CN113174498A - Resource treatment and recovery method for waste mercury liquid and compounds - Google Patents
Resource treatment and recovery method for waste mercury liquid and compounds Download PDFInfo
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Abstract
The invention relates to a method for recycling waste mercury liquid and compounds, which comprises the steps of firstly adding calcium oxide into mercury-containing hazardous waste, uniformly mixing, then adding a mixture of calcium hypochlorite and calcium oxide, adding water, uniformly stirring, heating, keeping the temperature, standing for a period of time, sequentially preheating materials, primary roasting, secondary roasting, sequentially condensing by a primary multi-return tube condenser and a secondary brine cooler, and performing concentrated recycling treatment on condensate obtained after condensation to obtain high-purity mercury simple substance; and purifying the gas obtained after condensation by a two-stage purification tower sprayed by potassium permanganate solution, and adsorbing the obtained gas by activated carbon to meet the air emission standard. The resource treatment and recovery method of the waste mercury liquid and the compound basically comprises all mercury hazardous waste treatment, not only has a wider treatment range for mercury-containing hazardous waste, but also is clean and pollution-free in the extraction treatment and treatment of mercury in subsequent waste, and accords with the rear-end conventional treatment.
Description
Technical Field
The invention belongs to the technical field of hazardous waste treatment, and particularly relates to a resource treatment and recovery method for waste mercury liquid and compounds.
Background
Along with the living standard of people and the increasingly developed industrialized social process, the application of mercury in the production life of people has a closely related and irreplaceable relationship, which not only influences the social life of people, but also promotes the forward development of society. However, since mercury itself is a highly toxic substance, once it is damaged, discarded or leaked intentionally in the using process, it is not disposable and disposable, and needs to be collected and stored properly, because waste mercury-containing liquid and other mercury-containing compounds are dangerous wastes with high toxicity or high toxicity, tens of thousands of tons of various mercury-containing wastes and other mercury-containing compounds are generated in our country due to industrial production every year, and such dangerous wastes are always a difficult problem of headache in the industry, and have a serious challenge to the treatment and disposal thereof.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a resource treatment and recovery method for waste mercury liquid and compounds. According to the resource treatment and recovery method of the waste mercury liquid and the compounds, calcium oxide is added into dangerous waste containing mercury, a mixture of calcium hypochlorite and calcium oxide is added after the calcium oxide and the calcium oxide are uniformly mixed, water is added for stirring and uniformly mixing, the mixture is heated and kept warm and then stands for a period of time, materials are sequentially preheated, primarily roasted and secondarily roasted, and then primarily multi-return tube condenser condensation and secondary brine cooler condensation are sequentially carried out, and after condensation liquid is obtained after condensation, high-purity mercury simple substance is obtained after concentrated recovery treatment; the gas obtained after condensation is adsorbed by active carbon and purified by a two-stage purification tower sprayed by potassium permanganate solution, and the air emission standard is met.
A resource treatment and recovery method for waste mercury liquid and compounds comprises the following steps:
(1) adding calcium oxide into the dangerous waste containing mercury, fully stirring and mixing for a certain time, adding a mixture of calcium hypochlorite and calcium oxide, adding water, fully stirring uniformly, heating to 70-150 ℃, and preserving heat for a period of time;
(2) standing the mixture for 20-40h after the heat preservation time is up, and stirring for 5min every 30min in the middle;
(3) adding the material obtained in the step (2) into a rotary preheater to obtain preheated hazardous waste;
(4) adding the preheated hazardous waste obtained in the step (3) into a primary rotary circulating heater for heating to 450-560 ℃ for primary roasting, and keeping the temperature for 4-7 hours in a rotary manner;
(5) after the heat preservation in the step (4) is finished, adding the materials into a secondary rotary circulating heater, continuously heating to the temperature of 700-;
(6) introducing the steam generated in the step (5) into the step (4) to carry out heat exchange on the primary rotary circulating heater and then cool, then introducing the steam into the primary multi-return-stroke tubular condenser to carry out condensation, and then introducing the steam into the secondary brine cooler to carry out cooling condensation;
after the condensate obtained after condensation is subjected to centralized recovery treatment, high-purity mercury simple substance is obtained;
the condensed gas is purified by a two-stage purification tower sprayed by potassium permanganate solution, and then is treated by a water-steam separator, the generated water returns to the front end of the process together, and the gas obtained after the water-steam separation is adsorbed by activated carbon and meets the air emission standard.
The mass ratio of the mercury-containing hazardous waste to the calcium oxide is 1-2: 1.5-3.5.
In the step (1), the stirring and mixing time is 1-3 h.
In the step (1), the mass ratio of calcium hypochlorite to calcium oxide is 1: 2;
the added water is condensed reuse water generated in the back-end step (6).
In the step (1), heating to 70-150 ℃ and then preserving heat for 1-3 h.
In the step (2), during the standing period of the mixture, the condensed reuse water generated in the rear end step (6) is supplemented by atomization and spraying to adjust the thin consistency and prevent agglomeration. The reason is that after working for a period of time under heating conditions, mercury vapor, water vapor and other substances which are easy to volatilize can be taken away by negative pressure vacuum, and when water is lost, if water is not supplemented and interval stirring is carried out, most of the mercury vapor, the water vapor and other substances are hardened due to water shortage, and even agglomeration cannot meet the process requirement.
In the step (2), calcium oxide is also added during the standing period of the mixture. The purpose of calcium oxide supplementation is as follows: when the front-end calcium oxide is consumed in the reaction, the subsequent reaction is insufficient in calcium oxide, and the supplement amount is 0.5-3% of the mass of the initially added calcium oxide. Furthermore, calcium oxide supplementation also facilitates the maximized conversion of more mercury species and other compounds of mercury to lower boiling macromolecular compounds under better alkaline conditions.
In the step (3), theoretically, the higher the temperature after preheating is, the better the temperature is, one is for raising the temperature after heat exchange, and the other is for lowering the temperature by heat exchange because the temperature is higher. The higher the temperature after preheating, the smaller the temperature span the back end needs to be heated. The method mainly uses materials needing to be cooled, the temperature needed in the process is high, and the temperature of the materials after preheating in the process is about 150 ℃.
In the step (5), some dangerous wastes which are not completely converted through chemical reaction may exist during the disposal of some mercury compounds, so that the mercury compounds are thermally decomposed into mercury vapor in a form of raising the temperature (the second roasting temperature reaches 900 ℃) and then are recovered.
It should be noted that a large amount of calcium dust can be brought into the steam pulled out by the negative pressure in the steam generated in the step (5), preferably, before the heat exchange is performed, a set of ceramic cyclone dust collector is further arranged between the secondary rotary circulating heater and the primary rotary circulating heater, so that before the steam generated by the secondary rotary circulating heater is introduced into the primary rotary circulating heater for heat exchange, dust is firstly removed to well remove the calcium dust and ash in the steam and the steam, thereby effectively preventing the problem that a tube in the circulating heater is easy to scale, and enabling the circulating heater to have good heat exchange efficiency for a long time.
In addition, because the temperature in the process is higher, mercury vapor generated in the step (5) can be pumped away in time by negative pressure, mercury vapor cannot remain in the collected large-particle calcium dust, the standard for measuring whether the dust reaches the standard for emission is still that the mercury content is lower than 0.30mg/kg, and once the excess amount is detected, the process is continued to the front-end process, and the process procedures such as pretreatment, roasting and the like are carried out.
Preferably, a set of ceramic dust removal device is arranged between the one-level rotary circulation heater and the one-level multi-return tube array condenser, so that the steam generated in the step (5) is firstly introduced into the one-level rotary circulation heater for heat exchange and then is cooled, and then enters the one-level multi-return tube array condenser for condensation, even if the steam contains smaller particles, the dust can be removed by the ceramic dust removal device, and the scaling rate of the tubes in the two-level cooling system is greatly reduced.
In the step (6), after the condensation is carried out by the first-stage multi-return-stroke tube still condenser, the temperature is 15-35 ℃. After being cooled by the secondary brine cooler, the temperature is 0-5 ℃.
The working principle of the primary multi-return-stroke tubular condenser is as follows: one is that heat is transferred from outside to inside, and the transfer is temperature rise; one is that heat transmission and transmission are carried out from inside to outside to reduce the temperature, mercury vapor and water vapor to be reduced are arranged in the tubes, the inner jacket is circulating water or saline water, when steam airflow with higher temperature enters the condenser for multiple return strokes, the steam airflow is equivalently led to be turned back for multiple times in the condenser to increase the joint time and the joint times with cooling water, so that the heat exchange effect between the steam airflow and the cooling water is increased, the cooling speed of the steam is accelerated, the lower the cooling is, the better the steam condensation effect is, the circulating water is, and the cooling significance of the multi-return-stroke condenser is realized.
The reason for adopting the brine for cooling is that the temperature of the general circulating water is 15-35 ℃, and the brine is used for cooling so as to prevent the water vapor, the mercury vapor and the azeotropic gas of the mercury from being completely condensed because of incomplete cooling, so that a brine condenser for cooling at 0-5 ℃ is used for cooling, and the pollution after the mercury vapor comes out can be completely solved.
In the step (6), the precipitate obtained after purification in the purification tower returns to the front end for mixing and then is roasted again.
After multiple times of roasting, detecting that the mercury content in the sludge is lower than 0.30mg/kg, and then treating in an incineration rotary kiln.
The invention has the beneficial effects that:
(1) the resource treatment and recovery method for the waste mercury liquid and the compounds has the advantages of strong treatment pertinence, low cost investment, simpler treatment process flow and no complex process and technical requirements.
(2) The method for recycling the waste mercury liquid and the compounds has wider mercury hazardous waste disposal area, can meet the treatment and disposal of all mercury wastes, is not limited to solid and liquid types, and can treat and dispose other mercury compounds or polymers.
(3) The resource treatment and recovery method for the waste mercury liquid and the compounds can maximize treatment and utilization, and can also recycle mercury simple substances to generate secondary utilization value, so that the method is a desirable method and is also supported and advocated by the state.
(4) According to the resource treatment and recovery method for the waste mercury liquid and the compounds, mechanical equipment is adopted for sealing treatment in the whole process, so that safe, thorough and pollution-free treatment is guaranteed to the maximum extent when manual treatment operation is reduced.
(5) The resource treatment and recovery method of the waste mercury liquid and the compound basically comprises all mercury hazardous waste treatment, not only has a wider treatment range for mercury-containing hazardous waste, but also is clean and pollution-free in the extraction treatment and treatment of mercury in subsequent waste, and accords with the rear-end conventional treatment.
(6) According to the method for recycling the waste mercury liquid and the compounds, the mercury-containing waste is recycled and extracted into the pure mercury simple substance for recycling, so that the mercury-containing waste is recycled and applied to the production and the life of people, and the slag materials are reasonably treated and disposed.
(7) According to the resource treatment and recovery method for the waste mercury liquid and the compounds, water and steam generated in the process treatment are recycled, water and steam are not generated and leaked, the whole process is extracted and recovered in the equipment under negative pressure, and redundant condensate water is returned to the front-end equipment of the process for recycling.
(8) According to the method for recycling the waste mercury liquid and the compounds, calcium oxide is added firstly, and then the mixture of calcium hypochlorite and calcium oxide is added, so that the reaction rate and effect are improved, and the intermediate reaction time is shortened to achieve the purpose of efficient treatment.
(9) According to the resource disposal and recovery method for the waste mercury liquid and the compounds, a preheating cooling system is added, a two-stage cooling system is additionally arranged for safety, and the two-stage cooling system is respectively a one-stage multi-return tube array condenser and a two-stage brine cooler, so that residual mercury vapor in gas can be condensed into elemental mercury to be collected and reused to the maximum extent, and pollution cannot be caused.
(10) According to the method for recycling the waste mercury liquid and the compounds, the gas after temperature reduction is finally subjected to full spraying and washing by two stages of potassium permanganate solutions, so that the mercury content of the tail gas is less than or equal to 0.010mg/Nm3The generated sludge sediment returns to the front end to be continuously disposed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a process flow diagram of the method for recycling waste mercury liquid and compounds according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1
The embodiment provides a resource disposal and recovery method for mercury-containing waste dry batteries, the process flow is shown in figure 1, and the method comprises the following steps:
(1) mechanically disassembling and separating the collected waste dry batteries, roughly separating aluminum alloy outer skins, iron caps, iron shells, carbon rods, powder and the like in the waste dry batteries by using a 3 x 3mm screen, sending filtered substances (namely materials below the screen of the screen and hazardous waste materials containing mercury in the filtered substances) into stirring and mixing equipment, soaking and washing filtered large particles for 2 hours respectively by using 25% potassium permanganate, filtering, washing the filtered large particles for 1 hour by using 20% calcium hypochlorite solution, and oxidizing and washing the large particles to be clean as the large particles are pollutants of mercury so as to recycle the large particles; after the potassium permanganate flushing liquid and the sodium hypochlorite flushing liquid are stood, the generated precipitate and the filter of the screen are used as mercury-containing hazardous waste and sent into stirring and mixing equipment;
adding calcium oxide into the mercury-containing hazardous waste in a stirring and mixing device, wherein the mass ratio of the mercury-containing hazardous waste to the calcium oxide is 2:3.5, fully stirring and mixing for 3 hours, adding a mixture of calcium hypochlorite and calcium oxide, wherein the mass ratio of the calcium hypochlorite to the calcium oxide is 1:2, adding reuse water generated at the rear end, fully stirring uniformly, heating to 150 ℃, and preserving heat for 2 hours;
(2) standing the mixture for 40h after the heat preservation time is up, and stirring for 5min every 30min in the middle; during the standing period of the mixture, the condensed reuse water generated in the rear end step (6) is added by atomization and spraying to adjust the thin consistency, and calcium oxide is also added; preventing caking;
(3) adding the material obtained in the step (2) into a rotary preheater to obtain preheated hazardous waste at the temperature of 150 ℃;
(4) adding the preheated hazardous waste obtained in the step (3) into a primary rotary circulating heater, heating to 560 ℃ for primary roasting, and keeping the temperature for 4 hours in a rotary manner; introducing the steam generated in the step (4) into the rotary preheater in the step (3) for heat exchange and then cooling, then introducing the steam into the first-stage multi-return-stroke tubular condenser for condensation to 35 ℃, and then introducing the steam into the second-stage brine cooler for cooling and condensation to 5 ℃;
(5) after the heat preservation in the step (4) is finished, adding the materials into a secondary rotary circulating heater, continuously heating to 700 ℃ for secondary roasting, and keeping the temperature for 6 hours in a rotary manner;
(6) introducing the steam generated in the step (5) into the step (4) to carry out heat exchange on the primary rotary circulating heater and then cool the steam, then introducing the steam into the primary multi-return-stroke tubular condenser to condense the steam to 35 ℃, and then introducing the steam into the secondary brine cooler to cool and condense the steam to 5 ℃; after the condensate obtained after condensation is subjected to centralized recovery treatment, mercury simple substance with the purity of 99.99 percent is obtained;
the gas obtained after condensation is purified by a two-stage purification tower sprayed by potassium permanganate solution, and then passes through a water-vapor separator, and the generated water returns to the front end of the process together for disposal; the obtained gas is adsorbed by active carbon and meets the air emission standard; and (3) returning the precipitate obtained after purification in the purification tower to the front end for mixing, then carrying out roasting treatment again, detecting that the mercury content in the sludge is lower than 0.30mg/kg after roasting for multiple times, and then entering an incineration rotary kiln for treatment.
It should be noted that, a large amount of calcium dust is brought into the steam drawn out by the negative pressure of the steam generated in the step (5), so that preferably, before the heat exchange is performed, a set of ceramic cyclone dust collector (as shown in fig. 1) is further arranged between the secondary rotary circulating heater and the primary rotary circulating heater, so that before the steam generated by the secondary rotary circulating heater is introduced into the primary rotary circulating heater for heat exchange, dust is removed first, so as to remove the calcium dust and ash in the steam and the steam well, thereby effectively preventing the problem that a tube array in the circulating heater is easy to scale, and enabling the circulating heater to have good heat exchange efficiency for a long time.
In addition, because the temperature in the process is higher, mercury vapor generated in the step (5) can be pumped away in time by negative pressure, mercury vapor cannot remain in the collected large-particle calcium dust, the standard for measuring whether the dust reaches the standard for emission is still that the mercury content is lower than 0.30mg/kg, and once the excess amount is detected, the process is continued to the front-end process, and the process procedures such as pretreatment, roasting and the like are carried out.
As a preferred embodiment, a set of ceramic dust removal device (as shown in fig. 1) is arranged between the primary rotary circulation heater and the primary multi-return tube array condenser, so that the steam generated in the step (5) is firstly introduced into the primary rotary circulation heater for heat exchange and then is cooled, and then enters the primary multi-return tube array condenser for condensation, and even if the steam contains smaller-particle dust, the dust can be removed by the ceramic dust removal device, thereby being beneficial to greatly reducing the scaling rate of the tubes in the two-stage cooling system.
Example 2
The embodiment provides a resource treatment and recovery method of waste mercury liquid and compounds, which comprises the following steps:
(1) mechanically disassembling and separating the collected waste dry batteries, roughly separating the aluminum alloy outer skin, the iron cap, the iron shell, the carbon rod, the powder and the like in the waste dry batteries by using a 3 x 3mm screen, conveying the filtered substances into a stirring and mixing device, soaking and washing the filtered large particles for 1 hour respectively by using 25% potassium permanganate, filtering, washing the filtered large particles for 1 hour by using 10% calcium hypochlorite solution after drying, standing the potassium permanganate washing solution and the sodium hypochlorite washing solution, and conveying the generated precipitate and the screen filtered substances into the stirring and mixing device together as mercury-containing hazardous waste;
adding calcium oxide into the mercury-containing hazardous waste in a stirring and mixing device, wherein the mass ratio of the mercury-containing hazardous waste to the calcium oxide is 1:1.5, fully stirring and mixing for 1h, adding a mixture of calcium hypochlorite and calcium oxide, wherein the mass ratio of the calcium hypochlorite to the calcium oxide is 1:2, adding reuse water generated at the rear end, fully stirring uniformly, heating to 70 ℃, and preserving heat for 2.5 h;
(2) standing the mixture for 20h after the heat preservation time is up, and stirring for 5min every 30min in the middle; during the standing period of the mixture, the condensed reuse water generated in the rear end step (6) is added by atomization and spraying to adjust the thin consistency, and calcium oxide is also added; preventing caking;
(3) adding the material obtained in the step (2) into a rotary preheater to obtain preheated hazardous waste;
(4) adding the preheated hazardous waste obtained in the step (3) into a primary rotary circulating heater, heating to 450 ℃ for primary roasting, and keeping the temperature for 7 hours in a rotary manner; introducing the steam generated in the step (4) into the rotary preheater in the step (3) for heat exchange and then cooling, then introducing the steam into the first-stage multi-return-stroke tubular condenser for condensation to 15 ℃, and then introducing the steam into the second-stage brine cooler for cooling and condensation to 3 ℃;
(5) after the heat preservation in the step (4) is finished, adding the materials into a secondary rotary circulating heater, continuously heating to 700 ℃ for secondary roasting, and keeping the temperature for 8 hours in a rotary manner;
(6) introducing the steam generated in the step (5) into the step (4) to carry out heat exchange on the primary rotary circulating heater and then cool the steam, then introducing the steam into the primary multi-return-stroke tubular condenser to condense the steam to 15 ℃, and then introducing the steam into the secondary brine cooler to cool and condense the steam to 2 ℃;
after the condensate obtained after condensation is subjected to centralized recovery treatment, mercury simple substance with the purity of 99.99 percent is obtained;
the gas obtained after condensation is purified by a two-stage purification tower sprayed by potassium permanganate solution, and then passes through a water-vapor separator, the generated water returns to the front end of the process for disposal, and the obtained gas is adsorbed by active carbon and meets the air emission standard; and (3) returning the precipitate obtained after purification in the purification tower to the front end for mixing, then carrying out roasting treatment again, detecting that the mercury content in the sludge is lower than 0.30mg/kg after roasting for multiple times, and then entering an incineration rotary kiln for treatment.
Example 3
The embodiment provides a resource treatment and recovery method of waste mercury liquid and compounds, which comprises the following steps:
(1) mechanically disassembling and separating the collected waste dry batteries, roughly separating the aluminum alloy outer skin, the iron cap, the iron shell, the carbon rod, the powder and the like in the waste dry batteries by using a 3 x 3mm screen, conveying the filtered substances into stirring and mixing equipment, soaking and washing the filtered large particles for 1.5 hours respectively by using 16% potassium permanganate, filtering, washing the filtered large particles for 0.8 hour by using 15% calcium hypochlorite solution after drying, standing the potassium permanganate washing solution and the sodium hypochlorite, and conveying the generated precipitate and the filtered substances of the screen as hazardous waste containing mercury into the stirring and mixing equipment;
adding calcium oxide into the mercury-containing dangerous waste in a stirring and mixing device, wherein the mass ratio of the mercury-containing dangerous waste to the calcium oxide is 1.5:2.5, fully stirring and mixing for 2 hours, adding a mixture of calcium hypochlorite and calcium oxide, wherein the mass ratio of the calcium hypochlorite to the calcium oxide is 1:2, adding reuse water generated at the rear end, fully stirring uniformly, heating to 110 ℃, and preserving heat for 3.5 hours;
(2) standing the mixture for 30h after the heat preservation time is up, and stirring for 5min every 30min in the middle; during the standing period of the mixture, the condensed reuse water generated in the rear end step (6) is added by atomization and spraying to adjust the thin consistency, and calcium oxide is also added; preventing caking;
(3) adding the material obtained in the step (2) into a rotary preheater to obtain preheated hazardous waste;
(4) adding the preheated hazardous waste obtained in the step (3) into a primary rotary circulating heater, heating to 500 ℃ for primary roasting, and keeping the temperature for 6 hours in a rotary manner; introducing the steam generated in the step (4) into the rotary preheater in the step (3) for heat exchange and then cooling, then introducing the steam into the first-stage multi-return-stroke tubular condenser for condensation to 25 ℃, and then introducing the steam into the second-stage brine cooler for cooling and condensation to 2 ℃;
(5) after the heat preservation in the step (4) is finished, adding the materials into a secondary rotary circulating heater, continuously heating to 800 ℃ for secondary roasting, and keeping the temperature for 7 hours in a rotary manner;
(6) introducing the steam generated in the step (5) into the step (4) to carry out heat exchange on the primary rotary circulating heater and then cool the steam, then introducing the steam into the primary multi-return-stroke tubular condenser to condense the steam to 25 ℃, and then introducing the steam into the secondary brine cooler to cool and condense the steam to 2 ℃;
after the condensate obtained after condensation is subjected to centralized recovery treatment, mercury simple substance with the purity of 99.99 percent is obtained;
the gas obtained after condensation is purified by a two-stage purification tower sprayed by potassium permanganate solution, and then passes through a water-vapor separator, the generated water returns to the front end of the process for disposal, and the obtained gas is adsorbed by active carbon and meets the air emission standard; and (3) returning the precipitate obtained after purification in the purification tower to the front end for mixing, then carrying out roasting treatment again, detecting that the mercury content in the sludge is lower than 0.30mg/kg after roasting for multiple times, and then entering an incineration rotary kiln for treatment.
It should be noted that, the above embodiment is described by taking waste dry batteries as an example, and in actual operation, the method of the present invention is also applicable to the treatment of other hazardous wastes containing mercury, including but not limited to: (1) various waste mercury compounds, standard solutions, waste mercury solutions and the like are generated in laboratories and laboratories; (2) solid other mercury-containing waste collected from the market; (3) a higher concentration of mercury-containing waste liquid; (4) mercury-containing adsorbents and catalysts, etc.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A resource treatment and recovery method for waste mercury liquid and compounds is characterized by comprising the following steps:
(1) adding calcium oxide into the dangerous waste containing mercury, fully stirring and mixing for a certain time, adding a mixture of calcium hypochlorite and calcium oxide, adding water, fully stirring uniformly, heating to 70-150 ℃, and preserving heat for a period of time;
(2) standing the mixture for 20-40h after the heat preservation time is up, and stirring for 5min every 30min in the middle;
(3) adding the material obtained in the step (2) into a rotary preheater to obtain preheated hazardous waste;
(4) adding the preheated hazardous waste obtained in the step (3) into a primary rotary circulating heater for heating to 450-560 ℃ for primary roasting, and keeping the temperature for 4-7 hours in a rotary manner;
(5) after the heat preservation in the step (4) is finished, adding the materials into a secondary rotary circulating heater, continuously heating to the temperature of 700-;
(6) introducing the steam generated in the step (5) into the step (4) to carry out heat exchange on the primary rotary circulating heater and then cool, then introducing the steam into the primary multi-return-stroke tubular condenser to carry out condensation, and then introducing the steam into the secondary brine cooler to carry out cooling condensation;
after the condensate obtained after condensation is subjected to centralized recovery treatment, high-purity mercury simple substance is obtained;
the gas obtained after condensation is purified by a two-stage purification tower sprayed by potassium permanganate solution and then passes through a water-vapor separator, and the obtained gas is adsorbed by active carbon and meets the air emission standard.
2. A resource treatment and recovery method for waste mercury liquid and compounds as claimed in claim 1, wherein in the step (1), the mass ratio of the mercury-containing hazardous waste to the calcium oxide is 1-2: 1.5-3.5.
3. A method for recycling waste mercury liquid and compounds as resources according to claim 1, wherein in step (1), the time for stirring and mixing is 1-3 h.
4. The method for recycling waste mercury liquid and compounds as resources according to claim 1, wherein in the step (1), the mass ratio of calcium hypochlorite to calcium oxide is 1: 2;
the added water is condensed reuse water generated in the back-end step (6).
5. The method for recycling and disposing of waste mercury liquid and compounds as claimed in claim 1, wherein in step (1), the waste mercury liquid and compounds are heated to 70-150 ℃ and then kept warm for 1-3 h.
6. A method for recycling waste mercury liquid and compounds as resources according to claim 1, characterized in that in step (2), during the standing of the mixture, the condensed reuse water generated in the back-end step (6) is supplemented by atomization and spraying to adjust the consistency.
7. A method for recycling waste mercury liquid and compounds as resources according to claim 1, wherein in the step (2), calcium oxide is added during the standing period of the mixed material.
8. A method as claimed in claim 1, wherein the temperature of the condensed waste mercury liquid and compound in step (6) is 15-35 ℃ after the condensed waste mercury liquid and compound are condensed by the first-stage multi-pass tube-in-tube condenser. After being cooled by the secondary brine cooler, the temperature is 0-5 ℃.
9. A method for recycling waste mercury liquid and compounds as resources according to claim 1, wherein in step (6), the precipitate obtained after purification in the purification tower is returned to the front end for mixing and then re-roasting treatment.
10. A method as claimed in claim 9, wherein after multiple roasting, the mercury content in the sludge is detected to be less than 0.30mg/kg, and the sludge is treated in a rotary kiln for incineration.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113604674A (en) * | 2021-08-23 | 2021-11-05 | 云南金鼎锌业有限公司 | Synergistic waste mercury regeneration technology and soaking precipitation pool thereof |
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| CN112251606A (en) * | 2020-10-29 | 2021-01-22 | 新晃鲁湘钡业有限公司 | Distillation recovery method of waste mercury catalyst |
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Application publication date: 20210727 |