CN111195647A - Flash evaporation treatment system and method for recycling multi-element mercury-containing dangerous solid waste resources - Google Patents
Flash evaporation treatment system and method for recycling multi-element mercury-containing dangerous solid waste resources Download PDFInfo
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- CN111195647A CN111195647A CN202010164714.1A CN202010164714A CN111195647A CN 111195647 A CN111195647 A CN 111195647A CN 202010164714 A CN202010164714 A CN 202010164714A CN 111195647 A CN111195647 A CN 111195647A
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 184
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- 238000001704 evaporation Methods 0.000 title claims abstract description 49
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- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
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- 238000013329 compounding Methods 0.000 description 2
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- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- JJWSNOOGIUMOEE-UHFFFAOYSA-N Monomethylmercury Chemical compound [Hg]C JJWSNOOGIUMOEE-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
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- -1 sulfur ions Chemical class 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a flash evaporation treatment system for recycling multi-element mercury-containing dangerous solid waste resources, which comprises an enrichment and reduction device, a crushing device, an electrode oxidation pretreatment device, a low-temperature flash evaporation device, a micron heat filter, refrigerant ultra-cold separation treatment equipment and a dynamic membrane separation and recovery treatment device which are sequentially connected; the low-temperature flash evaporation device is also connected with the discharging device, and the refrigerant ultra-cold separation treatment equipment is sequentially connected with the mercury deep treatment adsorption and capture device and the nano-scale microporous tail gas filter through a vacuum pump; the mercury advanced treatment adsorption capture device and the filler waste discharge port of the nano-scale microporous tail gas filter are both connected with the crushing device, and the waste discharge port of the dynamic membrane separation recovery treatment device is connected with the enrichment and reduction device; the waste discharge port of the micron heat filter is connected with a low-temperature flash evaporation device; the mercury-containing dangerous solid waste realizes the recovery of mercury resources and the treatment of solid waste through the system.
Description
Technical Field
The invention belongs to the field of environmental protection treatment and resource recovery, and relates to harmless treatment and resource recovery of mercury-containing polluted waste, arsenic-containing polluted waste and organic-containing polluted waste, in particular to a flash evaporation treatment system and a flash evaporation treatment method for resource recovery of multi-element mercury-containing dangerous solid waste.
Background content
In recent years, with the continuous development of industrial production, environmental pollution is becoming more serious, and the accumulation, migration and transformation of solid waste pollutants in the environment seriously endanger the ecological environment and human health. Such as municipal sludge, industrial water treatment sludge, municipal domestic waste, sludge produced during oil and gas field mining, smelting slag, tailing slag, and the like. In addition, with the rapid promotion of urbanization in China, a large number of heavily polluted enterprises are closed, and the reserved sites which are not treated are polluted. These complex pollutions with heavy metals-heavy metals, organic matters-organic matters, heavy metals-organic matters, etc. have become one of the focuses of the current technical research and treatment at home and abroad.
Mercury is one of the most toxic heavy metal pollutants, but unlike other heavy metals, it is volatile. An international convention with legal restrictions, water guarantee convention, exclusively related to mercury was globally agreed in 2013, which formally became effective at 8/16/2017 and became the highest-ranking international law, as was the stockholm convention related to persistent organic pollutants. China is the biggest mercury producing country, using country and discharging country in the world, the problem of mercury pollution to the environment of China is very prominent, and most of the mercury and organic compound pollution is caused, and even more serious methyl mercury pollution problem occurs in many places due to the existence of the compound pollution. The low cost, the cooperative removal of mercury and organic multi-element pollution and the cooperative purification of the generated mixed secondary pollution 'water, gas and slag' in the treatment process become practical problems which need to be solved by the technical personnel in the field.
The thermal desorption system and the thermal desorption method for treating mercury-contaminated soil, which are disclosed by the invention patent with the publication number of CN106424113A, only consider a single mercury pollution source from a thermal desorption unit to a tail gas purification system, do not consider other possible pollution factors such as petroleum hydrocarbons, hydrogen sulfide, ammonia nitrogen and the like, and in addition, pollutants such as light hydrocarbon and the like can generate potential safety hazards such as explosion and the like under the condition of the existence of air, so that the thermal desorption system and the thermal desorption method are not suitable for thermal desorption treatment of mercury-containing and organic multi-element pollutants.
The invention patent of the indirect thermal desorption equipment with the publication number of CN101780467A and the skid-mounted soil thermal separation equipment with the publication number of CN104815842A do not adopt a vacuum mode, and the pollutants can be thermally desorbed only by adopting high temperature, so the operation cost is high.
Although the patent publication No. CN208626924U discloses an indirect thermal desorption repair system for treating mercury-containing solid waste and soil and the patent publication No. CN109045898A discloses an indirect thermal desorption repair system and method for treating mercury-containing solid waste and soil, the continuous treatment cannot realize high vacuum, so the treatment temperature needs to reach the high temperature of 400 ℃ or even 800 ℃, the operation cost is high, the service life of a ceramic membrane thermal filter is greatly reduced due to the high temperature, the process tail gas treatment process is complex, a comprehensive treatment scheme is not provided for multi-element mixed tail gas, a large amount of sewage is generated due to the tail gas purification mode, and a complex water treatment process is added in the patent.
The invention patent of the publication No. CN107096790A polluted soil pyrolysis desorption restoration device and method only considers the thermal desorption treatment method of organic pollutants, and does not consider mercury-containing multi-element tail gas treatment and mercury resource recovery.
The invention patent of the patent publication No. CN110586621A, which relates to a complete set of high-efficiency treatment equipment and method for mercury-containing or organic polluted solid waste, relates to the disposal of multi-element mercury-containing waste but does not adopt a vacuum pyrolysis mode.
Although the invention patent with the publication number of CN109226225A, a novel modularized sequencing batch vacuum extraction thermal desorption treatment system and method, adopts a vacuum mode, does not consider comprehensive treatment of 'water, gas and dust' of multi-element secondary pollution caused by multi-element pollutants, does not consider blockage of a subsequent tail gas treatment system caused by dust removal, and simultaneously adopts a high-temperature treatment mode to cause higher operation cost, so that the invention patent is not suitable for actual engineering.
The invention patent of a method for recovering mercury from multi-element mercury-containing dangerous solid waste through high-temperature rotary roasting with publication number CN104532018A takes multi-element mercury-containing dangerous waste as a disposal object, but adopts a high-temperature and complex tail gas treatment process, which can increase the operation cost and does not consider the safety risk of mixing hydrocarbon and air.
Conventional thermal desorption techniques are only suitable for disposal of a single mercury contamination source. From the current patent technology and related academic research journals, no report on a method or technology for treating multi-element mercury-containing dangerous solid waste and recovering resources by high-vacuum low-temperature flash evaporation is found. Therefore, the development of a method or a treatment system for treating multi-element dangerous solid waste by distillation and recovering resources is imperative to the mercury pollution treatment development in China and the performance responsibility of the international mercury convention in view of safety, environmental protection, cost and the like.
Disclosure of Invention
The invention aims to overcome the defects of explosive safety, environmental protection secondary pollution, toxic and harmful gas dissipation, difficult resource recovery, high treatment cost and the like generated when a traditional method is used for treating multi-element dangerous waste, and provides a flash evaporation treatment system for recovering multi-element mercury-containing dangerous solid waste and resources.
The technical scheme of the invention is as follows:
a flash evaporation treatment system for recycling multi-element mercury-containing dangerous solid waste resources comprises an enrichment and reduction device, a crushing device, an electrode oxidation pretreatment device, a low-temperature flash evaporation device, a micron heat filter, refrigerant extreme cold separation treatment equipment and a dynamic membrane separation and recovery treatment device which are sequentially connected; the low-temperature flash evaporation device is also connected with the discharging device, and the refrigerant ultra-cold separation treatment equipment is sequentially connected with the mercury deep treatment adsorption and capture device and the nano-scale microporous tail gas filter through a vacuum pump; the mercury advanced treatment adsorption capture device and the filler waste discharge port of the nano-scale microporous tail gas filter are both connected with the crushing device, and the waste discharge port of the dynamic membrane separation recovery treatment device is connected with the enrichment and reduction device; the waste discharge port of the micron heat filter is connected with a low-temperature flash evaporation device.
The processing method comprises the following steps:
a) by utilizing an enrichment and reduction device, aiming at the mercury-containing hazardous waste with higher water content, a trapping agent and a stabilizing agent are added to trap and fix mercury pollutants in solid substances, and then the mercury pollutants are dehydrated to fully reduce the water content of the mercury pollutants, so that the content of the mercury pollutants in the solid conditions is increased, and the multi-element mercury-containing hazardous solid waste is formed; the treatment efficiency is improved, and the treatment cost is reduced.
b) Feeding the multi-element dangerous solid waste containing mercury into a crushing device, fully crushing the multi-element dangerous solid waste into particles of 0.5cm-5cm, and feeding the particles into the next unit;
c) the method comprises the steps of feeding crushed multi-element mercury-containing dangerous solid waste into an electrode oxidation pretreatment device, adding solid salt with the content of 1% -5% of the total amount of the dangerous solid waste, continuously stirring for 30-90 min to enhance conversion of mercury-containing compounds, wherein certain functional groups of pollutants have electrochemical activity, and the structure of the functional groups is changed through the forced action of an electric field, so that the chemical properties of the pollutants are changed. The electrochemical method of electrode oxidation degrades organic matters such as petroleum hydrocarbon and the like into carbon dioxide, water and other inorganic salts, hydrogen sulfide is oxidized into sulfate, ammonia nitrogen and nitrogen oxide are converted into nitrate, and mercury compounds are converted into mercury oxide; and the subsequent flash evaporation efficiency is improved.
d) C, conveying the multi-element dangerous solid waste containing mercury after electrode oxidation pretreatment into a low-temperature flash evaporation device with the absolute pressure of 30mbar-300mbar, then starting heating, keeping the absolute pressure constant all the time, utilizing the principle of vacuum heating, the heating temperature is 150 ℃ -450 ℃, and the heating time is 0.5h-3h, so that the dangerous solid waste containing mercury formed in the step c is evaporated and extracted under the vacuum environment to form mercury-containing steam, water vapor and dust, and then enters a next micron heat filter; the residual clean solid waste after evaporation and extraction is collected by a discharging device in a centralized way and is recycled by hot clean slag;
e) d, in the micron thermal filter, adopting a suction principle to remove dust and filter the mercury-containing steam and water vapor generated in the step d, and enabling the mercury-containing steam and water vapor which are formed after dust removal and filtration to enter next refrigerant ultra-cold separation treatment equipment; and the filtered dust is recovered to a low-temperature flash evaporation device for treatment again, so that dust-free treatment is realized.
f) In the refrigerant ultra-cold separation treatment equipment, controlling the temperature to be 20-50 ℃, condensing and recovering mercury-containing steam and water vapor to form liquid mercury and mercury-containing wastewater, and feeding the liquid mercury and the mercury-containing wastewater into a next dynamic membrane separation and recovery treatment device for treatment; and the other part of the mercury-containing waste gas which is not condensed enters the next mercury advanced treatment adsorption capture device through the vacuum pump for advanced treatment;
g1) liquid mercury and mercury-containing wastewater are recycled in a dynamic membrane separation and recovery treatment device, and then an irregular dynamic membrane is adopted to form a filter layer with a thickness of 3-5cm and a dense pore canal of 3-5 ten thousand meshes in an irregular shape under a negative pressure state, so that the mercury-containing wastewater is subjected to microfiltration grade precise filtration; realizing the purification treatment of the mercury-containing wastewater, and filtering the residual mercury; the treated irregular dynamic membrane carries filtered residual mercury and returns to the enrichment and reduction device through a waste discharge port for retreatment; the recovered liquid mercury can be reused industrially, and water resources after the mercury-containing wastewater is purified can be reused or discharged;
g2) in the mercury advanced treatment adsorption capture device, adsorption treatment is carried out on the mercury-containing waste gas which is not condensed through activated carbon or resin filler with the mercury removal function filled in the mercury advanced treatment adsorption capture device; finally, the tail gas is deeply filtered by a nano-grade microporous tail gas filter, so that tail gas which meets the environmental protection standard is formed and is discharged; after the filling materials in the mercury advanced treatment adsorption and capture device and the nano-scale microporous tail gas filter are subjected to saturation treatment after long-term operation, the saturated filling materials and dust intercepted by the nano-scale microporous tail gas filter are recycled to the crushing device through the waste discharge port for cyclic treatment;
in step c, the electrode oxidation pretreatment device adopts a catalytic oxidation electrode as follows: any one or two of metal oxide electrode, metal carbide electrode, carbon-based electrode and stainless steel electrode.
In step c, the solid salt added in the electrode oxidation pretreatment device is: one or two or more of sodium hydroxide, sodium carbonate, sodium chloride and sodium sulfate.
In the step e, the aperture of the micron thermal filter is 1-50 microns, and the temperature of the micron thermal filter is consistent with that of the low-temperature flash evaporation device, so that the blocking phenomenon caused by condensation of water vapor and the like is avoided.
In step g1, the membrane used by the dynamic membrane separation recovery processing device is an irregular dynamic ecological membrane which is formed by compounding and modifying different fiber materials such as plant fibers, inorganic mineral fibers and the like.
Compared with the prior art, the invention has obvious economic and social benefits and has the following concrete advantages:
by adopting the electrode oxidation pretreatment device, organic matters such as petroleum hydrocarbon and the like can be degraded into carbon dioxide, water and other inorganic salts, hydrogen sulfide is oxidized into sulfate, ammonia nitrogen and nitrogen oxide are converted into nitrate, and mercury compounds are converted into mercury oxide. The subsequent treatment flows of organic pollution tail gas such as desulfurization and denitrification, hydrogen sulfide, dioxin and the like are reduced, the operation cost is greatly reduced, and the mercury form is unified so as to facilitate the subsequent low-temperature flash evaporation treatment;
the whole treatment process adopts a sequencing batch type sealing device, so that the loss of harmful and toxic gases can be thoroughly inhibited;
the processing of the hazardous pollutants can be realized to the utmost extent at low temperature through the low-temperature flash distillation device by the multi-element hazardous waste materials, the follow-up resource recovery is facilitated, and the operation cost is greatly reduced. Meanwhile, explosion caused by contact of hydrocarbons and oxygen is avoided under the vacuum oxygen-free condition, so that potential safety hazards of production are greatly reduced;
the low-temperature flash evaporation mode is adopted, so that the generation amount of tail gas can be greatly reduced, the generation of dust in the tail gas can be greatly reduced by matching with a heat filter, the tail gas pipeline cannot be blocked, and the whole set of tail gas purification system is simple;
the tail gas purification unit does not relate to water; avoiding the pollution and waste of water resources.
The invention can treat multiple hazardous wastes, such as mercury and various mercury compounds, arsenic and various arsenic compounds, petroleum hydrocarbon and other volatile semi-volatile organic pollutants.
Drawings
FIG. 1 is a schematic structural diagram of the present invention
1-enrichment and reduction device, 2-crushing device, 3-electrode oxidation pretreatment device, 4-low temperature flash evaporation device, 5-micron heat filter, 6-refrigerant ultra-cold separation treatment equipment, 7-dynamic membrane separation and recovery treatment device, 8-vacuum pump, 9-mercury deep treatment adsorption and capture device, 10-nano-scale microporous tail gas filter and 11-discharging device.
Detailed Description
As shown in fig. 1, a flash evaporation treatment system for recycling multi-element mercury-containing hazardous solid waste resources is characterized by comprising an enrichment and reduction device 1, a crushing device 2, an electrode oxidation pretreatment device 3, a low-temperature flash evaporation device 4, a micron thermal filter 5, a refrigerant ultra-cold separation treatment device 6 and a dynamic membrane separation and recovery treatment device 7 which are sequentially connected; the low-temperature flash evaporation device 4 is also connected with a discharging device 11, and the refrigerant ultra-cold separation treatment equipment 6 is sequentially connected with a mercury deep treatment adsorption capture device 9 and a nano-scale microporous tail gas filter 10 through a vacuum pump 8; the mercury advanced treatment adsorption capture device 9 and the filler waste discharge port of the nano-scale microporous tail gas filter 10 are both connected with the crushing device 2, and the waste discharge port of the dynamic membrane separation recovery processing device 7 is connected with the enrichment and reduction device 1; the waste discharge port of the micron thermal filter 5 is connected with the low-temperature flash evaporation device 4.
The method for recycling and treating the multi-element mercury-containing dangerous solid waste resources through the flash evaporation treatment system comprises the following steps:
a) by utilizing the enrichment and reduction device 1, aiming at the mercury-containing hazardous waste with higher water content, the mercury pollutants are captured and fixed in the solid substances by adding the capture agent and the stabilizing agent, and then the mercury pollutants are dehydrated to fully reduce the water content of the mercury pollutants, so that the content of the mercury pollutants in the solid conditions is increased, and the multi-element mercury-containing hazardous solid waste is formed;
b) feeding the multi-element mercury-containing dangerous solid waste into a crushing device 2, fully crushing and feeding the crushed waste into the next unit;
c) sending the crushed multi-element dangerous solid waste containing mercury into an electrode oxidation pretreatment device 3, adding solid salt which contains 1-5% of the total amount of the dangerous solid waste, continuously stirring for 30-90 min to enhance the conversion of mercury-containing compounds, wherein certain functional groups of pollutants have electrochemical activity, and the structure of the functional groups is changed through the forced action of an electric field, so that the chemical properties of the pollutants are changed. The electrochemical method of electrode oxidation degrades organic matters such as petroleum hydrocarbon and the like into carbon dioxide, water and other inorganic salts, hydrogen sulfide is oxidized into sulfate, ammonia nitrogen and nitrogen oxide are converted into nitrate, and mercury compounds are converted into mercury oxide;
d) c, conveying the multi-element dangerous solid waste containing mercury after electrode oxidation pretreatment into a low-temperature flash evaporation device 4 with the absolute pressure of 30mbar-300mbar, then starting heating, keeping the absolute pressure constant all the time, and utilizing the principle of vacuum heating, wherein the heating temperature is 150 ℃ -450 ℃, and the heating time is 0.5h-3h, so that the dangerous solid waste containing mercury formed in the step c is evaporated and extracted under the vacuum environment to form mercury-containing steam, water vapor and dust, and then enters a next micron heat filter 5; the residual clean solid waste after evaporation and extraction is collected in a centralized way through a discharging device 11;
e) d, in the micron thermal filter 5, adopting a suction principle to remove dust and filter the mercury-containing steam and water vapor generated in the step d, and enabling the mercury-containing steam and water vapor which are formed after dust removal and filtration to enter next refrigerant ultra-cold separation treatment equipment 6; the filtered dust is recovered to a low-temperature flash evaporation device 4 for treatment again;
f) in the refrigerant ultra-cold separation treatment equipment 5, the temperature is controlled to be 20-50 ℃, clean mercury-containing steam and water vapor are condensed and recovered to form liquid mercury and mercury-containing wastewater, and the liquid mercury and the mercury-containing wastewater enter the next dynamic membrane separation and recovery treatment device 7 for treatment; and the other part of the mercury-containing waste gas which is not condensed enters a next mercury advanced treatment adsorption capture device (9) through a vacuum pump 8 for advanced treatment;
g1) liquid mercury and mercury-containing wastewater are recycled in a dynamic membrane separation and recovery treatment device 7, and then an irregular dynamic membrane is adopted to form a filter layer with a thickness of 3-5cm and a dense pore canal of 3-5 ten thousand meshes in an irregular shape under a negative pressure state, so that the mercury-containing wastewater is subjected to microfiltration-grade precise filtration; realizing the purification treatment of the mercury-containing wastewater, and filtering the residual mercury; the treated irregular dynamic membrane carries filtered residual mercury and returns to the enrichment and reduction device 1 through a waste discharge port for retreatment;
g2) the mercury-containing waste gas which is not condensed is subjected to adsorption treatment in a mercury advanced treatment adsorption capture device 9 through activated carbon or resin filler which is filled in the mercury advanced treatment adsorption capture device and has a demercuration function; finally, the tail gas is deeply filtered through a nano-grade microporous tail gas filter 10, so that tail gas which meets the environmental protection standard is formed and is discharged; after the filling materials in the mercury advanced treatment adsorption and capture device 9 and the nano-scale microporous tail gas filter 10 are subjected to saturation treatment in long-term operation, the saturated filling materials and dust intercepted by the nano-scale microporous tail gas filter 10 are recycled to the crushing device 2 through respective waste discharge ports for circular treatment;
the electrode oxidation pretreatment device 3 adopts a catalytic oxidation electrode as follows: any one or two of a metal oxide electrode, a metal carbide electrode, a carbon-based electrode and a stainless steel electrode are mixed; the solid salt added in the electrode oxidation pretreatment device 3 is: one or two or more of sodium hydroxide, sodium carbonate, sodium chloride and sodium sulfate.
The pore size of the micron heat filter (5) is 1-50 μm, and the temperature of the micron heat filter is consistent with that of the low-temperature flash evaporation device.
The membrane adopted by the dynamic membrane separation and recovery processing device (7) is an irregular dynamic ecological membrane and is formed by compounding and modifying different fiber materials such as plant fibers, inorganic mineral fibers and the like.
Example 1
Disposing the waste demercuration adsorbent produced in the oil-gas field exploitation process, wherein the weight content of mercury element is 4% (existing in the form of simple substance mercury and mercuric sulfide), and the weight content of petroleum hydrocarbon is 0.3%; firstly, the mercury pollutants are collected into an enrichment and reduction device 1, a capture agent and a stabilizing agent are added to capture and fix the mercury pollutants in solid substances, and then the solid substances are dehydrated to form multi-element dangerous solid wastes containing mercury; then sending the mixture to a crushing device 2 for crushing, wherein the crushing granularity is 5cm, entering an electrode oxidation pretreatment device 3 of a boron-doped diamond electrode, adding sodium hydroxide containing 1% of the total amount of dangerous solid waste, continuously stirring for 60min, degrading organic matters such as petroleum hydrocarbon and the like into carbon dioxide, water and other inorganic salts, oxidizing sulfur ions into sulfate, and simultaneously converting mercury sulfide and partial elementary mercury thereof into mercury oxide; the treatment is carried out by using a low-temperature flash evaporation device 4, air is firstly pumped out in the device to enable the absolute pressure to reach 50mbar, then heating is started, and the absolute pressure is kept constant all the time, wherein the heating temperature is 390 ℃, and the heating time is 2 h. Dedusting and filtering mixed vapor generated in the flash evaporation process by adopting a micron thermal filter 5 with the aperture of 50 mu m, wherein the temperature of the micron thermal filter 5 is consistent with that of a low-temperature flash evaporation device 4, condensing water vapor and mercury vapor at 25 ℃ by adopting refrigerant ultra-cold separation treatment equipment 6, preliminarily recovering liquid mercury by adopting a dynamic membrane separation and recovery treatment device 7, and treating mercury-containing wastewater according to a dynamic membrane separation technology; and (3) other mercury-containing waste gas which cannot be condensed in the refrigerant ultra-cold separation treatment equipment 6 enters a demercuration adsorption tower serving as a mercury advanced treatment adsorption capture device 9 through a vacuum pump 8 to deeply recover residual mercury in the mercury-containing tail gas, and finally, a nano-scale microporous tail gas filter 10 with the pore diameter of 50nm is adopted to deeply purify the tail gas. The treatment effect is shown in table 1.
TABLE 1 Effect of treating waste demercuration agent for oil and gas field
Example 2
Disposing the waste low-mercury catalyst in the polyvinyl chloride catalytic conversion section, wherein the weight content of mercury element is 1.2% (existing in the forms of mercuric chloride and mercurous chloride); firstly, the mercury pollutants are collected into an enrichment and reduction device 1, a capture agent and a stabilizing agent are added to capture and fix the mercury pollutants in solid substances, and then the solid substances are dehydrated to form multi-element dangerous solid wastes containing mercury; and then sending the mixture to a crushing device 2 for crushing, wherein the crushing granularity is 2cm, entering an electrode oxidation pretreatment device of a metal oxide electrode, adding sodium chloride containing 5% of the total amount of dangerous solid waste, continuously stirring for 45min, and converting all mercury chloride and mercurous chloride into mercury oxide. The treatment is carried out by adopting a low-temperature flash evaporation device, air is firstly pumped out in the device to enable the absolute pressure to reach 100mbar, then heating is started, and the absolute pressure is kept constant all the time, wherein the heating temperature is 380 ℃, and the heating time is 1.5 h. Dedusting and filtering mixed vapor generated in the flash evaporation process by adopting a micron heat filter with the aperture of 25 mu m, wherein the temperature of the micron heat filter is consistent with that of a low-temperature flash evaporation device, respectively condensing and primarily recovering water vapor and mercury vapor at 35 ℃ by adopting refrigerant ultra-cold separation treatment equipment, primarily recovering liquid mercury by adopting a dynamic membrane separation and recovery treatment device, and treating mercury-containing wastewater according to a dynamic membrane separation technology; and (3) deeply recovering residual mercury in the mercury-containing tail gas by using a demercuration adsorption tower through a vacuum pump 8 and finally deeply purifying the tail gas by using a nano-scale microporous tail gas filter 10 with the pore diameter of 50nm in other mercury-containing waste gas which cannot be condensed in the refrigerant ultra-cold separation treatment equipment 6. The treatment effect is shown in table 2.
TABLE 2 Effect of treating waste Low-Mercury catalyst
Example 3
Disposing a multi-element polluted site containing mercury and polychlorinated biphenyl, wherein the weight content of mercury element is 0.53 percent (wherein elementary substance mercury is used as the main component, and mercury oxide is contained), and the weight content of polychlorinated biphenyl is 0.6172 percent; firstly, the mercury pollutants are collected into an enrichment and reduction device 1, a capture agent and a stabilizing agent are added to capture and fix the mercury pollutants in solid substances, and then the solid substances are dehydrated to form multi-element dangerous solid wastes containing mercury; and then the mixture is sent to a crushing device 2 for crushing, the crushing granularity is 2cm, the mixture enters a titanium carbide electrode oxidation pretreatment device, sodium sulfate containing 3% of the total amount of dangerous solid wastes is added, the mixture is continuously stirred for 90min, organic matters such as polychlorinated biphenyl and the like are degraded into carbon dioxide, water and other inorganic salts, and meanwhile, other mercury forms such as elemental mercury and mercury oxide thereof are completely converted into mercury oxide. The treatment is carried out by adopting a low-temperature flash evaporation device, air is firstly pumped out in the device to enable the absolute pressure to be 200mbar, then heating is started, and the absolute pressure is kept constant all the time, wherein the heating temperature is 410 ℃, and the heating time is 1 h. Dedusting and filtering mixed vapor generated in the flash evaporation process by adopting a micron heat filter with the aperture of 5 mu m, wherein the temperature of the micron heat filter is consistent with that of a low-temperature flash evaporation device, respectively condensing and primarily recovering water vapor and mercury vapor at 40 ℃ by adopting refrigerant ultra-cold separation treatment equipment, primarily recovering liquid mercury by adopting a dynamic membrane separation and recovery treatment device, and treating mercury-containing wastewater according to a dynamic membrane separation technology; and (3) deeply recovering residual mercury in the mercury-containing tail gas by using a demercuration adsorption tower through a vacuum pump 8 and finally deeply purifying the tail gas by using a nano-scale microporous tail gas filter 10 with the pore diameter of 30nm in other mercury-containing waste gas which cannot be condensed in the refrigerant ultra-cold separation treatment equipment 6. The treatment effect is shown in table 3.
TABLE 3 Effect of treating multi-element hazardous waste containing Hg and polychlorinated biphenyl
The above description is only a part of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention without departing from the technical solution of the present invention.
Claims (6)
1. A flash evaporation treatment system for recycling multi-element mercury-containing dangerous solid waste resources is characterized by comprising an enrichment and reduction device (1), a crushing device (2), an electrode oxidation pretreatment device (3), a low-temperature flash evaporation device (4), a micron heat filter (5), refrigerant ultra-cold separation treatment equipment (6) and a dynamic membrane separation and recovery treatment device (7) which are sequentially connected; the low-temperature flash evaporation device (4) is also connected with a discharging device (11), and the refrigerant ultra-cold separation treatment equipment (6) is sequentially connected with a mercury deep treatment adsorption and capture device (9) and a nano-scale microporous tail gas filter (10) through a vacuum pump (8); the mercury advanced treatment adsorption capture device (9) and the filler waste discharge ports of the nano-scale microporous tail gas filter (10) are both connected with the crushing device (2), and the waste discharge port of the dynamic membrane separation recovery treatment device (7) is connected with the enrichment and reduction device (1); the waste discharge port of the micron heat filter (5) is connected with the low-temperature flash evaporation device (4).
2. The method for recycling and treating the multi-element mercury-containing dangerous solid waste resources by using the flash evaporation treatment system as described in 1 is characterized by comprising the following steps:
a) by utilizing the enrichment and reduction device (1), aiming at the mercury-containing hazardous waste with higher water content, the mercury pollutants are captured and fixed in the solid substances by adding the capture agent and the stabilizing agent, and then the mercury pollutants are dehydrated to fully reduce the water content of the mercury pollutants, so that the content of the mercury pollutants in the solid conditions is increased, and the multi-element mercury-containing hazardous solid waste is formed;
b) feeding the multi-element mercury-containing dangerous solid waste into a crushing device (2), fully crushing and feeding into the next unit;
c) sending the crushed multi-element dangerous solid waste containing mercury into an electrode oxidation pretreatment device (3), adding solid salt with the content of 1-5% of the total amount of the dangerous solid waste, continuously stirring for 30-90 min, enhancing the conversion of mercury-containing compounds, simultaneously degrading organic matters such as petroleum hydrocarbon and the like into carbon dioxide, water and other inorganic salts by an electrochemical method of electrode oxidation, oxidizing hydrogen sulfide into sulfate, converting ammonia nitrogen and nitrogen oxide into nitrate, and converting mercury and mercury compounds into mercury oxide;
d) c, conveying the multi-element dangerous solid waste containing mercury after electrode oxidation pretreatment into a low-temperature flash evaporation device (4) with the absolute pressure of 30mbar-300mbar, then starting heating, keeping the absolute pressure constant all the time, and utilizing the principle of vacuum heating, wherein the heating temperature is 150 ℃ -450 ℃, and the heating time is 0.5h-3h, so that the dangerous solid waste containing mercury formed in the step c is evaporated and extracted under the vacuum environment to form mercury-containing steam, water vapor and dust, and then the dangerous solid waste containing mercury enters a next micron heat filter (5); the residual clean solid waste after evaporation and extraction is collected intensively by a discharging device (11) and is recycled by hot clean slag;
e) d, in the micron heat filter (5), the mercury-containing steam and the water vapor generated in the step d are subjected to dust removal and filtration by adopting a suction principle, and the mercury-containing steam and the water vapor which are cleaned after dust removal and filtration enter the next refrigerant ultra-cold separation treatment device (6); the filtered dust is recovered to a low-temperature flash evaporation device (4) for treatment again;
f) in the refrigerant ultra-cold separation treatment equipment (5), the temperature is controlled to be 20-50 ℃, clean mercury-containing steam and water vapor are condensed and recovered to form liquid mercury and mercury-containing wastewater, and the liquid mercury and the mercury-containing wastewater enter the next dynamic membrane separation recovery treatment device (7) for treatment; and the other part of the mercury-containing waste gas which is not condensed enters the next mercury advanced treatment adsorption capture device (9) through a vacuum pump (8) for advanced treatment;
g1) liquid mercury and mercury-containing wastewater are recycled in a dynamic membrane separation and recovery treatment device (7), and then an irregular dynamic membrane is adopted to form a filtering layer with a thickness of 3-5cm and dense pore canals of 3-5 ten thousand meshes in an irregular shape under a negative pressure state, so that the mercury-containing wastewater is subjected to microfiltration grade precise filtration; realizing the purification treatment of the mercury-containing wastewater, and filtering the residual mercury; the treated irregular dynamic membrane carries filtered residual mercury and returns to the enrichment and reduction device (1) through a waste discharge port for retreatment;
g2) the mercury-containing waste gas which is not condensed is subjected to adsorption treatment in a mercury advanced treatment adsorption capture device (9) through activated carbon or resin filler which is filled in the mercury advanced treatment adsorption capture device and has a mercury removal function; finally, tail gas is deeply filtered through a nano-grade microporous tail gas filter (10), so that tail gas reaching the environmental protection standard is formed and discharged; after the filling materials in the mercury advanced treatment adsorption and capture device (9) and the nano-scale microporous tail gas filter (10) are subjected to saturation treatment in long-term operation, the saturated filling materials and dust intercepted by the nano-scale microporous tail gas filter (10) are recycled to the crushing device (2) through respective waste discharge ports for cyclic treatment.
3. The method for recycling and treating multi-element mercury-containing hazardous solid waste resources according to claim 2, wherein in the step c, the electrode oxidation pretreatment device (3) adopts a catalytic oxidation electrode to: any one or two of metal oxide electrode, metal carbide electrode, carbon-based electrode and stainless steel electrode.
4. The method for recycling and treating multi-element mercury-containing hazardous solid waste resources according to claim 2, wherein in step c, the solid salt added in the electrode oxidation pretreatment device (3) is: one or two or more of sodium hydroxide, sodium carbonate, sodium chloride and sodium sulfate.
5. The method for recycling and treating the multi-element mercury-containing hazardous solid waste resource according to claim 2, wherein in the step e, the pore size of the micron thermal filter (5) is 1-50 μm, and the temperature of the micron thermal filter is consistent with that of the low-temperature flash evaporation device.
6. The method for recycling and treating multi-element mercury-containing hazardous solid waste resources of claim 2, wherein in the step g1, the membrane adopted by the dynamic membrane separation and recycling device (7) is an irregular dynamic ecological membrane which is formed by compositely modifying different fiber materials such as plant fibers, inorganic mineral fibers and the like.
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