl ammonium chloride, the modified Chinese medicine slag are prepared by following manner:
The modified Chinese medicine slag is prepared by following manner:
A. prepare fluid matrix: by weight by 0.05 part of vitamin B1,1-5 parts of tween, 25-35 parts of potassium dihydrogen phosphate, 5-15 parts of epsom salt, 0.1-1 parts of calcium chloride dihydrate, 1-5 parts of ammonium tartrate and 100-200 parts of micro-mixed liquor are mixed It closes；
B. it is added in fluid matrix into the Chinese medicine slag after dries pulverizing, 5.0% yellow archespore Mao Pingge is accessed after sterilizing It is sealed after bacterium bacteria suspension, cultivates at 37 DEG C 7-10 days, then dry Chinese medicine slag at 60-70 DEG C；
The cross-linked rectorite is handled by following manner:
C. by cross-linked rectorite be crushed to after 60-80 mesh be 350-400 DEG C in temperature at calcination processing 1-2 hour, cool down Ball-milling treatment 2-4 hours after the aqueous citric acid solution that the concentration that equivalent weight is added afterwards is 15%, slurries are collected；
D. pH to 7-8 is adjusted after sodium hydrate aqueous solution is added dropwise into slurries, stands 3- after 40-50 minutes sonicated It 5 hours, collects cooling after sediment is calcined 1-2 hours at 600-700 DEG C of temperature；
The bagasse is through following process:
E. bagasse powder is broken to 80-100 mesh, the sodium hydroxide solution that concentration is 20% is then added, is stirred under room temperature 3-4 hours, with deionized water washes clean repeatedly after filtering, in temperature be at 60-70 DEG C it is 12-14 hours dry；
F. after bagasse processed in step e being mixed with concentration for 5% sodium hydroxide solution and epoxychloropropane It is heated to 50-60 DEG C of stirring 5-6 hours, will generate after product filters and deionized water stirring is added, it is 27% that concentration, which is then added, Ethylenediamine solution and concentration be 1.5% sodium bicarbonate solution, 80-100 DEG C of reaction 5-6 hours is then heated to, by gained Being washed in turn with acetone and deionized water to product pH value after product filtering is neutrality, is finally filtered gained bagasse in temperature It is 12-13 hours dry at 60-70 DEG C；
Further, the compound formulation raw material includes following components by weight:
15 parts of sodium pyrosulfites, 7 parts of polyepoxy sodium succinates, 3 parts of tetren dithiocar-bamates, extrudings 2 parts of powdered rice hulls, 3 parts of cross-linked rectorite, 7 parts of shell powder, 2 parts of flocculant, 6 parts of calcium hydroxide, modified 6 parts of Chinese medicine slag, trichlorine Change 2 parts of iron, 3 parts of bagasse, 3 parts of aminodithioformic acid chitosan, 2 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride；
Further, the flocculant is the mixture of polyacrylamide, dehydration polymerization ferric sulfate and polyglutamic acid, by quality Than polyacrylamide: dehydration polymerization ferric sulfate: polyglutamic acid=2:3:1；
Further, the modified Chinese medicine slag is the mixture of Radix Isatidis and cape jasmine；
Further, the Phanerochaete chrysosporium content of the Phanerochaete chrysosporium bacteria suspension is 1.0 × 106A/mL；
Further, in step b, the Chinese medicine slag after drying is crushed to 40-60 mesh.
Beneficial effects of the present invention: the composite treating agent of comprehensive removal heavy metal out of electroplating wastewater of the invention, Neng Goujia The sinking speed of fast heavy metal ion, can preferably adsorb the heavy metal in waste water, improve the contact probability of reaction, to increase Contact effect of the metal traps with heavy metal is aggravated, chelatropic reaction, redox validity is improved, effectively removes in system Various heavy enables the total removal rate of comprehensive wastewater heavy metal to reach 99% or more.It is poly- by aminodithioformic acid shell Heavy metal is effectively fixed in the components such as sugar, by Expanded rice husk powder, cross-linked rectorite and shell powder, modified Chinese medicine slag etc. other Directly with heavy metal ion such as lead, cadmiums chemistry, physical absorption and ion exchange adsorption occur for component, wherein modified Chinese medicine slag tool There is larger and more absorption hole, large specific surface area is capable of providing more adsorption sites, achieve the effect that multiple absorption, The sludge yield of sodium pyrosulfite is low, small toxicity, acts on heavy metal ion unrestraint, calcium hydroxide, ferric trichloride, hydroxide Calcium and sodium pyrosulfite act synergistically, and accelerate the precipitating of small molecule heavy metal particles, and processed bagasse is inhaled with multilayer Attached effect, to Cr3+、Cu2+And Pb2+Suction-operated with super strength.
Specific embodiment
Embodiment one
The composite treating agent of the comprehensive removal heavy metal out of electroplating wastewater of the present embodiment, the compound formulation raw material is by weight Part includes following components:
10 parts of sodium pyrosulfites, 5 parts of polyepoxy sodium succinates, 1 part of tetren dithiocar-bamate, extruding 1 part of powdered rice hulls, 1 part of cross-linked rectorite, 5 parts of shell powder, 1 part of flocculant, 4 parts of calcium hydroxide, modified 4 parts of Chinese medicine slag, trichlorine Change 1 part of iron, 1 part of bagasse, 1 part of aminodithioformic acid chitosan, 1 part of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, institute Modified Chinese medicine slag is stated to prepare by following manner:
A. fluid matrix is prepared: by weight by 0.05 part of vitamin B1,3 parts of tween, 30 parts of potassium dihydrogen phosphate, seven water sulphur 5 parts of sour magnesium, 1 part of calcium chloride dihydrate, 4 parts of ammonium tartrate and 180 parts of micro-mixed liquor mixing；
B. it is added in fluid matrix to dries pulverizing into the cape jasmine of 55 mesh and the Radix Isatidis dregs of a decoction, 5.0% is accessed after sterilizingPhanerochaete chrysosporium bacteria suspension (content be 1.0 × 106A/mL) seal afterwards, cultivate 7 days at 37 DEG C, then will in The dregs of a decoction are dried at 64 DEG C；
The cross-linked rectorite is handled by following manner:
C. by cross-linked rectorite be crushed to after 60 mesh be 350 DEG C in temperature at calcination processing 1 hour, be added after cooling same Ball-milling treatment 2 hours after the aqueous citric acid solution that the concentration of weight is 15%, slurries are collected；
D. pH to 7 is adjusted after sodium hydrate aqueous solution is added dropwise into slurries, it is sonicated to stand 3 hours after forty minutes, It collects cooling after sediment is calcined 1 hour at 600 DEG C of temperature；
The bagasse is through following process:
E. bagasse powder is broken to 80 mesh, the sodium hydroxide solution that concentration is 20% (w/w) is then added, is stirred under room temperature 3 hours, with deionized water washes clean repeatedly after filtering, in temperature be at 60 DEG C it is 12 hours dry；
F. bagasse processed in step e and concentration is mixed for the sodium hydroxide solution and epoxychloropropane of 5% (w/w) It is heated to 50 DEG C after conjunction to stir 5 hours, will generate after product filters and deionized water stirring is added, it is 27% that concentration, which is then added, (w/w) sodium bicarbonate solution that ethylenediamine solution and concentration is 1.5% (w/w), is then heated to 80 DEG C and reacts 5 hours, will Being washed in turn with acetone and deionized water to product pH value after products therefrom filtering is neutrality, finally filters and gained bagasse exists Temperature is 12 hours dry at 60 DEG C.
Embodiment two
The composite treating agent of the comprehensive removal heavy metal out of electroplating wastewater of the present embodiment, the compound formulation raw material is by weight Part includes following components:
It is 20 parts of sodium pyrosulfites, 10 parts of polyepoxy sodium succinates, 5 parts of tetren dithiocar-bamates, swollen Change 3 parts of powdered rice hulls, 5 parts of cross-linked rectorite, 10 parts of shell powder, 3 parts of flocculant, 8 parts of calcium hydroxide, modified 8 parts of Chinese medicine slag, three 3 parts of iron chloride, 5 parts of bagasse, 5 parts of aminodithioformic acid chitosan, 3 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, The modified Chinese medicine slag is prepared by following manner:
A. fluid matrix is prepared: by weight by 0.08 part of vitamin B1,1 part of tween, 35 parts of potassium dihydrogen phosphate, seven water sulphur 5 parts of sour magnesium, 1 part of calcium chloride dihydrate, 1 part of ammonium tartrate and 200 parts of micro-mixed liquor mixing；
B. it is added in fluid matrix to dries pulverizing into the cape jasmine of 40 mesh and the Radix Isatidis dregs of a decoction, 5.0% is accessed after sterilizingPhanerochaete chrysosporium bacteria suspension (content be 1.0 × 106A/mL) it seals afterwards, it cultivates at 37 DEG C 10 days, then will Chinese medicine slag is dried at 60 DEG C.
The cross-linked rectorite is handled by following manner:
C. by cross-linked rectorite be crushed to after 80 mesh be 400 DEG C in temperature at calcination processing 2 hours, be added after cooling same Ball-milling treatment 4 hours after the aqueous citric acid solution that the concentration of weight is 15%, slurries are collected；
D. pH to 8 is adjusted after sodium hydrate aqueous solution is added dropwise into slurries, stands 5 hours after sonicated 50 minutes, It collects cooling after sediment is calcined 2 hours at 700 DEG C of temperature；
The bagasse is through following process:
E. bagasse powder is broken to 100 mesh, the sodium hydroxide solution that concentration is 20% (w/w) is then added, is stirred under room temperature Mix 4 hours, with deionized water washes clean repeatedly after filtering, in temperature be at 70 DEG C it is 14 hours dry；
F. bagasse processed in step e and concentration is mixed for the sodium hydroxide solution and epoxychloropropane of 5% (w/w) It is heated to 60 DEG C after conjunction to stir 6 hours, will generate after product filters and deionized water stirring is added, it is 27% that concentration, which is then added, (w/w) sodium bicarbonate solution that ethylenediamine solution and concentration is 1.5% (w/w), is then heated to 100 DEG C and reacts 6 hours, will Being washed in turn with acetone and deionized water to product pH value after products therefrom filtering is neutrality, finally filters and gained bagasse exists Temperature is 13 hours dry at 70 DEG C.
Embodiment three
The composite treating agent of the comprehensive removal heavy metal out of electroplating wastewater of the present embodiment, the compound formulation raw material is by weight Part includes following components:
It is 10 parts of sodium pyrosulfites, 10 parts of polyepoxy sodium succinates, 1 part of tetren dithiocar-bamate, swollen Change 3 parts of powdered rice hulls, 1 part of cross-linked rectorite, 10 parts of shell powder, 1 part of flocculant, 8 parts of calcium hydroxide, modified 4 parts of Chinese medicine slag, three 3 parts of iron chloride, 1 part of bagasse, 5 parts of aminodithioformic acid chitosan, 1 part of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, The modified Chinese medicine slag is prepared by following manner:
A. fluid matrix is prepared: by weight by 0.05 part of vitamin B1,1 part of tween, 35 parts of potassium dihydrogen phosphate, seven water sulphur 5 parts of sour magnesium, 1 part of calcium chloride dihydrate, 1 part of ammonium tartrate and 200 parts of micro-mixed liquor mixing；
B. it is added in fluid matrix to dries pulverizing into the cape jasmine of 40 mesh and the Radix Isatidis dregs of a decoction, 5.0% is accessed after sterilizingPhanerochaete chrysosporium bacteria suspension (content be 1.0 × 106A/mL) it seals afterwards, it cultivates at 37 DEG C 10 days, then will Chinese medicine slag is dried at 60 DEG C.
The cross-linked rectorite is handled by following manner:
C. by cross-linked rectorite be crushed to after 60 mesh be 400 DEG C in temperature at calcination processing 1 hour, be added after cooling same Ball-milling treatment 4 hours after the aqueous citric acid solution that the concentration of weight is 15%, slurries are collected；
D. pH to 7 is adjusted after sodium hydrate aqueous solution is added dropwise into slurries, stands 3 hours after sonicated 50 minutes, It collects cooling after sediment is calcined 1 hour at 700 DEG C of temperature；
The bagasse is through following process:
E. bagasse powder is broken to 80 mesh, the sodium hydroxide solution that concentration is 20% (w/w) is then added, is stirred under room temperature 3 hours, with deionized water washes clean repeatedly after filtering, in temperature be at 70 DEG C it is 14 hours dry；
F. bagasse processed in step e and concentration is mixed for the sodium hydroxide solution and epoxychloropropane of 5% (w/w) It is heated to 50 DEG C after conjunction to stir 6 hours, will generate after product filters and deionized water stirring is added, it is 27% that concentration, which is then added, (w/w) sodium bicarbonate solution that ethylenediamine solution and concentration is 1.5% (w/w), is then heated to 80 DEG C and reacts 6 hours, will Being washed in turn with acetone and deionized water to product pH value after products therefrom filtering is neutrality, finally filters and gained bagasse exists Temperature is 13 hours dry at 60 DEG C.
Example IV
The composite treating agent of the comprehensive removal heavy metal out of electroplating wastewater of the present embodiment, the compound formulation raw material is by weight Part includes following components:
20 parts of sodium pyrosulfites, 5 parts of polyepoxy sodium succinates, 5 parts of tetren dithiocar-bamates, extrudings 1 part of powdered rice hulls, 5 parts of cross-linked rectorite, 5 parts of shell powder, 3 parts of flocculant, 4 parts of calcium hydroxide, modified 8 parts of Chinese medicine slag, trichlorine Change 1 part of iron, 5 parts of bagasse, 1 part of aminodithioformic acid chitosan, 3 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, institute Modified Chinese medicine slag is stated to prepare by following manner:
A. fluid matrix is prepared: by weight by 0.08 part of vitamin B1,5 parts of tween, 35 parts of potassium dihydrogen phosphate, seven water sulphur 15 parts of sour magnesium, 1 part of calcium chloride dihydrate, 5 parts of ammonium tartrate and 200 parts of micro-mixed liquor mixing；
B. it is added in fluid matrix to dries pulverizing into the cape jasmine of 60 mesh and the Radix Isatidis dregs of a decoction, 5.0% is accessed after sterilizingPhanerochaete chrysosporium bacteria suspension (content be 1.0 × 106A/mL) it seals afterwards, it cultivates at 37 DEG C 10 days, then will Chinese medicine slag is dried at 70 DEG C.
The cross-linked rectorite is handled by following manner:
C. by cross-linked rectorite be crushed to after 80 mesh be 350 DEG C in temperature at calcination processing 2 hours, be added after cooling same Ball-milling treatment 2 hours after the aqueous citric acid solution that the concentration of weight is 15%, slurries are collected；
D. pH to 8 is adjusted after sodium hydrate aqueous solution is added dropwise into slurries, it is sonicated to stand 5 hours after forty minutes, It collects cooling after sediment is calcined 2 hours at 600 DEG C of temperature；
The bagasse is through following process:
E. bagasse powder is broken to 100 mesh, the sodium hydroxide solution that concentration is 20% (w/w) is then added, is stirred under room temperature Mix 4 hours, with deionized water washes clean repeatedly after filtering, in temperature be at 60 DEG C it is 12-14 hours dry；
F. bagasse processed in step e and concentration is mixed for the sodium hydroxide solution and epoxychloropropane of 5% (w/w) It is heated to 60 DEG C after conjunction to stir 5 hours, will generate after product filters and deionized water stirring is added, it is 27% that concentration, which is then added, (w/w) sodium bicarbonate solution that ethylenediamine solution and concentration is 1.5% (w/w), is then heated to 100 DEG C and reacts 5 hours, will Being washed in turn with acetone and deionized water to product pH value after products therefrom filtering is neutrality, finally filters and gained bagasse exists Temperature is 12 hours dry at 70 DEG C.
Embodiment five
The composite treating agent of the comprehensive removal heavy metal out of electroplating wastewater of the present embodiment, the compound formulation raw material is by weight Part includes following components:
15 parts of sodium pyrosulfites, 5 parts of polyepoxy sodium succinates, 5 parts of tetren dithiocar-bamates, extrudings 2 parts of powdered rice hulls, 1 part of cross-linked rectorite, 10 parts of shell powder, 2 parts of flocculant, 6 parts of calcium hydroxide, modified 4 parts of Chinese medicine slag, trichlorine Change 3 parts of iron, 4 parts of bagasse, 2 parts of aminodithioformic acid chitosan, 1 part of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, institute Modified Chinese medicine slag is stated to prepare by following manner:
A. fluid matrix is prepared: by weight by 0.05 part of vitamin B1,1 part of tween, 25 parts of potassium dihydrogen phosphate, seven water sulphur 5 parts of sour magnesium, 0.1 part of calcium chloride dihydrate, 1 part of ammonium tartrate and 100 parts of micro-mixed liquor mixing；
B. it is added in fluid matrix to dries pulverizing into the cape jasmine of 40 mesh and the Radix Isatidis dregs of a decoction, 5.0% is accessed after sterilizingPhanerochaete chrysosporium bacteria suspension (content be 1.0 × 106A/mL) seal afterwards, cultivate 7 days at 37 DEG C, then will in The dregs of a decoction are dried at 60 DEG C.
The cross-linked rectorite is handled by following manner:
C. by cross-linked rectorite be crushed to after 70 mesh be 380 DEG C in temperature at calcination processing 1.5 hours, be added after cooling same Etc. weight concentration be 15% aqueous citric acid solution after ball-milling treatment 2.5 hours, collect slurries；
D. pH to 7 is adjusted after sodium hydrate aqueous solution is added dropwise into slurries, stands 4 hours after sonicated 45 minutes, It collects cooling after sediment is calcined 1.5 hours at 620 DEG C of temperature；
The bagasse is through following process:
E. bagasse powder is broken to 90 mesh, the sodium hydroxide solution that concentration is 20% is then added, stirring 3.5 is small under room temperature When, with deionized water washes clean repeatedly after filtering, in temperature be at 65 DEG C it is 13 hours dry；
F. after bagasse processed in step e being mixed with concentration for 5% sodium hydroxide solution and epoxychloropropane It is heated to 55 DEG C to stir 5.5 hours, will generate after product filters and deionized water stirring is added, the second that concentration is 27% is then added The sodium bicarbonate solution that diamine solution and concentration are 1.5% is then heated to 90 DEG C and reacts 5.5 hours, products therefrom is filtered It is neutral for being washed in turn with acetone and deionized water to product pH value afterwards, is finally filtered gained bagasse in the case where temperature is 65 DEG C It is 12.5 hours dry.
Embodiment six
The composite treating agent of the comprehensive removal heavy metal out of electroplating wastewater of the present embodiment, the compound formulation raw material is by weight Part includes following components:
15 parts of sodium pyrosulfites, 7 parts of polyepoxy sodium succinates, 3 parts of tetren dithiocar-bamates, extrudings 2 parts of powdered rice hulls, 3 parts of cross-linked rectorite, 7 parts of shell powder, 2 parts of flocculant, 6 parts of calcium hydroxide, modified 6 parts of Chinese medicine slag, trichlorine Change 2 parts of iron, 3 parts of bagasse, 3 parts of aminodithioformic acid chitosan, 2 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride；Institute Modified Chinese medicine slag is stated to prepare by following manner:
A. fluid matrix is prepared: by weight by 0.06 part of vitamin B1, tween 3,30 parts of potassium dihydrogen phosphate, seven water sulfuric acid 10 parts of magnesium, 0.61 part of calcium chloride dihydrate, 3 parts of ammonium tartrate and 150 parts of micro-mixed liquor mixing；
B. it is added in fluid matrix to dries pulverizing into the cape jasmine of 50 mesh and the Radix Isatidis dregs of a decoction, 5.0% is accessed after sterilizingPhanerochaete chrysosporium bacteria suspension (content be 1.0 × 106A/mL) seal afterwards, cultivate 8 days at 37 DEG C, then will in The dregs of a decoction are dried at 65 DEG C；
The cross-linked rectorite is handled by following manner:
C. by cross-linked rectorite be crushed to after 75 mesh be 360 DEG C in temperature at calcination processing 1.8 hours, be added after cooling same Etc. weight concentration be 15% aqueous citric acid solution after ball-milling treatment 2.5 hours, collect slurries；
D. pH to 8 is adjusted after sodium hydrate aqueous solution is added dropwise into slurries, it is small that 3.8 are stood after sonicated 48 minutes When, it collects cooling after sediment is calcined 1.8 hours at 680 DEG C of temperature；
The bagasse is through following process:
E. bagasse powder is broken to 90 mesh, the sodium hydroxide solution that concentration is 20% is then added, stirring 3 is small under room temperature When, with deionized water washes clean repeatedly after filtering, in temperature be at 68 DEG C it is 12 hours dry；
F. after bagasse processed in step e being mixed with concentration for 5% sodium hydroxide solution and epoxychloropropane It is heated to 58 DEG C to stir 5.5 hours, will generate after product filters and deionized water stirring is added, the second that concentration is 27% is then added The sodium bicarbonate solution that diamine solution and concentration are 1.5% is then heated to 95 DEG C and reacts 5.5 hours, products therefrom is filtered It is neutral for being washed in turn with acetone and deionized water to product pH value afterwards, is finally filtered gained bagasse in the case where temperature is 68 DEG C It is 12 hours dry.
In above-described embodiment, the flocculant is the mixture of polyacrylamide, dehydration polymerization ferric sulfate and polyglutamic acid, Polyacrylamide in mass ratio: dehydration polymerization ferric sulfate: polyglutamic acid=2:3:1；The molecular weight of polyacrylamide is 4,000,000, The modified Chinese medicine slag is the mixture of Radix Isatidis and cape jasmine；The Phanerochaete chrysosporium of the Phanerochaete chrysosporium bacteria suspension Content is 1.0 × 106A/mL.
Electroplating wastewater processing is carried out using the composite treating agent of the comprehensive removal heavy metal out of electroplating wastewater of this method compounding, Treatment effect is as follows, unit mg/L:
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this In the scope of the claims of invention.

Claims (6)

1. a kind of composite treating agent of comprehensive removal heavy metal out of electroplating wastewater, it is characterised in that: the compound formulation raw material is pressed Parts by weight include following components:
10-20 parts of sodium pyrosulfites, 5-10 parts of polyepoxy sodium succinates, 1-5 parts of tetren dithiocar-bamates, 1-3 parts of Expanded rice husk powder, 5-10 parts of shell powder, 1-3 parts of flocculant, 4-8 parts of calcium hydroxide, is modified 1-5 parts of cross-linked rectorite 4-8 parts of Chinese medicine slag, 1-3 parts of ferric trichloride, 1-5 parts of bagasse, 1-5 parts of aminodithioformic acid chitosan, methacryloxypropyl 1-3 parts of ethyl-trimethyl salmiac；
The modified Chinese medicine slag is prepared by following manner:
A. fluid matrix is prepared: by weight by 0.05 part of vitamin B1,1-5 parts of tween, 25-35 parts of potassium dihydrogen phosphate, seven water 5-15 parts of magnesium sulfate, 0.1-1 parts of calcium chloride dihydrate, 1-5 parts of ammonium tartrate and 100-200 parts of micro-mixed liquor mixing；
B. it is added in fluid matrix into the Chinese medicine slag after dries pulverizing, 5.0% Phanerochaete chrysosporium bacterium is accessed after sterilizing It is sealed after suspension, cultivates at 37 DEG C 7-10 days, then dry Chinese medicine slag at 60-70 DEG C；
The cross-linked rectorite is handled by following manner:
C. by cross-linked rectorite be crushed to after 60-80 mesh be 350-400 DEG C in temperature at calcination processing 1-2 hour, add after cooling Ball-milling treatment 2-4 hours after the aqueous citric acid solution that the concentration for entering equivalent weight is 15%, slurries are collected；
D. pH to 7-8 is adjusted after sodium hydrate aqueous solution is added dropwise into slurries, it is small to stand 3-5 after 40-50 minutes sonicated When, it collects cooling after sediment is calcined 1-2 hours at 600-700 DEG C of temperature
The bagasse is through following process:
E. bagasse powder is broken to 80-100 mesh, the sodium hydroxide solution that concentration is 20% is then added, stirring 3-4 is small under room temperature When, with deionized water washes clean repeatedly after filtering, in temperature be at 60-70 DEG C it is 12-14 hours dry；
F. it is heated after bagasse processed in step e being mixed with concentration for 5% sodium hydroxide solution and epoxychloropropane To 50-60 DEG C stirring 5-6 hours, will generate product filter after be added deionized water stirring, then be added concentration be 27% second The sodium bicarbonate solution that diamine solution and concentration are 1.5%, is then heated to 80-100 DEG C of reaction 5-6 hours, by products therefrom It is neutral for being washed in turn to product pH value after filtering with acetone and deionized water, finally filters and is in temperature by gained bagasse It is 12-13 hours dry at 60-70 DEG C.
2. the composite treating agent of comprehensive removal heavy metal out of electroplating wastewater according to claim 1, it is characterised in that: described Compound formulation raw material includes following components by weight:
15 parts of sodium pyrosulfites, 7 parts of polyepoxy sodium succinates, 3 parts of tetren dithiocar-bamates, extruding rice husk 2 parts of powder, 3 parts of cross-linked rectorite, 7 parts of shell powder, 2 parts of flocculant, 6 parts of calcium hydroxide, modified 6 parts of Chinese medicine slag, ferric trichloride 2 Part, 3 parts of bagasse, 3 parts of aminodithioformic acid chitosan, 2 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
3. the composite treating agent of comprehensive removal heavy metal out of electroplating wastewater according to claim 1, it is characterised in that: described Flocculant is the mixture of polyacrylamide, dehydration polymerization ferric sulfate and polyglutamic acid, in mass ratio polyacrylamide: dehydration is poly- Close ferric sulfate: polyglutamic acid=2:3:1.
4. the composite treating agent of comprehensive removal heavy metal out of electroplating wastewater according to claim 3, it is characterised in that: described Modified Chinese medicine slag is the mixture of Radix Isatidis and cape jasmine.
5. the composite treating agent of comprehensive removal heavy metal out of electroplating wastewater according to claim 4, it is characterised in that: described The Phanerochaete chrysosporium content of Phanerochaete chrysosporium bacteria suspension is 1.0 × 106A/mL.
6. the composite treating agent of comprehensive removal heavy metal out of electroplating wastewater according to claim 5, it is characterised in that: step In b, the Chinese medicine slag after drying is crushed to 40-60 mesh.
CN201811320911.7A 2018-11-07 2018-11-07 The composite treating agent of comprehensive removal heavy metal out of electroplating wastewater Pending CN109384277A (en)

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