CN114074104A - Method for co-processing chromium-containing hazardous waste and zinc-containing waste residue - Google Patents
Method for co-processing chromium-containing hazardous waste and zinc-containing waste residue Download PDFInfo
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- CN114074104A CN114074104A CN202111300125.2A CN202111300125A CN114074104A CN 114074104 A CN114074104 A CN 114074104A CN 202111300125 A CN202111300125 A CN 202111300125A CN 114074104 A CN114074104 A CN 114074104A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for the cooperative treatment of chromium-containing hazardous waste and zinc-containing waste residue, and belongs to the field of harmless treatment and disposal of heavy metal waste. According to the method, dried chromium-containing hazardous waste, zinc-containing waste residue and kyanite tailings are used as raw materials, a spinel solid solution and a precursor are formed by a chromium component, a zinc component, an aluminum component, an iron component and a silicon component in the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings through a mechanochemical action, so that part of heavy metal ions such as chromium, zinc and the like are structurally fixed and activated, and then secondary solidification is carried out through high-temperature rapid melting, so that efficient and stable solidification of the chromium-containing hazardous waste and the zinc-containing waste residue is realized, and meanwhile, the kyanite tailings are utilized and treated, and the effects of harmlessness and resource synergistic treatment of various solid wastes are achieved.
Description
Technical Field
The invention relates to the field of harmless treatment and disposal of heavy metal waste, in particular to a method for the cooperative treatment of chromium-containing hazardous waste and zinc-containing waste residue.
Background
Chromium-containing hazardous waste and zinc-containing waste residues are typical hazardous waste which relates to heavy metals and nonferrous metals, and the heavy metals can migrate into soil, organisms or sediments along with rainwater, surface water, underground water and the like and further enter a food chain to cause serious environmental pollution and harm the health and safety of human beings. How to safely dispose chromium-containing hazardous waste and zinc-containing waste residue is a technical problem in the field of environmental engineering.
In the prior art, the invention patent with the application number of CN201410855721.0 discloses a method and a device for recovering zinc and chromium in heavy metal sludge, and the separation of the zinc and the chromium in the heavy metal sludge can be realized by carrying out pretreatment, leaching, neutralization, evaporation and electrolysis on the heavy metal sludge. However, although the scheme can realize waste recycling, the processes of evaporation, electrolysis and the like belong to high energy consumption links, the overall treatment cost is high, and the popularization is not facilitated.
Therefore, how to realize low-cost and high-reliability hazardous waste disposal for chromium-containing hazardous wastes and zinc-containing waste residues is a technical problem to be solved urgently at present.
Disclosure of Invention
The invention aims to solve the problem that the environmental safety is affected by the fact that heavy metals are easy to leach out after chromium-containing hazardous waste and zinc-containing waste residues are solidified, and provides a method for the cooperative treatment of the chromium-containing hazardous waste and the zinc-containing waste residues.
The kyanite tailings are tailings produced after quartz type kyanite ore separation, are fine in granularity, low in kyanite grade, rich in quartz, mica and other impurities, and high in iron content. A large amount of nonrenewable kyanite tailings are stacked in the open air, so that a large amount of land is occupied, and the ecological environment is seriously polluted. If the chromium component, the zinc component, the aluminum component, the iron component, the silicon component and the like in the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings can be efficiently utilized, the chromium-containing hazardous waste and the zinc-containing waste residue are efficiently and stably solidified, and the kyanite tailings are utilized and treated at the same time, so that the effects of harmless and resource cooperative treatment of various solid wastes are achieved, which has important influence on the safe treatment of the chromium-containing hazardous waste and the zinc-containing waste residue, the efficient utilization of the kyanite ore and the popularization of the comprehensive utilization of the tailings.
Thus, the inventive concept of the present invention is: the method comprises the steps of taking chromium-containing hazardous waste, zinc-containing waste residues and kyanite tailings as raw materials, enabling a chromium component, a zinc component, an aluminum component, an iron component and a silicon component to form a precursor of a spinel solid solution and a spinel solid solution under the condition of normal temperature through a mechanochemical action, achieving an activation effect, then carrying out high-temperature rapid melting and cooling, thereby completing secondary solidification to generate the spinel solid solution containing heavy metals, and achieving the effect of safe disposal of pollutants.
In order to achieve the above purpose, the invention specifically adopts the following technical scheme:
the invention provides a method for the cooperative treatment of chromium-containing hazardous waste and zinc-containing waste residue, which comprises the following steps:
s1, uniformly mixing the dried chromium-containing hazardous waste, zinc-containing waste residues and kyanite tailings according to a ratio, adding the mixed materials into a high-speed mill, and grinding for not less than 4 hours at a rotating speed of 550-900 rpm to obtain an activated ground product;
and S2, carrying out rapid melting solidification on the ground product obtained in the S1 under the air atmosphere condition and at the temperature of not lower than 1000 ℃ for not more than 40 minutes, and cooling to obtain the spinel solidified body containing heavy metals.
Preferably, the chromium-containing hazardous waste is chromium-containing sludge (such as HW21 in national hazardous waste catalogue (2021 edition)) from wastewater treatment generated by metal surface treatment. .
Preferably, the zinc-containing waste residue is zinc-containing tailings (such as HW48 in national hazardous waste catalogue (2021 edition)) after hydrometallurgy of non-ferrous waste.
Preferably, the kyanite tailings are tailings produced after quartz type kyanite ore sorting.
Preferably, in S1, if the moisture content of the original chromium-containing hazardous waste, zinc-containing waste slag and kyanite tailings is high, drying should be performed to reduce the moisture content to a specified range.
Preferably, in the step S1, the moisture content of the dried chromium-containing hazardous waste, the zinc-containing waste slag and the kyanite tailings is less than 10 wt%.
Preferably, in the S1 mixed material, the mass percentage of the chromium-containing hazardous waste is 5-35%, the mass percentage of the zinc-containing waste residue is 5-35%, and the mass percentage of the kyanite tailings is 30-90% in terms of dry mass percentage. Furthermore, in the mixed material, the mass percent of the chromium-containing hazardous waste dry basis is 5-30%, the mass percent of the zinc-containing waste residue dry basis is 10-35%, and the mass percent of the kyanite tailing dry basis is 35-75%. The proportion of the dry base ensures the stoichiometric ratio of the raw materials for synthesizing the spinel solid solution.
Preferably, in the S1, the high-speed mill is an upright planetary ball mill.
Preferably, in S1, the rotation speed of the high-speed mill is 600-900 rpm, and the grinding time is 4-12 h. The main component of the ground product obtained after grinding is a precursor of the spinel solid solution, and the spinel solid solution also contains a small amount of the spinel solid solution. The rotation speed of the mill enables the process of generating the spinel solid solution and the precursor of the spinel solid solution by the mechanochemical reaction of the raw materials to be smoothly carried out, and the activation effect is achieved, so that the subsequent high-temperature melting and solidification are facilitated; similarly, the grinding time ensures the completion of the mechanochemical reaction of the raw materials, forms partial spinel solid solution and precursors thereof and achieves the activation effect. The precursor of the activated spinel solid solution can be quickly converted into the spinel solid solution in the subsequent melting and curing process, so that the melting and curing effect is enhanced.
Preferably, in S2, the melting and solidifying of the ground product is performed in a high temperature furnace.
Preferably, in the step S2, the melting and solidifying temperature is 1000-1800 ℃, and the melting and solidifying time is not more than 30 minutes.
It should be noted that the proportion of the mixture, the rotation speed and time of the high-speed mill grinding, and the temperature and time of the melting and solidifying are determined by a large number of tests, and the object of the invention can be better achieved only under the proportion of the mixture, the rotation speed and time of the high-speed ball mill grinding, and the temperature and time of the melting and solidifying.
According to the method, spinel solid solution and precursor are formed by a chromium component, a zinc component, an aluminum component, an iron component and a silicon component in the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings under the mechanochemical action, so that the structural fixation and activation of part of heavy metal ions such as chromium, zinc and the like are realized, and then the secondary solidification is carried out through high-temperature rapid melting (no more than 40 minutes), so that the high-efficiency stable solidification of the chromium-containing hazardous waste and the zinc-containing waste residue is realized, and the kyanite tailings are utilized and treated at the same time, so that the effects of harmless and resource cooperative treatment of various solid wastes are achieved.
According to the invention, after the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings are subjected to mechanochemical reaction to generate the spinel solid solution and the precursor, the mobility of chromium and zinc is greatly reduced, the reaction activity is improved, meanwhile, the structural fixation of heavy metal ions such as chromium, zinc and the like is enhanced by adopting high-temperature curing, the environmental release risk of chromium and zinc components in a solidified body is further reduced, and test results show that the chromium-containing hazardous waste and the zinc-containing waste residue are subjected to mechanochemical action pretreatment, and then the high-temperature curing is carried out, so that the solidification/stabilization of not less than 95% of chromium and zinc in the chromium-containing hazardous waste and the zinc-containing waste residue can be realized.
Drawings
FIG. 1 is a process flow diagram of the present invention for the co-treatment of chromium-containing hazardous waste and zinc-containing waste residue.
FIG. 2 is an XRD diffraction pattern of the cured body in the example.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
The TCLP (proximity chromatography learning procedure) used in the following examples is a general method for detecting the dissolubility and mobility of heavy metal elements in solid media or waste; the TCLP leach process is the standard toxic leach process recommended by the united states environmental protection agency. TCLP is the most widely applied ecological risk evaluation method in the world currently as the latest legal heavy metal pollution evaluation method in the United states.
The specific types and sources of the chromium-containing hazardous wastes, zinc-containing waste residues and kyanite tailings used in the following examples are collectively described as follows: the adopted chromium-containing hazardous waste is wastewater treatment chromium-containing sludge generated by metal surface treatment, the waste category in the national hazardous waste catalogue (2021 edition) is HW21, and the waste code is: 336-100-21; the zinc-containing waste residue is zinc-containing tailings obtained after hydrometallurgical processing of non-ferrous metal wastes, the waste category in the national hazardous waste catalogue (2021 edition) is HW48, and the waste codes are as follows: 900-; the adopted kyanite tailings are tailings generated after separation of quartz type kyanite ores in the south of Henan.
However, it should be noted that the specific types and sources of the chromium-containing hazardous waste, the zinc-containing waste slag and the kyanite tailings used in the following examples are only exemplary, but not limited thereto, and other sources of corresponding solid wastes may be used instead. In general, the three components in the mixture satisfy the following ratio ranges in dry mass percent: the chromium-containing hazardous waste accounts for 5-35% by mass, the zinc-containing waste residues accounts for 5-35% by mass, and the kyanite tailings account for 30-90% by mass.
Example 1
In this embodiment, the chromium-containing hazardous waste and the zinc-containing waste residue are co-processed, as shown in fig. 1, which is specifically performed as follows:
and drying the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings to reduce the water content of the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings from 24 percent, 18 percent and 12 percent to below 3 percent respectively.
And (2) drying the chromium hazardous waste, the zinc-containing waste slag and the kyanite tailings in a dry basis weight percentage of 12%: 20%: 68 percent of the mixture is mixed evenly, and the mixture is added into an upright planetary ball mill to be ground for 6 hours at the rotating speed of 650 revolutions per minute. And after grinding, putting the obtained ground product into a high-temperature furnace for high-temperature melting and solidification, wherein the melting temperature is 1300 ℃, and the melting time is 9 minutes. After cooling, a solidified body A was obtained1。
Meanwhile, in order to show the role of mechanical grinding in the synergistic treatment method, another control group is provided, which specifically comprises the following steps:
the same dried chromium hazardous waste, zinc-containing waste residue and kyanite tailings are used as raw materials, and the chromium hazardous waste, the zinc-containing waste residue and the kyanite tailings are mixed by mass percent on a dry basis of 12%: 20%: after 68 percent of the mixture is uniformly mixed, the mixture is directly put into a high-temperature furnace for high-temperature melting and solidification, the melting temperature is 1300 ℃, and the melting time is 9 minutes. After cooling, a solidified body A was obtained2。
Measured, cured product A1The total chromium and the total zinc in the raw materials are about 97 percent of the total chromium and the total zinc in the raw materials, and a solidified body A2The total chromium and zinc content is about 80% of the total chromium and zinc content in the raw materials.
The heavy metal leaching toxicity of the solidified bodies A1 and A2 in a severe erosion environment (seawater erosion + freeze-thaw cycle for 30 days) is further analyzed by a TCLP method, the leaching toxicity of chromium and zinc in the solidified body A1 is far lower than an environmental threshold, but the leaching toxicity of chromium and zinc in the solidified body A2 is higher than the environmental threshold.
The comparison test results show that the chromium hazardous waste, the zinc-containing waste residue and the kyanite tailings are subjected to mechanochemical reaction in advance before high-temperature melting and solidification, so that the solidification rate of chromium and zinc can be greatly improved, and the migration of chromium and zinc in a final solidified body is greatly reduced. The spinel solid solution and the precursor thereof are formed by the high-speed grinding in the ball mill through the mechanochemical reaction of chromium-containing hazardous waste, zinc-containing waste residue and chromium components, zinc components, aluminum components, iron components and silicon components in kyanite tailings, so that the structural fixation of partial heavy metal ions such as chromium, zinc and the like is preliminarily realized, and the reaction activity is improved. The activated spinel solid solution precursor can be quickly converted into the spinel solid solution in a short time (9 minutes in the embodiment) in the subsequent high-temperature melting and curing process, so that the high-temperature melting time is shortened while the high-efficiency immobilization and stabilization of chromium and zinc are ensured, and the energy consumption is reduced.
Example 2
In this embodiment, the chromium-containing hazardous waste and the zinc-containing waste residue are co-processed, as shown in fig. 1, which is specifically performed as follows:
and drying the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings to reduce the water content of the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings from 24 percent, 18 percent and 12 percent to below 3 percent respectively.
And (2) drying the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings in a mass percentage of 8% on a dry basis: 20%: 72 percent of the mixture is mixed evenly, and the mixture is added into an upright planetary ball mill to be ground for 5.5 hours at the rotating speed of 620 revolutions per minute. And after grinding, putting the obtained ground product into a high-temperature furnace for high-temperature melting and solidification, wherein the melting temperature is 1250 ℃, and the melting time is 15 minutes. After cooling, a solidified body B was obtained.
The total chromium and zinc content in the cured body B was determined to be about 98% of the total chromium and zinc content in the raw materials. And further analyzing the heavy metal leaching toxicity of the solidified body B in a severe erosion environment (seawater erosion + freeze-thaw cycle for 30 days) by adopting a TCLP method, wherein the detection result is lower than an environmental threshold value.
Example 3
In this embodiment, the chromium-containing hazardous waste and the zinc-containing waste residue are co-processed, as shown in fig. 1, which is specifically performed as follows:
and drying the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings to reduce the water content of the chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings from 24 percent, 18 percent and 12 percent to below 3 percent respectively.
And (2) drying the chromium hazardous waste, the zinc-containing waste slag and the kyanite tailings in a mass percentage of 18% on a dry basis: 12%: 70 percent of the mixture is mixed evenly, and the mixture is added into an upright planetary ball mill to be ground for 6.5 hours at the rotating speed of 650 r/min. And after grinding, putting the obtained ground product into a high-temperature furnace for high-temperature melting and solidification, wherein the melting temperature is 1300 ℃, and the melting time is 10 minutes. After cooling, a solidified body C was obtained.
The total chromium and zinc content in the cured product C was determined to be about 97% of the total chromium and zinc content in the raw materials. And further analyzing the heavy metal leaching toxicity of the solidified body C in a severe erosion environment (seawater erosion + freeze-thaw cycle for 30 days) by adopting a TCLP method, wherein the detection result is lower than an environmental threshold value.
In each of the above examples, the crystal structure and composition of the finally obtained cured body were analyzed by X-ray diffraction. Taking the cured body C obtained in example 3 as an example, fig. 2 shows the XRD diffractogram thereof, and analysis of fig. 2 can reveal that chromium and zinc are indeed uniformly embedded in the cured body and that they exist in the form of spinel-type structures. The cured body results for the remaining examples are similar and are not individually exemplified.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for the cooperative treatment of chromium-containing hazardous waste and zinc-containing waste residue is characterized by comprising the following steps:
s1, uniformly mixing the dried chromium-containing hazardous waste, zinc-containing waste residues and kyanite tailings according to a ratio, adding the mixed materials into a high-speed mill, and grinding for not less than 4 hours at a rotating speed of 550-900 rpm to obtain an activated ground product;
and S2, carrying out rapid melting solidification on the ground product obtained in the S1 under the air atmosphere condition and at the temperature of not lower than 1000 ℃ for not more than 40 minutes, and cooling to obtain the spinel solidified body containing heavy metals.
2. The method of claim 1, wherein: the chromium-containing hazardous waste is waste water treatment chromium-containing sludge generated by metal surface treatment.
3. The method of claim 1, wherein: the zinc-containing waste residue is zinc-containing tailings obtained after the non-ferrous metal waste is smelted by a wet method.
4. The method of claim 1, wherein: the kyanite tailings are tailings generated after quartz type kyanite ore separation.
5. The method of claim 1, wherein: in the S1, the water content of the dried chromium-containing hazardous waste, the zinc-containing waste residue and the kyanite tailings is lower than 10 wt%.
6. The method of claim 1, wherein: in the S1 mixed material, the mass percent of the chromium-containing hazardous waste is 5-35%, the mass percent of the zinc-containing waste residue is 5-35%, and the mass percent of the kyanite tailings is 30-90% in terms of dry basis mass percent.
7. The method of claim 1, wherein: in the S1, the high-speed mill adopts a vertical planetary ball mill.
8. The method of claim 1, wherein: in the S1, the rotating speed of the high-speed grinding machine is 600-900 rpm, and the grinding time is 4-12 h.
9. The method of claim 1, wherein: in S2, the melt-solidification of the ground product is performed in a high-temperature furnace.
10. The method of claim 1, wherein: in the S2, the melting and solidifying temperature is 1000-1800 ℃, and the melting and solidifying time is not more than 30 minutes.
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