CN103978015A - Method and device for dry-type innocent chromium slag reduction treatment - Google Patents
Method and device for dry-type innocent chromium slag reduction treatment Download PDFInfo
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- CN103978015A CN103978015A CN201410211079.2A CN201410211079A CN103978015A CN 103978015 A CN103978015 A CN 103978015A CN 201410211079 A CN201410211079 A CN 201410211079A CN 103978015 A CN103978015 A CN 103978015A
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Abstract
The invention provides a method and a device for dry-type innocent chromium slag reduction treatment. The method comprises the following steps: mixing and pelletizing chromium slags, tar and bonding agents, preheating under oxygen insulation, and carbonizing tar fully so as to prepare carbon-contained chromium slag pellets; and then carrying out carbon gasification and gas-solid reduction reaction on coke and Cr<6+> in the chromium slag pellets by taking high-temperature flue gas containing CO and CO2 as a reducing agent and a heating source so as to convert Cr<6+> into Cr<3+>, thereby achieving the innocent stabilized treatment of the chromium slags, wherein high-temperature flue gas containing CO and CO2 is generated by incomplete combustion of biomass. The device provided by the invention comprises a biomass combustion chamber and a chromium slag reduction chamber which are respectively used for combusting biomass and reducing chromium slags. Because low-cost and recyclable biomass and pyrolysis tar are utilized as the heat source and the reducing agent which are required for chromium slag reduction, the economical value of biomass energy is developed fully; the cost for innocent and stabilized treatment of the chromium slags is reduced.
Description
Technical field
The present invention relates to the innoxious process for treating field of chromium slag, be specifically related to a kind of method and apparatus of chromium slag dry type reduction harmless treatment.
Background technology
Chromium slag output is large, toxicity is violent, be serious pollution of ecological environment and human health hazardous waste.The Cr that chromium slag contains
2o
7 2-, CrO
4 2-anion is the main cause that causes environmental pollution.
At present, the method for innocent treatment of chromium slag is had to chemical method, microbial method and solidification method etc. both at home and abroad.Although microbial method cost is low, environmental pollution is little, because microorganism survival rate is lower and proliferative speed is slower, processes the quantity of slag little, and efficiency is low, thereby microbial method is only limited to the research of laboratory or pilot-scale mostly.It is to adopt stabilization agent to be fixed with harmful substances that curing/stabilizing is processed, by forming lattice structure and chemical bond, harmful constituent and matrix are combined, thus the Leaching of harmful constituent in reduction hazardous waste.Although treatment effect is good, volume increase is larger, and has the problems such as long-time stability.Therefore; the most frequently used in harmless treatment means is chemical method, by destroying the harmful components in solid waste or throwing in chemical agent, poisonous chemical substance is converted into nontoxic form and guarantees that the product after chemical detoxication step is little and stable compared with the harm of beginning chemical substance.Conventional chemical method has two kinds of dry detoxified and wet method detoxifcations, needs to consume a large amount of sodium carbonate and acid in wet method detoxifcation, and disposal cost is higher, has the area that spent acid alkali produces to implement near being adapted at.It is dry detoxified in chemical method, applying maximum, but is reducing agent mainly with non-renewable coal, easily produces exhaust gas dust and cause secondary pollution in calcination process.
In view of above-mentioned, study the green technology of the innoxious and recycling treatment of practicable chromium slag, chromium slag contaminated to alleviating, promote the sustainable development of China's chromic salts industry and environment to there is realistic meaning.
Biomass energy is unique a kind of reproducible green carbon source, has the advantages such as widely distributed, cheap and easy to get, aboundresources, neutral carbon, harmful element content are low, biomass combustion produce containing CO and CO
2high-temperature flue gas, can meet the requirement of chromium slag reduction to reducing agent and heat.If living beings are reasonably applied to chromic slag harmlessness processing procedure, bring surely innovation and the optimization of production technology and cost.
Summary of the invention
The invention provides a kind of method and apparatus of chromium slag dry type reduction harmless treatment, by chromium slag and domestic waste or agriculture and forestry organic waste material pyrolysis fuel oil and binding agent mixed pelletizing, under oxygen barrier, preheating makes the abundant carbonization of tar produce carbon containing chromium slag pelletizing, then with living beings imperfect combustion, produce containing CO and CO
2high-temperature flue gas as reducing agent and thermal source, with coke and the Cr in chromium slag pelletizing
6+there is charcoal gasification and gas-solid reduction reaction, by Cr
6+be converted into Cr
3+, and then realize innoxious, the stabilization processes of chromium slag.For achieving the above object, the present invention adopts following technical proposals to be achieved:
The device that the invention provides a kind of chromium slag dry type reduction harmless treatment, is characterized in that:
This device comprises that biomass combustion chamber and chromium slag reduction chamber two parts form: bottom, described biomass combustion chamber is provided with a plurality of biomass fuel imports, and bottom is provided with the outlet of biomass combustion ash content, and top is provided with combustion product gases outlet; Described chromium slag reduction chamber is positioned at top, biomass combustion chamber, and reduction bottom, chamber is provided with biomass combustion gas approach and the outlet of chromium slag pelletizing, and top is provided with the outlet of reduction tail gas, and top has the import of chromium slag pelletizing;
The present invention also provides a kind of method of chromium slag dry type reduction harmless treatment, it is characterized in that it comprises the following steps:
(1) by chromium slag and domestic waste or agriculture and forestry organic waste material pyrolysis fuel oil and binding agent mixed pelletizing according to a certain percentage;
(2), by the preheating under oxygen barrier condition of chromium slag pelletizing, prepare carbon containing chromium slag pelletizing;
(3) with living beings imperfect combustion, produce containing CO and CO
2high-temperature flue gas as reducing agent and thermal source, with coke in chromium slag pelletizing and the gasification of Cr VI generation charcoal and gas-solid reduction reaction, Cr VI is converted into trivalent chromium, realizes innoxious, the stabilization processes of chromium slag;
Compared with prior art, advantage of the present invention and good effect are:
(1) using reproducible green carbon source living beings as the required thermal source of chromium slag reduction, the tar that the cracking such as domestic waste, living beings of usining produce, as chromium slag reduction agent, reduces chromic slag harmlessness processing cost, realizes the high-efficiency resource recycling of tar;
(2) high-temperature flue gas producing with biomass combustion directly heats chromium slag pelletizing, and in reduction process, heat transference efficiency is higher; The CO containing in flue gas can participate in reduction, CO directly
2by carbon gasification, further promote the carrying out of chromium slag reduction reaction;
(3) biomass combustion chamber and chromium slag reduction chamber are separate, are convenient to the accurate control of realization response condition.
Read by reference to the accompanying drawings after the specific embodiment of the present invention, it is clearer that the other features and advantages of the invention will become.
Accompanying drawing explanation
Fig. 1 is chromium slag dry type reduction harmless treatment flow chart.
Fig. 2 is the direct-fired chromium slag of living beings dry type reduction harmless treatment device structural representation.
The specific embodiment
Embodiment 1
As shown in Figure 2, the invention provides a kind of device of chromium slag dry type reduction harmless treatment, this device comprises that biomass combustion chamber 1 and chromium slag reduction chamber 5 two parts form, and carry out respectively biomass combustion and chromium slag reduction; 1 bottom, described biomass combustion chamber is provided with biomass fuel import 2, and bottom is provided with biomass combustion ash content outlet 3, and top is provided with combustion product gases outlet 4; Described chromium slag reduction chamber 5 is positioned at 1 top, biomass combustion chamber, and reduction 5 bottoms, chamber are provided with biomass combustion gas approach 6 and chromium slag pelletizing outlet 7, and top is provided with reduction tail gas outlet 8, and top has chromium slag pelletizing import 9;
5 bottoms, described chromium slag reduction chamber are conical, and the heated contact surface that increases combustion chamber 1 flue gas and chromium slag reduction chamber 5 is long-pending.
In 5 inside, described chromium slag reduction chamber, be provided with screw type blade 10, to increase the caloic transmission efficiency in chromium slag reduction chamber 5.
Between described biomass combustion chamber 1 exhanst gas outlet 4 and chromium slag reduction chamber gas approach 6, be provided with high-temperature dust removing device 11, to prevent that ash content from entering in reduction chamber 5 with flue gas stream.
Described in the present embodiment, utilize the method for chromium slag dry type reduction harmless treatment as follows:
(1) chromium slag and tar and binding agent are carried out to mixed pelletizing according to the ratio of 85:10:5, pelletizing diameter is 10mm;
(2) by chromium slag pelletizing preheating 5min at 300 ℃;
(3) biomass combustion excess air coefficient is for being controlled at 0.6, and combustion zone temperature is 600 ℃, and reducing zone temperature is 400 ℃, and chromium slag is 5min in the reducing zone reaction time.
After reaction, separated through row to product, Cr in chromium slag
6+mass concentration is 121mg/ kg, lower than the Cr in chromium slag before reduction
6+(3100 mg/ kg), exchangeable species and carbonate reduce in conjunction with state chromium content, and most of chromium has changed into stable combination state and residual form, has greatly reduced the harm of chromium slag.
Embodiment 2
Described in the present embodiment, utilize the method for chromium slag dry type reduction harmless treatment as follows:
(1) chromium slag and tar and binding agent are carried out to mixed pelletizing according to the ratio of 80:15:5, pelletizing diameter is 8mm;
(2) by chromium slag pelletizing preheating 10min at 400 ℃;
(3) biomass combustion excess air coefficient is for being controlled at 0.7, and combustion zone temperature is 650 ℃, and reducing zone temperature is 450 ℃, and chromium slag is 10min in the reducing zone reaction time.
After reaction, separated through row to product, Cr in chromium slag
6+mass concentration is 101mg/ kg, lower than the Cr in chromium slag before reduction
6+(3100 mg/ kg), exchangeable species and carbonate reduce in conjunction with state chromium content, and most of chromium has changed into stable combination state and residual form, has greatly reduced the harm of chromium slag.
Embodiment 3
Described in the present embodiment, utilize the method for chromium slag dry type reduction harmless treatment as follows:
(1) chromium slag and tar and binding agent are carried out to mixed pelletizing according to the ratio of 70:25:5, pelletizing diameter is 5mm;
(2) by chromium slag pelletizing preheating 10min at 450 ℃;
(3) biomass combustion excess air coefficient is for being controlled at 0.9, and combustion zone temperature is 800 ℃, and reducing zone temperature is 550 ℃, and chromium slag is 10min in the reducing zone reaction time.
After reaction, separated through row to product, Cr in chromium slag
6+mass concentration is 55mg/ kg, lower than the Cr in chromium slag before reduction
6+(3100 mg/ kg), exchangeable species and carbonate reduce in conjunction with state chromium content, and most of chromium has changed into stable combination state and residual form, has greatly reduced the harm of chromium slag.
Above embodiment is only in order to technical scheme of the present invention to be described, but not is limited; Although the present invention is had been described in detail with reference to previous embodiment, for the person of ordinary skill of the art, the technical scheme that still can record previous embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (9)
1. a device for chromium slag dry type reduction harmless treatment, is characterized in that:
This device comprises that biomass combustion chamber and chromium slag reduction chamber two parts form: bottom, described biomass combustion chamber is provided with biomass fuel and combustion air inlet, and bottom is provided with the outlet of biomass combustion ash content, and top is provided with combustion product gases outlet; Described chromium slag reduction chamber is positioned at top, biomass combustion chamber, and reduction bottom, chamber is provided with biomass combustion gas approach and the outlet of chromium slag pelletizing, and top is provided with the outlet of reduction tail gas, and top has the import of chromium slag pelletizing.
2. the device of chromium slag dry type reduction harmless treatment according to claim 1, is characterized in that: bottom, described reduction chamber is for conical.
3. the device of chromium slag dry type reduction harmless treatment according to claim 1, is characterized in that: described reduction chamber interior is provided with screw type blade.
4. the device of chromium slag dry type reduction harmless treatment according to claim 1, is characterized in that: between described gas fume of combustion chamber outlet and reduction chamber gas approach, be provided with high-temperature dust removing device.
5. utilize the device described in claim 1 to carry out chromium slag dry type reduction method for innocent treatment, it is characterized in that it comprises the following steps:
(1) by chromium slag and domestic waste or agriculture and forestry organic waste material pyrolysis fuel oil and binding agent mixed pelletizing according to a certain percentage;
(2), by the preheating under oxygen barrier condition of chromium slag pelletizing, prepare carbon containing chromium slag pelletizing;
(3) with living beings imperfect combustion, produce containing CO and CO
2high-temperature flue gas as reducing agent and thermal source, with coke in chromium slag pelletizing and the gasification of Cr VI generation charcoal and gas-solid reduction reaction, Cr VI is converted into trivalent chromium, realizes innoxious, the stabilization processes of chromium slag.
6. the method for chromium slag dry type reduction harmless treatment according to claim 5, is characterized in that: described chromium slag pelletizing mixed proportion is chromium slag 70 ~ 85%, tar 10 ~ 25%, binding agent 5%.
7. the method for chromium slag dry type reduction harmless treatment according to claim 5, is characterized in that: described chromium slag pelletizing preheat temperature is 300-500 °, and be 5 ~ 10min preheating time.
8. the method for chromium slag dry type according to claim 5 reduction harmless treatment, it is characterized in that: described biomass combustion excess air coefficient is 0.6 ~ 1.0, combustion zone temperature is 600 ~ 800 ℃, and reducing zone temperature is more than 400 ℃, and the recovery time is 5 ~ 10min.
9. the method for chromium slag dry type reduction harmless treatment according to claim 5, is characterized in that: described chromium slag pelletizing diameter is between 5 ~ 20mm.
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Cited By (9)
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|---|---|---|---|---|
| CN105524637A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Method for preparing energy source product by PVC (polyvinyl chloride) plastics and simultaneously performing harmless treatment on chromium slag |
| CN105524636A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Technology for synchronously recycling plastics and performing harmless treatment on chromium slag |
| CN105542813A (en) * | 2016-01-19 | 2016-05-04 | 青岛理工大学 | Biomass recycling and chromium slag harmless synchronization technique |
| CN105623690A (en) * | 2016-01-19 | 2016-06-01 | 青岛理工大学 | Method for preparing gas energy by utilizing chlorine-containing plastic and carrying out harmless treatment on chromium slag at same time |
| CN107739831A (en) * | 2017-10-19 | 2018-02-27 | 大连理工大学 | A kind of abandoned biomass hydrothermal reduction detoxification chromium slag and the method for reclaiming compound |
| CN109780546A (en) * | 2018-12-29 | 2019-05-21 | 义马环保电力有限公司 | Improve the chromium residue detoxifying system and method that chromium slag mixes ratio |
| CN111252882A (en) * | 2020-02-29 | 2020-06-09 | 广州绿邦环境技术有限公司 | Chromium slag resource utilization equipment and treatment process thereof |
| CN112709990A (en) * | 2020-12-21 | 2021-04-27 | 绍兴越信环保科技有限公司 | Preparation method of energy-saving waste salt ball for pyrolysis |
| CN114087612A (en) * | 2022-01-04 | 2022-02-25 | 山西省安装集团股份有限公司 | Distributed biomass and garbage incineration treatment system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105542813B (en) * | 2016-01-19 | 2019-08-20 | 青岛理工大学 | A kind of biomass as resources and chromic slag harmlessness synchronous method |
| CN105524636A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Technology for synchronously recycling plastics and performing harmless treatment on chromium slag |
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| CN105623690A (en) * | 2016-01-19 | 2016-06-01 | 青岛理工大学 | Method for preparing gas energy by utilizing chlorine-containing plastic and carrying out harmless treatment on chromium slag at same time |
| CN105524637A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Method for preparing energy source product by PVC (polyvinyl chloride) plastics and simultaneously performing harmless treatment on chromium slag |
| CN105623690B (en) * | 2016-01-19 | 2019-05-03 | 青岛理工大学 | A method of being prepared using plastic containing chlorine can source gas while innoxious chromium slag |
| CN105524637B (en) * | 2016-01-19 | 2019-10-22 | 青岛理工大学 | A method of energy products innoxious chromium slag simultaneously is prepared using PVC plastic |
| CN105524636B (en) * | 2016-01-19 | 2019-08-20 | 青岛理工大学 | A kind of plastic resource and chromic slag harmlessness synchronous method |
| CN107739831A (en) * | 2017-10-19 | 2018-02-27 | 大连理工大学 | A kind of abandoned biomass hydrothermal reduction detoxification chromium slag and the method for reclaiming compound |
| CN107739831B (en) * | 2017-10-19 | 2019-05-28 | 大连理工大学 | A kind of abandoned biomass hydrothermal reduction detoxification chromium slag and the method for recycling compound |
| CN109780546A (en) * | 2018-12-29 | 2019-05-21 | 义马环保电力有限公司 | Improve the chromium residue detoxifying system and method that chromium slag mixes ratio |
| CN111252882A (en) * | 2020-02-29 | 2020-06-09 | 广州绿邦环境技术有限公司 | Chromium slag resource utilization equipment and treatment process thereof |
| CN112709990A (en) * | 2020-12-21 | 2021-04-27 | 绍兴越信环保科技有限公司 | Preparation method of energy-saving waste salt ball for pyrolysis |
| CN112709990B (en) * | 2020-12-21 | 2023-03-24 | 绍兴越信环保科技有限公司 | Preparation method of energy-saving waste salt ball for pyrolysis |
| CN114087612A (en) * | 2022-01-04 | 2022-02-25 | 山西省安装集团股份有限公司 | Distributed biomass and garbage incineration treatment system |
| CN114087612B (en) * | 2022-01-04 | 2022-04-26 | 山西省安装集团股份有限公司 | Distributed biomass and garbage incineration treatment system |
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Effective date of registration: 20181219 Address after: 266011 Xueyuan Hotel, No. 18 Fushun Road, North District, Qingdao City, Shandong Province Patentee after: Guangda Institute of Environmental Technology (Qingdao) Co., Ltd. Address before: No. 11, Fushun Road, North District, Qingdao, Shandong Patentee before: Qingdao Technological University |