CN110052106A - Cupric industrial sludge comprehensive administration of three wastes system and method - Google Patents

Cupric industrial sludge comprehensive administration of three wastes system and method Download PDF

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Publication number
CN110052106A
CN110052106A CN201910407233.6A CN201910407233A CN110052106A CN 110052106 A CN110052106 A CN 110052106A CN 201910407233 A CN201910407233 A CN 201910407233A CN 110052106 A CN110052106 A CN 110052106A
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CN
China
Prior art keywords
tower
sewage
pond
king
spray
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Pending
Application number
CN201910407233.6A
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Chinese (zh)
Inventor
余志新
李江枫
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Kaiping Xinlong Recycling And Processing Factory Co Ltd
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Kaiping Xinlong Recycling And Processing Factory Co Ltd
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Priority to CN201910407233.6A priority Critical patent/CN110052106A/en
Publication of CN110052106A publication Critical patent/CN110052106A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D50/00Combinations of methods or devices for separating particles from gases or vapours
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/122Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/13Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/44Details; Accessories
    • F23G5/46Recuperation of heat
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/061Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
    • F23G7/065Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23JREMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00Arrangements of devices for treating smoke or fumes
    • F23J15/02Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
    • F23J15/022Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23JREMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J15/00Arrangements of devices for treating smoke or fumes
    • F23J15/08Arrangements of devices for treating smoke or fumes of heaters
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26DRYING
    • F26BDRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
    • F26B21/14Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects using gases or vapours other than air or steam, e.g. inert gases
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00Charging; Discharging; Manipulation of charge
    • F27D3/0084Charging; Manipulation of SC or SC wafers
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F2001/007Processes including a sedimentation step
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/18Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents

Abstract

The present invention relates to a kind of cupric industrial sludge comprehensive administration of three wastes system and methods, belong to environmental technology field.The processing equipment, it include: fixed-end forces equipment, waste gas treatment equipment and sewage disposal device, above-mentioned cupric industrial sludge comprehensive administration of three wastes system, it is matched with fixed-end forces equipment, waste gas treatment equipment and sewage disposal device, the technique that comprehensive improvement can be effectively carried out to the solid, liquid, gas three-phase of hazardous waste sludge containing heavy metal, reaches to the minimizing of the hazardous waste sludge three wastes, innoxious, recycling purpose.And exhaust-gas treatment is carried out by pretreater collaboration absorption tower (WLT tower); the severe property of flue gas, preparatory removing part flue dust, sulfur dioxide, reduction smoke temperature are adjusted by pretreater while improving desulfurization degree, dust removal efficiency and protect subsequent WLT tower internal unit, has the advantages that extend follow-up equipment service life.

Description

Cupric industrial sludge comprehensive administration of three wastes system and method
Technical field
The present invention relates to environmental technology fields, more particularly to a kind of cupric industrial sludge comprehensive administration of three wastes system and side Method.
Background technique
With the development of the times, it is increasingly recognised that the importance of environmental protection, environmental protection have become country and the people One of important leverage condition of race's sustainable development.However, inevitably generating some dirts again in modernization industry production Mud, industrial sludge can be divided into hazardous waste and general industry waste according to management attribute again, the processing for hazardous waste sludge, always Since be difficult point and emphasis in industry.
Currently, not having comprehensive Processing tecchnics, this patent for dangerous waste solid, liquid, gas three-phase in dangerous waste treatment industry yet A set of technique that comprehensive improvement can be effectively carried out to the solid, liquid, gas three-phase of hazardous waste sludge containing heavy metal is innovatively designed, Reach to the minimizing of the hazardous waste sludge three wastes, innoxious, recycling purpose.
Summary of the invention
Based on this, it is necessary in view of the above-mentioned problems, a kind of cupric industrial sludge comprehensive administration of three wastes system and method is provided, Copper, nickel compound in hazardous waste sludge are recycled by filters pressing, drying and melting means using the device and method, and right The waste water containing heavy metal component, the exhaust gas generated in production process carries out harmless treatment, recycles, qualified discharge.
A kind of cupric industrial sludge comprehensive administration of three wastes system, comprising:
Fixed-end forces equipment, including filter press, drying component, brickmaking machine and smelting furnace, the filter press, drying component, Brickmaking machine and smelting furnace are set gradually by process flow;
Waste gas treatment equipment, including multistage surface air cooler, the first sack cleaner and the second sack cleaner, and including logical Cross pretreater, absorption tower and wet cottrell that pipeline is sequentially communicated, first sack cleaner and the second pocket type Deduster is connected to the pretreater, and the gas exhaust piping of the drying component connects the first sack cleaner, the smelting furnace Gas exhaust piping the second sack cleaner is connected to by the multistage surface air cooler;
Sewage disposal device, including dope pond and clean solution tank, and include the primary sedimentation tank being sequentially communicated by pipeline, adjust acid Pond, oxidation pond, alkali tune pond, coagulating basin, flocculation basin, mudpan, sand filtering device, carbon filter device, cotton filter and reverse osmosis Saturating device is equipped with anti-seepage membrane in the reverse osmosis unit, the reverse osmosis unit is divided into dope chamber and clear liquid chamber, described dense Sap cavity is connected to the dope pond, and the clear liquid chamber is connected to the clean solution tank;The blowdown of the primary sedimentation tank and the filter press Pipeline connection, the dope pond are connected to the primary sedimentation tank.
Above-mentioned cupric industrial sludge comprehensive administration of three wastes system, at fixed-end forces equipment, waste gas treatment equipment and sewage Reason equipment matches, and the technique that comprehensive improvement can be effectively carried out to the solid, liquid, gas three-phase of hazardous waste sludge containing heavy metal reaches To the minimizing of the hazardous waste sludge three wastes, innoxious, recycling purpose.And it is carried out by pretreater collaboration absorption tower (WLT tower) Exhaust-gas treatment adjusts the severe property of flue gas, in advance removing part cigarette by pretreater while improving desulfurization degree, dust removal efficiency Dirt, sulfur dioxide reduce the subsequent WLT tower internal unit of smoke temperature protection, have the advantages that extend follow-up equipment service life.
The mudpan is equipped with sludge reflux pipeline with primary sedimentation tank bottom and is connected to institute in one of the embodiments, State filter press;
The reuse pool passes through absorption tower and the wet cottrell described in pipeline connection.
The waste gas treatment equipment further includes the sprayed slurry circulatory system, and the sprayed slurry circulatory system includes passing through pipe Calcium-base absorbing agent warehouse, slaking apparatus, slurrying pond and the circulatory pool that road is sequentially communicated, the circulatory pool are provided by feeding pipe Fresh absorption slurries are connected to the pretreater and absorb the bottom of the tower by recovery pipe to the pretreater and absorption tower Recycling absorbs slurries.
The sprayed slurry circulatory system further includes sedimentation basin, oxidation tank, calcium base recycling filtering equipment and oxidation fan, institute Oxidation tank is stated by circulatory pool and the sedimentation basin described in pipeline connection, the oxidation fan is equipped with aeration tube, the aeration tube It stretches in the oxidation tank;The precipitating bottom of pond portion is equipped with calcium base described in pipeline connection and recycles filtering equipment.
The reuse pool is respectively communicated with the slaking apparatus, circulatory pool by pipeline.
The fixed-end forces equipment further includes automatic feeding system in one of the embodiments, the self-feeding system System include packaged type Material collecting box for harvesting, first mechanical arm, second mechanical arm, third mechanical arm, the 4th mechanical arm, the 5th mechanical arm, 6th mechanical arm, the first conveyer belt, the second conveyer belt, third conveyer belt;The filter press filter cake outlet end and the Material collecting box for harvesting Initial position it is corresponding;First conveyer belt one end corresponds to the initial position of Material collecting box for harvesting, and the other end corresponds to the baking Dry component, the first mechanical arm are set between the initial position and first conveyer belt of the Material collecting box for harvesting, and being used for will be described Material collecting box for harvesting crawl is placed on first conveyer belt, and the second mechanical arm is set to first conveyer belt and the drying component Between, for Material collecting box for harvesting crawl to be placed in the drying component;Second conveyer belt one end corresponds to the drying Component, the other end correspond to the brickmaking machine, the third mechanical arm be set to the drying component and second transmission belt it Between, for Material collecting box for harvesting crawl to be placed in second conveyer belt, the 4th mechanical arm is set to second conveyer belt Between the brickmaking machine, for material crawl in the Material collecting box for harvesting to be poured into the brickmaking machine;The third conveyer belt One end corresponds to the brickmaking machine, and the other end corresponds to the smelting furnace, and the 5th mechanical arm is set to the brickmaking machine and institute It states between third conveyer belt, is placed in the third conveyer belt for grabbing material after brickmaking by Material collecting box for harvesting, the described 6th Mechanical arm is set between the third conveyer belt and the smelting furnace, described for material crawl in the Material collecting box for harvesting to be poured into In smelting furnace.
Dangerous waste processing melting process is often fed intake using manpower at present, forklift transport, heavier to worker's burden and dependence, And the present invention carries out material transportation, loading and unloading using automation equipment, makes drying, smelter while mitigating manpower burden significantly Sequence is more coherent, quick, improves smelting efficiency.
The drying component includes drying room, takes off material mechanical arm, warm and humid probe, infrared sensor and PLC control system;Institute It states drying room and is divided into the bottom for accommodating fuel and the upper layer for accommodating material drying;The warm and humid probe is in vertical direction On be arranged at intervals at the upper layer, warm and humid pop one's head in is also provided at room door, air outlet and the smoke outlet of the drying room;It is described PLC control system is electrically connected with the material mechanical arm of taking off and controls this and take off material mechanical arm;The warm and humid probe is controlled with the PLC System is electrically connected and sends a signal to the PLC control system;The infrared sensor is set to the drying room predetermined altitude simultaneously Send a signal to the PLC control system.
The baking process of dangerous waste processing at present relies on manual operation and bears worker that grievous hurt is big, and the present invention above-mentioned is used for The drying component of baking process uses automation equipment, anti-as detection probe real-time monitoring using warm and humid probe and infrared sensor Feedback, automation equipment are fed, take off material and material transportation, loading and unloading, make baking process more while mitigating manpower burden It is coherent, quick increase on the influence of exhaust emission analyte detection flue gas oxygen content to reduce and open drying room door because of long-time.
The fixed-end forces equipment is additionally provided with dope spray system, and the dope spray system is set to the smelting furnace Slag chilling spray, the primary sedimentation tank are connected to by the dope spray system with the primary sedimentation tank.
The sewage disposal device further includes the automatic feeding system for automatic charging in one of the embodiments, The automatic feeding system includes that reagent reservoirs, metering pump and discharging counterbalance valve, the reagent reservoirs are sequentially communicated by pipeline Metering pump and discharging counterbalance valve;
The automatic feeding system further includes pulsation damper, protective loop and flow correction circuit, the damping of pulsation Device is set on the pipeline between the reagent reservoirs and the metering pump, and the protective loop is connected to the metering pump and described Reagent reservoirs, and the protective loop is equipped with pressure gauge and protection counterbalance valve;Described in flow correction circuit one end connection Reagent reservoirs, the other end are connected to the pipeline between the metering pump and the reagent reservoirs.
The sour pond of the tune, oxidation pond, alkali tune pond, coagulating basin and flocculation basin are provided with the automatic feeding system.
The primary sedimentation tank adjusts sour pond, oxidation pond, alkali tune pond, coagulating basin, flocculation basin, is equipped in mudpan and is used for The stirring system of liquid in stirring pool.
It further include dual firing chamber in one of the embodiments, in the waste gas treatment equipment, the dual firing chamber is set to described It dries between component gas exhaust piping and the first sack cleaner, the dual firing chamber is additionally provided with the spray of the fuel for spraying fuel system It unites and for combustion-supporting blower system.
It further include waste heat boiler and heating heat exchange equipment, the waste heat boiler and heating are changed in the waste gas treatment equipment Hot equipment is sequentially communicated between the dual firing chamber and first sack cleaner, and the flue of the waste heat boiler with The drying room connection.
Waste heat boiler collects high-temperature flue gas heat and is back to drying room, is down to high-temperature flue gas smoke temperature suitable for subsequent pocket type 220 DEG C~300 DEG C of the operating condition smoke temperature of deduster, and the heating heat exchange equipment of a set of anti-condensation is also set up in dual firing chamber outlet, The heating heat exchange equipment major function is the higher cigarette of humidity of flue gas when drying room underrun and dual firing chamber's repair and maintenance Temperature is lower, and by external heating or heat recovery mode, (heating tube, heater box is controlled by temperature, power supply is warm in pipeline Pipe heat is to 120 degree), improve flue-gas temperature to 120 DEG C or more, avoid subsequent cloth bag because humidity it is excessively high caused by paste bag damage filtrate.
It further include for collecting the heavy grey cylinder of the drying of the drying component dust and smelting furnace in the waste gas treatment equipment The heavy grey cylinder of the melting of dust, the heavy grey cylinder of drying is set on the pipeline between the drying component and the dual firing chamber, described The heavy grey cylinder of melting is set on the pipeline between the smelting furnace and the multistage surface air cooler.
Above-mentioned fallout is worth with melting again, but block must be made up of brickmaking machine can just reenter melting Furnace melting, because ash shape particle is directly fluidized state under 1300-1500 DEG C of burning situation, effective slag yield is low.Therefore will Fallout, at brick melting again, can be improved slag yield, reduce oxygen-containing flue gas, reduction fuel consumption, raising synthesis by brickmaking machine Processing capacity.
The pretreater and the absorption tower are tower body made of glass reinforced plastic in one of the embodiments,.By glass For in the tower of fume treatment containing heavy metal component, can be avoided carbon steel material tower, in production load variation, (interval produces glass steel material It is raw), period maintenance when the tower body metal material galvanic corrosion problems that occur.
The pretreater is equipped with pretreatment spray system, and the pretreatment spray system includes pre-processing inversely spraying layer With the radial spraying layer of pretreatment, the inversely spraying layer of pretreatment is set to below the radial spraying layer of the pretreatment, described pre- The nozzle of inversely spraying layer is handled towards the pretreater bottom, the nozzle for pre-processing radial spraying layer is parallel to described The cross-wise direction of pretreater.
The pretreatment spray system is equipped with the radial spraying layer of three layers of pretreatment and one layer of inversely spraying layer of pretreatment.It can be with Understand, above-mentioned pretreatment radial direction spraying layer and pre-process inversely spraying layer can also according to actual requirement flexible setting, such as one Layer pre-processes radial spraying layer and the inversely spraying layer of three layers of pretreatment, the radial spraying layer of two layers of pretreatment and two layers of pretreatment are reverse Spraying layer etc., but need to be at least provided with the radial spraying layer of one layer of pretreatment and one layer of inversely spraying layer of pretreatment.
The absorption tower is equipped with king-tower spray system, and the king-tower spray system includes the inversely spraying layer of king-tower and king-tower diameter To spraying layer, the inversely spraying layer of king-tower is set to below the king-tower radial direction spraying layer, the inversely spraying layer of king-tower Nozzle is parallel to the cross-wise direction on the absorption tower towards the absorb the bottom of the tower, the nozzle of the king-tower radial direction spraying layer;
The pretreatment spray system, king-tower spray system are connected to the circulatory pool, the pretreater and absorption Tower bottom is equipped with recovery pipe and is connected to the circulatory pool.
The king-tower spray system is from top to bottom successively arranged the first king-tower radial direction spraying layer, the second king-tower and radially sprays Layer, third king-tower radial direction spraying layer, the 4th king-tower radial direction spraying layer and one layer of inversely spraying layer of king-tower.
It should be understood that above-mentioned king-tower radial direction spraying layer and the inversely spraying layer of king-tower can also flexibly be set according to actual requirement It sets, such as one layer of king-tower radial direction spraying layer and the inversely spraying layer of three layers of king-tower, two layers of king-tower radial direction spraying layer and two layers of king-tower are reverse Spraying layer etc., but need to be at least provided with one layer of king-tower radial direction spraying layer and one layer of inversely spraying layer of king-tower.
The absorption tower is additionally provided with the first turbulent liquid film generator and the second turbulent liquid film generator, the described first turbulent liquid Film generator is set between the inversely spraying layer of the king-tower and king-tower radial direction spraying layer, and the described second turbulent liquid film generator is set It is placed between the second king-tower radial direction spraying layer and third king-tower radial direction spraying layer.
The absorption tower is additionally provided with the demister system at the top of the absorption tower in one of the embodiments, described Demister system includes demister and demisting backwashing system, and the demisting backwashing system is equipped with the spray towards the water spray of the demister Mouth and water supply pipe;
The demister includes the upper demister from top to bottom set gradually and lower demister, and the demisting backwashing system exists The lower demister upper and lower is equipped with nozzle, and the demisting backwashing system is only equipped with nozzle below the upper demister.
The wet cottrell includes the wet electric current equalizer, wet electric field module set gradually with flue gas flow direction, The wet electric field module includes anode canister and cathode line, and the same pole span in the wet electric field module is 250-400mm;It is described Wet cottrell is additionally provided with wet electric back-purge system, and the nozzle of the wet electric back-purge system is placed in the anode canister and yin Above polar curve.
The waste gas treatment equipment further includes Anti-corrosive chimney, and the Anti-corrosive chimney is connected to the wet cottrell flue gas Outlet end, for discharging purifying smoke.
The invention also discloses a kind of closed-loop process methods for hazardous waste sludge, using above-mentioned cupric industrial sludge three Useless comprehensive treatment system, this method includes below scheme:
Fixed-end forces process:
Filters pressing: hazardous waste sludge to be processed is carried out to filters pressing in filter press and removes moisture removal, obtains filter cake;
Drying: being added carbon dust in filter cake and quick lime is uniformly mixed, and dries in drying component;
Brickmaking: the siccative of drying brickmaking in brickmaking machine;
Melting: the brick through brickmaking is poured into smelting furnace and carries out melting, obtains melting product;
Exhaust-gas treatment process:
Bag-type dusting: being sent to the first sack cleaner dedusting for the exhaust gas that the baking step generates, will be described molten The exhaust gas that refining step generates is sent to the second sack cleaner dedusting after multistage surface air cooler is cooling;
Pretreatment: will transport to pretreater by the first sack cleaner and the flue gas of the second sack cleaner dedusting, with Lime white handles flue gas as fresh absorption slurries;
Wet desulphurization: pretreated flue gas transports to absorption tower, and flue gas is handled using lime white as fresh absorption slurries;
Electrostatic precipitation: the flue gas through wet desulphurization transports to wet cottrell, and cigarette is carried out by way of electrostatic precipitation Gas purification, is then discharged;
Waste water processes:
Just heavy: the sewage of waste water and other sources that the filters pressing step is generated introduces the primary sedimentation tank, utilizes gravity Deposition carries out solid-liquid separation treatment to sewage;
Adjust acid: the upper layer sewage after primary sedimentation tank is separated by solid-liquid separation enters the sour pond of tune, adds sulfuric acid and ferrous sulfate, is subsequent Oxidation process provides acidic environment and ferrous ion;
Oxidation: the sewage after adjusting acid enters oxidation pond, adds hydrogen peroxide, makes hydrogen peroxide under the catalysis of ferrous ion Hydroxyl radical free radical is produced, so that dropping oxidation operation in sewage in acid condition is decomposed into small-molecule substance;
Alkali tune: oxidized sewage enters alkali tune pond, adds sodium hydroxide, adjusts pH value of sewage water to neutral or weak base Property, and generation heavy metal precipitation object is reacted with the metallic compound that rushes in sewage;
Coagulation: the sewage after alkali tune enters coagulating basin, adds aluminium polychloride, and the colloid in sewage is made to form precipitating;
Flocculation: the sewage after coagulation enters flocculation basin, adds polyacrylamide, the colloid in sewage is made to lose stabilization, Mutually collision, cohesion form precipitating;
Sludge settling: the sewage after flocculating enters mudpan, is separated by solid-liquid separation by gravitational settling to sewage;
Sand filtration: the sewage after sludge settling enters husky filter device filtering;
Carbon filter: the sewage after dirty sand filtration enters carbon filter device filtering;
Cotton core filtering: the sewage after carbon is filtered enters the filtering of cotton core filter device;
It is reverse osmosis: to enter reverse osmosis unit through the filtered sewage of cotton core, be filtered with reverse osmosis membrane, obtain needing to flow back To first heavy step process dope and can reuse clear liquid, complete sewage treatment.
Above-mentioned processing equipment is used in one of the embodiments, and the settled sludge that the just heavy step generates extracts It is handled to the filters pressing step;
The settled sludge that the sludge settling step generates, which is extracted to the filters pressing step, to be handled;
The clear liquid generated in the reverse osmosis step is delivered to the wet desulphurization and electrostatic precipitation step uses, described anti- The dope generated in impregnation step is delivered in the bag-type dusting step to be back to just for the dope spray system after Heavy step process.
Above-mentioned processing equipment is used in one of the embodiments, and the exhaust-gas treatment process further includes sprayed slurry Circulating process, the sprayed slurry circulating process the following steps are included:
Protopepsia: calcium-base absorbing agent is reacted in slaking apparatus with water and is digested;
Second level digestion: so that the slurries of above-mentioned protopepsia is entered the slurrying pond, carry out second level digestion, obtain fresh absorption Slurries;
Recycle: fresh absorption slurries enter circulatory pool storage, and enter the pretreater and absorption by pipeline Tower sprays, the absorption slurry reflux after spray to circulatory pool.
In the exhaust-gas treatment process, the fresh density for absorbing slurries is 1030-1100kg/m3, described tentatively to disappear Change and the time of second level digestion is 3-5h.
Using above-mentioned processing equipment, the sprayed slurry circulating process includes going back following steps:
Slurries processing: the fresh absorption slurries extracted in the circulatory pool enter oxidation tank, carry out outside pond in oxidation tank Oxidation makes calcium sulfite oxidation calcium sulfate indissoluble object by oxidation fan aeration, and the aeration air quantity of the oxidation fan is The SO of 1moL2Blasting statement dry air volume is 0.2~0.8m3/ h, then by after aeration reaction slurries import sedimentation basin precipitate into Row is separated by solid-liquid separation, and obtained solid sludge is extracted to the filters pressing step and handled.
The clear liquid generated in the reverse osmosis step is delivered to the protopepsia and recycles step moisturizing use.
Above-mentioned processing equipment is used in one of the embodiments, and in the fixed-end forces process, the filter cake is placed in In the Material collecting box for harvesting, successively to the drying component, brickmaking machine and smelting furnace feeding and fed intake by automatic feeding system.
Above-mentioned processing equipment is used in one of the embodiments, in the baking step, using warm and humid probe to baking Dry chamber carries out temperature and water capacity detection, and every the one group of data sampling of progress in 10-20 minutes, detection probe is fed back by electric signal To PLC control system, the drying degree in baking room is monitored;After drying carries out 2-3 hours, by taking off material mechanical arm using machinery The steel rake structure of hand carries out taking off material processing, it is heated more evenly to make siccative, while adding filter cake by second mechanical arm;20-30 points Clock carries out once taking off material and charging, until drying room reaches maximum capacity, siccative level height reaches infrared sensor for charging Setting height, stops charging.
In one of the embodiments, in the waste water processes, in the sour step of the tune, adjusting pH value of sewage water is 3- 4;
In the alkali tune step, adjusting pH value of sewage water is 7.5-8;
In the reverse osmosis step, the retention aperture of the reverse osmosis membrane is 0.0001 micron.
Above-mentioned processing equipment is used in one of the embodiments, is opened when the pressure for the counterbalance valve that discharges reaches 1mPa Discharging is opened, the unlatching when protecting counterbalance valve pressure to reach predetermined value, connective protection circuit.
Above-mentioned processing equipment is used in one of the embodiments, further includes secondary combustion in the exhaust-gas treatment process Step is burnt, the exhaust gas that baking step generates first is sent to the dual firing chamber, sprays natural gas and/or diesel oil in the dual firing chamber, And by combustion-supporting CO, carbon dust and the dioxin in 1000-1100 DEG C of progress second-time burning, after-flame exhaust gas of oxidation fan, reduce Flue gas oxygen content, then it is sent to the first sack cleaner dedusting.
Above-mentioned processing equipment is used in one of the embodiments, in the pre-treatment step, with 50~60L/min Flow and 1~2bar the fresh absorption slurries of pressure injection, and the nozzle injection coverage area summation be the pretreatment The 200-300% of tower radial cross-sectional area.
Above-mentioned processing equipment is used in one of the embodiments, in the wet desulphurization step, the radial spray Layer with the fresh absorption slurries of the pressure injection of the flow of 150~250L/min and 1~2bar, the inversely spraying layer with 100~ The fresh absorption slurries of the pressure injection of the flow and 1~2bar of 150L/min, and the injection flow of the radial spraying layer is less than The injection flow of the inversely spraying layer;And the nozzle injection coverage area summation is the absorption tower radial cross-sectional area 200-300%.
Compared with prior art, the invention has the following advantages:
A kind of cupric industrial sludge comprehensive administration of three wastes system of the invention, for the high sludge of content of beary metal, sewage With the discharge of the three wastes such as exhaust gas, matched with fixed-end forces equipment, waste gas treatment equipment and sewage disposal device, it can be effectively right The solid, liquid, gas three-phase of hazardous waste sludge containing heavy metal carries out the technique of comprehensive improvement, reaches to the minimizing of the hazardous waste sludge three wastes, nothing Evilization, recycling purpose.And exhaust-gas treatment is carried out by pretreater collaboration absorption tower (WLT tower), improves desulfurization degree, dedusting After adjusting the severe property of flue gas, in advance removing part flue dust, sulfur dioxide, reduction smoke temperature protection by pretreater while rate Continuous WLT tower internal unit has the advantages that extend follow-up equipment service life.
Above-mentioned processing equipment is directed to the industries such as Treatment of Metal Surface and heat treatment process, glass manufacture, electronic components fabrication The copper-contained sludge of generation, the dangerous waste solid, liquid, gas three-phase comprehensive of surface treatment waste are administered with significant benefit.
A kind of closed-loop process method for hazardous waste sludge of the invention, for during processing hazardous waste sludge, because it contains The special compositions such as copper, nickel can make the flue gas of subsequent exhaust-gas treatment with heavy metal component, not located specifically in a kind of industry The special smoke components of science and engineering skill sizing, the present invention innovatively pass through a whole set of desulfurization, the comprehensive waste gas treatment process of dedusting, Remove the harmful components such as the dioxins in flue gas, heavy metal, flue dust, sulfur dioxide and qualified discharge.
And for heavy metal containing sewage caused by baking process filters pressing in dangerous waste industry generally without specific processing method, and The present invention makes the Industrial Waste Water Treatments process of a set of maturation also for the sewage containing heavy metal component, make hazardous waste sludge and The sewage that exhaust-gas treatment generates obtains harmless treatment, and recycles moisturizing, cooling and the spray that auxiliary system is supplied for exhaust-gas treatment Process is backwashed, achievees the purpose that zero outlet of sewage and circulation is rinsed for equipment cleaning, place in daily production, mitigate work Station-service water burden.
Detailed description of the invention
Fig. 1 is processing equipment connection relationship diagram in embodiment;
Fig. 2 is processing method process flow diagram in embodiment;
Fig. 3 is pretreater and absorption tower structural schematic diagram in embodiment;
Fig. 4 is inversely spraying schematic diagram of a layer structure in embodiment;
Fig. 5 is radial spraying layer structural schematic diagram in embodiment;
Fig. 6 is turbulent liquid film generator structural schematic diagram in embodiment;
Fig. 7 is demister structural schematic diagram in embodiment;
Fig. 8 is I Part Methods schematic diagram in Fig. 7;
Fig. 9 is automatic feeding system connection relationship diagram in embodiment;
Wherein: 1100. filter presses;1200. drying component;1210. drying room;1300. brickmaking machine, 1400. smelting furnace; 1410. dope spray system;1510. Material collecting box for harvesting;1521. first mechanical arm;1522. second mechanical arm;1523. third is mechanical Arm;1524. the 4th mechanical arms;1525. the 5th mechanical arms;1526. the 6th mechanical arms;1527. take off material mechanical arm;1531. first Conveyer belt;1532. the second conveyer belt;1533. third conveyer belt;
2100. dual firing chamber;2110. waste heat boiler;2200. multistage surface air cooler;2310. the first sack cleaner;2311. rising Warm heat exchange equipment;2320. the second sack cleaner;2400. pretreater;The 2410. inversely spraying layers of pretreatment;2420. pre- place Manage radial spraying layer;2500. absorption tower;The inversely spraying layer of 2510. king-towers;2521. first king-tower radial direction spraying layers;2522. the Two king-tower radial direction spraying layers;2523. third king-tower radial direction spraying layers;2524. the 4th king-tower radial direction spraying layers;2531. first is disorderly Flow liquid film generator;2532. second turbulent liquid film generators;2541. demister;2542. demisting backwashing system;2600. wet type Electrostatic precipitator;2700. Anti-corrosive chimney;2810. calcium-base absorbing agent warehouse;2820. slaking apparatus;2830. slurrying pond;2840. Circulatory pool;2850. sedimentation basin;2860. oxidation tank;2870. oxidation fan;The heavy grey cylinder of 2910. drying;The heavy grey cylinder of 2920. meltings;
3100. moisture trap;3210. primary sedimentation tank;3220. adjust sour pond;3230. oxidation pond;3240. alkali tune pond;3250. Coagulating basin;3260. flocculation basin;3270. mudpan;3310. sand filtering device;3320. carbon filter device;3330. cotton core filters Device;3340. reverse osmosis unit;3341. reuse pool;3342. dope pond;3400. automatic feeding system;3410. reagent reservoirs; 3420. metering pump;3430. discharge counterbalance valve;3440. pulsation damper;3450. pressure gauge;3460. protecting counterbalance valve.
Specific embodiment
To facilitate the understanding of the present invention, a more comprehensive description of the invention is given in the following sections with reference to the relevant attached drawings.In attached drawing Give presently preferred embodiments of the present invention.But the invention can be realized in many different forms, however it is not limited to this paper institute The embodiment of description.On the contrary, purpose of providing these embodiments is keeps the understanding to the disclosure more thorough Comprehensively.
It should be noted that it can directly on the other element when element is referred to as " connection " in another element Or there may also be elements placed in the middle.When an element is considered as " connection " another element, it can be direct connection To another element or it may be simultaneously present centering elements.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases Any and all combinations of the listed item of pass.
Embodiment
A kind of cupric industrial sludge comprehensive administration of three wastes method, using processing equipment of the invention, as shown in Figure 1, including Three fixed-end forces equipment, waste gas treatment equipment and sewage disposal device modules;Above-mentioned processing method is as shown in Fig. 2, include solid Useless process flow, exhaust-gas treatment process and the big process of waste water processes three;Specific descriptions are described as follows.
One, fixed-end forces.
Fixed-end forces equipment includes filter press 1100, drying component 1200, brickmaking machine 1300 and smelting furnace 1400, the pressure Filter, drying component, brickmaking machine and smelting furnace are set gradually by process flow.
The fixed-end forces equipment of the present embodiment further includes automatic feeding system, and the automatic feeding system includes packaged type Material collecting box for harvesting 1510, first mechanical arm 1521, second mechanical arm 1522, third mechanical arm 1523, the 4th mechanical arm 1524, the 5th machine Tool arm 1525, the 6th mechanical arm 1526, the first conveyer belt 1531, the second conveyer belt 1532, third conveyer belt 1533;The filters pressing Machine filter cake outlet end is corresponding with the initial position of the Material collecting box for harvesting;First conveyer belt one end corresponds to the initial of Material collecting box for harvesting Position, the other end correspond to the drying component, and the first mechanical arm is set to the initial position and described the of the Material collecting box for harvesting Between one conveyer belt, for Material collecting box for harvesting crawl to be placed in first conveyer belt, the second mechanical arm is set to described Between first conveyer belt and the drying component, for Material collecting box for harvesting crawl to be placed in the drying component;Described second Conveyer belt one end corresponds to the drying component, and the other end corresponds to the brickmaking machine, and the third mechanical arm is set to the baking Between dry component and second transmission belt, it is placed in second conveyer belt for grabbing the Material collecting box for harvesting, the described 4th Mechanical arm is set between second conveyer belt and the brickmaking machine, described for material crawl in the Material collecting box for harvesting to be poured into In brickmaking machine;Third conveyer belt one end corresponds to the brickmaking machine, and the other end corresponds to the smelting furnace, the 5th machine Tool arm is set between the brickmaking machine and the third conveyer belt, described for material after brickmaking to be placed in by Material collecting box for harvesting crawl On third conveyer belt, the 6th mechanical arm is set between the third conveyer belt and the smelting furnace, for gathering materials described Material crawl is poured into the smelting furnace in case.
1, filters pressing.
In the targeted hazardous waste sludge of the present embodiment, moisture, content of ashes are very high, moisture generally 70%~80% it Between, cupric 2%~15%, nickeliferous 0.1%~1.1%.
Main component in the hazardous waste sludge of the present embodiment is as shown in the table.
The high cupric of table 1., nickel-containing sludge main component (butt)
2. solid state surface of table handles waste main chemical compositions (butt)
Above-mentioned high cupric, nickel-containing sludge are from the row such as glass manufacture, common non-ferrous metal metallurgy, electronic components fabrication Industry mainly includes useless tank liquor, slot slag and the wastewater treatment sludge that metallization copper facing generation is carried out using copper sulphate, pyrometallurgical smelting Dust-slag collection, the filter-press residues, wastewater treatment sludge that gas cleaning generates are refined, the useless copper etching liquor generated in wiring board production process makes The waste liquid and wastewater treatment sludge of copper oxidation processes generation, the spent etching solution and waste water generated in copper sheet etching process are carried out with acid Handle sludge etc..
Solid state surface handles biowaste origin in Treatment of Metal Surface and heat treatment process industry, and main includes using protochloride Tin, zinc chloride, ammonium chloride carry out the waste residue and wastewater treatment sludge of sensitized treatment generation;Electroplating technology is for example zinc-plated, cadmium plating, plating Useless tank liquor, slot slag and the wastewater treatment sludge of the generations such as nickel, gold-plated, copper facing, black chromium plating, metal and frosting sour (alkali) wash, Oil removing, washing, phosphatization, goes out light, changes at the waste corrosive liquid, useless cleaning solution, useless tank liquor, slot slag and waste water for throwing technique generation at derusting Manage sludge, waste liquid, slot slag and the wastewater treatment sludge generated in coating strip, using chromium compound carry out coating against corrosion, Useless tank liquor, slot slag and the wastewater treatment sludge etc. that resist layer chemicosolidifying, frosting roughening generate.The two is mainly reflected in original Material source differences, and specific metal component proportional difference, but since raw material is not fixed, both materials variance will lead to metal component Proportional difference changes.
Hazardous waste sludge is manually transported to by filter press from storage area by forklift, will be dirty first through high-pressure pressure filter filters pressing For mud from the filter cake of 70% filters pressing of average moisture content to aqueous 50%, the filter cake moisture content after filters pressing belongs to meta-alkali generally 50% Property substance, for pH value between 6.70~9.77, color has brownish black, brown, brownish black, blackish green etc., the metals such as copper in filter cake Content is about 1%~9%, mainly with Cu (OH)2、Ni(OH)2Form exist.
Filter-pressing process generates the filters pressing water of 2000t/a (about 9.6t/d), filters pressing water and is sent to sewage treatment by blowoff line For the fresh absorption slurries in waste gas treatment equipment for operations such as auxiliary moisturizing, backwash and equipment cleanings after equipment processing.
2, it dries.
The cupric 11%~14% that above-mentioned filter-pressing process obtains, nickeliferous 0.3%~0.6% filter cake with 0.8 × 0.5 × 0.5m3Material collecting box for harvesting load, baking is transported to 0.5m/s speed by first mechanical arm (six shaft mechanical arms) and the first conveyer belt The drying room 1210 of dry component is dried, and is uniformly mixed filter cake, carbon dust, quick lime according to the ratio of about 10:1:1, wherein carbon dust Granularity requirements in 0.5~1mm, in 1~2mm, the purpose of being mixed into higher quick lime ratio is digestion for the granularity requirements of quick lime Heat release raising material temperature and rate of set, having preferable wet dissolubility to make, siccative is more stable, quality is higher, and is conducive to exhaust-gas treatment The desulfurization of calcium method and melting process provide calcium ion supplement.Baking room divides upper layer and lower layer, and bottom spreads the sawdust as fuel, upper layer The sludge filter cake of paving after mixing after lighting bottom sawdust, closes drying room door and carries out baking process.
The drying component includes drying room, takes off material mechanical arm 1527, warm and humid probe, infrared sensor and PLC control system System;The drying room is divided into the bottom for accommodating fuel and the upper layer for accommodating material drying;The warm and humid probe is perpendicular Histogram is arranged at intervals at the upper layer upwards, warm and humid pop one's head in is also provided at room door, air outlet and the smoke evacuation of the drying room Mouthful;The PLC control system is electrically connected with the material mechanical arm of taking off and controls this and take off material mechanical arm;It is described it is warm and humid probe with it is described PLC control system is electrically connected and sends a signal to the PLC control system;The infrared sensor is predetermined set on the drying room Height simultaneously sends a signal to the PLC control system.
In baking step, air blast is carried out in drying room bottom by drum oxidation fan first;Baking room temperature is maintained at 500 ~600 DEG C, warm and humid probe is used to layout as 8 angles in drying room drying room progress temperature and water capacity detection, warm and humid probe Fall, room door, air outlet, smoke outlet and siccative floor are every 1~1.5m, every the one group of data sampling of progress in 15 minutes.Detection is visited Head feeds back to PLC control system by electric signal, monitors the drying degree in baking room.After drying carries out 2~3 hours, pass through It takes off material mechanical arm to carry out taking off material processing using the steel rake structure of manipulator, keeps siccative heated more evenly while mechanical by second Arm adds 2~3 casees filter cakes.It carries out within about 20~30 minutes once taking off material and charging, charging is until drying room reaches maximum capacity 15t, siccative level height reach infrared sensor setting height, stop charging.
Baking process continue two day time, one day to filter cake carry out drying and dewatering, placement cooling was carried out to siccative in one day.It dries The loading and unloading of dry chamber and material transportation are carried out by second mechanical arm and third mechanical arm (six shaft mechanical arms) and the second conveyer belt, Automatic operation keeps drying process more coherent, fast.Take off material, charging process closes drum oxidation fan, reduction flue gas oxygen content increasing Add.
Above-mentioned baking process main purpose is: reducing the water content of material, material is made to sinter even compact body into.
In above-mentioned baking process, partial oxidation calcium consumption sulfur dioxide in flue gas, which generates calcium sulfate, makes subsequent smelter Sequence is gone on smoothly, and reaction equation is as follows:
CaO+SO2(under hot conditions) → 2CaSO3+O2→2CaSO4
Baking process obtains cupric 23%~26%, and nickeliferous 0.8%~1.1%, the siccative of moisture content~10%.
3, brickmaking.
Above-mentioned siccative is placed in Material collecting box for harvesting, is transported to brickmaking by third mechanical arm and the 4th mechanical arm and the second conveyer belt Siccative is pressed into 250 × 110 × 50mm using high pressure by machine feeding, brickmaking machine3Calculon.
Appropriate slag former is added during this brickmaking, which is 5% silicate, 25%SiO2And 70%CaO is subsequent melting process slag making, and additive amount is the SiO made in melting raw material2, CaO weight ratio be 1:3.
4, melting.
After the completion of brickmaking process, the Material collecting box for harvesting equipped with calculon is clamped to by third by the 5th mechanical arm (six shaft mechanical arms) Conveyer belt is transported to by smelting furnace with 0.5m/s speed, will be in Material collecting box for harvesting followed by the 6th mechanical arm (six shaft mechanical arms) Brick pours into smelting furnace and carries out melting process.
Melting process is using the pyrometallurgical smelting technique that process is simple, intermediate link is few.
Specifically: material brick carries out high temperature reduction in furnace, coke is added in furnace as fuel and reducing agent, while supplementing one Quantitative slag former, makes SiO2, CaO reach 1:3 ratio.
About 1300 DEG C of fusion process furnace temperature.Brick is run from top to bottom, and bottom tuyeres are fusion zone, and brick reaches tuyere area Fusing.Air is blasted through air port, so that coke is burnt in tuyere area, and the high-temperature reductibility flue gas of generation is run from bottom to top, with brick Block antikinesis carries out heat exchange, and brick is made gradually to be heated and complete various reducing and smelting processes.Continuous with brick is melted Change, the discharge of slag and copper water, furnace charge face constantly declines, and furnace charge is continuously replenished, and furnace roof material is made to keep the horizontal charge level of homeostasis.
The fixed-end forces equipment is additionally provided with dope spray system, and the dope spray system is set to the smelting furnace Slag chilling spray, the primary sedimentation tank are connected to by the dope spray system with the primary sedimentation tank.Slag after melting is through institute Dope spray system chilling spray is stated, the dope of recycling enters primary sedimentation tank and handled.
Smelting technology principle is as follows:
CaSO under high temperature action, in material4It decomposes reaction, generates sulfur dioxide, the Cu (OH) in material2、 Ni(OH)2Deng generation oxide, sulfur dioxide, which preferentially reacts with metal oxide, produces sulfide (matte), sulfur dioxide When insufficient, metal oxide is directly reduced to metal by carbon.
A, the SO in material2Generation:
2CaSO4+ C (under hot conditions) → 2CaO+2SO2+CO2
B, metal oxyhydroxide resolves into metal oxide in material
M(OH)2(under hot conditions) → MO+H2O (gas)
If c, there is SO2When can preferentially with reactive metal oxide generate sulfide (blister copper)
4CuO+2SO2+4C→2Cu2S (blister copper)+4CO2
6NiO+4SO2+7C→2Ni3S2+7CO2
If d, without SO2In the presence of, metal oxide directly redeems a vow to a god into metal simple-substance by carbon
2CuO+C→2Cu+CO2
2NiO+C→2Ni+CO2
E, with above-mentioned c, d, other metal oxides are also restored by solid carbon by following reaction
PbO+C→Pb+CO
2PbO+C→2Pb+CO2
In the presence of CO of the ferriferous oxide in material in high concentration, iron oxide is reduced into metallic iron, but when in material Lead oxide or sulfide in the presence of, and replaced, react by iron are as follows:
PbO+Fe→Pb+FeO
PbS+Fe→Pb+FeS
2Cu+FeS→Cu2S+Fe
FeO and silicon, calcium slag making, specific gravity float on above metal cupola well compared with less serious case, and timing is released, and it is solid to obtain clinker glass state Solution.
CaO+SiO2(under hot conditions) → CaSiO3(slag)+CO2
The above reaction, the calcium silicates (CaSiO of melting occur for the slag former of above-mentioned addition3) become light specific gravity slag float Copper water can be reduced in copper water to contact with atmosphere, improve final product quality part harmful substance such as sulphur, phosphorus, gas and field trash simultaneously Etc. can enter in slag, it is pulled away when removing slag.
FeS and Cu2S、Ni3S2It is combined into blister copper, matte mixture, blister copper and its specific gravity of matte are larger, sink under cupola well Side, timing are released, and are layered after cooling and are obtained blister copper and matte.
Cupric about 90%, nickeliferous about 2.5% blister copper and cupric about 45%, nickeliferous about 7.5% are obtained by melting process Matte be placed in finished product Material collecting box for harvesting and transported by belt transporting apparatus to the storage of storage room by pouring cooling, as product It deposits.
Two, exhaust-gas treatment.
Waste gas treatment equipment includes multistage surface air cooler 2200, the first sack cleaner 2310 and the second sack cleaner 2320, and include the pretreater 2400 being sequentially communicated by pipeline, absorption tower 2500, wet cottrell 2600 and anti- Rotten chimney 2700, first sack cleaner and the second sack cleaner are connected to the pretreater, the drying component Gas exhaust piping connect the first sack cleaner, the gas exhaust piping of the smelting furnace is connected to second bag by the multistage surface air cooler Formula deduster.
The key technical indexes of original exhaust gas is as shown in the table in the present embodiment.
The key technical indexes of 3. raw flue gas of table
Index Unit Parameter Parameter
Production line quantity —— Smelting furnace Drying oven
Flue gas flow Nm3/h 13000 24000
Exhaust gas temperature 110 170
Flue gas flow Am3/h 17762 38945
Survey oxygen content —— ≤ 13.0% ≤ 13.0%
Original SO2Concentration conversion value mg/Nm3 3000~25000 ≤4000
Original dust concentration reduced value mg/Nm3 < 200 < 200
Nickel and its compound mg/Nm3 < 50 < 50
Copper and its compound mg/Nm3 < 200 < 600
1, bag-type dusting.
In the fixed-end forces process of the present embodiment, the drying component and the feed inlet of smelting furnace, discharge port (or copper Mouthful), slag-drip opening be equipped with gas gathering mask, collect after the flue gas of evolution by gas exhaust piping respectively with the first sack cleaner and second Sack cleaner connection.
Also, in the waste gas treatment equipment, further include the heavy grey cylinder of drying for collecting the drying component dust and The heavy grey cylinder of the melting of smelting furnace dust, the heavy grey cylinder of drying are set to the pipeline between the drying component and the dual firing chamber On, the heavy grey cylinder of the melting is set on the pipeline between the smelting furnace and the multistage surface air cooler.The flying dust of sedimentation collect to Melting again after progress brickmaking in brickmaking process.
It further include dual firing chamber 2100, waste heat boiler and heating heat exchange equipment, the dual firing chamber in the waste gas treatment equipment Between the drying component gas exhaust piping and the first sack cleaner, the dual firing chamber is additionally provided with the combustion for spraying fuel Expect spray system and for combustion-supporting blower system., further include that waste heat boiler and heating heat exchange are set in the waste gas treatment equipment Standby, the waste heat boiler and heating heat exchange equipment are sequentially communicated between the dual firing chamber and first sack cleaner, and The flue of the waste heat boiler is connected to the drying room.
In baking process, about 170~200 DEG C of the smoke temperature of exhaust pass, be 500 DEG C~600 DEG C due to drying process temperature, low Temperature burning oxyhydroxide can generate dioxin violent in toxicity in conjunction with chloride, so being arranged one two in drying room exhaust pass Room is fired, dual firing chamber's volume is about 0.18m3, by sprinkling natural gas, diesel oil, drum oxidation fan air blast is combustion-supporting for dual firing chamber, carries out two Secondary burning, residence time are 2~3 seconds, and daily fuel consumption is about 12kg, and ignition temperature is about 1000 DEG C~1100 DEG C, removes flue gas The uncombusted ingredient of middle carbon dust etc., and after-flame severe toxicity gas dioxin.
Waste heat boiler collects high-temperature flue gas heat and is back to drying room, is down to high-temperature flue gas smoke temperature suitable for subsequent pocket type 220 DEG C~300 DEG C of the operating condition smoke temperature of deduster, and the heating heat exchange equipment of a set of anti-condensation is also set up in dual firing chamber outlet, The heating heat exchange equipment major function is the higher cigarette of humidity of flue gas when drying room underrun and dual firing chamber's repair and maintenance Temperature is lower, and by external heating or heat recovery mode, (heating tube, heater box is controlled by temperature, power supply is warm in pipeline Pipe heat is to 120 degree), improve flue-gas temperature to 120 DEG C or more, avoid subsequent cloth bag because humidity it is excessively high caused by paste bag damage filtrate.
The multistage surface air cooler does heat exchange cooled flue gas by cool ambient air.
800~900 DEG C of high-temperature flue gas of melting process exhaust pass can enter the pipeline of multistage surface air cooler, in multi-level table Flue gas is reduced to 100~120 DEG C by heat exchange, temperature in cooler.
Above-mentioned dual firing chamber's exhaust pass and multistage surface air cooler exhaust pass are respectively connected to the first sack cleaner and second bag Formula deduster carries out flue gas ash removal processing, and sack cleaner is arranged 500~700 filter bags and the flower of former flue gas and neat stress is isolated Plate, the dust filtering filtering formed by filter bag and flue dust can be by particulate matters objects such as dust, heavy metal solid compounds Content reduces by 98%, and most heavy metal solid compounds are captured by sack cleaner, the weight recycled into desulfurizing tower water Metal ignores the secondary pollution negligible, water can not be caused to recycle.
Flue dust, the heavy metal solid compounds of sock filtration are collected into dust collector ash hopper by soot blower system, money to be had Brickmaking melting again after the government department of matter handles or collects.
2, it pre-processes.
Then, the flue gas of the first sack cleaner and the second sack cleaner accesses pretreater after converging by flue.
The pretreater is equipped with pretreatment spray system, as shown in figure 3, the pretreatment spray system includes pretreatment Inversely spraying layer 2410 and the radial spraying layer 2420 of pretreatment, it is radial that the inversely spraying layer of pretreatment is set to the pretreatment Below spraying layer, towards the pretreater bottom, the pretreatment radially sprays the nozzle of the inversely spraying layer of pretreatment The nozzle of layer is parallel to the cross-wise direction of the pretreater.Specifically, the pretreatment spray system is equipped with three layers of pretreatment Radial spraying layer and one layer of inversely spraying layer of pretreatment.
100~130 DEG C of pretreater inlet flue gas temperature, tower body material is resistance to corrode glass steel material resistant to high temperature, is equipped with four Layer spray structure, one layer is inversely spraying, and three layers of radial spray, spray liquid is lime white, with the flow of 50~60L/min and 1~ The fresh absorption slurries of the pressure injection of 2bar, spray head are 316 spiral nozzles, and spray head slurry spraying sprays area coverage (i.e. nozzle Injection coverage area summation is the absorption tower radial cross-sectional area) up to 200%~300%.
Pretreater effect is to adjust flue gas for subsequent absorption tower (WLT three-phase turbulent current barrel efficient desulfurizing and dust collecting tower) Matter divides flue dust using lime white liquid mist removing unit, reduces about 40% sulfur dioxide concentration in flue gas, make flue-gas temperature from 100 DEG C ~120 DEG C are reduced to 50~65 DEG C, prevent pernicious flue gas from accelerating the loss of WLT three-phase turbulent current barrel efficient desulfurizing and dust collecting tower, collaboration WLT tower is dusted desulfurization.
3, wet desulphurization.
Then, flue gas enters absorption tower after the pretreatment of pretreater, and flue-gas temperature is about 50-65 DEG C at this time.
The tower body material on the absorption tower encloses glass reinforced plastic, is equipped with king-tower spray system, as shown in figure 3, the king-tower sprays System includes the inversely spraying layer of king-tower and king-tower radial direction spraying layer, and the inversely spraying layer of king-tower is set to the king-tower and radially sprays Below drenching layer, the nozzle of the inversely spraying layer of king-tower is towards the absorb the bottom of the tower, the nozzle of the king-tower radial direction spraying layer It is parallel to the cross-wise direction on the absorption tower.
The king-tower spray system is successively arranged the inversely spraying layer 2510 of one layer of king-tower, the first king-tower from the bottom to top and radially sprays Drenching layer 2521, the second king-tower radial direction spraying layer 2522, third king-tower radial direction spraying layer 2523 and the 4th king-tower radial direction spraying layer 2524。
In above-mentioned five layers of spray structure, one layer inversely spraying (the inversely spraying layer of king-tower), as shown in figure 4, four layers of radial spray Drench (first to fourth king-tower radial direction spraying layer), as shown in figure 5, fresh absorptions slurries are lime white, radial spraying layer with 150~ The fresh absorption slurries of the pressure injection of the flow and 1~2bar of 250L/min, inversely spraying layer is with the flow of 100~150L/min With the fresh absorption slurries of pressure injection of 1~2bar, spray head is 316 spiral nozzles, and (i.e. nozzle sprays atomizing spray area coverage Coverage area summation is the absorption tower radial cross-sectional area) it can reach 200%~300%.
The absorption tower is additionally provided with the first turbulent liquid film generator 2531 and the second turbulent liquid film generator 2532, and described the One turbulent liquid film generator is set between the inversely spraying layer of the king-tower and king-tower radial direction spraying layer, the described second turbulent liquid film Generator is set between the second king-tower radial direction spraying layer and third king-tower radial direction spraying layer.
Using above-mentioned two layers turbulent liquid film generator (rotary wheel type liquid film generating device), subregion, tool are carried out to flue gas is administered Body, the Spiralism type structure of the turbulent flow liquid film generator makes flue gas flow equalizing, sufficiently as shown in fig. 6, can make to change flue gas flow direction With spray liquid hybrid reaction, generating device blade quantity is 10~15, and gradient is 20 °~40 °, and blade is by band ellipse head Stem be fixedly mounted.
The absorption tower is additionally provided with the demister system at the top of the absorption tower, and the demister system includes demister 2541 and demisting backwashing system 2542, in the present embodiment, the demister is by several pieces of high temperature resistants, fire retardant polyphenylene sulfide plate It constitutes, as Figure 7-8, the demisting backwashing system is equipped with nozzle and water supply pipe towards the water spray of the demister.
The demister includes the upper demister from top to bottom set gradually and lower demister, and the demisting backwashing system exists The lower demister upper and lower is equipped with nozzle, and the demisting backwashing system is only equipped with nozzle below the upper demister.
In the present embodiment, above-mentioned demister selects double-layer folded plate demister, is mounted at the top of absorption tower, to separate net cigarette The superfine dust of droplet and part of gas entrainment.However it will be appreciated that, tube bank also can be selected according to different operating conditions in demister Formula, ridge type etc., the outlet greater than 15 μm carry droplet≤50mg/Nm3(butt).And demister material is used with the resistance reinforced Polyphenylene sulfide plate is fired, high-velocity flow can be born and washed away, especially high-velocity flow caused by artificial flushing washes away.Mist eliminator flushing water System can rinse demister comprehensively, and demister is avoided to block.The spray range of adjacent nozzles should partly overlap, to ensure 100% Flushing effect.The pressure of flushing water should be monitored and be controlled, and the arrangement of flushing water main pipe should be able to be such that each nozzle transports substantially Row carries out moisturizing by clear water in reuse pool in average water pressure, demister back-purge system.
And upper demister and lower demister that above system is equipped with, can remove demister deposit, when device is run according to Given or transformable program, can both carry out auto-flushing, can also carry out artificial flushing.
The cooperation of above-mentioned pretreater and absorption tower, using calcium method method sulfur removal technology, desulfurization degree can reach 98% or more.Tower Interior spray mass transfer mode is organically combined using radial spray, inversely spraying and liquid film generator, and on the one hand radial atomizing spray exists Desulfurization is most of simultaneously to capture fine dust, enhances desulfurizing tower dust collection capacity;On the other hand, two are used simultaneously in same tower body Kind spray process significantly reduces serum recycle amount compared with single spray process.Atomizing spray, liquid film generating device and demisting Device cooperation carries out final dusting, removes fine particle and aerosol component in flue gas, dust removal efficiency is about 30%~50%.
In pretreatment and wet desulphurization, mostly important fresh absorption slurries are lime white, by following sprayed slurry The circulatory system provides.
The sprayed slurry circulatory system includes calcium-base absorbing agent warehouse 2810, the slaking apparatus being sequentially communicated by pipeline 2820, slurrying pond 2830 and circulatory pool 2840, the circulatory pool provide fresh absorption slurries to the pre- place by feeding pipe Tower and absorption tower are managed, and the pretreater and absorb the bottom of the tower recycling absorption slurries are connected to by recovery pipe.
The sprayed slurry circulatory system further includes sedimentation basin 2850, oxidation tank 2860 and oxidation fan 2870, the oxygen Change tank by circulatory pool and the sedimentation basin described in pipeline connection, the oxidation fan is equipped with aeration tube, and the aeration tube protrudes into In to the oxidation tank;The precipitating bottom of pond portion is equipped with filter press described in pipeline connection.
The pretreatment spray system, king-tower spray system are connected to the circulatory pool, the pretreater and absorption Tower bottom is equipped with recovery pipe and is connected to the circulatory pool.
In the sprayed slurry circulatory system, slurries raw material calcium-base absorbing agent is stored in about 70m3Vertical calcium-base absorbing agent warehouse Interior, calcium-base absorbing agent warehouse is opened and closed by gate valve, and star-shaped discharge valve controls blanking, in calcium-base absorbing agent warehouse calcium-base absorbing agent into Enter slaking apparatus to be digested, slaking apparatus carries out moisturizing by the clear liquid in reuse pool, and calcium-base absorbing agent reacts life with water At calcium hydroxide slurry enter pulping device carry out second level digestion, it is quenched, cooling, digestion with the slurrying residence time be about 4h. Agitating device is equipped in digestion and pulping device, purpose accelerates digestion rate, cooling, refinement slurries, the two agitator shaft speed About 40r/min.Obtaining density is about 1030~1100kg/m3Fresh absorption slurries.
Then, lime slurry (i.e. fresh absorption slurries) by water pump enters circulatory pool, circulatory pool conduct in pulping device The fresh intermediate vector for absorbing slurry storage, updating, recycling, passes through clear liquid, wet type wet static dedusting in reuse pool Device phegma carries out moisturizing, carries out spray liquid supplement by pretreater, the return pipe on absorption tower and slurrying pond pipeline, passes through Pond external oxidation device quantitatively extracts slurries in pond and carries out spray liquid update.
Detailed process are as follows: slurries are sprayed by slurries pumping to pretreater, each spraying layer in absorption tower in circulatory pool, Spray reaction after containing calcium bisulfite, the complete calcium hydroxide of unreacted using old spray liquid can by pretreater, The return pipe on absorption tower is back to circulatory pool and recycles, and the backwashing water in wet type wet cottrell is flowed back by return pipe Moisturizing is carried out to circulatory pool.Slurries are quantitatively pumped into oxidation unit by slurries and are updated in circulatory pool, avoid influencing slurries Quality.Agitating device is equipped in circulatory pool, it is therefore an objective to refine slurries, prevent deposition from blocking, agitator shaft speed is about 30r/ min。
Slurries into oxidation unit can carry out pond external oxidation, oxygen by Roots's oxidation fan and aeration tube in oxidation tank Change fan delivery 30m3/ h makes calcium bisulfite be oxidized to calcium sulfate indissoluble object by air blast, the slurries of main sulfur acid calcium into Enter to sedimentation basin and is separated by solid-liquid separation.
Sedimentation basin prevents the deposition blocking of bottom calcium sulfate slurries by agitating device, and agitator shaft speed is about 10r/min.It should Slurries recycle filtering equipment processing by slurries pumping to special calcium base in sedimentation basin.
The main chemical reactions formula of above-mentioned calcium base-gypsum wet sulfur removal technology is as follows:
SO2+H2O→H2SO3
Ca(OH)2+H2SO3→CaSO3+2H2O
CaSO3·1/2H2O+SO2+1/2H2O→Ca(HSO3)2
Ca(HSO3)2+Ca(OH)2→2Ca SO3·1/2H2O+H2O
CaSO3·1/2H2O+1/2O2+3/2H2O→CaSO4·2H2O (by-product)
Flue-gas temperature is about 40~50 DEG C at this time, and smoke moisture is about 90%~95%, dust concentration≤20g/m3
4, electrostatic precipitation.
Flue gas through wet desulphurization enters wet type wet cottrell by flue and carries out final dedusting.
The wet cottrell includes the wet electric current equalizer, wet electric field module set gradually with flue gas flow direction, The wet electric field module includes anode canister and cathode line, and the same pole span in the wet electric field module is 250-400mm;It is described Wet cottrell is additionally provided with wet electric back-purge system, and the nozzle of the wet electric back-purge system is placed in the anode canister and yin Above polar curve, while anode canister and cathode line can be rinsed.
Flue gas is flowed through electric current equalizer overly moist, and into wet electric field module, high-voltage electricity makes flue gas by cathode line electric discharge Middle flue dust is charged, is preferably 250mm~400mm with pole span, and charged flue dust orientation under Coulomb force effect moves to anode canister, anode canister Flue dust is collected as dust collecting electrode, setting back-purge system is sprayed above anode canister, so that the fixation of anode canister inner wall forms water Film washes away the flue dust containing heavy metal and aerosolized pollutant for being attracted to anode canister, and dust removal efficiency is about 60%, back-purge system Moisturizing is carried out by clear liquid in reuse pool, wet electricity backwash spray liquid enters circulatory pool as supplement water conservancy by return pipe and uses Not outlet.
After above-mentioned improvement, the flue gas the key technical indexes in the present embodiment is as shown in the table.
The key technical indexes of flue gas after table 4. is administered
Project name Parameter Remarks
Exhaust gas temperature ≈50
Survey oxygen content —— ≤ 13.0%
SO after purification2Concentration conversion value ㎎/Nm3 ≤80
Dust concentration reduced value after purification ㎎/Nm3 ≤50
Nickel and its compound ㎎/Nm3 ≤1
Copper and its compound ㎎/Nm3 ≤4
The waste gas treatment equipment further includes Anti-corrosive chimney, and the Anti-corrosive chimney is connected to the wet cottrell flue gas Outlet end, for discharging purifying smoke.Complete equipment processing is eventually passed through, the purifying smoke of stably reaching standard is arranged by Anti-corrosive chimney Into atmosphere.
Three, sewage treatment.
In the present embodiment, the waste water generated in fixed-end forces process and exhaust-gas treatment process not outlet passes through after collecting Waste water processes carry out harmless treatment, and recycle for exhaust-gas treatment for the moisturizing of auxiliary system, cooling and spray backwash Process, achievees the purpose that zero outlet of sewage and circulation is rinsed for equipment cleaning, place in daily production, mitigates service water Burden.
Sewage disposal device includes moisture trap 3100, dope pond 3342 and clean solution tank 3341, and including passing through pipe Primary sedimentation tank 3210 that road is sequentially communicated adjusts sour pond 3220, oxidation pond 3230, alkali tune pond 3240, coagulating basin 3250, flocculation basin 3260, mudpan 3270, sand filtering device 3310, carbon filter device 3320, cotton filter 3330 and reverse osmosis unit 3340, Be equipped with anti-seepage membrane in the reverse osmosis unit, the reverse osmosis unit be divided into dope chamber and clear liquid chamber, the dope chamber with The dope pond connection, the clear liquid chamber are connected to the clean solution tank;The blowoff line of the primary sedimentation tank and the filter press connects Logical, the dope pond is connected to by the dope spray system with the primary sedimentation tank.
In the present embodiment, the sewage disposal device further includes the automatic feeding system 3400 for automatic charging, such as Shown in Fig. 9, the automatic feeding system includes reagent reservoirs 3410, metering pump 3420 and discharging counterbalance valve 3430, the reagent Storage tank is sequentially communicated metering pump and discharging counterbalance valve by pipeline.
The automatic feeding system further includes pulsation damper 3440, protective loop and flow correction circuit, the pulsation Damper is set on the pipeline between the reagent reservoirs and the metering pump, the protective loop be connected to the metering pump and The reagent reservoirs, and the protective loop is equipped with pressure gauge 3450 and protection counterbalance valve 3460;The flow corrects circuit One end is connected to the reagent reservoirs, and the other end is connected to the pipeline between the metering pump and the reagent reservoirs.
The sour pond of the tune, oxidation pond, alkali tune pond, coagulating basin and flocculation basin are provided with the automatic feeding system.And it is described Primary sedimentation tank adjusts sour pond, oxidation pond, alkali tune pond, coagulating basin, flocculation basin, is equipped with for liquid in stirring pool in mudpan Stirring system.
Main pollutant is 85~95mg/L COD (amount for the reductive organic matter for needing to be oxidized) and dense in waste water Degree is heavy metals and the suspended matters such as 1~2mg/L copper.And the flue dust overwhelming majority in exhaust gas containing heavy metal can be reached by dust removal efficiency 98% sack cleaner capture, the heavy metal recycled into subsequent water are negligible.
In the present embodiment, main component is as shown in the table in industrial wastewater.
5. industrial wastewater main component of table
Note: ND expression is not detected.
1, just heavy.
The filters pressing water of filter press enters primary sedimentation tank after passing through moisture trap 3100, tentatively right using gravity sedimentation Sewage carries out solid-liquid separation treatment, and bottom slightly solubility particulate matter slurries can be evacuated to after filter press dehydration as solid waste original by water pump Material reaches the slightly solubility particulate matter purpose in removal sewage, and primary sedimentation tank, which is equipped with stirring system, prevents deposit agglomeration blocking, stirring Axis revolving speed is about 10r/min.
It should be understood that other industrial wastewaters and the sewage in other sources can also pass through equipment, the drainage pipeline of workshop Into primary sedimentation tank, handled in the sewage disposal device of the present embodiment.
2, acid is adjusted.
The upper layer sewage meeting overflow of primary sedimentation tank adjusts acid pond to add by automatic feeding system by water pump into sour pond is adjusted Add suitable sulfuric acid and ferrous sulfate, the pH value of sewage is made to be down to 3~4 from 10~12, and is the preparation of subsequent Fenton reagent Acidic environment and ferrous ion are provided, adjusting sour pond to be equipped with stirring system is uniformly mixed reagent with sewage, accelerate the reaction time, Agitator shaft speed is about 15r/min, and agitating shaft and agitating paddle material are strong corrosion resistant material glass reinforced plastic.
Automatic feeding system mainly includes reagent reservoirs, controls the metering pump of reagent additive amount, reduces for protection metering pump The pulsation damper of fluid impact, discharging counterbalance valve pressure open discharging when reaching 1mPa, guarantee pipeline inner pressure, protect back pressure Valve opens back the flowmeter that liquid constitutes protective loop and calibrated flow when loine pressure is excessive.
3, it aoxidizes.
It adjusts sour pond sewage meeting overflow or passes through water pump, into oxidation pond.Oxidation pond is added appropriate by automatic feeding system Hydrogen peroxide strong oxidizer, generating, there is the hydroxyl radical free radical of high reaction activity to carry out oxidative degradation organic pollutant.H2O2In Fe2+'s Hydroxyl radical free radical (OH) is generated under catalytic action, also known as Fenton reagent.
Since hydroxyl radical free radical (OH) has strong oxidizing property and electrophilic addition, can will give up in the acidic environment of pH value 3~4 Most of oxidation operations resolve into small-molecule substance in water, reach the organic pollutant COD reduced in oxidation water and constitute micro- The organic material component purpose of biology.
The excessively high generation and ferric hydroxide precipitate that can inhibit hydroxyl radical free radical (OH) of pH value, pH value is too low, and ferric iron is not It can be reduced into ferrous iron, catalysis reaction is caused to be obstructed, suitable pH value is 3~4.
Also, oxidation pond, which is equipped with stirring system, is uniformly mixed reagent with sewage, accelerates the reaction time, agitator shaft speed is about For 15r/min.
The reaction equation that above-mentioned Fenton reagent generates hydroxyl radical free radical is as follows:
Fe2++H++H2O2=Fe3++H2O+(·OH)
4, alkali tune.
The meeting overflow of oxidation pond sewage passes through water pump, into alkali tune pond.Added by automatic feeding system appropriate in alkali tune pond Sodium hydroxide solution makes pH value of sewage water rise to 7.5~8 from 3~4, prevents corrosion of the strong acidic environment to follow-up equipment, damage It is bad.
Hydroxyl and heavy metal compound copper sulphate etc. react simultaneously, generate the heavy metal precipitations objects such as Kocide SD. Alkali tune pond, which is equipped with stirring system, is uniformly mixed reagent with sewage, accelerates the reaction time, prevents sediment agglomeration blocking, agitating shaft Revolving speed is about 15r/min.
The reaction equation of above-mentioned hydroxyl and copper sulphate is as follows:
2NaOH+CuSO4=Cu (OH)2↓+NaSO4
5, coagulation.
Sewage meeting overflow in alkali tune pond passes through water pump, into coagulating basin.Coagulating basin is added appropriate by automatic feeding system Aluminium polychloride (abbreviation PAC).So that the colloid in sewage or sludge is quickly formed precipitating by it or it hydrolysate, is convenient for The particles sediment such as heavy metal in isolated sewage, the suitable PH range 7.5-8 of this reaction.Coagulating basin, which is equipped with stirring system, to be made to try Agent is uniformly mixed with sewage, accelerates the reaction time, prevents sediment agglomeration blocking, agitator shaft speed is about 15r/min.
6, it flocculates.
The meeting overflow of coagulating basin sewage passes through water pump, into flocculation basin.Flocculation basin is added appropriate by automatic feeding system Polyacrylamide (abbreviation PAM).After coagulant is added in raw water, it is sufficiently mixed with water body, most of colloidal impurity in water Stabilization is lost, steady colloidal solid is taken off and mutually collides, agglomerates in flocculation basin, eventually forms the wadding that can be removed with intermediate processing Body, the suitable PH range 7.5-8 of this reaction.Flocculation basin, which is equipped with stirring system, is uniformly mixed reagent with sewage, when accelerating reaction Between, sediment agglomeration blocking is prevented, agitator shaft speed is about 15r/min.
7, sludge settling.
The meeting overflow of flocculation basin sewage passes through water pump, into precipitating sludge pond.The sediments such as heavy metal in sewage are led to It crosses gravitational settling and carries out aqueous separation.The sludge of bottom deposit periodically passes through slurries pumping and carries out filter press concentration, pressure to filter press Filter the baking process that obtained filter cake enters in fixed-end forces, filtrate reenters the primary sedimentation tank at wastewater treatment center not outlet. Precipitating sludge pond, which is equipped with stirring system, prevents sediment agglomeration blocking, and agitator shaft speed is about 5r/min.
8, sand filtration.
Upper layer sewage meeting overflow in precipitating sludge pond passes through water pump, is filtered processing into sand filtering device.
9, carbon is filtered.
Sewage after dirty sand filtration enters carbon filter device and is filtered processing.
10, cotton core filters.
Sewage after carbon is filtered enters cotton core filter device and is filtered processing, this cotton filter is physically to filter, Using stainless steel casing, for PP cotton as filtration core, effect is that filtering large particle protects subsequent reverse osmosis unit.
Depth-type filtration is carried out above by sand filtration, carbon filter and cotton core filtering, 1 degree of turbidity or more of fine particles is removed, prevents Only fail to completely remove in pretreatment or newly generated suspended particulate enters counter-infiltration system, protects high-pressure pump and reverse osmosis membrane.
11, reverse osmosis.
Enter reverse osmosis unit through the filtered sewage of cotton core, processing is filtered with reverse osmosis membrane.
Filtrate by depth-type filtration enters RO water treatment system by high-pressure pump, and filtrate passes through under the action of high pressure Reverse osmosis membrane, solvent are permeated from high concentration to low concentration, and reverse osmosis membrane can retain the substance greater than 0.0001 micron, to make to filter Liquid achievees the purpose that separation, purification, concentration.
Reverse osmosis water treatment system can remove organic matter, dissolubility salt~98% and colloid in filtrate.By anti- Film process is permeated, clear liquid concentration of suspension about 4mg/L, COD concentration about 15mg/L, pH value are about 7.5~8, concentration of suspension drops Be down to 7~8mg/L, hexavalent chromium concentration~0.004mg/L, weight chromium concn be down to~0.004mg/L, copper concentration be down to~ 0.001mg/L, zinc concentration be down to~and 0.07mg/L, mercury concentration is down to~and 0.02mg/L, arsenic concentration be down to~0.1mg/L, and it is every Content of beary metal can qualified discharge.
The clear liquid enters reuse pool qualified discharge, for equipment cleaning and exhaust-gas treatment fresh absorption slurries moisturizing, Back-purge system, such as the anode canister and cathode of the demister back-purge system on the absorption tower, the wet cottrell The slaking apparatus and circulatory pool of the back-purge system of line, the sprayed slurry circulatory system.And the dope of reverse osmosis membrane retention then passes through Water pump is evacuated to dope pond, removes heavy pond processing not outlet for being back to after multistage surface air cooler chilling spray.
Four, MaterialBalance Computation.
The various materials of the closed-loop process method for hazardous waste sludge of the present embodiment and the investment and output of element are calculated, As a result as shown in the table.
The input-output equilibrium table of 6. material of table
7. element sulphur balance sheet of table
8. copper balance sheet of table
9. nickel element balance sheet of table
Above-mentioned material balance the result shows that, the equipment and treatment process of above-described embodiment can be realized the three wastes of industrial sludge Comprehensive treatment.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (10)

1. a kind of cupric industrial sludge comprehensive administration of three wastes system characterized by comprising
Fixed-end forces equipment, including filter press, drying component, brickmaking machine and smelting furnace, the filter press, drying component, brickmaking Machine and smelting furnace are set gradually by process flow;
Waste gas treatment equipment, including multistage surface air cooler, the first sack cleaner and the second sack cleaner, and including passing through pipe Pretreater, absorption tower and the wet cottrell that road is sequentially communicated, first sack cleaner and the second bag-type dusting Device is connected to the pretreater, and the gas exhaust piping of the drying component connects the first sack cleaner, the row of the smelting furnace Air pipe is connected to the second sack cleaner by the multistage surface air cooler;
Sewage disposal device, including dope pond and clean solution tank, and include the primary sedimentation tank being sequentially communicated by pipeline, adjust sour pond, Oxidation pond, alkali tune pond, coagulating basin, flocculation basin, mudpan, sand filtering device, carbon filter device, cotton filter and reverse osmosis dress It sets, anti-seepage membrane is equipped in the reverse osmosis unit, the reverse osmosis unit is divided into dope chamber and clear liquid chamber, the dope chamber It is connected to the dope pond, the clear liquid chamber is connected to the clean solution tank;The blowoff line of the primary sedimentation tank and the filter press Connection, the dope pond is connected to the primary sedimentation tank.
2. cupric industrial sludge comprehensive administration of three wastes system according to claim 1, which is characterized in that the sludge settling Pond is equipped with sludge reflux pipeline with primary sedimentation tank bottom and is connected to the filter press;
The reuse pool passes through absorption tower and the wet cottrell described in pipeline connection;
The waste gas treatment equipment further includes the sprayed slurry circulatory system, the sprayed slurry circulatory system include by pipeline according to Calcium-base absorbing agent warehouse, slaking apparatus, slurrying pond and the circulatory pool of secondary connection, the circulatory pool is provided fresh by feeding pipe Slurries are absorbed to the pretreater and absorption tower, and the pretreater and absorb the bottom of the tower recycling are connected to by recovery pipe Absorb slurries;
The sprayed slurry circulatory system further includes sedimentation basin, oxidation tank, calcium base recycling filtering equipment and oxidation fan, the oxygen Change tank by circulatory pool and the sedimentation basin described in pipeline connection, the oxidation fan is equipped with aeration tube, and the aeration tube protrudes into In to the oxidation tank;The precipitating bottom of pond portion is equipped with calcium base described in pipeline connection and recycles filtering equipment;
The reuse pool is respectively communicated with the slaking apparatus, circulatory pool by pipeline.
3. cupric industrial sludge comprehensive administration of three wastes system according to claim 1, which is characterized in that the fixed-end forces Equipment further includes automatic feeding system, and the automatic feeding system includes packaged type Material collecting box for harvesting, first mechanical arm, the second machinery Arm, third mechanical arm, the 4th mechanical arm, the 5th mechanical arm, the 6th mechanical arm, the first conveyer belt, the second conveyer belt, third transmission Band;The filter press filter cake outlet end is corresponding with the initial position of the Material collecting box for harvesting;First conveyer belt one end corresponds to The initial position of Material collecting box for harvesting, the other end correspond to the drying component, and the first mechanical arm is set to the initial of the Material collecting box for harvesting Between position and first conveyer belt, for Material collecting box for harvesting crawl to be placed in first conveyer belt, second machine Tool arm is set between first conveyer belt and the drying component, for Material collecting box for harvesting crawl to be placed in the drying component In;Second conveyer belt one end corresponds to the drying component, and the other end corresponds to the brickmaking machine, the third mechanical arm Between the drying component and second transmission belt, for Material collecting box for harvesting crawl to be placed in second conveyer belt On, the 4th mechanical arm is set between second conveyer belt and the brickmaking machine, for grabbing material in the Material collecting box for harvesting It takes and is poured into the brickmaking machine;Third conveyer belt one end corresponds to the brickmaking machine, and the other end corresponds to the melting Furnace, the 5th mechanical arm are set between the brickmaking machine and the third conveyer belt, are gathered materials for passing through material after brickmaking Case crawl is placed on the third conveyer belt, and the 6th mechanical arm is set between the third conveyer belt and the smelting furnace, For material crawl in the Material collecting box for harvesting to be poured into the smelting furnace;
The drying component includes drying room, takes off material mechanical arm, warm and humid probe, infrared sensor and PLC control system;The baking Dry chamber is divided into the bottom for accommodating fuel and the upper layer for accommodating material drying;It is described it is warm and humid probe in the vertical direction between Every be set to the upper layer, warm and humid pop one's head in is also provided at room door, air outlet and the smoke outlet of the drying room;The PLC Control system is electrically connected with the material mechanical arm of taking off and controls this and take off material mechanical arm;The warm and humid probe and PLC control system System is electrically connected and sends a signal to the PLC control system;The infrared sensor is set to the drying room predetermined altitude and passes The number of the delivering letters extremely PLC control system;
The fixed-end forces equipment is additionally provided with dope spray system, and the dope spray system is set to the slag to the smelting furnace Chilling spray, the primary sedimentation tank are connected to by the dope spray system with the primary sedimentation tank.
4. cupric industrial sludge comprehensive administration of three wastes system according to claim 1, which is characterized in that the sewage treatment Equipment further includes the automatic feeding system for automatic charging, and the automatic feeding system includes reagent reservoirs, metering pump and goes out Expect that counterbalance valve, the reagent reservoirs are sequentially communicated metering pump and discharging counterbalance valve by pipeline;
The automatic feeding system further includes that pulsation damper, protective loop and flow correction circuit, the pulsation damper are set It is placed on the pipeline between the reagent reservoirs and the metering pump, the protective loop is connected to the metering pump and the reagent Storage tank, and the protective loop is equipped with pressure gauge and protection counterbalance valve;Flow correction circuit one end is connected to the reagent Storage tank, the other end are connected to the pipeline between the metering pump and the reagent reservoirs;
The sour pond of the tune, oxidation pond, alkali tune pond, coagulating basin and flocculation basin are provided with the automatic feeding system;
The primary sedimentation tank adjusts sour pond, oxidation pond, alkali tune pond, coagulating basin, flocculation basin, is equipped with for stirring in mudpan The stirring system of liquid in pond.
5. cupric industrial sludge comprehensive administration of three wastes system according to claim 1, which is characterized in that the exhaust-gas treatment It further include dual firing chamber in equipment, the dual firing chamber is set between the drying component gas exhaust piping and the first sack cleaner, institute It states dual firing chamber and is additionally provided with fuel spray system for spraying fuel and for combustion-supporting blower system;
It further include waste heat boiler and heating heat exchange equipment in the waste gas treatment equipment, the waste heat boiler and heating heat exchange are set It is standby to be sequentially communicated between the dual firing chamber and first sack cleaner, and the flue of the waste heat boiler with it is described Drying room connection;
It further include for collecting the heavy grey cylinder of the drying of the drying component dust and smelting furnace dust in the waste gas treatment equipment The heavy grey cylinder of melting, the heavy grey cylinder of drying is set on the pipeline between the drying component and the dual firing chamber, the melting Heavy ash cylinder is set on the pipeline between the smelting furnace and the multistage surface air cooler.
6. cupric industrial sludge comprehensive administration of three wastes system according to claim 1, which is characterized in that the pretreater It is tower body made of glass reinforced plastic with the absorption tower;
The pretreater is equipped with pretreatment spray system, and the pretreatment spray system is including the inversely spraying layer of pretreatment and in advance Radial spraying layer is handled, the inversely spraying layer of pretreatment is set to below the radial spraying layer of the pretreatment, the pretreatment The nozzle of inversely spraying layer is parallel to the pre- place towards the pretreater bottom, the nozzle for pre-processing radial spraying layer Manage the cross-wise direction of tower;
The pretreatment spray system is equipped with the radial spraying layer of three layers of pretreatment and one layer of inversely spraying layer of pretreatment;
The absorption tower is equipped with king-tower spray system, and the king-tower spray system includes that the inversely spraying layer of king-tower and king-tower radially spray Drenching layer, the inversely spraying layer of king-tower are set to below the king-tower radial direction spraying layer, the nozzle of the inversely spraying layer of king-tower Towards the absorb the bottom of the tower, the nozzle of the king-tower radial direction spraying layer is parallel to the cross-wise direction on the absorption tower;
The pretreatment spray system, king-tower spray system are connected to the circulatory pool, the pretreater and absorption tower bottom Portion is equipped with recovery pipe and is connected to the circulatory pool;
The king-tower spray system is from top to bottom successively arranged the first king-tower radial direction spraying layer, the second king-tower radial direction spraying layer, Three king-tower radial direction spraying layers, the 4th king-tower radial direction spraying layer and one layer of inversely spraying layer of king-tower;
The absorption tower is additionally provided with the first turbulent liquid film generator and the second turbulent liquid film generator, the described first turbulent liquid film hair Raw device is set between the inversely spraying layer of the king-tower and king-tower radial direction spraying layer, and the described second turbulent liquid film generator is set to Between second king-tower radial direction spraying layer and third king-tower radial direction spraying layer;
The absorption tower is additionally provided with the demister system at the top of the absorption tower, and the demister system includes demister and demisting Backwashing system, the demisting backwashing system are equipped with nozzle and water supply pipe towards the water spray of the demister.
7. cupric industrial sludge comprehensive administration of three wastes system according to claim 1, it is characterised in that the demister packet The upper demister from top to bottom set gradually and lower demister are included, the demisting backwashing system is in the lower demister upper and lower It is equipped with nozzle, the demisting backwashing system is only equipped with nozzle below the upper demister;
The wet cottrell includes the wet electric current equalizer, wet electric field module set gradually with flue gas flow direction, described Wet electric field module includes anode canister and cathode line, and the same pole span in the wet electric field module is 250-400mm;The wet type Electrostatic precipitator is additionally provided with wet electric back-purge system, and the nozzle of the wet electric back-purge system is placed in the anode canister and cathode line Top;
The waste gas treatment equipment further includes Anti-corrosive chimney, and the Anti-corrosive chimney is connected to the wet cottrell exhanst gas outlet End, for discharging purifying smoke.
8. a kind of closed-loop process method for hazardous waste sludge, which is characterized in that contain using claim 1-7 is described in any item Copper Processing Industry sludge comprehensive administration of three wastes system, this method includes below scheme:
Fixed-end forces process:
Filters pressing: hazardous waste sludge to be processed is carried out to filters pressing in filter press and removes moisture removal, obtains filter cake;
Drying: being added carbon dust in filter cake and quick lime is uniformly mixed, and dries in drying component;
Brickmaking: the siccative of drying brickmaking in brickmaking machine;
Melting: the brick through brickmaking is poured into smelting furnace and carries out melting, obtains melting product;
Exhaust-gas treatment process:
Bag-type dusting: the exhaust gas that the baking step generates is sent to the first sack cleaner dedusting, the melting is walked Suddenly the exhaust gas generated is sent to the second sack cleaner dedusting after multistage surface air cooler is cooling;
Pretreatment: pretreater will be transported to by the first sack cleaner and the flue gas of the second sack cleaner dedusting, with lime Slurry handles flue gas as fresh absorption slurries;
Wet desulphurization: pretreated flue gas transports to absorption tower, and flue gas is handled using lime white as fresh absorption slurries;
Electrostatic precipitation: the flue gas through wet desulphurization transports to wet cottrell, and it is net that flue gas is carried out by way of electrostatic precipitation Change, then discharges;
Waste water processes:
Just heavy: the sewage of waste water and other sources that the filters pressing step is generated introduces the primary sedimentation tank, utilizes gravity sedimentation Solid-liquid separation treatment is carried out to sewage;
Adjust acid: the upper layer sewage after primary sedimentation tank is separated by solid-liquid separation enters the sour pond of tune, adds sulfuric acid and ferrous sulfate, is subsequent oxidation Process provides acidic environment and ferrous ion;
Oxidation: the sewage after adjusting acid enters oxidation pond, adds hydrogen peroxide, produces hydrogen peroxide under the catalysis of ferrous ion Hydroxyl radical free radical, so that dropping oxidation operation in sewage in acid condition is decomposed into small-molecule substance;
Alkali tune: oxidized sewage enters alkali tune pond, adds sodium hydroxide, adjusts pH value of sewage water to neutral or alkalescent, and Generation heavy metal precipitation object is reacted with the metallic compound that rushes in sewage;
Coagulation: the sewage after alkali tune enters coagulating basin, adds aluminium polychloride, and the colloid in sewage is made to form precipitating;
Flocculation: the sewage after coagulation enters flocculation basin, adds polyacrylamide, so that the colloid in sewage is lost stabilization, mutually Collision, cohesion form precipitating;
Sludge settling: the sewage after flocculating enters mudpan, is separated by solid-liquid separation by gravitational settling to sewage;
Sand filtration: the sewage after sludge settling enters husky filter device filtering;
Carbon filter: the sewage after dirty sand filtration enters carbon filter device filtering;
Cotton core filtering: the sewage after carbon is filtered enters the filtering of cotton core filter device;
It is reverse osmosis: to enter reverse osmosis unit through the filtered sewage of cotton core, be filtered with reverse osmosis membrane, obtain to be back to just The dope of heavy step process and can reuse clear liquid, complete sewage treatment.
9. the closed-loop process method according to claim 8 for hazardous waste sludge, which is characterized in that use claim 2 The processing equipment, the settled sludge that the just heavy step generates, which is extracted to the filters pressing step, to be handled;
The settled sludge that the sludge settling step generates, which is extracted to the filters pressing step, to be handled;
The clear liquid generated in the reverse osmosis step is delivered to the wet desulphurization and electrostatic precipitation step uses, described reverse osmosis The dope generated in step is delivered in the bag-type dusting step is back to just heavy step for the dope spray system after Rapid processing;
The exhaust-gas treatment process further includes sprayed slurry circulating process, the sprayed slurry circulating process the following steps are included:
Protopepsia: calcium-base absorbing agent is reacted in slaking apparatus with water and is digested;
Second level digestion: making the slurries of above-mentioned protopepsia enter the slurrying pond, carry out second level digestion, obtains fresh absorption slurry Liquid;
Recycle: fresh absorption slurries enter circulatory pool storage, and enter the pretreater and absorption tower spray by pipeline It drenches, the absorption slurry reflux after spray to circulatory pool;
In the exhaust-gas treatment process, the fresh density for absorbing slurries is 1030-1100kg/m3, the protopepsia and two The time of grade digestion is 3-5h;
The sprayed slurry circulating process includes going back following steps:
Slurries processing: the fresh absorption slurries extracted in the circulatory pool enter oxidation tank, and pond external oxidation is carried out in oxidation tank, Make calcium sulfite oxidation calcium sulfate indissoluble object by oxidation fan aeration, the aeration air quantity of the oxidation fan is 25-35m3/ H, then the slurries after aeration reaction are imported into sedimentation basin precipitating and are separated by solid-liquid separation, obtained solid sludge is extracted to the filters pressing and is walked Suddenly it is handled;
The clear liquid generated in the reverse osmosis step is delivered to the protopepsia and recycles step moisturizing use.
10. the closed-loop process method according to claim 8 for hazardous waste sludge, which is characterized in that use claim 3 The processing equipment, in the fixed-end forces process, the filter cake is placed in the Material collecting box for harvesting, by automatic feeding system according to It is secondary to the drying component, brickmaking machine and smelting furnace feeding and to feed intake;
In the baking step, temperature is carried out to drying room using warm and humid probe and water capacity detects, was carried out every 10-20 minutes One group of data sampling, detection probe feed back to PLC control system by electric signal, monitor the drying degree in baking room;Drying After carrying out 2-3 hours, carries out taking off material processing using the steel rake structure of manipulator by taking off material mechanical arm, keep siccative heated more It is even, while filter cake is added by second mechanical arm;It carries out within 20-30 minutes once taking off material and charging, charging is until drying room reaches Maximum capacity, siccative level height reach infrared sensor setting height, stop charging.
CN201910407233.6A 2019-05-15 2019-05-15 Cupric industrial sludge comprehensive administration of three wastes system and method Pending CN110052106A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110585866A (en) * 2019-10-10 2019-12-20 江门市同力环保科技有限公司 Desulfurization and dust removal method for copper-containing industrial sludge smelting flue gas
CN110804699A (en) * 2019-11-11 2020-02-18 宁波双能环保科技有限公司 Hazardous waste recycling production line
CN111689510A (en) * 2020-06-10 2020-09-22 福建通海镍业科技有限公司 Method for preparing industrial gypsum from flue gas of roasting furnace
TWI729883B (en) * 2020-07-16 2021-06-01 中石化綠能科技股份有限公司 Purification system for heavy metal and chlorine-containing contaminated soil

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110585866A (en) * 2019-10-10 2019-12-20 江门市同力环保科技有限公司 Desulfurization and dust removal method for copper-containing industrial sludge smelting flue gas
CN110804699A (en) * 2019-11-11 2020-02-18 宁波双能环保科技有限公司 Hazardous waste recycling production line
CN111689510A (en) * 2020-06-10 2020-09-22 福建通海镍业科技有限公司 Method for preparing industrial gypsum from flue gas of roasting furnace
TWI729883B (en) * 2020-07-16 2021-06-01 中石化綠能科技股份有限公司 Purification system for heavy metal and chlorine-containing contaminated soil

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