WO2014148623A1 - ダスト洗浄装置及びダスト洗浄方法 - Google Patents
ダスト洗浄装置及びダスト洗浄方法 Download PDFInfo
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- WO2014148623A1 WO2014148623A1 PCT/JP2014/057866 JP2014057866W WO2014148623A1 WO 2014148623 A1 WO2014148623 A1 WO 2014148623A1 JP 2014057866 W JP2014057866 W JP 2014057866W WO 2014148623 A1 WO2014148623 A1 WO 2014148623A1
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- Prior art keywords
- fluorine
- dust
- slurry
- cleaning
- concentration
- Prior art date
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- 239000000428 dust Substances 0.000 title claims abstract description 139
- 238000004140 cleaning Methods 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 113
- 239000011737 fluorine Substances 0.000 claims abstract description 113
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000011701 zinc Substances 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 20
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims description 80
- 239000007788 liquid Substances 0.000 claims description 42
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 23
- 229910001385 heavy metal Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- -1 fluorine ions Chemical class 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000002386 leaching Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004056 waste incineration 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
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
Definitions
- the present invention relates to a dust cleaning apparatus and a cleaning method used for cleaning dusts necessary for recycling discharged dust or the like as a raw material for zinc refining in a metal smelting process.
- Dust, scale, sludge, etc. generated when producing ordinary steel and stainless steel are reduced and reused by using metal reduction furnaces such as rotary hearth furnaces and electric resistance furnaces.
- the dust generated from the metal reduction furnace contains zinc, lead and cadmium as heavy metal components, and further fluorine is concentrated to 2% or more, but halogens such as fluorine and chlorine in the dust are Since it becomes hydrogen fluoride and hydrogen chloride in the furnace and damages the refractories that make up the furnace body, in order to make it possible to recycle dust as a raw material for zinc smelting, these halogens, especially fluorine, are removed. There was a need to do.
- the present invention relates to a cleaning apparatus and a cleaning method used for a process of cleaning and removing fluorine and the like from dust of a zinc refining raw material.
- trash discharged from business establishments and general households (referred to as “city trash” or “general waste”) is collected and incinerated at city trash incineration plants and industrial waste incineration plants. Yes.
- Incineration ash and fly ash (also referred to as primary dust) generated from the incinerator and the like at that time are deposited in the final disposal site after performing chemical treatment or intermediate treatment such as melting furnace and cement kiln treatment.
- primary dust (for example, converter dust T: about 60% Fe content) generated during iron refining is a rotary hearth furnace (rotary hearth type reducing furnace, for example, Patent Document 1) or a reductive melting rotary kiln. Reduced iron is produced by reduction in a reduction furnace such as a furnace (for example, Patent Document 2).
- This secondary dust contains a large amount of concentrated heavy metals such as zinc, lead, and cadmium along with chlorine, fluorine, sodium, and potassium. And a processing method was sought.
- Patent Document 3 discloses that a heavy metal-containing starch is obtained by solid-liquid separation after adjusting the pH to 12 or more using an alkaline agent.
- the chlorine concentration in the recovered sediment after the alkali leaching treatment can be reduced from 40% to 3% or less when the liquid phase portion in the recovered sediment is washed with water and the liquid phase portion containing chlorine is washed away.
- the effect of reducing fluorine is not disclosed.
- Patent Document 4 the crude zinc oxide powder is put into an alkaline solution, stirred while maintaining the pH at 10 or more, and further washed with alkali, washed with water, and dried, so that the halogen element in the crude zinc oxide powder is reduced.
- fluorine can be reduced from 1.0% to 0.3% or less, treatment of dust containing 2% or more of fluorine is not considered.
- Patent Document 3 and Patent Document 4 do not describe a processing apparatus and a processing method using secondary dust having such a large difference in leaching rate and large difference in concentration.
- the present invention provides a dust cleaning apparatus for stably and efficiently reducing fluorine in dust containing zinc, lead and cadmium as metal components and further containing 2% or more of fluorine.
- An object is to provide a dust cleaning method.
- a dust cleaning apparatus includes zinc, lead, and cadmium as heavy metal components, and further, dust containing 2% or more of fluorine and a cleaning liquid are mixed to form a slurry, and the dust is converted into fluorine.
- a fluorine ion concentration meter that measures the fluorine ion concentration of the slurry and a fluorine ion concentration control device that controls the fluorine ion concentration of the slurry measured by the fluorine ion concentration meter are mounted.
- the pH control device controls the pH of the slurry by adding an alkaline agent such as an aqueous NaOH solution to the slurry so that the pH value of the slurry measured by the pH meter is within a predetermined range.
- the fluorine concentration control device controls the amount of the fluorine ion concentration of the slurry by controlling the amount of the cleaning liquid added to the slurry so that the fluorine ion concentration of the slurry measured by the fluorine ion concentration meter is within a predetermined range. Take control.
- the fluorine ion concentration control device may control the fluorine ion concentration of the slurry in the range of 100 to 14000 mg / l.
- the pH control device may control the pH value of the slurry in the range of 10 to 13.
- a dust cleaning method includes zinc, lead, and cadmium as heavy metal components, and further, dust containing 2% or more of fluorine and a cleaning liquid are mixed to form a slurry, and the dust is converted into fluorine.
- a dust cleaning method in which the slurry is leached into the cleaning liquid and controlled so that the pH value of the slurry becomes 10 to 13, and stirring is performed until the fluorine concentration of the slurry is saturated. It has a washing step for collecting dust, and the washing step is carried out once or repeated twice or more until the fluorine concentration of the slurry before the collection becomes 2000 mg / l or less.
- the dust cleaning method according to one aspect of the present invention is the dust cleaning method according to (4), wherein the cleaning step is performed once until the fluorine concentration of the slurry before recovery is 500 mg / l or less. It may be performed repeatedly more than once. In the cleaning process, cleaning liquids of the same component may be used. Alternatively, in the cleaning process performed until the fluorine concentration of the slurry is saturated and the cleaning process of cleaning the dust until the fluorine concentration of the slurry reaches 2000 mg / l or less, using cleaning liquids adjusted to different components or pH values, respectively. You can go. Moreover, the washing
- concentration of a slurry 2000 mg / l or less may be repeated not only once but repeatedly.
- the pH value condition in the cleaning process may be set to a different range so that the pH value is in the range of 10 to 13 for each different cleaning process.
- the fluorine concentration of the dust after cleaning can be reduced to 1.0% or less by controlling the fluorine concentration of the slurry to be finally 1000 mg / l or less.
- the fluorine concentration of the dust after cleaning can be reduced to 0.5% or less by controlling the fluorine concentration of the slurry to be finally 500 mg / l or less.
- the present invention it is possible to stably wash and remove fluorine from dust discharged from the reduced iron production process and dust having a high fluorine content such as municipal waste secondary dust with low environmental impact. It is possible to provide a cleaning apparatus and a cleaning method that can have a low fluorine content and can effectively use the dust as a raw material for zinc smelting.
- Fig. 1 shows the relationship between pH and various metal ion concentrations in an aqueous solution. It is illustrated that zinc and lead have the lowest solubility near pH 9.2, and cadmium has the lowest solubility near pH 11.2.
- the metal component concentration and fluorine concentration of the slurry can be controlled.
- the pH may be increased, while zinc, lead and cadmium to be recovered also leach out.
- the solubility of zinc is 3 mg / l and the solubility of lead is 700 mg / l. If the amount of cleaning liquid is large, zinc and lead are leached from the dust and the loss increases. Therefore, it is necessary to reduce the amount of the cleaning liquid as much as possible.
- the reaction proceeds while consuming NaOH which is an alkaline agent. Therefore, the pH of the slurry is lowered.
- a control device for introducing an alkaline agent such as NaOH is required.
- the end point of the leaching reaction is a point in time when pH change is eliminated and pH control becomes unnecessary.
- Dust 50g, 100g, and 150g with a fluorine concentration of 6.6% are dispensed into separate containers, and 400 ml of water is placed in each container as a cleaning solution, stirred to form a slurry, and then 20% water is added to the slurry. A sodium oxide aqueous solution was added to adjust the pH of the slurry to 11.5 while monitoring with a pH meter.
- FIG. 3 shows the result of measuring and recording the fluorine ion concentration using a fluorine ion electrode. From the figure, the greater the amount of dust, the higher the fluorine concentration, but there is no significant difference between 100 g and 150 g. It is saturated around 12000 mg / l.
- an efficient fluorine leaching process can be performed in a short time. Thereafter, the slurry is subjected to solid-liquid separation, and the dust leached with fluorine is collected.
- the solid-liquid separation method is not particularly limited. For example, after a coagulant is added to the slurry and the dust settles, the supernatant liquid can be discarded and the dust can be recovered. A series of processes until the dust from which the fluorine is leached is collected is called “cleaning process” in the present invention.
- the saturation concentration of fluorine in the slurry was in the range of 9000 to 14000 mg / l, depending on the pH of the slurry and the dust composition.
- the time to reach the saturation concentration varies depending on the dust composition and the stirring conditions of the apparatus. For example, when the calcium concentration in the dust is high, the time becomes longer. This is considered to be caused by the generation of CaF 2 having a strong bond in the dust.
- the dust after the washing process recovered from the leached slurry by solid-liquid separation contains a large amount of moisture, and the moisture contains a large amount of fluorine ions together with sodium ions caused by alkali. Will be included.
- these elements can be washed away.
- a cleaning solution for example, tap water
- the pH is lowered while dust is being washed, and metals such as zinc, lead, and cadmium are leached, leading to a decrease in concentration. .
- the range where leaching of cadmium does not occur is pH 10 to 13.5.
- the cadmium discharge water standard of 0.1 mg / l or less can be satisfied. That is, leaching of cadmium hardly occurs if the pH of the washing water when washing the dust is adjusted to 10 to 13, preferably 10 to 11.
- the pH adjuster is preferably an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution that does not cause precipitation of fluorine ions.
- cadmium ions are mixed in the washing waste liquid. As shown in FIG. 1, cadmium ions do not precipitate in the neutral to acidic region. For example, it is necessary to introduce sulfide ions, precipitate them as cadmium sulfide, and separate them from the washing water, which is very inefficient.
- dust can be efficiently cleaned by attaching a pH meter and a pH control device to the cleaning device and always maintaining an appropriate pH in the dust cleaning process.
- FIG. 4 shows the relationship between the fluorine concentration in the dust after cleaning and the fluorine concentration in the slurry.
- the fluorine concentration in the dust is a value obtained by drying the washed dust and then analyzing it by an absorptiometric method of chemical analysis, and it took one week to obtain an analysis result.
- the fluorine concentration of the cleaning liquid is an indication value of a fluorine ion concentration meter equipped in the apparatus.
- the fluorine concentration in the slurry should be 500 mg / l or less. That is, if a fluorine ion concentration meter is attached to the cleaning device and the concentration is monitored, the end point of the dust cleaning process can be grasped.
- the relationship between the fluorine concentration in the slurry and the fluorine concentration in the dust varies depending on the dilution ratio of the cleaning liquid with respect to the dust amount.
- the lower limit of the fluorine concentration is not particularly limited, but since a large amount of cleaning liquid is required to reduce the fluorine concentration in dust, it is preferable to set the lower limit to 100 mg / l from an economical viewpoint.
- the fluorine concentration in the dust can be reduced to a predetermined fluorine concentration or less by repeating the cleaning process twice or more.
- a predetermined fluorine concentration can be obtained by a single cleaning process.
- the adjustment of the cleaning liquid is not particularly limited, and a plurality of cleaning liquids adjusted to different pHs may be prepared in advance.
- a single type of cleaning liquid whose pH value is adjusted to any one of 10 to 13 is prepared in advance, and the pH value of the cleaning liquid is readjusted according to conditions such as the amount of usable cleaning liquid or the temperature of the slurry. Thereafter, the cleaning liquid may be used for the cleaning process.
- a pH meter and pH control for a cleaning device that contains zinc, lead, and cadmium as heavy metal components and further mixes a dust containing 2% or more of fluorine with an alkaline cleaning solution to leach and clean fluorine from the dust. Equipped with a device, and further equipped with a fluorine ion concentration meter and a fluorine ion concentration control device, it is possible to efficiently control pH for the leaching treatment of fluorine from dust, and to grasp the progress and end point of the leaching treatment. . Furthermore, with regard to the cleaning process following the leaching process, it is possible to efficiently control the pH, judge the progress of the cleaning process, the necessity of additional cleaning process, and achieve the target fluorine concentration in dust. Become.
- FIG. 5 is a schematic diagram showing an example of the dust cleaning apparatus of the present invention.
- the example of the present invention is an example of an apparatus that performs all cleaning processes in the same tank.
- the washing tank is equipped with a stirrer M, a pH meter pH, and a fluorine ion concentration meter F.
- the pH control is performed by adding the aqueous solution from the NaOH aqueous solution tank to the cleaning tank through the pump p so that the pH value of the dust slurry measured by the pH meter pH is within a predetermined range.
- the fluorine concentration control is performed by the fluorine concentration control unit S, and the valve V is opened and closed by the control means C so that the fluorine ion concentration of the dust slurry measured by the fluorine ion concentration meter is within a predetermined range.
- the apparatus includes a water level gauge WL, and can grasp and control the amount of water.
- Dust containing 2% or more of fluorine whose weight was measured was put into the washing tank from the dust storage tank TD, and 5 times the amount of dust was added and stirred.
- an aqueous NaOH solution is added to the slurry, and the pH of the slurry is controlled to 11.5.
- the fluorine concentration of the slurry is monitored by the fluorine ion concentration meter F.
- the slurry concentration becomes almost constant at 12000 mg / l, that is, when the fluorine concentration of the slurry reaches a saturated state, it is commercially available from the flocculant tank by the pump p. After adding the flocculant, the stirring is stopped and the mixture is left to stand for solid-liquid separation.
- the fluorine concentration was 0.4%, and the target concentration was achieved. Moreover, when the component balance of the dust before and after cleaning was confirmed, it was confirmed that the yield was 99% zinc, 97% lead, and 100% cadmium.
- the present invention it is possible to stably wash and remove fluorine from dust discharged from the reduced iron production process and dust having a high fluorine content such as municipal waste secondary dust with low environmental impact.
- the fluorine content can be reduced, and the dust can be effectively used as a zinc smelting raw material.
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Abstract
Description
本発明は、亜鉛精錬用原料のダストからフッ素等を洗浄除去する処理に用いる洗浄装置及び洗浄方法に関する。
(I)アルカリ領域でフッ素化合物を溶解し、ダストに含有されるフッ素を洗浄液に浸出させるために必要な条件と装置、併せて有価金属である亜鉛成分を浸出させない条件と検知する装置を明確にする。
(II)洗浄液中のフッ素飽和濃度、および洗浄液へのフッ素浸出の終点の判別方法と必要な装置を明確にする。
(III)アルカリ領域でフッ素をダストから浸出させた場合、廃液の処理上の負荷となるカドミウム成分をダストから浸出させない条件と検知する装置を明確にする。
本発明は、上記条件及び判別方法を明らかにしたものであり、その要旨とするところは以下の通りである。
(1)本発明の一態様に係るダスト洗浄装置は、重金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素を2%以上含有するダストと、洗浄液とを混合してスラリーとし、ダストからフッ素を洗浄液中に浸出させて洗浄するダスト洗浄装置であって、スラリーのpH値を測定するpH計、およびpH計で測定したpH値に基づきスラリーのpH値を制御するpH制御装置を備え、さらにスラリーのフッ素イオン濃度を測定するフッ素イオン濃度計、およびフッ素イオン濃度計で測定したスラリーのフッ素イオン濃度を制御するフッ素イオン濃度制御装置を装着していることを特徴としている。
尚、pH制御装置は、pH計によって測定されたスラリーのpH値が所定の範囲内になるように、NaOH水溶液等のアルカリ剤をスラリーに添加することによって、スラリーのpH制御を行う。また、フッ素濃度制御装置は、フッ素イオン濃度計によって測定されたスラリーのフッ素イオン濃度が所定の範囲内になるように、洗浄液をスラリーに添加する量を制御することにより、スラリーのフッ素イオン濃度の制御を行う。
(2)(1)に記載のダスト洗浄装置において、フッ素イオン濃度制御装置が、スラリーのフッ素イオン濃度を100~14000mg/lの範囲で制御するものであっても良い。
(3)(1)又は(2)に記載のダスト洗浄装置において、pH制御装置が、スラリーのpH値を10~13の範囲に制御するものであっても良い。
(4) 本発明の一態様に係るダスト洗浄方法は、重金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素を2%以上含有するダストと、洗浄液とを混合してスラリーとし、ダストからフッ素を洗浄液中に浸出させて洗浄するダスト洗浄方法であって、スラリーのpH値が10~13になるように制御し、スラリーのフッ素濃度が飽和するまで攪拌し、その後攪拌を停止し、スラリーからダストを回収する洗浄工程を有し、回収する前のスラリーのフッ素濃度が2000mg/l以下になるまで洗浄工程を1回実施または2回以上繰り返して実施することを特徴としている。
(5) 本発明の一態様に係るダスト洗浄方法は、(4)に記載のダスト洗浄方法において、回収する前のスラリーのフッ素濃度が500mg/l以下になるまで洗浄工程を1回実施または2回以上繰り返して実施するものであっても良い。
尚、洗浄工程において、同一成分の洗浄液を用いて行われても良い。或いは、スラリーのフッ素濃度が飽和するまで行う洗浄工程と、スラリーのフッ素濃度が2000mg/l以下になるまでダストの洗浄を行う洗浄工程において、それぞれ異なる成分或いはpH値に調整された洗浄液を用いて行っても良い。また、スラリーのフッ素濃度が飽和するまで行う洗浄工程は、1回のみ行っても良く、それぞれ複数回行っても良い。また、スラリーのフッ素濃度を2000mg/l以下にする洗浄工程は1回に限らず、複数回繰り返して行っても良い。
また、洗浄工程におけるpH値の条件は、異なる洗浄工程毎にpH値が10~13の範囲内になるようにそれぞれ異なる範囲に設定しても良い。
また、図4に示されるように、スラリーのフッ素濃度が最終的に1000mg/l以下になるように制御することによって、洗浄後のダストのフッ素濃度を1.0%以下にすることができる。或いは、スラリーのフッ素濃度が最終的に500mg/l以下になるように制御することによって、洗浄後のダストのフッ素濃度を0.5%以下にすることができる。
PbClF+2NaOH ⇒ Pb(OH)2+NaCl+NaF (式1)
KZnF3+2NaOH ⇒ Zn(OH)2+KF+2NaF (式2)
この後、スラリーを固液分離し、フッ素が浸出したダストを回収する。固液分離方法は特に限定されない。例えばスラリーに凝固剤を投入して、ダストが沈殿した後、上澄み液を廃棄してダストを回収することができる。
以上のフッ素を浸出させたダストを回収するまでの一連の処理を、本発明において「洗浄処理」とよぶ。
以上のように、洗浄処理を2回以上繰り返すことにより、ダスト中のフッ素濃度を所定のフッ素濃度以下にすることができる。もちろん、1回の洗浄処理により所定のフッ素濃度が得ることもできる。また、洗浄液の調整は特に限定されず、異なるpHに調整された洗浄液を予め複数準備しておいても良い。或いはpH値が10~13のうちのいずれかに調整された単一種類の洗浄液を予め準備し、使用可能な洗浄液の量或いはスラリーの温度等の条件に応じて洗浄液のpH値を再調整した後、前記洗浄液を洗浄処理に使用しても良い。
本発明例では全ての洗浄処理を同じ槽にて行う装置例である。洗浄槽には、攪拌機M、pH計pH、フッ素イオン濃度計Fが備えられている。pH制御は、前記pH計pHによって測定されたダストスラリーのpH値が所定の範囲内になるように、NaOH水溶液タンクからポンプpを介して同水溶液を前記洗浄槽内に添加することによって行う。また、フッ素濃度制御は、フッ素濃度制御ユニットSによって行われ、前記フッ素イオン濃度計によって測定されたダストスラリーのフッ素イオン濃度が所定の範囲内になるように制御手段CによりバルブVの開閉を行い、水を前記洗浄槽内へ添加する量を制御することによって行う。また、装置は水位計WLを備え、水量の把握、制御が可能である。
Claims (5)
- 重金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素を2%以上含有するダストと、洗浄液とを混合してスラリーとし、当該ダストからフッ素を前記洗浄液中に浸出させて洗浄するダスト洗浄装置であって、
前記スラリーのpH値を測定するpH計、および前記pH計で測定したpH値に基づき前記スラリーのpH値を制御するpH制御装置を備え、さらに前記スラリーのフッ素イオン濃度を測定するフッ素イオン濃度計、および前記フッ素イオン濃度計で測定したフッ素イオン濃度に基づき前記スラリーのフッ素イオン濃度を制御するフッ素イオン濃度制御装置を装着していることを特徴とするダスト洗浄装置。 - 前記フッ素イオン濃度制御装置が、前記スラリーのフッ素イオン濃度を100~14000mg/lの範囲で制御することを特徴とする請求項1に記載のダスト洗浄装置。
- 前記pH制御装置が、前記スラリーのpH値を10~13の範囲に制御することを特徴とする請求項1又は2に記載のダスト洗浄装置。
- 重金属成分として亜鉛、鉛、カドミウムを含み、さらに、フッ素を2%以上含有するダストと、洗浄液とを混合してスラリーとし、当該ダストからフッ素を前記洗浄液中に浸出させて洗浄するダスト洗浄方法であって、
前記スラリーのpH値を測定し、前記測定したpH値に基づき前記スラリーのpH値を制御する工程を備え、さらに前記スラリーのフッ素イオン濃度を測定し、前記測定したフッ素イオン濃度に基づき前記スラリーのフッ素イオン濃度を制御する工程を備え、
前記スラリーのpH値が10~13になるように制御し、前記スラリーのフッ素濃度が飽和するまで攪拌し、その後撹拌を停止し、前記スラリーからダストを回収する洗浄工程を有し、回収する前のスラリーのフッ素濃度が2000mg/l以下になるまで前記洗浄工程を1回実施または2回以上繰り返して実施することを特徴とするダスト洗浄方法。 - 前記ダスト洗浄方法において、回収する前のスラリーのフッ素濃度が500mg/l以下になるまで前記洗浄工程を1回実施または2回以上繰り返して実施することを特徴とする請求項4に記載のダスト洗浄方法。
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