CN101775868B - Method for sintering and curing industrial waste residue - Google Patents
Method for sintering and curing industrial waste residue Download PDFInfo
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- CN101775868B CN101775868B CN2010103005564A CN201010300556A CN101775868B CN 101775868 B CN101775868 B CN 101775868B CN 2010103005564 A CN2010103005564 A CN 2010103005564A CN 201010300556 A CN201010300556 A CN 201010300556A CN 101775868 B CN101775868 B CN 101775868B
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Abstract
The invention discloses a method for sintering and curing industrial waste residue, in which manganese residue, shale, fly ash, cadmium residue, iron residue and calcium and magnesium residue which are dried to constant weight are mixed and ground according to a certain ratio or mixed after being ground respectively, and then are screened in accordance with a certain grading requirement to obtain preparation raw materials of waste residue mixed and cured sintered bricks, and then a certain amount of sodium humate stabilizer and water are added into the raw materials, the mixture is stirred evenly, aged for some time and then made into a sample block via a vacuum extruder, and finally the sample block is treated by the heat treatment processes of drying, roasting, cooling and the like to obtain a waste residue mixed and cured sintered product. The invention takes electrolytic manganese dioxide residue as main curing material, and takes the shale as an auxiliary curing material, various industrial solid wastes such as coal ash, cadmium residue, iron residue and the like are cured via the processes of burdening, pretreatment, moulding, drying, roasting and cooling, the sintering temperature is reduced via optimizing process parameters, and a waste residue fixed and cured sintered brick which can cure heavy metal waste residue is produced.
Description
Technical field
The invention belongs to industrial solid wastes harmless treatment and application technology as the second resource field, be a kind of be main curing materials with filter wash slag in the electrolytic manganese dioxide manufacturing process (hereafter " manganese slag ") and shale, adopt sintering process to solidify the method for handling multiple industrial residue, simultaneously the form of sintering curing product with wall body brick is used.
Background technology
Since the eighties, the rapid growth period that China's economy entering, industrial solid wastes generation and accumulating amount are the trend that increases year by year.Played the useless admittedly annual production of industry in 1992 all more than 600,000,000 t, annual production has surpassed 1,000,000,000 t after 2000, expect the solid waste of 2015 Industry Enterprises in China (comprising township enterprise) and the generation of hazardous waste and will reach 23.1 hundred million t and 0.57 hundred million t respectively, nearly more than 70 hundred million tons of China's industrial residues of piling up over the years, more than 100 ten thousand mu of land occupations.Solid waste of a great variety, complicated component, enormous amount is one of primary pollution source of environment, its extent of injury has been polluted not second to water and the degree of atmosphere pollution.
Modernization is handled and the technology of disposal of solid refuse mainly contains burning, compost, sanitary landfills and curing processing etc.These several processing methods respectively have pluses and minuses, and the scope of application also is not quite similar.Burn and generally be applied to municipal refuse, be considered to useless admittedly final disposal method, but the energy consumption height is easy to generate the pernicious gas secondary pollution; Compost is applicable to organic solid useless, and the processing cycle is longer; The sanitary landfills land occupation needs antiseepage filtrate contamination environment water; Curing can be effectively uselessly be carried out innoxious, stabilization processes to solid, and cured article can be used as resource and be used, and its special advantages is arranged, thereby be widely used.
Solidify the mode of handling and mainly contain high-temperature fusion curing, cement solidification, plastic material containing curing and brickmaking curing etc.High-temperature fusion curing energy consumption is very big, and treating capacity is limited; Cement solidification need consume a large amount of cement, has increased the amount of carbon dioxide that produces because of calcining cement clinker indirectly; It is high to contain plastic material self price of solidifying use, and complicated operation, only is suitable for handling high-risk refuse and a small amount of radwaste; Brickmaking solidify commonly used at present solid useless be the bed mud that produces in gangue, flyash, the Industrial Wastewater Treatment process and all kinds of mine tailing (as gypsum mine, pyrite slag, copper mine tailing, tailings of high silicon iron, asbestos tailings) etc.Preparation technology can be divided into high temperature sintering and low temperature steam press maintenance two big classes (steam curing process protects that energy consumption is low, and flow process is simple, but solidification effect is limited, and product strength is not as sintering curing, thereby range of application is narrower).Though these technologies of producing materials for wall have all obtained bigger progress, and in the building trade extensive use, but utilize the manganese slag to solidify the brickmaking complex manufacturing, difficulty is big, carry out its production technology of grasp and product quality needs suitable technical force and production experience comprehensively, the at present domestic precedent of also not utilizing the brickmaking of manganese slag to solidify industrial residue.Therefore domestic blank has not only been filled up in the exploitation of present technique, and product can resource be applied to building material industry, meets the requirement that materials for wall develops to energy-conservation, joint soil, sharp useless direction in the China's Agenda 21 development strategy.
Summary of the invention
Technical problem to be solved by this invention provides a kind ofly carries out innoxious, stabilization processes to heavy metal waste slag effectively, and cured article can be used as the method for the sintering and curing industrial waste residue that resource is used.
In order to solve the problems of the technologies described above, the method of sintering and curing industrial waste residue provided by the invention, with the manganese slag of drying to constant weight, shale, flyash, cadmium slag and scum and calcium magnesium slag are mixed together grinding according to a certain ratio or mix behind the grinding respectively again, and obtain the preparation raw material of the mixing cured clinker brick of waste residue after sieving by certain grating requirement, adding a certain amount of sodium humate stabilizing agent and clear water then stirs also ageing a period of time, make the sample piece through extruder again, last drying, roasting, it is mixing cured sintering finished that heat treatment steps such as cooling obtain waste residue, will be through 95-125 ℃ of manganese slag that is dried to the 20-40wt% of constant weight, the shale of 37-55wt%, the flyash of 3-5wt%, the cadmium slag of 1-3wt%, the scum of 11-15wt% and 4-6wt% calcium magnesium slag, together grinding or respectively grinding to feed particles maximum particle diameter be no more than 2.5mm, what 2mm was following accounts for more than 95%, what 1mm was following accounts for more than 90%, 0.5mm the following grating that accounts for more than 70% requires to obtain the preparation raw material of the mixing cured clinker brick of waste residue through mixing again; Be incorporated as then the raw material quality 3%-5% the sodium humate stabilizing agent and be the clear water of raw material quality 25%-35%, stirring is placed on indoor ageing 1-3d, allows moisture fully contact with raw material; Next put into extruder and make the sample piece, again in 120-140 ℃ of dry 8-24h or adopt outdoor natural air drying 6-8d; Be warming up to 850-950 ℃ of calcining 2-6h with the speed of 40-60 ℃/h at last, the speed air blast with 40-60 ℃/h is cooled to 550-650 ℃ of insulation 25-35 again) behind the min with the stove cooling, make the mixing cured sintered sample of waste residue.
The sample piece of making through extruder is of a size of 240mm * 115mm * 53mm.
Described extruder is a vacuum-extruder.
The mixing cured sintered sample of described waste residue is the mixing cured clinker brick sample of waste residue.
In this method, an amount of interpolation of scum and flyash has replenished SiO
2With Fe
2O
3, helping improving the performance of fragment of brick and strengthen its solidification effect heavy metal cadmium, manganese, a spot of unburned matter also helps and improves sintering effect in the flyash in addition, shortens sintering time, energy efficient; Cadmium slag incorporation is no more than at 3% o'clock, and the leaching toxicity index of cadmium, manganese two heavy metal species all is lower than 1mg/L in the clinker brick; Required calcining heat can be saved coal consumption 20-30% than low 150-250 ℃ of the calcining heat of loam brick when the adding of the calcium magnesium slag of the scum of 10-15% and 4%-6% can make the mixing cured clinker brick of preparation waste residue.
This method in " large " recycling manganese slag, taken into account " digestion " a certain amount of other industry solid useless.By the control preparation condition, heavy metal cadmium, the curing of manganese and the reduction of calcining heat have been realized simultaneously; By preprocessing means such as interpolation stabilizing agents, solved the deformation problems of fragment of brick in sintering procedure.Prepared clinker brick properties of sample meets " GB5101-2003 fired common brick " requirement, " radioactive material nucleic the limit the quantity of GB6566 2001 " requirement of limiting the quantity of and meet of radioactive ray inspections element, corrosivity and leaching oxicity analysis meet " discriminating of GB5085.1-2007 hazardous waste judging standard corrosivity " and " the hazardous waste judging standard leaches toxicity and differentiates GB 5085.3-2007 " requirement, and the radiation radon of indoor storage meets the requirement of " GB/T18883-2002 IAQ (indoor air quality) standard " in fact.The present invention has filled up the domestic technological gap that utilizes manganese slag brickmaking curing heavy metal waste residue.
In sum, the present invention is main curing materials with the electrolytic manganese dioxide slag, with shale as auxiliary curing materials, solidifying multiple industry such as handling flyash, cadmium slag, scum by batching preliminary treatment molding drying and roasting process for cooling gives up admittedly, and by optimizing technological parameter, reduce sintering temperature, prepared a kind of mixing cured clinker brick of waste residue of energy curing heavy metal waste residue.Realized the energy-saving and cost-reducing of " large " useless admittedly recycling and manufacturing process.
The used composition of useless raw material admittedly of additional copy invention (by the brickmaking industrial practice in main oxides) tabulation:
Table 1 manganese slag main component
| Composition | Loss on ignition | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | MnO | SO 3 |
| Wt％ | 14.65 | 20.67 | 4.77 | 8.43 | 12.04 | 2.51 | 6.837 | 29.50 |
Table 2 shale main component
| Composition | Loss on ignition | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | K 2O | SO 3 |
| Wt％ | 7.81 | 60.60 | 14.36 | 4.72 | 5.6 | 2.00 | 2.41 | 1.85 |
Table 3 flyash main component
| Composition | Loss on ignition | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | K 2O | SO 3 |
| Wt％ | 4.22 | 54.69 | 29.47 | 6.86 | 1.29 | 0.82 | 1.45 | 0.89 |
Table 4 cadmium slag main component
| Composition | Loss on ignition | SiO 2 | ?Al 2O 3 | ?Fe 2O 3 | ?CaO | ?MgO | ?P 2O 5 | ?Na 2O | ?CdO | ?SO 3 | ?ZrO 2 |
| ?Wt％ | 20.78 | ?18.62 | ?10.77 | ?3.58 | ?23.1 | ?2.17 | ?10.31 | ?2.84 | ?2.39 | ?2.5 | ?2.14 |
Annotate: the cadmium slag derives from the processing mud of acidified waste water and poaching wastewater in Xiang Tan gold ring pigment company cadmium pigment manufacturing process
Table 5 scum main component
| Composition | Loss on ignition | SiO 2 | Al 2O 3 | Fe 2O 3 | CaO | MgO | CuO | SO 3 |
| Wt％ | 18.24 | 29.53 | 6.04 | 17.58 | 5.88 | 5.00 | 1.875 | 14.75 |
Annotate: the filter residue that scum derives from the molten copper of raw material in Xiang Tan JinKe Co., Ltd copper cobalt nickel manufacturing process is the residue after deironing again
Table 6 calcium magnesium slag main component
| Composition | Loss on ignition | SiO 2 | Al 2O 3 | Fe 2O 3 | CaF 2 | MgF 2 | SO 3 | NaF | CuO |
| Wt％ | 14.47 | 5.21 | 8.88 | 1.57 | 19.89 | 25.83 | 8.00 | 13.33 | 2.12 |
Annotate: calcium magnesium slag derives from the residue behind the cobalt nickel filtrate removing calcium and magnesium in Xiang Tan JinKe Co., Ltd copper cobalt nickel manufacturing process
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
With a certain amount of manganese slag, shale and flyash are dried to constant weight under 95 ℃ of conditions, by quality than manganese slag: shale: flyash: cadmium slag: scum: calcium magnesium slag=20: 55: 5: (the feed particles maximum particle diameter is no more than 2.5mm to 3: 11: 6 grindings that are mixed to the grating requirement, what 2mm was following accounts for more than 95%, what 1mm was following accounts for more than 90%, 0.5mm following accounts for more than 70%), undersize material is raw material, adding a certain amount of sodium humate stabilizing agent (account for raw material quality 3%) and clear water (account for raw material quality 25%) then stirs evenly, behind the indoor ageing 3d, make the sample piece that specification is 240mm * 115mm * 53mm through vacuum-extruder, again in 120 ℃ of dry 24h (or placing outdoor 1 week of natural air drying), put into Muffle furnace at last and be warming up to 950 ℃ with the speed of 60 ℃/h, behind the insulation 2h, be cooled to behind 650 ℃ of insulation 25min with the stove cooling with the speed air blast of 40 ℃/h again, promptly make the mixing cured clinker brick of waste residue.
Embodiment 2:
With a certain amount of manganese slag, shale, flyash, cadmium slag and scum and calcium magnesium slag are dried to constant weight under 110 ℃ of conditions, (the feed particles maximum particle diameter is no more than 2.5mm to the grating requirement to distinguish grinding then, what 2mm was following accounts for more than 95%, what 1mm was following accounts for more than 90%, 0.5mm following accounts for more than 70%), the extracting screen underflow material by quality than manganese slag: shale: flyash: cadmium slag: scum: calcium magnesium slag=30: 46: 4: be mixed into raw material at 2: 13: 5, next adding a certain amount of sodium humate stabilizing agent (account for raw material quality 4%) and clear water (account for raw material quality 30%) stirs evenly, behind the indoor ageing 2d, make the sample piece that specification is 240mm * 115mm * 53mm through vacuum-extruder, again in 130 ℃ of dry 16h (or placing outdoor natural air drying 6 days), put into Muffle furnace at last and be warming up to 900 ℃ with the speed of 50 ℃/h, behind the insulation 4h, be cooled to behind 600 ℃ of insulation 30min with the stove cooling with the speed air blast of 50 ℃/h again, promptly make the mixing cured clinker brick of waste residue.
Embodiment 3:
With a certain amount of manganese slag, shale, flyash, cadmium slag and scum and calcium magnesium slag are dried to constant weight under 125 ℃ of conditions, (the feed particles maximum particle diameter is no more than 2.5mm to the grating requirement to distinguish grinding then, what 2mm was following accounts for more than 95%, what 1mm was following accounts for more than 90%, 0.5mm following accounts for more than 70%), the extracting screen underflow material by quality than manganese slag: shale: flyash: cadmium slag: scum: calcium magnesium slag=40: 37: 3: be mixed into raw material at 1: 15: 4, next adding a certain amount of sodium humate stabilizing agent (account for raw material quality 5%) and clear water (account for raw material quality 35%) stirs evenly, behind the indoor ageing 1d, make the sample piece that specification is 240mm * 115mm * 53mm through vacuum-extruder, again in 140 ℃ of dry 8h (or placing outdoor natural air drying 8 days), put into Muffle furnace at last and be warming up to 850 ℃ with the speed of 40 ℃/h, behind the insulation 6h, be cooled to behind 550 ℃ of insulation 35min with the stove cooling with the speed air blast of 60 ℃/h again, promptly make the mixing cured clinker brick of waste residue.
Claims (4)
1. the method for a sintering and curing industrial waste residue, with the manganese slag of drying to constant weight, shale, flyash, cadmium slag and scum and calcium magnesium slag are mixed together grinding according to a certain ratio or mix behind the grinding respectively again, and obtain the preparation raw material of the mixing cured clinker brick of waste residue after sieving by certain grating requirement, adding a certain amount of sodium humate stabilizing agent and clear water then stirs also ageing a period of time, make the sample piece through extruder again, last drying, roasting, it is mixing cured sintering finished that heat of cooling treatment process obtains waste residue, it is characterized in that: will be through 95-125 ℃ of manganese slag that is dried to the 20-40wt% of constant weight, the shale of 37-55wt%, the flyash of 3-5wt%, the cadmium slag of 1-3wt%, the scum of 11-15wt% and 4-6wt% calcium magnesium slag, together grinding or respectively grinding to feed particles maximum particle diameter be no more than 2.5mm, what 2mm was following accounts for more than 95%, what 1mm was following accounts for more than 90%, 0.5mm the following grating that accounts for more than 70% requires to obtain the preparation raw material of the mixing cured clinker brick of waste residue through mixing again; Be incorporated as then the raw material quality 3%-5% the sodium humate stabilizing agent and be the clear water of raw material quality 25%-35%, stirring is placed on indoor ageing 1-3d, allows moisture fully contact with raw material; Next put into extruder and make the sample piece, again in 120-140 ℃ of dry 8-24h or adopt outdoor natural air drying 6-8d; Be warming up to 850-950 ℃ of calcining 2-6h with the speed of 40-60 ℃/h at last, be cooled to behind the 550-650 ℃ of insulation 25-35min with the stove cooling with the speed air blast of 40-60 ℃/h again, make the mixing cured sintered sample of waste residue.
2. the method for sintering and curing industrial waste residue according to claim 1, it is characterized in that: the sample piece of making through extruder is of a size of 240mm * 115mm * 53mm.
3. the method for sintering and curing industrial waste residue according to claim 1 and 2, it is characterized in that: described extruder is a vacuum-extruder.
4. the method for sintering and curing industrial waste residue according to claim 1 and 2, it is characterized in that: the mixing cured sintered sample of described waste residue is the mixing cured clinker brick sample of waste residue.
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| CN105439537B (en) * | 2015-11-25 | 2018-06-26 | 张延荣 | Building brick fired using electroplating industry waste residue and preparation method thereof |
| CN106396635A (en) * | 2016-09-14 | 2017-02-15 | 铜仁学院 | Sludge sintered bricks, and preparation method thereof |
| CN107008724A (en) * | 2017-03-14 | 2017-08-04 | 华能国际电力股份有限公司 | Resource utilization method for converting waste flue gas denitration catalyst into fly ash |
| CN110357583B (en) * | 2019-08-27 | 2020-04-14 | 广西来宾东糖纸业有限公司 | Low-sulfur-emission white mud sintered brick and preparation method thereof |
| CN112083702B (en) * | 2020-09-27 | 2021-08-17 | 江苏恒宝智能系统技术有限公司 | Carbon fiber composite material curing process monitoring and management method and system |
| CN113429194A (en) * | 2021-05-20 | 2021-09-24 | 青海华信环保科技有限公司 | Method for preparing tailing dam permeability guiding material by using industrial solid waste |
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