CN104152206A - Recycling treatment method of fly ash, chromium slag and electroplating sludge dangerous waste - Google Patents
Recycling treatment method of fly ash, chromium slag and electroplating sludge dangerous waste Download PDFInfo
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- CN104152206A CN104152206A CN201410423517.1A CN201410423517A CN104152206A CN 104152206 A CN104152206 A CN 104152206A CN 201410423517 A CN201410423517 A CN 201410423517A CN 104152206 A CN104152206 A CN 104152206A
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- pelletizing
- additive
- chromium slag
- electroplating sludge
- pellets
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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Abstract
The invention relates to a recycling treatment method of a fly ash, a chromium slag and an electroplating sludge dangerous waste. The method includes following steps: adding an additive, which consists of pulverized coal, or carbon black, and calcium oxide, to dangerous waste with mixing uniformly; feeding a material into a primary pelletizing device with addition of an additive consisting of iron oxide red, bentonite, polyacrylamide, calcium sulfate and sodium carbonate with mixing uniformly and carrying out a primary pelletizing process; sieving pellets, wherein the pellets with granularities being larger than 5 mm are subjected to a secondary pelletizing process and the pellets with the granularities being smaller than 5 mm are fed back to the primary pelletizing device for continuous pelletization; feeding the pellets to the second pelletizing device with addition of calcium oxide and carrying out the second pelletizing process according to a technological process; coating surfaces of the pellets with a layer of an additive; feeding the pellets which are subjected to the second pelletizing process into a cement kiln or a sintering device for carrying out a roasting process. The method is clean and effective, can allow organic substances to be decomposed fully, can solidify heavy metals, is free of residual ash slag and secondary pollution and is energy-saving and environmental-protective. Combustibles in the waste release heat when being burnt so that original fuel is saved. Carbon dioxide generated in combustion is reduced and the greenhouse effect is reduced.
Description
Technical field
The present invention relates to a kind of innoxious, recycling processing method of Hazardous wastes, be specifically related to flying dust, chromium slag, electroplating sludge Hazardous wastes recycling processing method.
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Background technology
In order to properly settle domestic waste problem, waste incineration and generating electricity presents good growth momentum in the whole nation, but () such as lead, cadmium, mercury is with dioxin, and the content of heavy metal lead (Pb) is 738-79500mg/kg in residue-flying dust that waste incineration produces, to contain heavy metal; The content of cadmium (Cd) is 4-573mg/kg; Dioxin content, at 1000-50000ng-TEQ/kg, can not meet environmental requirement, hypertoxic organic pollutant dioxin, and its toxicity is the more than 1000 times of potassium cyanide, also can cause cancer and deformity even if take the photograph for a long time people in the situation that of denier.Be not good at the living environment to people to constitute a serious threat if processed.China's consumer waste incineration pollutes control criterion (GB18485-2001) and explicitly points out, and incineration of refuse flyash belongs to Hazardous wastes, and " national Hazardous Waste List " classifies incineration of refuse flyash as HW18 Hazardous wastes, arbitrarily landfill disposal.Flying dust must be processed according to the standard of Hazardous wastes, and how effectively processing and regeneration are undoubtedly important topic urgently to be resolved hurrily.
Chromic salts is widely used in the every field of national economy, and the great majority expendable industrial chemicals that is absolutely necessary.1 ton of chromic salts product of every production, can produce 2.5～3 tons of chromium slags.In chromium slag because containing 1～2% the yellow ultramarine with carcinogenic nature and 0.5～1% water-soluble hypertoxic Cr
6+and become poisonous Hazardous wastes.In chromium slag, contain magnesium, calcium, silicon, iron, aluminium and responseless chromium sesquioxide, also contain water-soluble chromic acid sodium (Na
2cr
2o
7), acid-soluble yellow ultramarine (Ca
2crO
4) etc.Objectionable constituent in chromium slag are mainly the hexavalent chromiums such as water-soluble chromic acid sodium, acid-soluble yellow ultramarine.First sexavalent chrome and its loss are spread and are formed the pollution hazard to ecotope, are secondly the strong basicity harm of chromium slag.
When chromium slag is stored up in the open, a large amount of Cr after long-term rain shower
6+ooze, run off, infiltrate earth's surface with rainwater is molten, thereby polluted underground water also pollutes rivers, lake, and then harm farmland, aquatic products and HUMAN HEALTH.Cr
6+very large to the murder by poisoning of HUMAN HEALTH, its compound has very strong oxygenizement, and digestive tube, respiratory tract, skin and mucous membrane to human body have harm, seriously may cause lung cancer.Cr in chromium slag
6+at high temperature can progressively be reduced to Cr
3+, and toxicity is declined so that disappear.In sintering process, the normal temps of zone of combustion is generally at 1150 ~ 1350 DEG C, and has local reducing atmosphere, possesses kinetics and the thermodynamic condition of chromium residue detoxifying completely.By sintering process the Cr in chromium slag
6+be reduced into Cr
3+, substantially remove the harm of chromium slag to environment and human body, there is significant environmental benefit and social benefit.
Electroplating industry is basic industry important in national economy, is also large one of the industry of polluting in the current whole world three.The electroplating sludge that electroplating industry produces, is the throw out taking heavy metal hydroxides such as copper, nickel, chromium as main component producing in electroplating wastewater processing process, complicated component.Investigation is found: main containing heavy metal compound and solubility salts thereof such as chromium, iron, nickel, copper, zinc in electroplating sludge; Electroplating sludge enrichment Cu in electroplating wastewater, Ni, Cr, the harmful heavy metals such as Zn, are listed in state key Hazardous wastes.Although China's electroplating industry is rapidly developed, but still there is scattered distribution, small scale, equipment is backward, level of management are low, causes the large and complicated component of sludge creation amount.Most of electroplating sludge still just carries out simple landfill, even arbitrarily stacks, and not only environment is caused to severe contamination, is also the waste to heavy metal resources.
In addition, leather industry also produces more leather-making mud, the main component of leather-making mud is: the muriate of protein, rich mixture, chromium, sodium etc., sulfide, vitriol and a small amount of heavy metallic salt etc., also contain the trace elements such as Al, Mn, Pb, Ti, Fe, chromium, calcium, sodium, sulfide, vitriol and muriatic content are higher.Leather-making mud also can be considered as, containing chromium refuse, also belonging to Hazardous wastes.Because leather-making mud has certain calorific value, and tool spontaneous combustion ability, so can adopt the way processing of burning, so also can thoroughly eliminate wherein a large amount of bacteriums, virus, parasitic ovum etc.After leather-making mud burns, the recyclable chromium recycling of remaining ash content, remaining ash content can be used as fertilizer.But owing to containing trivalent chromium in leather-making mud, in high temperature (1l00 DEG C) burning, and have in the situation of alkaline matter existence, trivalent chromium will become sexavalent chrome, for ash processing makes troubles.The secondary pollution causing except sexavalent chrome need to solve, also must solve excessive dust, sulfurous gas and oxynitrides in stack gas simultaneously.
How to Hazardous wastess such as flying dust, chromium slag, electroplating sludges (leather-making mud) owing to having that toxicity is large, inflammable and explosive, corrodibility is strong and the hazard property such as infectivity is strong, can cause persistence to pollute and be difficult to soil, atmosphere, water body eliminates, how it being carried out to innoxious, recycling treatment, is a problem in the urgent need to address.
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Summary of the invention
For the problems referred to above of prior art existence, the object of this invention is to provide flying dust, chromium slag, the electroplating sludge Hazardous wastes recycling processing method of a kind of energy-conserving and environment-protective, recycling.
For achieving the above object, the present invention adopts following technical scheme: 1, flying dust, chromium slag, electroplating sludge Hazardous wastes recycling processing method, is characterized in that comprising the steps:
1) collect flying dust, chromium slag, electroplating sludge, flying dust, chromium slag, electroplating sludge, with the ratio that quality is greater than 0% separately, are prepared burden;
2) in batching, add additive A, mix;
Described additive A is mixture, is made up of coal dust or carbon black and unslaked lime, and the mass percent of coal dust or carbon black is 70-85%, and Lime Quality per-cent is 15-30%; The mass percent that additive A accounts for whole batching is 15%-20%;
Add the material after additive, if moisture is excessively wet, need carry out drying and processing, make material moisture be less than 7%; As excessively thick in granularity, need carry out levigate processing, make granularity be less than 200 its quality of object material and be greater than 70%;
3) enter in a palletizing device, and add additive B; After mixing, according to technical process, carry out pelletizing one time;
Additive B is a kind of compound binding agent, is powdery solid, and its quality formula is:
Component A: 0.5-2.0 part;
Red iron oxide: be greater than 0-2.0 part;
Wilkinite: be greater than 0-3.0 part;
Described component A is made up of polyacrylamide, calcium sulfate, sodium carbonate, and its quality proportioning is:
Polyacrylamide 3-5 part;
Calcium sulfate 7-10 part;
Sodium carbonate is greater than 0-10 part;
The mass percent that additive B accounts for whole batching is 1-5%;
The pelletizing that pelletizing obtains sieves, and granularity is greater than 5mm and carries out secondary pelletizing, is less than 5mm and returns to a balling equipment and continue pelletizing;
4) after a pelletizing, granularity is greater than the pelletizing of 5mm, enters in secondary palletizing device, and adds addition of C, according to technical process, carries out secondary pelletizing; At pelletizing surface parcel one deck additive;
Addition of C is unslaked lime, and its mass percent that accounts for whole batching is 1-3%;
5) pelletizing that secondary pelletizing obtains, enters cement kiln or agglomerating plant and carries out roasting
Further feature: Hazardous wastes also comprises leather-making mud, forms the mixture of flying dust, chromium slag, electroplating sludge and four kinds of formations of leather-making mud.
With respect to prior art, method tool of the present invention has the following advantages:
(1) effectively clean: thoroughly decomposing organic matter, curing heavy metal, without residue lime-ash, non-secondary pollution.
(2) energy-conserving and environment-protective: the heat release when combustiblematerials in refuse burns, save crude fuel, reduce the CO that burning produces
2, reduce Greenhouse effect.And be expected to realize the integrated of manufacture of cement and Hazardous wastes, Disposal of Domestic, make Cement industry become the environment-protecting industrial of 21st century maximum.
(3) economical and practical: compared with newly-built special incineration plant, utilize the investment of cement kiln burning disposal little, only needing increases pre-processing device, can save a large amount of fund inputs.Utilize new dry process rotary kiln burning disposal domestic refuse and danger wastes, both can solve part of fuel source, again can curing heavy metal ion, thus the effective processing that realizes waste and heavy metal ion is rationally curing, has great environment protection significance.
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Brief description of the drawings
fig. 1 is treatment process process flow sheet of the present invention.
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Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Referring to Fig. 1, flying dust of the present invention, chromium slag, electroplating sludge Hazardous wastes recycling processing method, it comprises the steps:
1, collect flying dust, chromium slag, electroplating sludge, flying dust, chromium slag, electroplating sludge, with the ratio that quality is greater than 0% separately, are prepared burden;
2, in batching, add additive A, mix;
Described additive A is mixture, main plays reduction, inhales chlorine, katalysis, is made up of coal dust or carbon black and unslaked lime, and the mass percent of coal dust or carbon black is 70-85%, and Lime Quality per-cent is 15-30%; The mass percent that additive A accounts for whole batching is 15%-20%; Unslaked lime moisture do not consider, coal dust or carbon black moisture general requirement are less than 7%, as moisture is excessively wet, dries, and dries and is less than 7% to moisture;
Add the material after additive, if moisture is excessively wet, need carries out drying and processing, as enter drying machine drying or heating, drying, make material moisture be less than 7%; As excessively thick in raw meal particle size, need carry out levigate processing, as enter roller mill and carry out levigately, make granularity be less than 200 its quality of object material and be greater than 70%;
3, enter in a palletizing device, and add additive B; After mixing, according to technical process, carry out pelletizing one time;
Poor because of the balling-up of pelletizing material, add this binding agent to be conducive to material balling-up, and can improve green ball strength.Additive B is a kind of pelletizing adhesive special, is a kind of compound binding agent, is powdery solid, is made up of inorganics and organism, and inorganics is wilkinite, calcium sulfate, sodium carbonate; Organism is polyacrylamide.This binding agent quality formula is:
Component A: 0.5-2.0 part;
Red iron oxide: be greater than 0-2.0 part;
Wilkinite: be greater than 0-3.0 part; Component A mixes with red iron oxide and wilkinite;
Component A is made up of polyacrylamide, calcium sulfate, sodium carbonate, and its proportioning is:
Polyacrylamide 3-5 part;
Calcium sulfate 7-10 part;
Sodium carbonate is greater than 0-10 part;
The mass percent that additive B accounts for whole batching is 1-5%, specifically according to the balling-up of material and the requirement of strength to green-ball, determines its best additional proportion.In additive B, be less than 200 orders and be greater than 90%, its general 5-8% of moisture, does not dry separately, adds pelletizing material to mix.
The pelletizing that pelletizing obtains sieves, and granularity is greater than 5mm and carries out secondary pelletizing, is less than 5mm and returns to a balling equipment and continue pelletizing, i.e. pelletizing together with waste material;
4, after a pelletizing, granularity is greater than the pelletizing of 5mm, enters in secondary palletizing device, and adds addition of C, according to technical process, carries out secondary pelletizing; At pelletizing surface parcel one deck additive;
Addition of C is one matter, is unslaked lime, mainly plays desulfurization, firmly effect, and its mass percent that accounts for whole batching is 1-3%, and it is white solid powder, is less than 200 orders and is greater than 80%, does not consider moisture, does not dry, and directly adds balling disk (-sc) to use.
5, the pelletizing that secondary pelletizing obtains, enters cement kiln or agglomerating plant and carries out roasting;
After a balling-up, sieve, be greater than 5mm and carry out secondary pelletizing, be less than 5mm and return to balling equipment pelletizing together with waste material, after secondary pelletizing, sieve again, be less than 8mm and return to secondary pelletizing system, then carry out pelletizing, be greater than that 8mm enters cement kiln as finished product or agglomerating plant carries out roasting.The object of secondary pelletizing is to wrap up one deck additive in the bead outside of once causing again, and makes refuse tightly be wrapped in the inside, prevents in roasting process, and low melting point metal gasification is overflowed.Balling equipment can be that balling disc can be also drum pelletizer, and balling disc is better than drum pelletizer.
Hazardous wastes also comprises leather-making mud, forms the mixture of flying dust, chromium slag, electroplating sludge and four kinds of formations of leather-making mud, and the ratio mixing that is greater than 0% according to quality separately, adopts aforesaid treatment step, carries out resource utilization, harmless treatment; Can process flying dust, chromium slag, electroplating sludge and four kinds of Hazardous wastess of leather-making mud.
The present invention adopts the feature of cement mill cooperative disposal mud
(1) flame temperature can reach 1600 DEG C in cement kiln, in rotary kiln in temperature generally between 1350～1650 DEG C, even higher, combustion gases residence time when higher than 800 DEG C is greater than 8s, during higher than 1100 DEG C, the residence time is greater than 3s.In dry-process rotory kiln, in the time of 1400～1600 DEG C, the total residence time of combustion gases is about 20s to gas at 6～10s the residence time, and organism almost all decomposes.Waste gas Zhong dioxin, the discharge of furans is far below the Incineration of waste 2000/76/EC of European Union instruction <0.1ngTEQ/m
3standard, most <0.02ngTEQ/m
3.In the process of burning clinker of cement, cement kiln seldom or not can produce dioxin, furans.
(2) to the persistence organic pollutant that may bring in combustible waste material (furans, many aromatic protons hydrocarbon, polychlorobiphenyl etc.), in the art production process of cement kiln, 99.999% can be chlorinated decomposition, destroys removal by fire.
(3) the heavy metal major part of bringing in combustible waste material is cured in the crystalline structure of clinker mineral or in the hydrated product of cement, form undissolved mineral substance, leaching rate <1.5% in cement mortar body or concrete structure, most of <1.4%.The heavy metal discharging in cement kiln waste gas is generally all less than 5% of kiln system intake; Its emission concentration is all far below european union directive specified standards, some solid-state heavy metal can be attached in the kiln ash that dust-precipitator traps in addition, factory can consider kiln ash is returned in raw material homogenizing silo or kiln feeding according to the difference of alkali chlorine sulphur wherein and heavy metal content, or mixes in right amount cement and make blended material.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (2)
1. flying dust, chromium slag, electroplating sludge Hazardous wastes recycling processing method, is characterized in that comprising the steps:
1) collect flying dust, chromium slag, electroplating sludge, flying dust, chromium slag, electroplating sludge, with the ratio that quality is greater than 0% separately, are prepared burden;
2) in batching, add additive A, mix;
Described additive A is mixture, is made up of coal dust or carbon black and unslaked lime, and the mass percent of coal dust or carbon black is 70-85%, and Lime Quality per-cent is 15-30%; The mass percent that additive A accounts for whole batching is 15%-20%;
Add the material after additive, if moisture is excessively wet, need carry out drying and processing, make material moisture be less than 7%; As excessively thick in the granularity of material, need carry out levigate processing, make granularity be less than 200 its quality of object material and be greater than 70%;
3) enter in a palletizing device, and add additive B; After mixing, according to technical process, carry out pelletizing one time;
Additive B is a kind of compound binding agent, is powdery solid, and its quality formula is:
Component A: 0.5-2.0 part;
Red iron oxide: be greater than 0-2.0 part;
Wilkinite: be greater than 0-3.0 part;
Described component A is made up of polyacrylamide, calcium sulfate, sodium carbonate, and its quality proportioning is:
Polyacrylamide 3-5 part;
Calcium sulfate 7-10 part;
Sodium carbonate is greater than 0-10 part;
The mass percent that additive B accounts for whole batching is 1-5%;
The pelletizing that pelletizing obtains sieves, and granularity is greater than 5mm and carries out secondary pelletizing, is less than 5mm and returns to a balling equipment and continue pelletizing;
4) after a pelletizing, granularity is greater than the pelletizing of 5mm, enters in secondary palletizing device, and adds addition of C, according to technical process, carries out secondary pelletizing; At pelletizing surface parcel one deck additive;
Addition of C is unslaked lime, and its mass percent that accounts for whole batching is 1-3%;
5) pelletizing that secondary pelletizing obtains, enters cement kiln or agglomerating plant and carries out roasting.
2. flying dust, chromium slag, electroplating sludge Hazardous wastes recycling processing method as claimed in claim 1, it is characterized in that: Hazardous wastes also comprises leather-making mud, the ratio mixing that is greater than 0% according to quality separately, the mixture of formation flying dust, chromium slag, electroplating sludge and four kinds of formations of leather-making mud.
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| CN201410423517.1A CN104152206B (en) | 2014-08-26 | 2014-08-26 | Flying dust, chromium slag, electroplating sludge hazardous waste recycling processing method |
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| CN201410423517.1A CN104152206B (en) | 2014-08-26 | 2014-08-26 | Flying dust, chromium slag, electroplating sludge hazardous waste recycling processing method |
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| CN104152206B CN104152206B (en) | 2016-04-06 |
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Cited By (18)
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| CN104726699A (en) * | 2015-03-25 | 2015-06-24 | 甘肃酒钢集团宏兴钢铁股份有限公司 | High-strength composite metallized pellets produced by using iron-containing metallurgical dust and production process thereof |
| CN105845247A (en) * | 2016-04-06 | 2016-08-10 | 段宝荣 | Environment-friendly high intensity high flame resistance cable prepared by utilizing tannery chromium-containing sludge |
| CN105907950A (en) * | 2016-04-29 | 2016-08-31 | 浙江大学 | Treatment method for metallurgy sintering of abandoned SCR flue gas denitrification catalyst |
| CN105907973A (en) * | 2016-05-25 | 2016-08-31 | 重庆伟晋环保科技有限公司 | Solid water and dangerous waste treatment method |
| CN106148685A (en) * | 2016-07-28 | 2016-11-23 | 重庆大学 | A kind of municipal sludge and iron-containing waste prepare the method for acid pellet |
| CN106755981A (en) * | 2016-11-25 | 2017-05-31 | 江苏省沙钢钢铁研究院有限公司 | Method for producing metallized pellets by using iron ore tailings |
| CN106918044A (en) * | 2015-12-24 | 2017-07-04 | 南京索益盟环保科技有限公司 | A kind of method for suppressing Cr (III) oxidations in leather-making mud burning process |
| CN106986516A (en) * | 2015-04-28 | 2017-07-28 | 江苏理工学院 | Stabilization and solidification method of electroplating sludge |
| CN107267745A (en) * | 2017-05-22 | 2017-10-20 | 中南大学 | The extracting method of valuable element in a kind of iron vitriol slag |
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| CN104726699A (en) * | 2015-03-25 | 2015-06-24 | 甘肃酒钢集团宏兴钢铁股份有限公司 | High-strength composite metallized pellets produced by using iron-containing metallurgical dust and production process thereof |
| CN106986516A (en) * | 2015-04-28 | 2017-07-28 | 江苏理工学院 | Stabilization and solidification method of electroplating sludge |
| CN106918044A (en) * | 2015-12-24 | 2017-07-04 | 南京索益盟环保科技有限公司 | A kind of method for suppressing Cr (III) oxidations in leather-making mud burning process |
| CN105845247A (en) * | 2016-04-06 | 2016-08-10 | 段宝荣 | Environment-friendly high intensity high flame resistance cable prepared by utilizing tannery chromium-containing sludge |
| CN105845247B (en) * | 2016-04-06 | 2017-05-03 | 江苏三旗线缆有限公司 | Environment-friendly high intensity high flame resistance cable prepared by utilizing tannery chromium-containing sludge |
| CN105907950B (en) * | 2016-04-29 | 2018-03-09 | 浙江大学 | A kind of discarded SCR catalyst for denitrating flue gas metallurgy sintering processing method |
| CN105907950A (en) * | 2016-04-29 | 2016-08-31 | 浙江大学 | Treatment method for metallurgy sintering of abandoned SCR flue gas denitrification catalyst |
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