CN110316855A - The processing method and system of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water are removed simultaneously - Google Patents

The processing method and system of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water are removed simultaneously Download PDF

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Publication number
CN110316855A
CN110316855A CN201810271101.0A CN201810271101A CN110316855A CN 110316855 A CN110316855 A CN 110316855A CN 201810271101 A CN201810271101 A CN 201810271101A CN 110316855 A CN110316855 A CN 110316855A
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chromium
total
waste water
zinc
cold rolling
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叶倩
郭道清
李恩超
葛高峰
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C02F1/705—Reduction by metals
    • 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
    • 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
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C02F2201/007—Modular design
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention belongs to water-treatment technology fields, more particularly to the processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously, include the following steps: that the cold rolling chromium zinc waste water enters pipe-line mixer, reducing agent is squeezed into pipe-line mixer, reduction adsorption agent and cold rolling chromium zinc waste water sequentially enter agitating reaction pond, inclined-plate clarifying basin after being sufficiently mixed in pipe-line mixer, inclined-plate clarifying basin is divided into two parts, front, which is divided into, is stirred area, rear portion is sloping plate deposition district, and polyacrylamide and polysaccharide flocculation aid is added being stirred area；Sloping plate deposition district is entered back into, adsorption tower is finally entered, cold rolling chromium zinc waste water passes through draining pump qualified discharge after adsorption tower.After cold rolling chromium zinc treatment process of the invention, cold rolling chromium zinc wastewater pH is 7~9, Cr6+Lower than 0.02mg/L, total chromium is lower than 0.03mg/L, and total zinc is lower than 0.5mg/L.

Description

Simultaneously remove Cr VI in cold rolling chromium zinc waste water, total chromium and total zinc processing method and System
Technical field
The invention belongs to water-treatment technology fields, and in particular to Cr VI, total chromium and total zinc in a kind of cold rolling chromium zinc waste water Technology method and system.
Background technique
Cold rolling needs to be rinsed belt steel surface with pure water after containing chromium passivating and electroplating work procedure, useless after rinsing strip Water is emitted into waste water station, main component is Cr since there are also hexavalent chromium, trivalent chromic ion and zinc ions mostly6+, total chromium and Total zinc.
Water Cr is discharged in " steel and iron industry pollutant emission standard " (GB13456-2012) regulation newly promulgated, cold rolling6+It is lower than 0.05mg/L, total chromium are lower than 0.5mg/L, and total zinc is lower than 1.0mg/L.
The treatment process that chromium zinc waste water mainly uses at present is mainly sodium hydrogensulfite two-stage reductive and sedimentation, but Effluent quality is difficult to meet the requirement of new national standard.In addition chromium zinc waste water is handled using nanofiltration and hyperfiltration, it is at high cost, in concentrated water The chromium zinc of enrichment is more difficult.
The electronation precipitation method are that domestic and international application is also a kind of widest chromium containing waste water treatment method earliest.The processing Technology is generally first adjusted the pH value of waste water under the acid condition of 2-3 with sulfuric acid, chemical reducing agent is used later, by solution In hexavalent chrome reduction at trivalent chromium, then adjust pH value to 7-9 with sodium hydroxide or milk of lime, make the trivalent of its generation indissoluble Chromium precipitating is separated from water body, is achieved the purpose that except chromium.It discloses and contains application No. is the patent of invention of CN104030478A Chromium wastewater treatment method.The following steps are included: (1), by chromate waste water acid adding, pH is adjusted between 2-3；(2) oxytropism is useless containing chromium Reducing agent is added in water, hexavalent chromium is reduced into trivalent chromic ion；(3) by b step treated solution adds alkali, pH is adjusted To between 8-9, trivalent chromic ion is converted to chromium hydroxide precipitation.
However up to the present, there are no the processing sides for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously Method and technique, water quality indicator meets " steel and iron industry pollutant emission standard " (GB13456-2012) after processing.Mesh of the invention Be exactly that economic, efficient pollutant process technique is developed, to recycle benefit according to the water quality and quantity situation of cold rolling chromium zinc waste water It is main task with energy-saving and emission-reduction, reduces environmental pollution, responds actively increasingly strict legislations of environmental protection.
Summary of the invention
Present invention firstly provides it is complete removal cold rolling chromium zinc waste water in Cr VI, total chromium and total zinc technical method and System.The invention belongs to the environmentally protective production-process systems of steel.
To achieve the purpose of the present invention, The technical solution adopted by the invention is as follows:
The processing method of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water is removed simultaneously, which is characterized in that including as follows Step:
(1) the cold rolling chromium zinc waste water enters pipe-line mixer, and reducing agent is squeezed by the dosing pump in Automatic Dosing case In pipe-line mixer, reduction adsorption agent and cold rolling chromium zinc waste water are sufficiently mixed in pipe-line mixer；Cold rolling chromium zinc waste water and medicine Residence time of the agent in pipe-line mixer is 2~4 minutes；
The reducing agent is sodium bentonite load iron base reductant solution；The reducing agent by following methods prepare and At:
1) sodium bentonite screening and activation: selection sodium bentonite, partial size are 1.7~4.2mm；Main component quality point Number percentage: smectite 34~46%, silica are 27~59%, and aluminum oxide is 3~15%, di-iron trioxide 0 ~2%, magnesia is 0~2%, and calcium oxide is 0~1.5%, and titanium dioxide is 0~0.9%；
2) cleaning of sodium bentonite: by Na-bentonite soil particle be immersed in mass percent concentration 1~2.5% it is dilute It 10~15 hours in phosphoric acid, takes out, with pure water to neutrality, is dried in 105 degree of air dry ovens, it is cooling stand-by；
3) by volume by the iron liquor of the solution of ferrous chloride of 3.8~7.9mol/L and 0.5~1.7mol/L 1:3~5 is mixed, and forms combination solution；
4) combination solution pH value is adjusted to 2.2~3.6 with 2~5% dilute hydrochloric acid, by combination solution mechanical stirring 15~ 26 minutes, mechanical stirring revolving speed was 60~90 revs/min；
5) sodium bentonite is put into combination solution by solid-to-liquid ratio 1:6~8 and forms mixed solution, then mixed solution is put Enter in barrel plating drum, mixed solution is heated to 87~98 degree first, for rotating plating cylinder using zinc metal sheet as cathode, graphite is anode, yin Spacing is 10~12cm between anode, and current density is 22~36A；The entire barrel plating process time is 35~48 minutes, barrel plating rolling In cylinder, sodium bentonite load iron base reductant is formed；The sodium bentonite that solid content is finally configured to 24~29% loads Iron-based reducing agent solution；
(2) the cold rolling chromium zinc waste water and medicament enter agitating reaction pond, chromium zinc waste water after pipe-line mixer mixes Residence time be 10~25 minutes；
(3) then the chromium zinc waste water enters inclined-plate clarifying basin, and inclined-plate clarifying basin is divided into two parts, and it is mixed that front is divided into stirring Area is closed, rear portion is sloping plate deposition district, and 1~4mg/L of polyacrylamide is added being stirred Qu Tongshuan flocculation aid medicine system, more 0.5~2mg/L of carbohydrate flocculation aid；Sloping plate deposition district is entered back into, the sloping plate deposition district residence time is 30~45 minutes；
(4) after inclined-plate clarifying basin, cold rolling chromium zinc waste water enters adsorption tower, and a modified medical stone huge sum of money is housed in adsorption tower Belong to absorbent filter medium；Modified medical stone heavy metal adsorption filtrate is the 85~95% of adsorption tower total volume；Cold rolling chromium zinc waste water is being inhaled Residence time in attached tower is 31~42 minutes；Cold rolling chromium zinc waste water passes through draining pump qualified discharge after adsorption tower.
The processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to the present invention, step (1) in sodium bentonite load iron base reductant, the iron content in sodium bentonite is between 7.2~9.9%, water swelling Degree reaches 22~27 times, and green compression strength is 0.3 × 105~0.4 × 105Pa, hot wet compressive strength are 1.8 × 106~2.3 × 106Pa, specific surface area are 9.3~12.6m2/g。
The processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to the present invention, step (1) Automatic Dosing case is made of grug feeding jar, dosing pump and robot control system(RCS) in, can determine added amount of chemical according to water；Reduction The dosage of agent is 560~1220mg/L.
The processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to the present invention, step (1) material of pipe-line mixer is polyvinyl chloride in, and internal element is made of double or three ducts, and the dislocation in adjacent cells duct is 90~120 degree, flight is placed in duct, dispersion degree is 0.5~4 μm, and mixing nonuniformity coefficient is 0.1~2%.
The processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to the present invention, in step Suddenly there are 3~5 mechanical agitators in (2) in agitating reaction pond, revolving speed is 35~55 revs/min.
The processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to the present invention, in step Suddenly there are two storage tanks for double flocculation aid medicine systems in (3), place polyacrylamide and polysaccharide flocculation aid respectively；Double flocculation aids Flocculation aid is accurately added according to water by robot control system(RCS) and dosing pump in medicine system；Stirring area agitator speed be 90~ 120 revs/min, the residence time of chromium zinc waste water is 1~3 minute.
The processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to the present invention, in step Suddenly modified medical stone heavy metal adsorption filtrate is prepared by following methods in (4):
1) screening of medical stone filtrate: the medical stone filtrate of 100~150 mesh of selection, density are 1.23~2.98g/cm3；
2) acid activation and cleaning of carrier: medical stone carrier stirs 1 hour in 55 degree of 13~16% dust technology, takes 5~8 times wash with distilled water after out, dried in 105 degree of air dry ovens, it is spare after cooling；
3) preparation of maceration extract: preparation solution concentration is 7~9mol/L ferrous sulfate solution, and 1 is added in ferrous sulfate The hexa of~3mg/L stirs 30min as precipitating reagent, with 70 turns of speed mechanical per minute, is formed and is mixed with dipping Solution；
4) dipping of medical stone: medical stone is placed in dipping solution in the ratio of solid-to-liquid ratio 1:5~8, dipping 10~12 Hour；Medical stone carrier is taken out, at room temperature naturally dry；
5) impregnated medical stone carrier high temperature sintering: is placed in the air dry oven of 120~150 degree of conditions dry 2 Hour, 550~580 degree are warming up to 10~12 degree/min, constant temperature calcining 3~5 hours, modified wheat was prepared in natural cooling Meal stone heavy metal adsorption filtrate, specific surface area are 1.2~1.9m2/ g, total pore volume are 0.007~0.04m3/g。
The processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to the present invention,
The chromium zinc waste water of the high concentration is water quality characteristic before handling: pH is 6~9, Cr6+For 5.4~42.9mg/L, total chromium For 19.3~79.5mg/L, total zinc is 8.9~106.7mg/L；
After cold rolling chromium zinc treatment process of the invention, cold rolling chromium zinc wastewater pH is 7~9, Cr6+Lower than 0.02mg/L, Total chromium is lower than 0.03mg/L, and total zinc is lower than 0.5mg/L.
The present invention also provides a kind of processing system for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously, on It states while the processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water can be applied to the system, the system packet Include sequentially connected intake pump 1, pipe-line mixer 2, agitating reaction pond 5, level-one elevator pump 6, inclined-plate clarifying basin 8, two-stage hoisting Pump 9, adsorption tower 10 and draining pump 12；Medicament dosing tank 3 is set in the pipe-line mixer 2, medicament dosing tank 3 is built-in with swelling Flocculation aid medicine system 7 is arranged, in the adsorption tower 10 in native load iron base reductant solution above the inclined-plate clarifying basin 8 Built-in modified medical stone heavy metal adsorption filtrate.
Detailed description of the invention:
Processing system that is a kind of while removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water, including intake pump, pipeline Mixer, medicament dosing tank, the iron-based reducing agent solution of alta-mud load, agitating reaction pond, level-one elevator pump, flocculation aid dosing system System, inclined-plate clarifying basin, two-stage hoisting pump, adsorption tower, modified medical stone heavy metal adsorption filtrate, draining pump.
The chromium zinc waste water of the high concentration is water quality characteristic: pH is 6~9, Cr6+For 5.4~42.9mg/L, total chromium is 19.3 ~79.5mg/L, total zinc are 8.9~106.7mg/L.
The chromium zinc waste water enters pipe-line mixer by intake pump, and reducing agent is beaten by the dosing pump in Automatic Dosing case Enter in pipe-line mixer, reduction adsorption agent and chromium zinc waste water are sufficiently mixed in pipe-line mixer.Automatic Dosing case by grug feeding jar, Dosing pump and robot control system(RCS) composition, can determine added amount of chemical according to water.The dosage of reducing agent is 560~1220mg/ L.The material of pipe-line mixer is polyvinyl chloride, and internal element is made of double or three ducts, and the dislocation in adjacent cells duct is 90 ~120 degree, flight is placed in duct, dispersion degree is 0.5~4 μm, and mixing nonuniformity coefficient is 0.1~2%.Chromium zinc waste water and Residence time of the medicament in pipe-line mixer is 2~4 minutes.
The reducing agent is prepared according to the water quality characteristics of cold rolling chromium zinc waste water.1) sodium bentonite screening and activation: Sodium bentonite is selected, partial size is 1.7~4.2mm.Main component (mass fraction %): smectite 34~46%, silica Be 27~59%, aluminum oxide be 3~15%, di-iron trioxide be 0~2%, magnesia be 0~2%, calcium oxide be 0~ 1.5%, titanium dioxide is 0~0.9%.2) cleaning of sodium bentonite: by Na-bentonite soil particle be immersed in concentration 1~ 10~15 hours in the phosphoric acid,diluted of 2.5% (mass percent) (diluted acid activation), then take out, with pure water to neutrality, 105 degree of air dry oven drying, it is then cooling stand-by.Sodium bentonite specific surface area increases 10~28% than original after activation. 2) by the iron liquor of the solution of ferrous chloride of 3.8~7.9mol/L and 0.5~1.7mol/L, 1:3~5 are mixed by volume It closes, forms combination solution.3) combination solution pH value is adjusted to 2.2~3.6 with 2~5% dilute hydrochloric acid, by combination solution machinery Stirring 15~26 minutes, mechanical stirring revolving speed are 60~90 revs/min.4) sodium bentonite is put by solid-to-liquid ratio 1:6~8 multiple With mixed solution is formed in solution, then mixed solution is put into barrel plating drum, mixed solution is heated to 87~98 first Degree, for rotating plating cylinder using zinc metal sheet as cathode, graphite is anode, between anode and cathode spacing be 10~12cm, current density be 22~ 36A.The entire barrel plating process time is 35~48 minutes.In rotating plating cylinder, sodium bentonite load iron base reductant is formed.Then It is configured to sodium bentonite load iron base reductant solution of the solid content 24~29%.Analysis is found after testing, and sodium base is swollen Moisten in native load iron base reductant, the iron content in sodium bentonite between 7.2~9.9%, water swelling degree reaches 22~ 27 times, green compression strength is 0.3 × 105~0.4 × 105Pa, hot wet compressive strength are 1.8 × 106~2.3 × 106Pa, specific surface Product is 9.3~12.6m2/g。
The chromium zinc waste water and medicament enter agitating reaction pond after pipe-line mixer mixes, and have 3 in agitating reaction pond ~5 mechanical agitators, revolving speed are 35~55 revs/min, and the residence time of chromium zinc waste water is 10~25 minutes.
Then the chromium zinc waste water enters inclined-plate clarifying basin by level-one elevator pump, and inclined-plate clarifying basin is divided into two parts, preceding To be stirred area, rear portion is sloping plate deposition district for part.Flocculation aid medicine system addition polypropylene is crossed being stirred Qu Tongshuan 1~4mg/L of amide, 0.5~2mg/L of polysaccharide flocculation aid.There are two storage tanks for double flocculation aid medicine systems, place poly- third respectively Acrylamide and polysaccharide flocculation aid.Double flocculation aid medicine systems be accurately added by robot control system(RCS) and dosing pump according to water help it is solidifying Agent.Agitator speed in stirring area is 90~120 revs/min, and the residence time of chromium zinc waste water is 1~3 minute.Subsequently into Sloping plate deposition district, sloping plate deposition district residence time are 30~45 minutes.
After inclined-plate clarifying basin, cold rolling chromium zinc waste water enters adsorption tower by two-stage hoisting pump, is equipped with and changes in adsorption tower Property medical stone heavy metal adsorption filtrate.Modified medical stone heavy metal adsorption filtrate is the 85~95% of adsorption tower total volume.Cold rolling Residence time of the chromium zinc waste water in adsorption tower is 31~42 minutes.
Modification medical stone heavy metal adsorption filtrate of the invention is prepared according to the characteristic of power plant desulfurization wastewater.1) wheat meal The screening of stone filtrate: the medical stone filtrate of 100~150 mesh of selection, density are 1.23~2.98g/cm3.2) acid activation of carrier And cleaning: medical stone carrier stirs 1 hour in 55 degree of 13~16% dust technology, wash with distilled water 5~8 after taking-up It is secondary, then dried in 105 degree of air dry ovens, it is spare after cooling.3) preparation of maceration extract: prepare solution concentration be 7~ Then the hexa of 1~3mg/L is added as precipitating reagent, with every in 9mol/L ferrous sulfate solution in ferrous sulfate The speed mechanical of 70 turns of minute stirs 30min, is formed and is mixed with dipping solution.4) dipping of medical stone: medical stone presses solid-to-liquid ratio 1:5 ~8 ratio is placed in dipping solution, is impregnated 10~12 hours；Then medical stone carrier is taken out, is dried in the air naturally at room temperature It is dry.5) high temperature sintering: being placed on drying 2 hours in the air dry oven of 120~150 degree of conditions for impregnated medical stone carrier, 550~580 degree are warming up to 10~12 degree/min, constant temperature calcining 3~5 hours, then natural cooling, was prepared modified wheat meal Stone heavy metal adsorption filtrate, specific surface area are 1.2~1.9m2/ g, total pore volume are 0.007~0.04m3/ g, with modified ratio The raising of surface area and total pore volume, heavy metal adsorption greatly improve.
Cold rolling chromium zinc waste water passes through draining pump qualified discharge after adsorption tower.
After cold rolling chromium zinc treatment process of the invention, cold rolling chromium zinc wastewater pH is 7~9, Cr6+Lower than 0.02mg/L, Total chromium is lower than 0.03mg/L, and total zinc is lower than 0.5mg/L.
The beneficial technical effect of the present invention:
The invention proposes the processing technique scheme for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously, warps After crossing cold rolling chromium zinc treatment process of the invention, cold rolling chromium zinc wastewater pH is 7~9, Cr6+Lower than 0.02mg/L, total chromium is lower than 0.03mg/L, total zinc are lower than 0.5mg/L.This technical solution solves the problems, such as the Heavy-metal Polluted Environment of cold rolling wastewater. Therefore the invention belongs to the environmentally protective production technologies of steel, have good social benefit and environmental benefit.
Detailed description of the invention
Fig. 1 is while removing Cr VI, total chromium and total zinc processing system in cold rolling chromium zinc waste water；
Wherein: intake pump -1, medicament dosing tank -3, the iron-based reducing agent solution -4 of alta-mud load, stirs pipe-line mixer -2 Mix reaction tank -5, level-one elevator pump -6, flocculation aid medicine system -7, inclined-plate clarifying basin -8, two-stage hoisting pump -9, adsorption tower -10, Modified medical stone heavy metal adsorption filtrate -11, draining pump -12.
Specific embodiment
Below with reference to embodiment, the present invention is further elaborated, it will be appreciated by those skilled in the art that the embodiment It is given for example only, and does not form any restrictions to the present invention.
Embodiment 1:
Processing system that is a kind of while removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water, including intake pump, pipeline Mixer, medicament dosing tank, the iron-based reducing agent solution of alta-mud load, agitating reaction pond, level-one elevator pump, flocculation aid dosing system System, inclined-plate clarifying basin, two-stage hoisting pump, adsorption tower, modified medical stone heavy metal adsorption filtrate, draining pump.
The chromium zinc waste water of the high concentration is water quality characteristic: pH 7.9, Cr6+For 34.9mg/L, total chromium is 67.2mg/L, Total zinc is 89.3mg/L.
The chromium zinc waste water enters pipe-line mixer by intake pump, and reducing agent is beaten by the dosing pump in Automatic Dosing case Enter in pipe-line mixer, reduction adsorption agent and chromium zinc waste water are sufficiently mixed in pipe-line mixer.Automatic Dosing case by grug feeding jar, Dosing pump and robot control system(RCS) composition, can determine added amount of chemical according to water.The dosage of reducing agent is 1150mg/L.Pipeline The material of mixer is polyvinyl chloride, and internal element is made of double or three ducts, and the dislocation in adjacent cells duct is 90 degree, duct Interior placement flight, dispersion degree are 2 μm, and mixing nonuniformity coefficient is 1.3%.Chromium zinc waste water and medicament are in pipe-line mixer Residence time is 2 minutes.
The reducing agent is prepared according to the water quality characteristics of cold rolling chromium zinc waste water.1) sodium bentonite screening and activation: Select sodium bentonite, partial size 3.8mm.Main component (mass fraction %): smectite 42%, silica 48%, three Al 2 O is 7%, di-iron trioxide 1%, magnesia 1%, calcium oxide 0.6%, titanium dioxide 0.4%.2) sodium The cleaning of base bentonite: Na-bentonite soil particle is immersed in concentration 12 hours in the phosphoric acid,diluted of 1.5% (mass percent) (diluted acid activation), then takes out, and with pure water to neutrality, dries in 105 degree of air dry ovens, then cooling stand-by.Activation Sodium bentonite specific surface area increases 17% than original afterwards.2) by the acetic acid of the solution of ferrous chloride of 3.9mol/L and 1.2mol/L 1:5 is mixed ferrous iron solution by volume, forms combination solution.3) combination solution pH value is adjusted to 2.6 with 3% dilute hydrochloric acid, By combination solution mechanical stirring 17 minutes, mechanical stirring revolving speed was 60 revs/min.4) sodium bentonite is put by solid-to-liquid ratio 1:6 Enter and form mixed solution in combination solution, then mixed solution is put into barrel plating drum, mixed solution is heated to 91 first Degree, for rotating plating cylinder using zinc metal sheet as cathode, graphite is anode, and spacing is 10cm, current density 26A between anode and cathode.Entire rolling The depositing process time is 39 minutes.In rotating plating cylinder, sodium bentonite load iron base reductant is formed.Then solid content is configured to exist 25% sodium bentonite load iron base reductant solution.Analysis is found after testing, sodium bentonite load iron base reductant In, the iron content in sodium bentonite is between 7.9%, and water swelling degree reaches 24 times, and green compression strength is 0.3 × 105Pa, heat Wet compressive strength is 1.9 × 106Pa, specific surface area 9.9m2/g。
The chromium zinc waste water and medicament enter agitating reaction pond after pipe-line mixer mixes, and have 3 in agitating reaction pond ~5 mechanical agitators, revolving speed are 40 revs/min, and the residence time of chromium zinc waste water is 13 minutes.
Then the chromium zinc waste water enters inclined-plate clarifying basin by level-one elevator pump, and inclined-plate clarifying basin is divided into two parts, preceding To be stirred area, rear portion is sloping plate deposition district for part.Flocculation aid medicine system addition polypropylene is crossed being stirred Qu Tongshuan Amide 2mg/L, polysaccharide flocculation aid 1mg/L.Double flocculation aid medicine systems there are two storage tank, place respectively polyacrylamide and Polysaccharide flocculation aid.Flocculation aid is accurately added according to water by robot control system(RCS) and dosing pump in double flocculation aid medicine systems.It is stirring The agitator speed in area is 95 revs/min, and the residence time of chromium zinc waste water is 2 minutes.Subsequently into sloping plate deposition district, inclined plate is heavy The shallow lake area residence time is 35 minutes.
After inclined-plate clarifying basin, cold rolling chromium zinc waste water enters adsorption tower by two-stage hoisting pump, is equipped with and changes in adsorption tower Property medical stone heavy metal adsorption filtrate.Modified medical stone heavy metal adsorption filtrate is the 95% of adsorption tower total volume.Cold rolling chromium zinc Residence time of the waste water in adsorption tower is 35 minutes.
Modification medical stone heavy metal adsorption filtrate of the invention is prepared according to the characteristic of power plant desulfurization wastewater.1) wheat meal The screening of stone filtrate: the medical stone filtrate of 100 mesh of selection, density 1.87g/cm3.2) acid activation and cleaning of carrier: wheat meal Stone carrier stirs 1 hour in 55 degree of 14% dust technology, then dry in 105 degree of air blast 5 times wash with distilled water after taking-up It is dried in dry case, it is spare after cooling.3) preparation of maceration extract: preparation solution concentration is 7mol/L ferrous sulfate solution, is then existed The hexa of 2mg/L is added in ferrous sulfate as precipitating reagent, 30min is stirred with 70 turns of speed mechanical per minute, It is formed and is mixed with dipping solution.4) dipping of medical stone: medical stone is placed in dipping solution in the ratio of solid-to-liquid ratio 1:6, dipping 11 hours；Then medical stone carrier is taken out, at room temperature naturally dry.5) high temperature sintering: by impregnated medical stone carrier It is placed in the air dry oven of 135 degree of conditions 2 hours dry, is warming up to 550 degree with 10 degree/min, constant temperature calcining 4 hours, then Modified medical stone heavy metal adsorption filtrate, specific surface area 1.5m is prepared in natural cooling2/ g, total pore volume 0.02m3/ G, with the raising of modified specific surface area and total pore volume, heavy metal adsorption is greatly improved.
Cold rolling chromium zinc waste water passes through draining pump qualified discharge after adsorption tower.
After the cold rolling chromium zinc treatment process of invention, cold rolling chromium zinc wastewater pH is 8.1, Cr6+For 0.004mg/ L, total chromium are 0.009mg/L, and total zinc is 0.2mg/L.
Embodiment 2:
Processing system that is a kind of while removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water, including intake pump, pipeline Mixer, medicament dosing tank, the iron-based reducing agent solution of alta-mud load, agitating reaction pond, level-one elevator pump, flocculation aid dosing system System, inclined-plate clarifying basin, two-stage hoisting pump, adsorption tower, modified medical stone heavy metal adsorption filtrate, draining pump.
The chromium zinc waste water of the high concentration is water quality characteristic: pH 6.5, Cr6+For 22.3mg/L, total chromium is 55.9mg/L, Total zinc is 67.1mg/L.
The chromium zinc waste water enters pipe-line mixer by intake pump, and reducing agent is beaten by the dosing pump in Automatic Dosing case Enter in pipe-line mixer, reduction adsorption agent and chromium zinc waste water are sufficiently mixed in pipe-line mixer.Automatic Dosing case by grug feeding jar, Dosing pump and robot control system(RCS) composition, can determine added amount of chemical according to water.The dosage of reducing agent is 860mg/L.Pipeline The material of mixer is polyvinyl chloride, and internal element is made of double or three ducts, and the dislocation in adjacent cells duct is 110 degree, hole Flight is placed in road, dispersion degree is 0.7 μm, and mixing nonuniformity coefficient is 0.6%.Chromium zinc waste water and medicament are in pipe-line mixer The interior residence time is 4 minutes.
The reducing agent is prepared according to the water quality characteristics of cold rolling chromium zinc waste water.1) sodium bentonite screening and activation: Select sodium bentonite, partial size 4.0mm.Main component (mass fraction %): smectite 45%, silica 43%, three Al 2 O is 8%, di-iron trioxide 1.6%, magnesia 1.2%, calcium oxide 1.1%, titanium dioxide 0.1%. 2) Na-bentonite soil particle the cleaning of sodium bentonite: is immersed in concentration 15 in the phosphoric acid,diluted of 2.4% (mass percent) It hour (diluted acid activation), then takes out, with pure water to neutrality, is dried in 105 degree of air dry ovens, it is then cooling stand-by. Sodium bentonite specific surface area increases 21% than original after activation.2) by the solution of ferrous chloride of 5.6mol/L and 0.7mol/L 1:5 is mixed iron liquor by volume, forms combination solution.3) combination solution pH value is adjusted to 5% dilute hydrochloric acid 3.3, by combination solution mechanical stirring 25 minutes, mechanical stirring revolving speed was 80 revs/min.4) sodium bentonite is pressed into solid-to-liquid ratio 1: 8 are put into combination solution and form mixed solution, and then mixed solution is put into barrel plating drum, is first heated to mixed solution 93 degree, for rotating plating cylinder using zinc metal sheet as cathode, graphite is anode, and spacing is 12cm, current density 34A between anode and cathode.Entirely The barrel plating process time is 42 minutes.In rotating plating cylinder, sodium bentonite load iron base reductant is formed.Then it is configured to solid content In 27% sodium bentonite load iron base reductant solution.Analysis is found after testing, and sodium bentonite loads iron-based reduction In agent, the iron content in sodium bentonite is between 8.9%, and water swelling degree reaches 26 times, and green compression strength is 0.4 × 105Pa, Hot wet compressive strength is 2.3 × 106Pa, specific surface area 11.1m2/g。
The chromium zinc waste water and medicament enter agitating reaction pond after pipe-line mixer mixes, and have 3 in agitating reaction pond ~5 mechanical agitators, revolving speed are 35~55 revs/min, and the residence time of chromium zinc waste water is 25 minutes.
Then the chromium zinc waste water enters inclined-plate clarifying basin by level-one elevator pump, and inclined-plate clarifying basin is divided into two parts, preceding To be stirred area, rear portion is sloping plate deposition district for part.Flocculation aid medicine system addition polypropylene is crossed being stirred Qu Tongshuan Amide 4mg/L, polysaccharide flocculation aid 0.5mg/L.There are two storage tanks for double flocculation aid medicine systems, place polyacrylamide respectively With polysaccharide flocculation aid.Flocculation aid is accurately added according to water by robot control system(RCS) and dosing pump in double flocculation aid medicine systems.It is stirring The agitator speed for mixing area is 90~120 revs/min, and the residence time of chromium zinc waste water is 3 minutes.Subsequently into sloping plate deposition Area, sloping plate deposition district residence time are 45 minutes.
After inclined-plate clarifying basin, cold rolling chromium zinc waste water enters adsorption tower by two-stage hoisting pump, is equipped with and changes in adsorption tower Property medical stone heavy metal adsorption filtrate.Modified medical stone heavy metal adsorption filtrate is the 85~95% of adsorption tower total volume.Cold rolling Residence time of the chromium zinc waste water in adsorption tower is 33 minutes.
Modification medical stone heavy metal adsorption filtrate of the invention is prepared according to the characteristic of power plant desulfurization wastewater.1) wheat meal The screening of stone filtrate: the medical stone filtrate of 150 mesh of selection, density 2.88g/cm3.2) acid activation and cleaning of carrier: wheat meal Stone carrier stirs 1 hour in 55 degree of 16% dust technology, then dry in 105 degree of air blast 6 times wash with distilled water after taking-up It is dried in dry case, it is spare after cooling.3) preparation of maceration extract: preparation solution concentration is 9mol/L ferrous sulfate solution, is then existed The hexa of 1mg/L is added in ferrous sulfate as precipitating reagent, 30min is stirred with 70 turns of speed mechanical per minute, It is formed and is mixed with dipping solution.4) dipping of medical stone: medical stone is placed in dipping solution in the ratio of solid-to-liquid ratio 1:8, dipping 10 hours；Then medical stone carrier is taken out, at room temperature naturally dry.5) high temperature sintering: by impregnated medical stone carrier It is placed in the air dry oven of 120 degree of conditions 2 hours dry, is warming up to 575 degree with 10 degree/min, constant temperature calcining 5 hours, then Modified medical stone heavy metal adsorption filtrate, specific surface area 1.8m is prepared in natural cooling2/ g, total pore volume 0.032m3/ G, with the raising of modified specific surface area and total pore volume, heavy metal adsorption is greatly improved.
Cold rolling chromium zinc waste water passes through draining pump qualified discharge after adsorption tower.
After the cold rolling chromium zinc treatment process of invention, cold rolling chromium zinc wastewater pH is 7.5, Cr6+For 0.002mg/ L, total chromium are 0.01mg/L, and total zinc is 0.1mg/L.
In conclusion present invention firstly provides the technical solution of complete cold rolling chromium zinc wastewater treatment, system is solved The problem of cold rolling wastewater Heavy-metal Polluted Environment, therefore the invention belongs to the environmentally protective production-process systems of steel.
Certainly, those skilled in the art in the art are it should be appreciated that above-described embodiment is intended merely to illustrate this hair It is bright, rather than it is used as limitation of the invention, as long as transformation, change in spirit of the invention, to above-described embodiment Shape will all be fallen within the scope of the claims.

Claims (9)

1. removing the processing method of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously, which is characterized in that including walking as follows It is rapid:
(1) the cold rolling chromium zinc waste water enters pipe-line mixer, and reducing agent squeezes into pipeline by the dosing pump in Automatic Dosing case In mixer, reduction adsorption agent and cold rolling chromium zinc waste water are sufficiently mixed in pipe-line mixer；Cold rolling chromium zinc waste water and medicament exist Residence time in pipe-line mixer is 2~4 minutes；
The reducing agent is sodium bentonite load iron base reductant solution；The reducing agent is prepared by following methods:
1) sodium bentonite screening and activation: selection sodium bentonite, partial size are 1.7~4.2mm；Main component mass fraction hundred Point ratio: smectite 34~46%, silica be 27~59%, aluminum oxide be 3~15%, di-iron trioxide be 0~ 2%, magnesia is 0~2%, and calcium oxide is 0~1.5%, and titanium dioxide is 0~0.9%；
2) Na-bentonite soil particle the cleaning of sodium bentonite: is immersed in phosphoric acid,diluted of the mass percent concentration 1~2.5% In 10~15 hours, take out, with pure water to neutrality, dried in 105 degree air dry ovens, it is cooling for use；
3) by the iron liquor of the solution of ferrous chloride of 3.8~7.9mol/L and 0.5~1.7mol/L by volume 1:3~ 5 mixing, form combination solution；
4) combination solution pH value is adjusted to 2.2~3.6 with 2~5% dilute hydrochloric acid, by 15~26 points of combination solution mechanical stirring Clock, mechanical stirring revolving speed are 60~90 revs/min；
5) sodium bentonite is put into combination solution by solid-to-liquid ratio 1:6~8 and forms mixed solution, then mixed solution is put into rolling It plates in drum, mixed solution is heated to 87~98 degree first, for rotating plating cylinder using zinc metal sheet as cathode, graphite is anode, anode and cathode Between spacing be 10~12cm, current density be 22~36A；The entire barrel plating process time is 35~48 minutes, in rotating plating cylinder, Form sodium bentonite load iron base reductant；The sodium bentonite load that solid content is finally configured to 24~29% is iron-based also Former agent solution；
(2) the cold rolling chromium zinc waste water and medicament enter agitating reaction pond after pipe-line mixer mixes, and chromium zinc waste water stops Staying the time is 10~25 minutes；
(3) then the chromium zinc waste water enters inclined-plate clarifying basin, and inclined-plate clarifying basin is divided into two parts, and front, which is divided into, to be stirred Area, rear portion are sloping plate deposition district, pass through double flocculation aid medicine systems addition 1~4mg/L of polyacrylamide being stirred area, more 0.5~2mg/L of carbohydrate flocculation aid；Sloping plate deposition district is entered back into, the sloping plate deposition district residence time is 30~45 minutes；
(4) after inclined-plate clarifying basin, cold rolling chromium zinc waste water enters adsorption tower, inhales in adsorption tower equipped with modified medical stone heavy metal Attached filtrate；Modified medical stone heavy metal adsorption filtrate is the 85~95% of adsorption tower total volume；Cold rolling chromium zinc waste water is in adsorption tower In residence time be 31~42 minutes；Cold rolling chromium zinc waste water passes through draining pump qualified discharge after adsorption tower.
2. remove the processing method of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to claim 1, it is special Sign is, in step (1) in sodium bentonite load iron base reductant, iron content in sodium bentonite 7.2~9.9% it Between, water swelling degree reaches 22~27 times, and green compression strength is 0.3 × 105~0.4 × 105Pa, hot wet compressive strength be 1.8 × 106~2.3 × 106Pa, specific surface area are 9.3~12.6m2/g。
3. remove the processing method of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to claim 1, it is special Sign is that Automatic Dosing case is made of grug feeding jar, dosing pump and robot control system(RCS) in step (1), can determine medicament according to water Dosage；The dosage of reducing agent is 560~1220mg/L.
4. a kind of processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to claim 1, It is characterized in that, the material of pipe-line mixer is polyvinyl chloride in step (1), internal element is made of double or three ducts, adjacent The dislocation in unit duct is 90~120 degree, and flight is placed in duct, and dispersion degree is 0.5~4 μm, and mixing nonuniformity coefficient is 0.1~2%.
5. remove the processing method of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to claim 1, it is special Sign is there are 3~5 mechanical agitators in agitating reaction pond in step (2), and revolving speed is 35~55 revs/min.
6. remove the processing method of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to claim 1, it is special Sign is that there are two storage tanks for double flocculation aid medicine systems in step (3), and placement polyacrylamide and polysaccharide help solidifying respectively Agent；Flocculation aid is accurately added according to water by robot control system(RCS) and dosing pump in double flocculation aid medicine systems；Blender in stirring area Revolving speed is 90~120 revs/min, and the residence time of chromium zinc waste water is 1~3 minute.
7. remove the processing method of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to claim 1, it is special Sign is,
Modified medical stone heavy metal adsorption filtrate is prepared by following methods in step (4):
1) screening of medical stone filtrate: the medical stone filtrate of 100~150 mesh of selection, density are 1.23~2.98g/cm3；
2) acid activation and cleaning of carrier: medical stone carrier stirs 1 hour in 55 degree of 13~16% dust technology, after taking-up It 5~8 times wash with distilled water, is dried in 105 degree of air dry ovens, it is spare after cooling；
3) preparation of maceration extract: preparation solution concentration be 7~9mol/L ferrous sulfate solution, in ferrous sulfate be added 1~ The hexa of 3mg/L stirs 30min as precipitating reagent, with 70 turns of speed mechanical per minute, and it is molten to form hybrid infusion Liquid；
4) dipping of medical stone: medical stone is placed in dipping solution in the ratio of solid-to-liquid ratio 1:5~8, is impregnated 10~12 hours； Medical stone carrier is taken out, at room temperature naturally dry；
5) high temperature sintering: being placed on drying 2 hours in the air dry oven of 120~150 degree of conditions for impregnated medical stone carrier, 550~580 degree are warming up to 10~12 degree/min, constant temperature calcining 3~5 hours, modified medical stone weight was prepared in natural cooling Metal adsorption filtrate, specific surface area are 1.2~1.9m2/ g, total pore volume are 0.007~0.04m3/g。
8. remove the processing method of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously according to claim 1, it is special Sign is,
The chromium zinc waste water of the high concentration is water quality characteristic before handling: pH is 6~9, Cr6+For 5.4~42.9mg/L, total chromium is 19.3~79.5mg/L, total zinc are 8.9~106.7mg/L；
After cold rolling chromium zinc treatment process of the invention, cold rolling chromium zinc wastewater pH is 7~9, Cr6+Lower than 0.02mg/L, total chromium Lower than 0.03mg/L, total zinc is lower than 0.5mg/L.
9. the processing system of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water is removed simultaneously, described in claim any one of 1-8 The processing method for removing Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water simultaneously can be applied to the system, it is characterised in that: institute The system of stating includes sequentially connected intake pump (1), pipe-line mixer (2), agitating reaction pond (5), level-one elevator pump (6), inclined plate Sedimentation basin (8), two-stage hoisting pump (9), adsorption tower (10) and draining pump (12)；Add in the pipe-line mixer (2) setting medicament Medicine-chest (3), medicament dosing tank (3) are built-in with the iron-based reducing agent solution of alta-mud load, set above the inclined-plate clarifying basin (8) Flocculation aid medicine system (7) are set, in medical stone heavy metal adsorption filtrate modified built in the adsorption tower (10).
CN201810271101.0A 2018-03-29 2018-03-29 The processing method and system of Cr VI, total chromium and total zinc in cold rolling chromium zinc waste water are removed simultaneously Pending CN110316855A (en)

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Application publication date: 20191011