US20190070649A1 - Recycling method and apparatus for soil contaminated with mercury and dioxin - Google Patents
Recycling method and apparatus for soil contaminated with mercury and dioxin Download PDFInfo
- Publication number
- US20190070649A1 US20190070649A1 US15/840,237 US201715840237A US2019070649A1 US 20190070649 A1 US20190070649 A1 US 20190070649A1 US 201715840237 A US201715840237 A US 201715840237A US 2019070649 A1 US2019070649 A1 US 2019070649A1
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- dust
- exhaust
- rotary furnace
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- mercury
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- 239000002689 soil Substances 0.000 title claims abstract description 85
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title claims abstract 13
- 238000007599 discharging Methods 0.000 claims abstract description 11
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- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 abstract description 11
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 56
- 239000002245 particle Substances 0.000 description 10
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- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
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- B09C1/065—Reclamation of contaminated soil thermally by pyrolysis
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- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/20—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having rotating or oscillating drums
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- F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
- F23J15/025—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow using filters
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- F27—FURNACES; KILNS; OVENS; RETORTS
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- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
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- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F27B2007/2091—Means for eliminating compounds from gases by condensation, e.g. alkali metals
Definitions
- the present disclosure relates to recycling methods and apparatus for contaminated soil, and more specifically, to a recycling method and apparatus for soil contaminated with mercury and dioxin.
- the existing techniques which have been disclosed for treatment of this kind of highly contaminated soil include heat treatment, adsorption, bacterial degradation and organic solvent extraction methods.
- the heat treatment method employs thermal desorption to isolate the contaminants from the soil, and such a heat treatment technique has been described in TW 201408389. It is well known that a considerable amounts of dust will be generated during treatment of the soil, hence, in the process described in TW 201408389, it is easy to block the system by the contaminants since the heat treatment is performed directly, resulting in the problem of instability of the process.
- an apparatus for treating oil contaminated with mercury and dioxin which includes: an indirect heating rotary furnace for housing and heat treating the contaminated soil, so as for the mercury and the dioxin to desorb from the contaminated soil, thereby generating exhaust containing mercury and dioxin and treated soil; a treated soil storage tank in communication with the indirect heating rotary furnace and configured for receiving the treated soil; a first dust-collecting unit in fluid communication with the indirect heating rotary furnace to collect dust in the exhaust; a condensing and recovering unit in fluid communication with the first dust-collecting unit to condense mercury vapor in the exhaust and to discharge liquid mercury; a secondary indirect burner in fluid communication with the condensing and recovering unit and configured for heat treating the condensed exhaust and decomposing dioxin in the condensed exhaust; a second dust-collecting unit in fluid communication with the secondary indirect burner to collect dust in the exhaust from the secondary indirect burner; and a chimney communicated with the second dust-collecting unit to discharge the exhaust from the second dust-collect
- the present disclosure further provides a recycling method for soil contaminated with mercury and dioxin, which includes: performing a heat treatment on the contaminated soil with an indirect heating rotary furnace, so as for the mercury and the dioxin to desorb from the contaminated soil, thereby generating exhaust containing mercury and dioxin and treated soil; collecting dust in the exhaust by a first dust-collecting unit; receiving the exhaust from the first dust-collecting unit by a condensing and recovering unit to condense mercury vapor in the exhaust and discharge liquid crude mercury; passing the condensed exhaust through a secondary indirect burner to decompose the dioxin in the condensed exhaust; adsorbing dust in exhaust from the secondary indirect burner by a second dust-collecting unit; and discharging the exhaust from the second dust-collecting unit into the air through a chimney in communication with the second dust-collecting unit.
- soil highly contaminated with mercury and dioxin can be treated at the same time to make the treated soil and off-gas meet the regulation standards with the cost less than the existing techniques for treatment of contaminated soil.
- dust generated during the treatment of contaminated soil can also be decreased to avoid air pollution caused by dust escaping and to prevent the system from being blocked by the contaminants, thereby improving the overall stability of the process.
- FIG. 1 is a flow chart involving an apparatus for treating soil contaminated with mercury and dioxin
- FIG. 2 is a schematic diagram showing the structure of an indirect heating rotary furnace
- FIG. 3 is a schematic diagram showing a first dust-collecting unit according to an embodiment
- FIG. 4 is a schematic diagram showing a second dust-collecting unit according to an embodiment
- FIG. 5 is a flow chart involving a second example of the apparatus for treating soil contaminated with mercury and dioxin
- FIG. 6 is a flow chart involving a third example of the apparatus for treating soil contaminated with mercury and dioxin
- FIG. 7 is a schematic diagram showing a dewatering unit according to an embodiment.
- FIG. 8 is a flow chart involving a fourth example of the apparatus for treating soil contaminated with mercury and dioxin.
- the apparatus includes the followings, in sequence: an indirect heating rotary furnace 11 , a treated soil storage tank 110 , a first dust-collecting unit 12 , a condensing and recovering unit 13 , a secondary indirect burner 14 , a second dust-collecting unit 15 and a chimney 16 , wherein the indirect heating rotary furnace 11 is used for holding and heat treating the contaminated soil 100 .
- the maximum throughput of contaminated soil is 6 tons/hr, such allows mercury to be desorbed from the contaminated soil 100 and most of dioxin to be decomposed.
- the indirect heating rotary furnace 11 differs from a direct heating furnace in that the increase in difficulty for subsequent treatment caused by air pollution with contaminated soil can be avoided by using the indirect heating rotary furnace, and therefore, the use of the indirect inner rotary furnace can save investment on apparatus and variable cost of operation.
- FIG. 2 illustrates the structure of the indirect heating rotary furnace 11 .
- the indirect heating rotary furnace 11 includes a feed hopper 112 , an inner rotary furnace 114 in communication with the feed hopper 112 , an outer fixed furnace 113 covering the inner rotary furnace 114 , and a discharging chamber 115 .
- the feed hopper 112 is used for feeding of the contaminated soil 100 .
- the main body of the indirect heating rotary furnace 11 is an inclined (generally, at an inclining angle of 1.25 to 4.75 degrees) cylinder kiln, which includes the outer fixed furnace 113 and the inner rotary furnace 114 , and a space between the outer fixed furnace 113 and the inner rotary furnace 114 full of liquid fuel, such as diesel oil.
- the inner rotary furnace 114 is heated indirectly by burning diesel oil, wherein the temperature can be set to 550 to 650° C., and the heat treatment period using the indirect heating rotary furnace 11 is 20 to 60 minutes.
- the primary cause for the temperature of the indirect heating rotary furnace 11 of the present disclosure being capable of being set to 550 to 650° C. is as follows.
- the heating device used in the present disclosure heats indirectly, subjecting the contaminated soil 100 to oxygen-deficient combustion in the inner rotary furnace 114 .
- the contaminated soil 100 is agitated through friction of the threads inside the inner rotary furnace 114 , and is heated uniformly by rotating the inner rotary furnace 114 at a speed of 1 to 7 rpm. This is helpful to desorb and destroy most of dioxin contaminant, and thereby being capable of carrying out a thermal desorption treatment at a lower temperature.
- the end of the cylinder kiln is in communication with the discharging chamber 115 , to allow the exhaust, which contains mercury and dioxin and is generated during the thermal desorption treatment, to be delivered through an exhaust outlet 115 b into the first dust-collecting unit 12 via a pipeline 111 .
- the output of soil treated by thermal desorption treatment is 1.5 to 4 tons/hr
- the treated soil can be discharged through a treated soil outlet 115 a into the treated soil storage tank 110 where the treated soil is allowed to cool for detection
- the contaminated soil after treatment contains mercury in an amount less than 20 mg/kg and dioxin in an amount less than 1,000 ng International Toxicity Equivalency Quantity (ng I-TEQ/kg).
- ng I-TEQ/kg International Toxicity Equivalency Quantity
- the first dust-collecting unit 12 includes two ceramic filters 122 , 123 disposed in parallel, as shown in FIG. 3 .
- the ceramic filters 122 , 123 receive exhaust from pipeline 111 , and the exhaust after thermal desorption treatment is sent to the condensing and recovering unit 13 through pipeline 121 .
- the first dust-collecting unit 12 can further include a multitubular dust collector (also called “multitubular cyclone dust collector,” not shown in the flow chart) which performs primary screening on larger particles in exhaust from pipeline 111 , and then catches smaller particles with the ceramic filters 122 , 123 .
- a multitubular dust collector also called “multitubular cyclone dust collector,” not shown in the flow chart
- No catalyst is placed in the ceramic filters 122 , 123 , since the exhaust discharged from the indirect heating rotary furnace has a high temperature of 550 to 650° C.
- the ceramic filters 122 , 123 can be resistant to a high temperature of 900° C., and catch most of dust particles with size of about 0.1 ⁇ m using their microporous ceramic fibers.
- the condensing and recovering unit 13 receives exhaust from pipeline 121 , allows mercury vapor in the exhaust to be cooled at a low temperature, and discharges as liquid mercury 130 , wherein the temperature of the condensing and recovering unit is set to ⁇ 30 to 4° C.
- the liquid mercury is output at a rate of 0 to 0.6 kg/hr and collected and sealed in a barrel made of polyethylene.
- the liquid mercury 130 is crude mercury (with a mercury content of about 95 wt %), which needs further rectifying for purification to give pure mercury with a purity of 99.99 wt %.
- the condensing and recovering unit 13 may includes two stages, wherein exhaust from pipeline 121 is cooled to 4° C.
- a sulfur-modified active carbon tank (not shown in the flow chart) can be disposed downstream of the condensing and recovering unit 13 , and exhaust from the condensing and recovering unit 13 is allowed to adsorb residual mercury and is then sent via a pipeline 131 to the secondary indirect burner 14 where the exhaust is treated to decompose of residual dioxin.
- the secondary indirect burner 14 is used for heat treatment of exhaust from the pipeline 131 and decomposition of residual dioxin in the exhaust.
- the secondary indirect burner 14 is placed horizontally, and has a structure including an outer furnace and an inner furnace, wherein the inner furnace is not a rotary furnace and is heated indirectly by liquid fuel, such as diesel oil, at a temperature set to 850 to 950° C.
- the decomposition treatment is performed in the secondary indirect burner 14 for at least 2 sec to completely decompose and crack residual dioxin in the exhaust.
- a heat exchanger (not shown in the flow chart) can be further disposed downstream of the secondary indirect burner 14 . Rhw materials in pipeline 141 is cooled to 180 to 220° C. in the heat exchanger by thermal convection with those in the pipeline 131 prior to being sent to the second dust-collecting unit 15 , and thereby preventing dioxin from de-novo reaction at the high temperature.
- the second dust-collecting unit 15 is used for adsorbing dust in exhaust from the pipeline 141 .
- the second dust-collecting unit 15 includes at least two dust filters disposed in series, and a catalyst is placed inside at least one of the dust filters. In the embodiment as shown in FIG.
- the second dust-collecting unit 15 includes four dust filters 152 , 153 , 154 , 155 disposed in series, and a catalyst is placed in at least one of the dust filters, wherein the dust filter 152 is preferably a ceramic filter for receiving high temperature exhaust from the secondary indirect burner 14 , and dust filter 154 is particularly preferably a catalyst dust filter and has an air-to-cloth ratio under standard conditions of 1-10 m/hr (NM 3 /M 2 /hr).
- the catalyst is utilized to decompose residual dioxin in exhaust from the pipeline 141 by contact oxidation taking place at the active sites on surface of the catalyst at a temperature controlled between 200 and 274° C., and thereby decomposing dioxin into oxidation products including CO 2 , H 2 O, HCl, etc.
- the active ingredient of the catalyst can be at least one selected from V 2 O 5 , W 2 O 3 and MoO 3
- the supporting material of the catalyst is TiO 2 and oxides thereof
- the form of the catalyst can be at least one selected from particles, honeycombs, blocks and foams.
- a sulfur-modified active carbon tank (not shown in the flow chart) can be arranged downstream of the second dust-collecting unit 15 to do completely adsorb residual mercury vapor from the exhaust, and the exhaust finally is delivered via the pipeline 151 to chimney 16 for discharge.
- the discharged exhaust has a temperature of 180 to 240° C., and generally, contains mercury in an amount less than 0.05 mg/Nm 3 , dioxin in an amount less than 0.1 ng I-TEQ/m 3 (ng I-TEQ/Nm 3 ), particle contaminants in an amount less than 80 mg/Nm 3 , and HCl in an amount less than 40 ppm.
- an active carbon jetting unit 71 is further disposed in parallel to the second dust-collecting unit 15 .
- fume exhaust passes through the pipeline 710 , and is infused into the active carbon for adsorption of dioxin prior to entering each of the dust filters 152 , 153 , 154 , 155 .
- dioxin contaminants are transformed from vapor to solid, and then removed by the dust filters 152 , 153 , 154 , 155 .
- dioxin in exhaust is removed at an efficiency of 80 to 90%.
- enhancement on collection efficiency of dust is achieved by disposing drafting devices 21 , 22 downstream of the first dust-collecting unit 12 and the second dust-collecting unit 15 to make the apparatus in a negative pressure environment using a wind pressure, and thereby drawing dust into the first dust-collecting unit 12 and the second dust-collecting unit 15 to prevent formation of filth and subsequent disability of the apparatus caused by dust accumulation.
- the dewatering unit 31 in order to enhance efficiency of condensing mercury vapor and operation stability of the condensing and recovering unit 13 , prior to heat treating the contaminated soil 100 in the indirect heating rotary furnace 11 , water in the contaminated soil 100 is removed by the dewatering unit 31 , and the condensed wastewater 310 is discharged after subsequent treatment.
- the dewatering unit 31 is arranged upstream and communicated with the indirect heating rotary furnace 11 , the dewatered contaminated soil is directed via the pipeline 311 into the indirect heating rotary furnace 11 , and gas generated during dewatering from contaminated soil 100 is delivered via the pipeline 312 into the condensing and recovering unit 13 .
- FIG. 7 illustrates one embodiment of the dewatering unit 31 , which includes another indirect heating rotary furnace 313 , a dust-collecting device 314 and a cooling device 315 in fluid communication with one another in sequence, wherein the another indirect heating rotary furnace 313 has the same structure as the indirect heating rotary furnace 11 , and utilizes the same liquid fuel as the latter one.
- cylinder kiln of the another indirect heating rotary furnace 313 inclines at an angle of 1.25 to 5.15 degree, rotates at a speed of 1 to 5 rpm, and runs at a temperature set to 100-200° C., preferably, at a temperature set to 120- to 150° C. for a heat treatment period of 25 to 50 minutes.
- the dewatered contaminated soil from the another indirect heating rotary furnace 313 is delivered to the indirect heating rotary furnace 11 via the pipeline 311 .
- the cooling device 315 cools exhaust containing water vapor to 50° C., and allows water vapor to be condensed into liquid wastewater 310 , which is discharged after further treatment.
- the dewatered exhaust is delivered from the cooling device 315 via the pipeline 312 to the condensing and recovering unit 13 .
- the dust-collecting device 314 is in communication with and between the another indirect heating rotary furnace 313 and the cooling device 315 via the pipelines 303 , 304 , and is used for adsorbing dust from exhaust generated by the another indirect heating rotary furnace 313 , so as to prevent dust from accumulating in the cooling device 315 at the back o avoid the influence on water condensation efficacy of the cooling device 315 .
- the another indirect heating rotary furnace 313 has the same structure as the indirect heating rotary furnace 11 , and includes a feed hopper; an inner rotary furnace in communication with the feed hopper; an outer fixed furnace covering the inner rotary furnace; and a discharging chamber, wherein the another indirect heating rotary furnace 313 and the indirect heating rotary furnace 11 are in communication with each other via a two-screwed conveyor arranged on the pipeline 311 .
- the inner rotary furnace of the another indirect heating rotary furnace 313 is in communication with the feed hopper of the indirect heating rotary furnace 11 , and the contaminated soil in which water vapor has been removed is delivered to the feed hopper (now shown in Figure) of the indirect heating rotary furnace 11 using the two-screwed conveyor.
- a heat exchanger 41 is further disposed and in communication with the first dust-collecting unit 12 and the condensing and recovering unit 13 to efficiently use thermal energy.
- the temperature of pipeline 121 is cooled to 180 to 220° C. and the temperature of pipeline 131 is elevated to 140 to 160° C. by thermal convection between of the lower temperature exhaust in the pipeline 131 from the condensing and recovering unit 13 and the higher temperature exhaust in the pipeline 121 from the first dust-collecting unit 12 , and thereby efficiently achieving heat energy recycle and reducing unnecessary energy consumption.
- dioxin immediately after decomposition is unstable and would undergo de-novo reaction at 250 to 400° C.
- the heat exchanger 41 allows the exhaust to be cooled from a high temperature of 550 to 650° C. down to 180 to 220° C. (which is lower than the temperature of 250° C. required for de-novo reaction). By slowing the de-novo reaction at a low temperature and the negative pressure design in the pipelines, the de-novo reaction is inhibited.
- pipelines mentioned in the present disclosure can be altered depending on the materials they deliver.
- Thermoresistant pipelines should be utilized if the materials they deliver have high temperature; and anti-corrosion pipelines should be utilized for delivering wastewater or exhaust.
- the selection of materials is well known to a person skilled in the art, and is thus not explained in details.
- Soil contaminated with mercury and dioxin was dewatered by passing through the another indirect heating rotary furnace of the dewatering unit at 6 tons/hr, wherein the another indirect heating rotary furnace inclined at an angle of 2.6 degree and rotated at 2 rpm, and the dewatering process was carried out at a temperature of 150° C. for about 35 minutes; after dewatering, contaminated soil was delivered through pipelines into the indirect heating rotary furnace for heat treatment, wherein the indirect heating rotary furnace inclined at an angle of 2.5 degrees and rotated at 2.5 rpm, and the heat treatment was carried out at a temperature of 650° C. for about 40 minutes for mercury and dioxin to desorb from contaminated soil. Finally, soil after heat treatment was discharged to the treated soil tank at 4 tons/hr.
- the exhaust after heat treatment was dedusted through the multitubular dust collector firstly and then through the first dust-collecting unit consisting of two high temperature ceramic filters arranged in parallel. Thereafter, the exhaust was cooled to 220° C. using the heat exchanger, and then was delivered to the condensing and recovering unit. Similarly, the dewatered exhaust was dedusted through the dust-collecting device firstly and then was cooled to 50° C. via the cooling device, and condensed wastewater was discharged.
- the dewatered exhaust and the aforementioned exhaust after heat treatment were combined via the pipelines, and delivered into the condensing and recovering unit; immediately, the combined exhaust was cooled to 4° C. via the first stage condenser and was cooled to ⁇ 30° C. via the second stage condenser to condense mercury vapor in the exhaust into liquid mercury which was discharged at an output rate of 0 to 0.6 kg/hr into a barrel made of polyethylene with the maximum wastewater discharging amount of 50 tons/day.
- the residual mercury in exhaust which had been completely condensed, was adsorbed in the sulfur modified active carbon tank, warmed gradually to 530° C. with the heat exchanger, and subjected to thermal decomposition of dioxin in the secondary indirect burner at a temperature of 900° C. for at least 2 sec.
- the exhaust was cooled to 220° C. with the heat exchanger to inhibit the de-novo reaction, then entered the four dust filters of the second dust-collecting unit for dust extraction and entered the active carbon jetting unit disposed in parallel for adsorption of dioxin, wherein the dust filters are a high temperature ceramic filter, a catalyst dust filter (REMEDIA; W. L. Gore & Associates, Inc.), and a dust filter in sequence.
- the exhaust was delivered to the chimney and discharged, wherein the discharging amount under standard conditions from the chimney is 1,000 m 3 /hr, and the temperature of the discharged exhaust is 65° C.
- Drafting devices are arranged downstream of each dust-collecting device aforementioned to facilitate dust collection.
- the recycling method and apparatus provided in the present disclosure do have the capacity of treating soil highly contaminated with mercury and dioxin at the same time, so as to allow the treated soil and the exhaust to meet the control standards and to reduce dust generated during treatment of the contaminated soil.
- the process also saves treatment cost for the contaminated soil, as compared to the conventional techniques, and brings about the effect of enhancing stability.
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Abstract
Description
- The present disclosure relates to recycling methods and apparatus for contaminated soil, and more specifically, to a recycling method and apparatus for soil contaminated with mercury and dioxin.
- The factory of CPDC (TAIL) An-shun site, Tainan, Taiwan was involved in the alkali-chlorine industry in the early years. Since sludge and wastewater were inappropriately discharged, soil at the area of the factory was highly contaminated with dioxin and mercury at the same time, which is very difficult to be remedied.
- The existing techniques which have been disclosed for treatment of this kind of highly contaminated soil include heat treatment, adsorption, bacterial degradation and organic solvent extraction methods. Among these, the heat treatment method employs thermal desorption to isolate the contaminants from the soil, and such a heat treatment technique has been described in TW 201408389. It is well known that a considerable amounts of dust will be generated during treatment of the soil, hence, in the process described in TW 201408389, it is easy to block the system by the contaminants since the heat treatment is performed directly, resulting in the problem of instability of the process.
- In addition, since the heat treatment process for contaminated soil will generate dust in an amount of 2-3%, about 25% of PM 2.5 based on the total volume of the dust, and additional air pollution problems will be caused if the dust without further treatment spreads into the air.
- In view of the foregoing, it is necessary to propose a highly stable recycling method and apparatus for treatment of soil contaminated with mercury and dioxin, in order to solve problems of the existing techniques.
- In order to solve above problems, the present disclosure provides an apparatus for treating oil contaminated with mercury and dioxin, which includes: an indirect heating rotary furnace for housing and heat treating the contaminated soil, so as for the mercury and the dioxin to desorb from the contaminated soil, thereby generating exhaust containing mercury and dioxin and treated soil; a treated soil storage tank in communication with the indirect heating rotary furnace and configured for receiving the treated soil; a first dust-collecting unit in fluid communication with the indirect heating rotary furnace to collect dust in the exhaust; a condensing and recovering unit in fluid communication with the first dust-collecting unit to condense mercury vapor in the exhaust and to discharge liquid mercury; a secondary indirect burner in fluid communication with the condensing and recovering unit and configured for heat treating the condensed exhaust and decomposing dioxin in the condensed exhaust; a second dust-collecting unit in fluid communication with the secondary indirect burner to collect dust in the exhaust from the secondary indirect burner; and a chimney communicated with the second dust-collecting unit to discharge the exhaust from the second dust-collecting unit into the air.
- The present disclosure further provides a recycling method for soil contaminated with mercury and dioxin, which includes: performing a heat treatment on the contaminated soil with an indirect heating rotary furnace, so as for the mercury and the dioxin to desorb from the contaminated soil, thereby generating exhaust containing mercury and dioxin and treated soil; collecting dust in the exhaust by a first dust-collecting unit; receiving the exhaust from the first dust-collecting unit by a condensing and recovering unit to condense mercury vapor in the exhaust and discharge liquid crude mercury; passing the condensed exhaust through a secondary indirect burner to decompose the dioxin in the condensed exhaust; adsorbing dust in exhaust from the secondary indirect burner by a second dust-collecting unit; and discharging the exhaust from the second dust-collecting unit into the air through a chimney in communication with the second dust-collecting unit.
- By using the recycling method and apparatus provided in the present disclosure, soil highly contaminated with mercury and dioxin can be treated at the same time to make the treated soil and off-gas meet the regulation standards with the cost less than the existing techniques for treatment of contaminated soil. In addition, dust generated during the treatment of contaminated soil can also be decreased to avoid air pollution caused by dust escaping and to prevent the system from being blocked by the contaminants, thereby improving the overall stability of the process.
-
FIG. 1 is a flow chart involving an apparatus for treating soil contaminated with mercury and dioxin; -
FIG. 2 is a schematic diagram showing the structure of an indirect heating rotary furnace; -
FIG. 3 is a schematic diagram showing a first dust-collecting unit according to an embodiment; -
FIG. 4 is a schematic diagram showing a second dust-collecting unit according to an embodiment; -
FIG. 5 is a flow chart involving a second example of the apparatus for treating soil contaminated with mercury and dioxin; -
FIG. 6 is a flow chart involving a third example of the apparatus for treating soil contaminated with mercury and dioxin; -
FIG. 7 is a schematic diagram showing a dewatering unit according to an embodiment; and -
FIG. 8 is a flow chart involving a fourth example of the apparatus for treating soil contaminated with mercury and dioxin. - Hereinafter, implementations of the present disclosure are illustrated in details by particular embodiments, such that anyone skilled in the art can understand easily the advantages and effects based on the content of the present specification. The present disclosure also can be practiced or applied by other different implementations. Every details in the present specification can be modified and altered differently based on different views and applications, without departing from the spirit of the present disclosure. Additionally, all of the ranges and values used herein are inclusive and combinable. Any value or point fallen within the ranges used herein, such as any integer, can be used as the minimum or maximum value to derive a sub-range.
- Referring to
FIG. 1 , which illustrates an apparatus treating for soil contaminated with mercury anddioxin 100 of the present disclosure, the apparatus includes the followings, in sequence: an indirect heatingrotary furnace 11, a treatedsoil storage tank 110, a first dust-collecting unit 12, a condensing and recoveringunit 13, a secondaryindirect burner 14, a second dust-collectingunit 15 and achimney 16, wherein the indirect heatingrotary furnace 11 is used for holding and heat treating the contaminatedsoil 100. In one embodiment, the maximum throughput of contaminated soil is 6 tons/hr, such allows mercury to be desorbed from the contaminatedsoil 100 and most of dioxin to be decomposed. The indirect heatingrotary furnace 11 differs from a direct heating furnace in that the increase in difficulty for subsequent treatment caused by air pollution with contaminated soil can be avoided by using the indirect heating rotary furnace, and therefore, the use of the indirect inner rotary furnace can save investment on apparatus and variable cost of operation. -
FIG. 2 illustrates the structure of the indirect heatingrotary furnace 11. The indirect heatingrotary furnace 11 includes afeed hopper 112, an innerrotary furnace 114 in communication with thefeed hopper 112, an outer fixedfurnace 113 covering the innerrotary furnace 114, and adischarging chamber 115. Thefeed hopper 112 is used for feeding of the contaminatedsoil 100. The main body of the indirect heatingrotary furnace 11 is an inclined (generally, at an inclining angle of 1.25 to 4.75 degrees) cylinder kiln, which includes the outer fixedfurnace 113 and the innerrotary furnace 114, and a space between the outer fixedfurnace 113 and the innerrotary furnace 114 full of liquid fuel, such as diesel oil. The innerrotary furnace 114 is heated indirectly by burning diesel oil, wherein the temperature can be set to 550 to 650° C., and the heat treatment period using the indirect heatingrotary furnace 11 is 20 to 60 minutes. Compared to conventional techniques, with which oxidation or decomposition of dioxin requires a temperature of at least 850° C., the primary cause for the temperature of the indirect heatingrotary furnace 11 of the present disclosure being capable of being set to 550 to 650° C. is as follows. The heating device used in the present disclosure heats indirectly, subjecting the contaminatedsoil 100 to oxygen-deficient combustion in the innerrotary furnace 114. The contaminatedsoil 100 is agitated through friction of the threads inside the innerrotary furnace 114, and is heated uniformly by rotating the innerrotary furnace 114 at a speed of 1 to 7 rpm. This is helpful to desorb and destroy most of dioxin contaminant, and thereby being capable of carrying out a thermal desorption treatment at a lower temperature. The end of the cylinder kiln is in communication with thedischarging chamber 115, to allow the exhaust, which contains mercury and dioxin and is generated during the thermal desorption treatment, to be delivered through anexhaust outlet 115 b into the first dust-collectingunit 12 via apipeline 111. In one embodiment, the output of soil treated by thermal desorption treatment is 1.5 to 4 tons/hr, the treated soil can be discharged through a treatedsoil outlet 115 a into the treatedsoil storage tank 110 where the treated soil is allowed to cool for detection, the contaminated soil after treatment contains mercury in an amount less than 20 mg/kg and dioxin in an amount less than 1,000 ng International Toxicity Equivalency Quantity (ng I-TEQ/kg). In the contaminated soil treated by the method of the present disclosure, mercury is reduced by 97%, and dioxin contaminant is reduced by 99.87%. - Since a considerable amount of dust is generated during the heat treatment from the contaminated
soil 100 and the dust contains 25% in volume of PM 2.5, it is necessary to dispose the first dust-collectingunit 12 downstream of the indirect heatingrotary furnace 11 to collect dust. In one embodiment, the first dust-collecting unit 12 includes twoceramic filters FIG. 3 . Theceramic filters pipeline 111, and the exhaust after thermal desorption treatment is sent to the condensing and recoveringunit 13 throughpipeline 121. The first dust-collectingunit 12 can further include a multitubular dust collector (also called “multitubular cyclone dust collector,” not shown in the flow chart) which performs primary screening on larger particles in exhaust frompipeline 111, and then catches smaller particles with theceramic filters ceramic filters ceramic filters - The condensing and recovering
unit 13 receives exhaust frompipeline 121, allows mercury vapor in the exhaust to be cooled at a low temperature, and discharges asliquid mercury 130, wherein the temperature of the condensing and recovering unit is set to −30 to 4° C. In one embodiment, the liquid mercury is output at a rate of 0 to 0.6 kg/hr and collected and sealed in a barrel made of polyethylene. Theliquid mercury 130 is crude mercury (with a mercury content of about 95 wt %), which needs further rectifying for purification to give pure mercury with a purity of 99.99 wt %. The condensing and recoveringunit 13 may includes two stages, wherein exhaust frompipeline 121 is cooled to 4° C. in the first stage, and then is cooled to −30° C. in the second stage. A sulfur-modified active carbon tank (not shown in the flow chart) can be disposed downstream of the condensing and recoveringunit 13, and exhaust from the condensing and recoveringunit 13 is allowed to adsorb residual mercury and is then sent via apipeline 131 to the secondaryindirect burner 14 where the exhaust is treated to decompose of residual dioxin. - The secondary
indirect burner 14 is used for heat treatment of exhaust from thepipeline 131 and decomposition of residual dioxin in the exhaust. The secondaryindirect burner 14 is placed horizontally, and has a structure including an outer furnace and an inner furnace, wherein the inner furnace is not a rotary furnace and is heated indirectly by liquid fuel, such as diesel oil, at a temperature set to 850 to 950° C. The decomposition treatment is performed in the secondaryindirect burner 14 for at least 2 sec to completely decompose and crack residual dioxin in the exhaust. A heat exchanger (not shown in the flow chart) can be further disposed downstream of the secondaryindirect burner 14. Rhw materials inpipeline 141 is cooled to 180 to 220° C. in the heat exchanger by thermal convection with those in thepipeline 131 prior to being sent to the second dust-collectingunit 15, and thereby preventing dioxin from de-novo reaction at the high temperature. - The second dust-collecting
unit 15 is used for adsorbing dust in exhaust from thepipeline 141. In one embodiment, the second dust-collectingunit 15 includes at least two dust filters disposed in series, and a catalyst is placed inside at least one of the dust filters. In the embodiment as shown inFIG. 4 , the second dust-collecting unit 15 includes fourdust filters dust filter 152 is preferably a ceramic filter for receiving high temperature exhaust from the secondaryindirect burner 14, anddust filter 154 is particularly preferably a catalyst dust filter and has an air-to-cloth ratio under standard conditions of 1-10 m/hr (NM3/M2/hr). The catalyst is utilized to decompose residual dioxin in exhaust from thepipeline 141 by contact oxidation taking place at the active sites on surface of the catalyst at a temperature controlled between 200 and 274° C., and thereby decomposing dioxin into oxidation products including CO2, H2O, HCl, etc. In addition, the active ingredient of the catalyst can be at least one selected from V2O5, W2O3 and MoO3, the supporting material of the catalyst is TiO2 and oxides thereof, and the form of the catalyst can be at least one selected from particles, honeycombs, blocks and foams. In addition, a sulfur-modified active carbon tank (not shown in the flow chart) can be arranged downstream of the second dust-collectingunit 15 to do completely adsorb residual mercury vapor from the exhaust, and the exhaust finally is delivered via thepipeline 151 tochimney 16 for discharge. The discharged exhaust has a temperature of 180 to 240° C., and generally, contains mercury in an amount less than 0.05 mg/Nm3, dioxin in an amount less than 0.1 ng I-TEQ/m3(ng I-TEQ/Nm3), particle contaminants in an amount less than 80 mg/Nm3, and HCl in an amount less than 40 ppm. - Referring to
FIG. 4 , in one embodiment, in order to completely remove dioxin in exhaust from thepipeline 141, an activecarbon jetting unit 71 is further disposed in parallel to the second dust-collectingunit 15. Thus, fume exhaust passes through thepipeline 710, and is infused into the active carbon for adsorption of dioxin prior to entering each of the dust filters 152, 153, 154, 155. For example, dioxin contaminants are transformed from vapor to solid, and then removed by the dust filters 152, 153, 154, 155. Generally, dioxin in exhaust is removed at an efficiency of 80 to 90%. - Referring to
FIG. 5 , in one embodiment, enhancement on collection efficiency of dust is achieved by disposingdrafting devices unit 12 and the second dust-collectingunit 15 to make the apparatus in a negative pressure environment using a wind pressure, and thereby drawing dust into the first dust-collectingunit 12 and the second dust-collectingunit 15 to prevent formation of filth and subsequent disability of the apparatus caused by dust accumulation. - Referring to
FIG. 6 , in one embodiment, in order to enhance efficiency of condensing mercury vapor and operation stability of the condensing and recoveringunit 13, prior to heat treating the contaminatedsoil 100 in the indirectheating rotary furnace 11, water in the contaminatedsoil 100 is removed by thedewatering unit 31, and thecondensed wastewater 310 is discharged after subsequent treatment. Thedewatering unit 31 is arranged upstream and communicated with the indirectheating rotary furnace 11, the dewatered contaminated soil is directed via thepipeline 311 into the indirectheating rotary furnace 11, and gas generated during dewatering from contaminatedsoil 100 is delivered via thepipeline 312 into the condensing and recoveringunit 13. -
FIG. 7 illustrates one embodiment of thedewatering unit 31, which includes another indirectheating rotary furnace 313, a dust-collectingdevice 314 and acooling device 315 in fluid communication with one another in sequence, wherein the another indirectheating rotary furnace 313 has the same structure as the indirectheating rotary furnace 11, and utilizes the same liquid fuel as the latter one. However, cylinder kiln of the another indirectheating rotary furnace 313 inclines at an angle of 1.25 to 5.15 degree, rotates at a speed of 1 to 5 rpm, and runs at a temperature set to 100-200° C., preferably, at a temperature set to 120- to 150° C. for a heat treatment period of 25 to 50 minutes. Further, the dewatered contaminated soil from the another indirectheating rotary furnace 313 is delivered to the indirectheating rotary furnace 11 via thepipeline 311. Additionally, thecooling device 315 cools exhaust containing water vapor to 50° C., and allows water vapor to be condensed intoliquid wastewater 310, which is discharged after further treatment. The dewatered exhaust is delivered from thecooling device 315 via thepipeline 312 to the condensing and recoveringunit 13. The dust-collectingdevice 314 is in communication with and between the another indirectheating rotary furnace 313 and thecooling device 315 via thepipelines heating rotary furnace 313, so as to prevent dust from accumulating in thecooling device 315 at the back o avoid the influence on water condensation efficacy of thecooling device 315. - In addition, the another indirect
heating rotary furnace 313 has the same structure as the indirectheating rotary furnace 11, and includes a feed hopper; an inner rotary furnace in communication with the feed hopper; an outer fixed furnace covering the inner rotary furnace; and a discharging chamber, wherein the another indirectheating rotary furnace 313 and the indirectheating rotary furnace 11 are in communication with each other via a two-screwed conveyor arranged on thepipeline 311. For example, the inner rotary furnace of the another indirectheating rotary furnace 313 is in communication with the feed hopper of the indirectheating rotary furnace 11, and the contaminated soil in which water vapor has been removed is delivered to the feed hopper (now shown in Figure) of the indirectheating rotary furnace 11 using the two-screwed conveyor. - Referring to
FIG. 8 , in one embodiment, aheat exchanger 41 is further disposed and in communication with the first dust-collectingunit 12 and the condensing and recoveringunit 13 to efficiently use thermal energy. The temperature ofpipeline 121 is cooled to 180 to 220° C. and the temperature ofpipeline 131 is elevated to 140 to 160° C. by thermal convection between of the lower temperature exhaust in thepipeline 131 from the condensing and recoveringunit 13 and the higher temperature exhaust in thepipeline 121 from the first dust-collectingunit 12, and thereby efficiently achieving heat energy recycle and reducing unnecessary energy consumption. Furthermore, since dioxin immediately after decomposition is unstable and would undergo de-novo reaction at 250 to 400° C. to re-form dioxin, theheat exchanger 41 allows the exhaust to be cooled from a high temperature of 550 to 650° C. down to 180 to 220° C. (which is lower than the temperature of 250° C. required for de-novo reaction). By slowing the de-novo reaction at a low temperature and the negative pressure design in the pipelines, the de-novo reaction is inhibited. - In addition, the pipelines mentioned in the present disclosure can be altered depending on the materials they deliver. Thermoresistant pipelines should be utilized if the materials they deliver have high temperature; and anti-corrosion pipelines should be utilized for delivering wastewater or exhaust. The selection of materials is well known to a person skilled in the art, and is thus not explained in details.
- Soil contaminated with mercury and dioxin was dewatered by passing through the another indirect heating rotary furnace of the dewatering unit at 6 tons/hr, wherein the another indirect heating rotary furnace inclined at an angle of 2.6 degree and rotated at 2 rpm, and the dewatering process was carried out at a temperature of 150° C. for about 35 minutes; after dewatering, contaminated soil was delivered through pipelines into the indirect heating rotary furnace for heat treatment, wherein the indirect heating rotary furnace inclined at an angle of 2.5 degrees and rotated at 2.5 rpm, and the heat treatment was carried out at a temperature of 650° C. for about 40 minutes for mercury and dioxin to desorb from contaminated soil. Finally, soil after heat treatment was discharged to the treated soil tank at 4 tons/hr.
- The exhaust after heat treatment was dedusted through the multitubular dust collector firstly and then through the first dust-collecting unit consisting of two high temperature ceramic filters arranged in parallel. Thereafter, the exhaust was cooled to 220° C. using the heat exchanger, and then was delivered to the condensing and recovering unit. Similarly, the dewatered exhaust was dedusted through the dust-collecting device firstly and then was cooled to 50° C. via the cooling device, and condensed wastewater was discharged. The dewatered exhaust and the aforementioned exhaust after heat treatment were combined via the pipelines, and delivered into the condensing and recovering unit; immediately, the combined exhaust was cooled to 4° C. via the first stage condenser and was cooled to −30° C. via the second stage condenser to condense mercury vapor in the exhaust into liquid mercury which was discharged at an output rate of 0 to 0.6 kg/hr into a barrel made of polyethylene with the maximum wastewater discharging amount of 50 tons/day.
- Subsequently, the residual mercury in exhaust, which had been completely condensed, was adsorbed in the sulfur modified active carbon tank, warmed gradually to 530° C. with the heat exchanger, and subjected to thermal decomposition of dioxin in the secondary indirect burner at a temperature of 900° C. for at least 2 sec. Thereafter, the exhaust was cooled to 220° C. with the heat exchanger to inhibit the de-novo reaction, then entered the four dust filters of the second dust-collecting unit for dust extraction and entered the active carbon jetting unit disposed in parallel for adsorption of dioxin, wherein the dust filters are a high temperature ceramic filter, a catalyst dust filter (REMEDIA; W. L. Gore & Associates, Inc.), and a dust filter in sequence. Finally, the exhaust was delivered to the chimney and discharged, wherein the discharging amount under standard conditions from the chimney is 1,000 m3/hr, and the temperature of the discharged exhaust is 65° C.
- Drafting devices are arranged downstream of each dust-collecting device aforementioned to facilitate dust collection.
- Several sampling points are set in the recycling apparatus of the present disclosure for sample analysis and the results are recorded in Tables 1 and 2.
-
TABLE 1 Gas outlet of indirect heating Inlet of Outlet of Inlet of Outlet of rotary Inlet of Outlet of condensing condensing second second furnace of first dust- first dust and and dust- dust dewatering collecting collecting recovering recovering collecting collecting Ex. 1 unit unit unit unit unit unit unit Water (%) 35.8 4.8 5.6 8.6 1.8 3.8 0.9 particle 981.00 473.20 3.22 7.15 1.68 2.35 0.68 contaminants (mg/m3) dioxin 873.70 178.60 82.70 97.30 31.50 2.50 0.05 (ng I-TEQ/ m3) Mercury 3145.00 1154.00 615.00 598.60 118.10 48.10 8.682 and compounds thereof (μg/m3) -
TABLE 2 Gas outlet of Inlet of Outlet of Inlet of Outlet of indirect heating Inlet of Outlet of condensing condensing second second rotary furnace first dust- first dust and and dust- dust of dewatering collecting collecting recovering recovering collecting collecting Ex. 2 unit unit unit unit unit unit unit Water (%) 38.9 5.7 5.65.3 6.1 2.1 4.9 1.7 Particle 1011.32 508.35 5.94 8.43 2.04 1.93 0.84 contaminants (mg/m3) Dioxin 1189.74 183.78 84.01 102.27 36.69 2.81 0.06 (ng I-TEQ/m3) Mercury and its 3987.24 2209.87 1098.66 784.10 279.44 205.98 28.964 compounds (μg/m3) - Quality detection results of the feed soil, treated soil, condensate wastewater, chimney off-gas and ambient air are recorded in Tables 3-6, respectively.
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TABLE 3 Ex. 1 Ex. 2 Standard Feeding Treated Feeding Treated Soil detection Value soil soil soil soil Mercury (mg/kg) 20 34 1.06 38.9 1.17 Average value of 1000 79200 205 71400 90.4 dioxin (ng I-TEQ/m3) -
TABLE 4 Quality detection of condensate Standard wastewater Value Ex. 1 Ex. 2 Suspended solids (mg/L) 25 <1.0 <1.0 Mercury (mg/L) 0.005 0.0049 0.0011 Average value of dioxin — 20.8 24.4 (pg I-TEQ/m3) -
TABLE 5 Standard Detection of chimney off-gas Value Ex. 1 Ex. 2 Particle contaminants (mg/m3) 80 ND 1.15 (<1.0) Hydrogen chloride (ppm) 40 0.00579 ND (<2.83) Mercury and compounds thereof 0.05 ND ND (mg/m3) (<0.0006) (<0.0006) Average value of dioxin 0.1 0.019 0.01 (ng I-TEQ/m3) *Note: ND means undetected, which is lower than the minimum value capable of being detected by the apparatus used. -
TABLE 6 Ambient air quality monitoring Standard (Annan detecting station) Value Ex. 1 Ex. 2 Daily average value of suspended 125 58 to 141 10 to 46 particles with sizes smaller than or (Monthly equal to 10 μm (PM10) (μg/m3) average, 78) 24 hrs value of suspended particles 35 20 to 74 ND to 24 with sizes smaller than or equal to (Monthly 25 μm (PM25) (μg/m3) average, 37) *Note: ND means undetected, which is lower than the minimum value capable of being detected by the apparatus used. - In conclusion, the recycling method and apparatus provided in the present disclosure do have the capacity of treating soil highly contaminated with mercury and dioxin at the same time, so as to allow the treated soil and the exhaust to meet the control standards and to reduce dust generated during treatment of the contaminated soil. The process also saves treatment cost for the contaminated soil, as compared to the conventional techniques, and brings about the effect of enhancing stability.
- The above examples are used for illustration, rather than for limiting the present disclosure. Anyone skilled in the art can make modifications and alterations on the above examples, without departing from the spirit and scope of the present disclosure. Therefore, the scope of the present application should be defined by the appended claims, and shall be encompassed in the technical content of the present specification so long as it has no influence on the effects and purposes.
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CN110006065A (en) * | 2019-05-27 | 2019-07-12 | 桂林航天工业学院 | Refuse burning system and method based on the selective catalytic denitrification process catalysis combustion integrative |
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CN113751485B (en) * | 2020-06-04 | 2023-03-21 | 中石化绿能科技股份有限公司 | Soil pollution's heat treatment system |
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CN110006065A (en) * | 2019-05-27 | 2019-07-12 | 桂林航天工业学院 | Refuse burning system and method based on the selective catalytic denitrification process catalysis combustion integrative |
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