CN112430739A - Method for recovering mercury in nonferrous smelting solid waste - Google Patents

Method for recovering mercury in nonferrous smelting solid waste Download PDF

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CN112430739A
CN112430739A CN202011366624.7A CN202011366624A CN112430739A CN 112430739 A CN112430739 A CN 112430739A CN 202011366624 A CN202011366624 A CN 202011366624A CN 112430739 A CN112430739 A CN 112430739A
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mercury
solid waste
flue gas
arsenic
selenium
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沈锋华
刘恢
向开松
李焌源
谢小峰
刘操
李超芳
陈昊
何书丹
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B43/00—Obtaining mercury
    • 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

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Abstract

The invention discloses a method for recovering mercury from non-ferrous smelting solid waste, which is characterized in that after the mercury-containing solid waste and an arsenic-selenium fixing agent are subjected to ball milling treatment, the obtained mixed material is subjected to pyrolysis treatment, and the mercury is condensed and recovered from pyrolysis flue gas. By adopting the method, the volatilization of toxic and harmful trace elements such as arsenic, selenium and the like into the flue gas can be effectively inhibited, and simultaneously, the mercury in the pyrolysis flue gas of the solid waste can be efficiently recovered, so that the recovery and the reutilization of mercury resources are realized, the economic benefit of nonferrous smelting is improved, and the environmental pollution is fully avoided.

Description

Method for recovering mercury in nonferrous smelting solid waste
Technical Field
The invention relates to a method for recovering mercury in non-ferrous smelting solid waste, in particular to a method for reducing volatilization of volatile trace elements such as arsenic and selenium in the solid waste and improving selective volatilization recovery of mercury by using an arsenic-selenium fixing agent, belonging to the field of mercury resource recovery.
Background
Mercury is a highly toxic heavy metal, has pollution characteristics of persistent existence, biological accumulation and long-distance migration in the environment, and has been highly concerned by the international society. China is the largest artificial mercury-emitting country in the world at present, and faces huge responsibility and pressure for mercury pollution emission reduction. The mercury emission of the nonferrous smelting industry accounts for more than 24 percent of the total mercury emission in China, and is one of the largest artificial mercury emission sources in China, and the problem of mercury pollution troubles the sustainable development of the nonferrous smelting industry for a long time. The non-ferrous smelting wet washing process can generate a large amount of solid wastes such as fly ash and acid sludge, the acid sludge contains a large amount of mercury, arsenic, selenium and other elements, and if the elements are not reasonably treated, the ecological environment is seriously damaged. On the other hand, mercury is also an important strategic resource, the annual mercury consumption of China is over 1000 tons, but the international mercury convention limits the exploitation of primary mercury ores, and the objective requirement is provided for acid sludge mercury recovery.
At present, the solid waste is treated mainly by a distillation method in China, which comprises the steps of firstly carrying out heat treatment on the mercury-containing solid waste to completely volatilize mercury, and then condensing and recovering metallic mercury. However, the above prior art solution still has the following drawbacks or disadvantages: firstly, in the method, in the heat treatment process of the solid waste, volatile elements such as arsenic, selenium and the like are volatilized, and are combined with mercury again in the condensation process, so that only mercury products polluted by the elements such as arsenic, selenium and the like can be obtained; secondly, the method needs heat treatment at the temperature of more than 700 ℃ to completely release mercury, and the energy consumption and the cost are high. Accordingly, there is a need in the art for further research and improvement to better meet the complex demands of the solid waste mercury recovery process of modern nonferrous smelting enterprises.
Disclosure of Invention
Aiming at the defects of the method for recovering mercury in the mercury-containing solid waste by a distillation method in the prior art, the invention aims to provide the method for efficiently and selectively recovering mercury in the mercury-containing solid waste, which can effectively fix volatile trace elements such as arsenic and selenium in the solid waste, efficiently recover mercury in pyrolysis flue gas of the solid waste, obtain a mercury product with lower impurity content, realize the recovery and reutilization of mercury resources, improve the economic benefit of nonferrous smelting and fully avoid environmental pollution.
In order to achieve the technical purpose, the invention provides a method for recovering mercury from non-ferrous smelting solid waste, which comprises the steps of carrying out ball milling treatment on mercury-containing solid waste and an arsenic-selenium fixing agent, carrying out pyrolysis treatment on the obtained mixed material, and condensing and recovering mercury from pyrolysis flue gas.
As a preferable scheme, the arsenic-selenium fixing agent comprises at least one of calcium oxide, iron oxide, aluminum oxide, red mud and slag. The preferred arsenic-selenium fixing agent can be used for exciting a chemical reaction with volatile elements such as arsenic, selenium and the like through high-energy ball milling treatment to generate arsenate, selenate and the like which are difficult to volatilize, so that the arsenic and the selenium can be fixed.
As a preferable scheme, the mass ratio of the arsenic-selenium fixing agent to the mercury-containing solid waste is 0.1: 1-2: 1; more preferably, the mass ratio of the arsenic-selenium fixing agent to the mercury-containing solid waste is 0.4: 1-0.6: 1. The dosage of the arsenic-selenium fixing agent is determined according to the content of high-temperature volatile elements such as actual mercury-containing solid waste selenium and arsenic.
As a preferred scheme, the conditions of the ball milling treatment are as follows: the ball-material ratio is 4: 1-12: 1, the ball milling rotation speed is 500-600 r/min, and the ball milling time is 2-6 hours. Under the optimal ball milling treatment condition, the contact area of the fixing agent and the arsenic and selenium in the mercury-containing solid waste can be increased by means of the action of mechanical force, the reaction activation energy between the mercury-containing solid waste and the arsenic-selenium fixing agent is reduced, and then the reaction between the fixing agent and the arsenic and selenium is strengthened by the arsenic-selenium, so that the reaction between the fixing agent and the arsenic and selenium is more sufficient after the ball milling treatment, and the fixing effect is enhanced.
As a preferable scheme, the pyrolysis is carried out for 0.5 to 3 hours at the temperature of 500 to 600 ℃ in the air or nitrogen atmosphere. Is preferably atAnd carrying out pyrolysis treatment on the solid waste under the air atmosphere. The air flow of the air is 20-100 m3H is used as the reference value. The amount of the flue gas generated by the pyrolysis treatment mode is less than that generated by the heat treatment modes such as incineration and the like, so that the flue gas purification process is facilitated, and the environmental protection is facilitated.
As a preferable scheme, the temperature in the process of condensing and recovering mercury is-4 ℃.
The invention provides a method for recovering mercury from nonferrous smelting solid waste, which comprises the following steps:
1) taking solid waste and an arsenic-selenium fixing agent, carrying out ball milling treatment on the solid waste and the arsenic-selenium fixing agent to obtain a pyrolysis raw material, wherein the arsenic-selenium fixing agent is used for adsorbing volatile trace elements such as arsenic and selenium of the solid waste under the pyrolysis treatment condition, and the solid waste is mercury-containing fly ash, acid mud and other solid waste generated by nonferrous smelting;
(2) pyrolyzing a pyrolysis raw material in the air or nitrogen atmosphere to obtain pyrolysis flue gas, wherein volatile trace elements such as arsenic and selenium are adsorbed and fixed by an arsenic-selenium fixing agent to obtain pyrolysis flue gas without arsenic and selenium, and the pyrolysis flue gas without arsenic and selenium contains flue gas mercury components;
(3) and condensing the mercury components in the flue gas in the pyrolysis flue gas without arsenic and selenium to obtain a mercury product.
The arsenic-selenium fixing agent in the invention can be one or a combination of more of calcium oxide, ferric oxide, aluminum oxide and the like, for example: it can be calcium oxide, iron oxide, aluminum oxide, or a mixture of iron oxide and calcium oxide, or a mixture of iron oxide and aluminum oxide, etc. The arsenic-selenium fixing agent is used for adsorbing trace elements in pyrolysis flue gas, wherein the trace elements can comprise: and trace elements such as arsenic, selenium and the like can be converted into a non-volatile form from a volatile form by the trace element fixing agent, so that the trace elements such as arsenic, selenium and the like are not released in the pyrolysis process. The pyrolysis flue gas is flue gas generated by pyrolysis of solid wastes, and the pyrolysis flue gas contains flue gas mercury components. And adsorbing the thermal-fixed trace elements by using the trace element fixing agent to prevent the thermal-fixed trace elements from volatilizing along with mercury in the pyrolysis process, so that the pyrolysis flue gas without the trace elements can be obtained, and the pyrolysis flue gas without the trace elements can be used for flue gas mercury recovery. By the implementation mode, toxic and harmful trace elements in the flue gas can be removed, and the pollution of the release of the trace elements to the environment is avoided.
The invention carries out condensation treatment on the pyrolysis flue gas without trace elements generated after the pyrolysis treatment, and the pyrolysis flue gas contains mercury components, so that a mercury product can be obtained after the condensation treatment, and the mercury recovery is realized. Meanwhile, after the mercury component of the pyrolysis flue gas is removed, the pollution of the mercury component of the flue gas to the environment can be further avoided, the recovered mercury can be recycled as a mercury resource, and the economic benefit of nonferrous smelting is improved.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the method for recovering mercury from non-ferrous smelting solid waste provided by the invention utilizes the arsenic-selenium fixing agent in combination with the ball milling treatment process, can effectively fix trace elements such as arsenic and selenium in the solid waste, avoids the trace elements and mercury from volatilizing at high temperature to interfere with the recovery of mercury, and is beneficial to recovering and obtaining a high-purity mercury product, so that the recycling of mercury resources is realized, the economic benefit of non-ferrous smelting is improved, and the environmental pollution is fully avoided.
Drawings
FIG. 1 is a process flow diagram for recovering mercury from nonferrous smelting solid waste.
FIG. 2 is an XRD spectrum of a typical smelting acid mud.
Fig. 3 is a mercury release profile during thermal treatment of acid sludge.
FIG. 4 shows the release rates of mercury, arsenic and selenium in acid sludge pyrolysis after mechanical force regulation.
FIG. 5 shows the recovery rate of mercury from the mercury-containing solid waste in examples 1 to 10.
FIG. 6 shows the arsenic and selenium contents of the mercury products of examples 1 to 10.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific embodiments. The present invention can be modified and implemented as appropriate within the scope of the main claim.
Example 1
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: performing ball milling treatment on 0.1 solid waste and calcium oxide for 2 hours, wherein the ball-material ratio in the ball milling treatment process is 4:1, the ball milling rotating speed is 400r/min, the main components of the solid waste are fly ash, acid mud and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 1 percent, and the arsenic and selenium contents are both 0.01 percent.
(2) And putting the solid waste and the calcium oxide after the ball milling treatment into an industrial furnace. Wherein the input amount of the solid waste is 50kg/h, and the input amount of the calcium oxide is 10 kg/h. At an air flow rate of 20m3And h, carrying out pyrolysis treatment on the solid waste for 0.5h under the condition that the pyrolysis treatment temperature is 500 ℃ to obtain pyrolysis flue gas, wherein calcium oxide in the industrial kiln can adsorb trace elements such as arsenic and selenium in the pyrolysis flue gas to obtain the pyrolysis flue gas without the trace elements, and the pyrolysis flue gas without the trace elements contains flue gas mercury components.
(3) And (3) carrying out condensation treatment on the flue gas mercury component in the pyrolysis flue gas after trace elements are removed at the temperature of-4 ℃ for 1min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic/selenium in the mercury product is about 100 ppm.
Example 2
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: 2, performing ball milling treatment on the solid waste and the ferric oxide for 6 hours, wherein the ball-to-material ratio in the ball milling treatment process is 12:1, the ball milling rotating speed is 800r/min, the main components of the solid waste are fly ash, acid mud and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 20%, and the arsenic and selenium contents are both 5%.
(2) And putting the solid waste and the ferric oxide after the ball milling treatment into an industrial furnace. Wherein the input amount of the solid waste is 1000kg/h, and the input amount of the ferric oxide is 300 kg/h. At an air flow rate of 100m3And h, pyrolyzing the solid waste for 3h at the pyrolysis treatment temperature of 600 ℃ to obtain pyrolysis flue gas, wherein iron oxide in the industrial kiln can adsorb trace elements such as arsenic and selenium in the pyrolysis flue gas to obtain the pyrolysis flue gas without the trace elements, and the pyrolysis flue gas without the trace elements contains flue gas mercury components.
(3) And (3) carrying out condensation treatment on the flue gas mercury component in the pyrolysis flue gas after the trace elements are removed at 4 ℃ for 5min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic/selenium in the mercury product is about 40 ppm.
Example 3
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: performing ball milling treatment on 0.1 solid waste and alumina for 6 hours, wherein the ball-to-material ratio in the ball milling treatment process is 4:1, the ball milling rotating speed is 800r/min, the main components of the solid waste are fly ash, acid mud and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 20%, and the arsenic and selenium contents are both 0.01%.
(2) And putting the solid waste and the alumina after the ball milling treatment into an industrial furnace. Wherein the input amount of the solid waste is 50kg/h, and the input amount of the alumina is 10 kg/h. At an air flow rate of 100m3And h, pyrolyzing the solid waste for 0.5h at the pyrolysis treatment temperature of 500 ℃ to obtain pyrolysis flue gas, wherein the aluminum oxide in the industrial kiln can adsorb trace elements such as arsenic and selenium in the pyrolysis flue gas to obtain the pyrolysis flue gas without the trace elements, and the pyrolysis flue gas without the trace elements contains flue gas mercury components.
(3) And (3) carrying out condensation treatment on the flue gas mercury component in the pyrolysis flue gas after trace elements are removed at the temperature of-4 ℃ for 5min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic/selenium in the mercury product is about 110 ppm.
Example 4
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: 2, performing ball milling treatment on the solid waste and the mixture of calcium oxide and ferric oxide for 2 hours, wherein the mass ratio of the mixture of calcium oxide and ferric oxide is 1:1, the ball-material ratio in the ball milling treatment process is 12:1, the ball milling speed is 400 r/min. The main components of the solid waste are fly ash, acid sludge and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 1%, and the arsenic content and the selenium content are both 5%.
(2) And putting the solid waste subjected to ball milling treatment and the mixture of calcium oxide and ferric oxide into an industrial furnace. Wherein the input amount of the solid waste is 1000kg/h, and the input amount of the mixture of the calcium oxide and the ferric oxide is 300 kg/h. At an air flow rate of 20m3And h, pyrolyzing the solid waste for 3h at the pyrolysis treatment temperature of 600 ℃ to obtain pyrolysis flue gas, wherein the mixture of calcium oxide and iron oxide in the industrial kiln can adsorb trace elements such as arsenic and selenium in the pyrolysis flue gas to obtain the pyrolysis flue gas without the trace elements, and the pyrolysis flue gas without the trace elements contains flue gas mercury components.
(3) And (3) condensing the flue gas mercury component in the pyrolysis flue gas after the trace elements are removed at 4 ℃ for 1min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic/selenium in the mercury product is about 50 ppm.
Example 5
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: 0.1, performing ball milling treatment on the solid waste and the mixture of calcium oxide and alumina, wherein the mass ratio of the calcium oxide to the mixture of alumina is 1:1, the ball-material ratio in the ball milling treatment process is 4:1, the ball milling speed is 800 r/min. The main components of the solid waste are fly ash, acid sludge and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 1%, and the arsenic and selenium contents are both 0.01%.
(2) And putting the solid waste subjected to ball milling treatment and the mixture of calcium oxide and aluminum oxide into an industrial furnace. Wherein the input amount of the solid waste is 50kg/h, and the input amount of the mixture of the calcium oxide and the ferric oxide is 10 kg/h. At an air flow rate of 20m3And h, pyrolyzing the solid waste for 0.5h at the pyrolysis treatment temperature of 500 ℃ to obtain pyrolysis flue gas, wherein the mixture of calcium oxide and aluminum oxide in the industrial kiln can adsorb trace elements such as arsenic and selenium in the pyrolysis flue gas to obtain the pyrolysis flue gas without the trace elements, and the pyrolysis flue gas without the trace elements contains flue gas mercury components.
(3) And (3) carrying out condensation treatment on the flue gas mercury component in the pyrolysis flue gas after trace elements are removed at the temperature of-4 ℃ for 1min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic/selenium in the mercury product is about 90 ppm.
Example 6
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: 2, performing ball milling treatment on the solid waste and the mixture of iron oxide and aluminum oxide for 6 hours, wherein the mass ratio of the mixture of iron oxide and aluminum oxide is 1:1, the ball-material ratio in the ball milling treatment process is 12:1, the ball milling speed is 800 r/min. The main components of the solid waste are fly ash, acid mud and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 20%, and the arsenic content and the selenium content are both 0.01%.
(2) And putting the solid waste subjected to ball milling treatment and the mixture of the iron oxide and the aluminum oxide into an industrial furnace. Wherein the input amount of the solid waste is 1000kg/h, and the input amount of the mixture of the ferric oxide and the alumina is 300 kg/h. At an air flow rate of 100m3The solid waste is pyrolyzed for 3 hours under the condition that the pyrolysis treatment temperature is 600 ℃ to obtain pyrolysis flue gas, the mixture of ferric oxide and aluminum oxide in the industrial kiln can adsorb trace elements such as arsenic, selenium and the like in the pyrolysis flue gas,obtaining the pyrolysis flue gas without the trace elements, wherein the pyrolysis flue gas without the trace elements contains mercury components in the flue gas.
(3) And (3) carrying out condensation treatment on the flue gas mercury component in the pyrolysis flue gas after trace elements are removed at the temperature of-4 ℃ for 5min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic/selenium in the mercury product is about 30 ppm.
Example 7
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: 0.1 of solid waste and a mixture of calcium oxide, iron oxide and aluminum oxide, wherein the mass ratio of the mixture of calcium oxide, iron oxide and aluminum oxide is 1: 1:1, the ball-material ratio in the ball milling treatment process is 4:1, the ball milling speed is 400 r/min. The main components of the solid waste are fly ash, acid sludge and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 20%, and the arsenic content and the selenium content are both 5%.
(2) And putting the solid waste subjected to ball milling treatment and the mixture of calcium oxide, iron oxide and aluminum oxide into an industrial furnace. Wherein the solid waste is added in an amount of 50kg/h, the mixture of calcium oxide, iron oxide and aluminum oxide is added in an amount of 10kg/h, and the air flow rate is 20m3And h, pyrolyzing the solid waste for 0.5h at the pyrolysis treatment temperature of 500 ℃ to obtain pyrolysis flue gas, wherein the mixture of calcium oxide, iron oxide and aluminum oxide in the industrial kiln can adsorb trace elements such as arsenic and selenium in the pyrolysis flue gas to obtain the pyrolysis flue gas without the trace elements, and the pyrolysis flue gas without the trace elements contains flue gas mercury components.
(3) And (3) carrying out condensation treatment on the flue gas mercury component in the pyrolysis flue gas after trace elements are removed at the temperature of-4 ℃ for 5min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic/selenium in the mercury product is about 60 ppm.
Example 8
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: 2 and a mixture of calcium oxide, iron oxide and aluminum oxide, wherein the mass ratio of the mixture of calcium oxide, iron oxide and aluminum oxide is 1: 1:1, the ball-material ratio in the ball milling treatment process is 12:1, the ball milling speed is 800 r/min. The main components of the solid waste are fly ash, acid sludge and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 1%, and the arsenic and selenium contents are both 0.01%.
(2) And putting the solid waste subjected to ball milling treatment and the mixture of calcium oxide, iron oxide and aluminum oxide into an industrial furnace. Wherein the input amount of the solid waste is 1000kg/h, and the input amount of the mixture of the calcium oxide, the ferric oxide and the aluminum oxide is 300 kg/h. At an air flow rate of 100m3And h, pyrolyzing the solid waste for 3h at the pyrolysis treatment temperature of 600 ℃ to obtain pyrolysis flue gas, wherein the mixture of calcium oxide, iron oxide and aluminum oxide in the industrial kiln can adsorb trace elements such as arsenic and selenium in the pyrolysis flue gas to obtain the pyrolysis flue gas without the trace elements, and the pyrolysis flue gas without the trace elements contains flue gas mercury components.
(3) And (3) carrying out condensation treatment on the flue gas mercury component in the pyrolysis flue gas after the trace elements are removed at 4 ℃ for 5min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic/selenium in the mercury product is about 50 ppm.
Example 9 (control example without arsenic-selenium fixing agent)
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking solid waste to perform ball milling treatment for 2 hours, wherein the ball-material ratio in the ball milling treatment process is 4:1, the ball milling rotating speed is 400r/min, the main components of the solid waste are mercury-containing solid waste such as fly ash and acid mud generated by nonferrous smelting, the mercury content in the solid waste is 1%, and the arsenic and selenium contents are both 0.01%.
(2) And putting the solid waste subjected to ball milling treatment into an industrial furnace. Wherein the input amount of the solid waste is 50 kg/h. At an air flow rate of 20m3And h, performing pyrolysis treatment on the solid waste at the pyrolysis treatment temperature of 500 ℃ to obtain pyrolysis flue gas.
(3) And (3) condensing the flue gas mercury component in the pyrolysis flue gas at 0 ℃ for 1min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the content of arsenic and selenium in the mercury product is about 3%.
Example 10 (comparative example without ball milling treatment)
A method for recovering mercury in nonferrous smelting solid waste comprises the following steps:
(1) taking the mass ratio of 1: 0.1 of solid waste and calcium oxide, wherein the main components of the solid waste are fly ash, acid mud and other mercury-containing solid waste generated by nonferrous smelting, the mercury content in the solid waste is 1 percent, and the arsenic and selenium contents are both 0.01 percent.
(2) Solid waste and calcium oxide are put into an industrial furnace. Wherein the input amount of the solid waste is 50kg/h, and the input amount of the calcium oxide is 10 kg/h. At an air flow rate of 20m3And h, carrying out pyrolysis treatment on the solid waste for 0.5h under the condition that the pyrolysis treatment temperature is 500 ℃ to obtain pyrolysis flue gas, wherein calcium oxide in the industrial kiln can adsorb trace elements such as arsenic and selenium in the pyrolysis flue gas to obtain the pyrolysis flue gas without the trace elements, and the pyrolysis flue gas without the trace elements contains flue gas mercury components.
(3) And (3) condensing the flue gas mercury component in the pyrolysis flue gas after trace elements are removed at the temperature of-4 ℃ for 1min to obtain a flue gas mercury product, wherein the recovery rate of the mercury product is 99%, and the contents of arsenic and selenium in the mercury product are both about 4%.
Through detection, the recovery rate of mercury obtained by the embodiment of the invention can reach 99%, and the recovery method of mercury in the pyrolysis flue gas of the solid waste provided by the embodiment of the invention can effectively recover mercury in the pyrolysis flue gas of the solid waste, thereby realizing the recovery and reutilization of mercury resources, improving the economic benefits of nonferrous smelting and fully avoiding environmental pollution.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.

Claims (6)

1. A method for recovering mercury in nonferrous smelting solid waste is characterized by comprising the following steps: after ball milling treatment is carried out on the mercury-containing solid waste and the arsenic-selenium fixing agent, pyrolysis treatment is carried out on the obtained mixed material, and mercury is condensed and recovered from pyrolysis flue gas.
2. The method for recovering mercury from nonferrous smelting solid waste according to claim 1, characterized in that: the arsenic-selenium fixing agent comprises at least one of calcium oxide, ferric oxide, aluminum oxide, red mud and furnace slag.
3. The method for recovering mercury from nonferrous smelting solid waste according to claim 1, characterized in that: the mass ratio of the arsenic-selenium fixing agent to the mercury-containing solid waste is 0.1: 1-2: 1.
4. The method for recovering mercury from nonferrous smelting solid waste according to claim 1, characterized in that: the ball milling treatment conditions are as follows: the ball-material ratio is 4: 1-12: 1, the ball milling rotation speed is 400-800 r/min, and the ball milling time is 2-6 hours.
5. The method for recovering mercury from nonferrous smelting solid waste according to claim 1, characterized in that: the pyrolysis treatment conditions are as follows: pyrolyzing the mixture for 0.5 to 3 hours at the temperature of 500 to 600 ℃ in the air or nitrogen atmosphere.
6. The method for recovering mercury from nonferrous smelting solid waste according to claim 1, characterized in that: the temperature in the process of condensing and recovering mercury is-4 ℃.
CN202011366624.7A 2020-11-30 2020-11-30 Method for recovering mercury in nonferrous smelting solid waste Pending CN112430739A (en)

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Application publication date: 20210302