JP2009136873A - Treatment method for dust in cement kiln extraction gas - Google Patents
Treatment method for dust in cement kiln extraction gas Download PDFInfo
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- 239000000428 dust Substances 0.000 title claims abstract description 35
- 239000004568 cement Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000000605 extraction Methods 0.000 title claims abstract description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 53
- 239000011669 selenium Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 239000007791 liquid phase Substances 0.000 claims abstract description 24
- -1 ferrous salt compound Chemical class 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 abstract description 19
- 238000003911 water pollution Methods 0.000 abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000000701 coagulant Substances 0.000 abstract 2
- 238000006298 dechlorination reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000706 filtrate Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical class [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LIKWJCOGLYRYIU-UHFFFAOYSA-N [Se](O)(O)(=O)=O.[Se] Chemical compound [Se](O)(O)(=O)=O.[Se] LIKWJCOGLYRYIU-UHFFFAOYSA-N 0.000 description 1
- BNBRHCPFVGXQRQ-UHFFFAOYSA-N [Se].O[Se](O)=O Chemical compound [Se].O[Se](O)=O BNBRHCPFVGXQRQ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
Description
本発明は、セメントキルンの塩素、アルカリ、及び硫黄の循環に低減するために、塩素バイパス等の抽気装置を用い焼成ガスの一部を抽気した際に同伴する、セレンを含むダスト(以下、抽気ダストと称す)の処理方法に関するものである。 In order to reduce the circulation of chlorine, alkali, and sulfur in a cement kiln, the present invention is a dust containing selenium (hereinafter referred to as extraction air) that accompanies extraction of a part of firing gas using an extraction device such as a chlorine bypass. (Referred to as dust).
塩素、アルカリ、硫黄含有物の多いセメント原料を使用した場合、セメントクリンカー中に含まれる塩素、アルカリ、硫黄の量が多くなり、セメントの品質に悪影響を与えるだけでなく、塩素、アルカリ、硫黄は蒸気圧の高い化合物を形成し、セメント装置内においてガス化して循環する前に、装置内の比較的温度の低い部分で凝縮してコーティングを形成するため、セメント製造上のトラブルの原因ともなっている。
この問題を解決するために、セメントキルンの窯尻部分から焼成ガスの一部を抽気して、セメント製造内を循環する塩素、アルカリ、硫黄の量を低減することが行われている。
When cement raw materials containing a large amount of chlorine, alkali, and sulfur are used, the amount of chlorine, alkali, and sulfur contained in the cement clinker increases, which not only adversely affects the quality of the cement, but also chlorine, alkali, and sulfur A compound with a high vapor pressure is formed, and before it is gasified and circulated in the cement equipment, it is condensed at a relatively low temperature in the equipment to form a coating. .
In order to solve this problem, part of the firing gas is extracted from the kiln bottom of the cement kiln to reduce the amount of chlorine, alkali, and sulfur circulating in the cement production.
しかし、このような焼成ガスの抽気を行うと、塩素、アルカリ、硫黄の含有量が多い抽気ダストが必然的に同伴し、このダストの処理方法が新たに問題になってくる。即ち、抽気ダストには塩素、アルカリ、硫黄以外にも鉛、カドミニウム、クロム、マンガン、鉄、セレンなど、水質汚濁防止法で規制された有害物質が含まれており、抽気ダストを未処理のまま埋め立て、廃棄を行えば環境汚染を引き起こすため、適切な方法で処理する必要がある。また、抽気ダストを廃棄するのではなく、セメント原料として再利用する場合にも、抽気ダスト中に含まれるアルカリ、塩素の量を低減した後に原料系に戻す必要がある。 However, when such calcination gas extraction is performed, extraction dust with a large content of chlorine, alkali and sulfur is inevitably accompanied, and this dust treatment method becomes a new problem. In other words, in addition to chlorine, alkali and sulfur, extracted dust contains lead, cadmium, chromium, manganese, iron, selenium and other harmful substances regulated by the Water Pollution Control Law, and the extracted dust remains untreated. Landfilling and disposal can cause environmental pollution and should be handled in an appropriate manner. Even when the extracted dust is not discarded but reused as a cement raw material, it is necessary to reduce the amount of alkali and chlorine contained in the extracted dust and then return to the raw material system.
抽気ダストに含まれるアルカリ、塩素化合物は水溶性であるから、除去するには水洗処理が最も適しているのは当然であり、既に公知である(例えば特許文献1及び2)。しかしながら、本文献では、第1鉄塩化物の添加量を制御する方法が明記されていなく、溶存している6価のセレン量が変動する抽気ダストの場合、実用化が困難になる恐れが生じる。 Since alkali and chlorine compounds contained in the bleed dust are water-soluble, it is a matter of course that a water washing treatment is most suitable for removal, and is already known (for example, Patent Documents 1 and 2). However, in this document, the method for controlling the addition amount of ferrous chloride is not specified, and in the case of extraction dust in which the amount of dissolved hexavalent selenium varies, there is a possibility that it may be difficult to put it to practical use. .
本発明は、セメントキルン抽気ダストを水洗処理し、固形分はセメント原料として再利用し、通常の3価の鉄イオンでは処理できないセレンが含有している水洗液を、水質汚濁防止法に係る排水基準値以下に除去して放流廃棄を可能にする処理方法を提供することを目的とする。 The present invention is a waste water treatment method for water pollution treatment, in which cement kiln extraction dust is washed with water, solid content is reused as a cement raw material, and selenium containing selenium that cannot be treated with normal trivalent iron ions is contained. It aims at providing the processing method which makes it possible to discharge and discard by removing below a reference value.
本発明者らは鋭意検討を行った結果、上記目的を達成し得ることを知見した。
すなわち、本発明は、以下の各工程からなることを特徴とするセメントキルン抽気ダストの処理方法に関する。
(1)セメントキルン抽気ダストに水を加えてスラリー化した後、固液分離する第1工程、
(2)第1工程で得られた固液分離後の液相(以下、原水と称す)に、該液相の酸化還元電位が−600mV以下になるまで第一鉄塩化合物を添加した後、pHを8〜10に調節し、高分子凝集剤を添加し、固液分離を行う第2工程、
(3)第2工程で得られた固液分離後の液相に、第二鉄塩化合物を添加し、pHを8〜12に調節した後、高分子凝集剤を添加し、固液分離を行う第3工程。
As a result of intensive studies, the present inventors have found that the above object can be achieved.
That is, this invention relates to the processing method of the cement kiln extraction dust characterized by including the following processes.
(1) A first step in which water is added to cement kiln extraction dust to form a slurry, followed by solid-liquid separation,
(2) After adding the ferrous salt compound to the liquid phase after solid-liquid separation obtained in the first step (hereinafter referred to as raw water) until the oxidation-reduction potential of the liquid phase becomes −600 mV or less, a second step of adjusting the pH to 8-10, adding a polymer flocculant, and performing solid-liquid separation;
(3) The ferric salt compound is added to the liquid phase after the solid-liquid separation obtained in the second step, the pH is adjusted to 8 to 12, and then the polymer flocculant is added to perform the solid-liquid separation. 3rd process to perform.
本発明のセメントキルン抽気ダストの処理方法を実施すると、除去が極めて困難な6価セレンを4価に還元し固相として捕集し、固液分離後の液相中の全セレン(4価セレン、6価セレン)を水質汚濁防止法に係る排水基準値を充分クリアする程度まで低減することができ、放流が可能になる。
また、還元剤として用いる第一鉄塩化合物の必要量がその場で判断可能であり、過剰添加を避けられるため、少量の高分子凝集剤の添加で沈降分離が短時間で容易になる。その為、固相である含水量の多いスラッジ量が少なくなりスラッジの脱水処理も容易になる。
さらに、固形分は、セメント原料としての再利用が可能になる。
When the cement kiln extraction dust processing method of the present invention is carried out, hexavalent selenium, which is extremely difficult to remove, is reduced to tetravalent and collected as a solid phase, and all selenium (tetravalent selenium in the liquid phase after solid-liquid separation) is collected. , Hexavalent selenium) can be reduced to a level that sufficiently satisfies the drainage standard value according to the Water Pollution Control Law, and can be discharged.
In addition, since the required amount of the ferrous salt compound used as the reducing agent can be determined on the spot and excessive addition can be avoided, sedimentation separation is facilitated in a short time by adding a small amount of the polymer flocculant. Therefore, the amount of sludge with a high water content which is a solid phase is reduced, and the sludge is easily dewatered.
Furthermore, the solid content can be reused as a cement raw material.
以下に本発明を詳細に説明する。また、本発明に係るセメントキルン抽気ダストの処理方法のフローを図1に示す。
本発明の第1工程は、セメントキルン抽気ダストに水を加えてスラリー化した後、固液分離する工程である。この工程で、塩化カリウム、塩化ナトリウム、及び塩化カルシウム等のアルカリ金属塩を溶出させ固相として捕集する。抽気ダストの主成分は、アルカリ金属塩であることから、生成スラリーは高pH値を示す。水の添加量は固液分離した液相の塩素濃度が2質量%以下になるように加える。一般に海水の塩素濃度は0.005〜2質量%であり、液相の塩素濃度が2質量%以下であれば、処理排水をそのまま放流可能である。
The present invention is described in detail below. Moreover, the flow of the processing method of the cement kiln extraction dust which concerns on this invention is shown in FIG.
The first step of the present invention is a step of solid-liquid separation after adding water to the cement kiln bleed dust to form a slurry. In this step, alkali metal salts such as potassium chloride, sodium chloride, and calcium chloride are eluted and collected as a solid phase. Since the main component of the extracted dust is an alkali metal salt, the resulting slurry exhibits a high pH value. The amount of water added is such that the concentration of chlorine in the liquid phase after solid-liquid separation is 2% by mass or less. Generally, the chlorine concentration of seawater is 0.005 to 2% by mass, and the treated wastewater can be discharged as it is if the chlorine concentration of the liquid phase is 2% by mass or less.
本発明の第2工程は、第1工程で固液分離した液相(原水)に、該液相の酸化還元電位が−600mV以下になるまで第一鉄塩化合物を添加した後、pHを8〜10に調節し、高分子凝集剤を添加し、固液分離を行う工程である。この工程で、原水中の6価セレン(セレン酸)を3価の水酸化鉄と共沈し易い4価セレン(亜セレン酸)に還元させる。
第一鉄塩化合物としては、例えば、塩化第一鉄、塩化第一鉄・二水和物、硫酸第一鉄、硫酸第一鉄・四水和物、硫酸第一鉄・五水和物、硫酸第一鉄・七水和物、ポリ硫酸第一鉄等が挙げられる。
第一鉄塩化合物の添加量は、該液相の酸化還元電位が−600mV以下、好ましくは−650mV以下になるまで添加する。液相の酸化還元電位が−600mV以下でないと
6価のセレンが4価に還元され難くなり、第3工程で生成する3価の水酸化鉄と共沈され難い6価のセレンが上澄み液に残るため好ましくない。
液相のpH調節剤としては、例えば、水酸化ナトリウム、水酸化カルシウム等が挙げられる。pHは8〜10、好ましくは9〜10に調節する。
In the second step of the present invention, the ferrous salt compound is added to the liquid phase (raw water) separated in the first step until the oxidation-reduction potential of the liquid phase becomes −600 mV or less, and then the pH is adjusted to 8. 10 to 10 and adding a polymer flocculant to perform solid-liquid separation. In this step, hexavalent selenium (selenic acid) in the raw water is reduced to tetravalent selenium (selenous acid) that easily coprecipitates with trivalent iron hydroxide.
Examples of ferrous salt compounds include ferrous chloride, ferrous chloride and dihydrate, ferrous sulfate, ferrous sulfate and tetrahydrate, ferrous sulfate and pentahydrate, Examples thereof include ferrous sulfate and heptahydrate, polyferrous sulfate and the like.
The ferrous salt compound is added until the oxidation-reduction potential of the liquid phase is −600 mV or less, preferably −650 mV or less. If the redox potential of the liquid phase is not −600 mV or less, hexavalent selenium is difficult to be reduced to tetravalent, and hexavalent selenium difficult to coprecipitate with the trivalent iron hydroxide produced in the third step is added to the supernatant. Since it remains, it is not preferable.
Examples of the liquid phase pH adjuster include sodium hydroxide and calcium hydroxide. The pH is adjusted to 8-10, preferably 9-10.
本発明の第3工程では、第2工程で得られた固液分離後の液相に、第二鉄塩化合物を添加し、pHを8〜12に調節した後、高分子凝集剤を添加し、固液分離を行う工程である。
第二鉄塩化合物としては、例えば、塩化第二鉄、塩化第二鉄・六水和物、硫酸第二鉄、硫酸第二鉄・三水和物、硫酸第二鉄・六水和物、硫酸第二鉄・七水和物、ポリ硫酸第二鉄等が挙げられる。
第二鉄塩化合物の添加量は、原水に溶存している全セレン量に対し、鉄イオン換算で50〜300倍モル量、好ましくは100〜250倍モル量である。
液相のpH調節剤としては、第2工程同様、例えば、水酸化ナトリウム、水酸化カルシウム等が挙げられる。pHは8〜12、好ましくは9〜11に調節する。
In the third step of the present invention, a ferric salt compound is added to the liquid phase after solid-liquid separation obtained in the second step, the pH is adjusted to 8 to 12, and then a polymer flocculant is added. This is a step of performing solid-liquid separation.
Examples of the ferric salt compound include ferric chloride, ferric chloride and hexahydrate, ferric sulfate, ferric sulfate and trihydrate, ferric sulfate and hexahydrate, And ferric sulfate heptahydrate, polyferric sulfate and the like.
The addition amount of the ferric salt compound is 50 to 300 times mol, preferably 100 to 250 times mol, in terms of iron ion, with respect to the total amount of selenium dissolved in the raw water.
Examples of the liquid phase pH adjuster include sodium hydroxide and calcium hydroxide as in the second step. The pH is adjusted to 8-12, preferably 9-11.
本発明の第2及び第3工程で添加する高分子凝集剤は、水酸化鉄を主成分とする沈殿の凝集を促進して固液分離を容易にする効果を示す。高分子凝集剤としては、ポリアクリルアミド、又はポリアクリル酸ソーダを含む高分子凝集剤であれば良く、ノニオン系、カチオン系、アニオン系を問わずに使用できる。また高分子凝集剤の添加量は、0.2〜4mg/l、好ましくは0.5〜2mg/lである。
本発明の第1〜3工程で行う固液分離する方法は、一般に行われている方法、例えば、ろ過法、遠心分離法、沈降分離法等を利用することができる。
第4工程の固液分離で重金属およびセレンを排水基準値以下に低減させた液相は、そのpHを中性付近にまで低下させた後、放流することができる。また、第1〜3工程で得られた固相は、鉄を含むため、鉄源としてセメント原料に再利用可能である。
The polymer flocculant added in the second and third steps of the present invention has an effect of facilitating solid-liquid separation by promoting aggregation of precipitates mainly composed of iron hydroxide. As the polymer flocculant, any polymer flocculant containing polyacrylamide or sodium polyacrylate may be used, regardless of nonionic, cationic or anionic. The addition amount of the polymer flocculant is 0.2 to 4 mg / l, preferably 0.5 to 2 mg / l.
As a method for solid-liquid separation performed in the first to third steps of the present invention, a commonly used method, for example, a filtration method, a centrifugal separation method, a sedimentation separation method, or the like can be used.
The liquid phase in which heavy metal and selenium are reduced to below the drainage standard value by solid-liquid separation in the fourth step can be discharged after the pH is lowered to near neutrality. Moreover, since the solid phase obtained in the first to third steps contains iron, it can be reused as a raw material for cement as an iron source.
以下に具体例を示し、本発明を詳細に説明する。また、以下の実施例、比較例の結果を表1に示す。
(実施例1)
抽気ダスト250gに水2500gを加え、3時間攪拌しスラリー化した。スラリーは1μmの孔径のメンブランフィルターで固液分離を行い、得られたろ液(以下、原水1と称す)のpHは13.0、酸化還元電位は−117mVであった。
The present invention will be described in detail with reference to specific examples. The results of the following examples and comparative examples are shown in Table 1.
Example 1
2500 g of water was added to 250 g of extracted dust and stirred for 3 hours to form a slurry. The slurry was subjected to solid-liquid separation with a membrane filter having a pore size of 1 μm, and the pH of the obtained filtrate (hereinafter referred to as raw water 1) was 13.0 and the oxidation-reduction potential was −117 mV.
この原水1に含まれる全セレンは、JIS K 0102に準拠し、以下の方法で定量した。
即ち、原水1に硫酸及び硝酸を添加し、加熱し硫酸白煙発生後、室温まで放冷し、塩酸を加え、90〜100℃で10分間加熱し、放冷し、試料液とした。この試料液を水素化合物発生原子吸光分析装置にて全セレンの定量を行った。また、4価セレンは原水を前処理せず、水素化合物発生原子吸光分析装置にて定量を行った。6価セレンは、全セレンから4価セレンを差し引いた値とした。
全セレン(4価セレンと6価セレン)および6価セレンの含有量は夫々13、12mg/lであった。
Total selenium contained in the raw water 1 was quantified by the following method in accordance with JIS K 0102.
That is, sulfuric acid and nitric acid were added to the raw water 1 and heated to generate sulfuric acid white smoke, then allowed to cool to room temperature, hydrochloric acid was added, heated at 90 to 100 ° C. for 10 minutes, allowed to cool, and used as a sample solution. This sample solution was quantified with a hydrogen compound generation atomic absorption spectrometer. Tetravalent selenium was quantified with a hydrogen compound generation atomic absorption spectrometer without pretreatment of raw water. Hexavalent selenium was obtained by subtracting tetravalent selenium from all selenium.
The contents of total selenium (tetravalent selenium and hexavalent selenium) and hexavalent selenium were 13, 12 mg / l, respectively.
上記原水1(250ml)のpHが8になるように水酸化ナトリウムを添加し、硫酸第一鉄・七水和物を添加した。この硫酸第一鉄・七水和物の添加量はこの液相の酸化還元電位が−656mVになるまで添加し、その後30分間攪拌混合した。
次いで上記高分子凝集剤を2mg/l添加して10分間攪拌混合し、静置10分後にこの処理液を5種Aのろ紙でろ過した。
Sodium hydroxide was added so that the pH of the raw water 1 (250 ml) was 8, and ferrous sulfate heptahydrate was added. The ferrous sulfate heptahydrate was added until the redox potential of this liquid phase was -656 mV, and then stirred and mixed for 30 minutes.
Next, 2 mg / l of the above polymer flocculant was added and stirred and mixed for 10 minutes. After 10 minutes of standing, this treatment liquid was filtered with 5 types A filter paper.
上記ろ液に1mol/lの塩化第二鉄・六水和物を10.2ml(原水1に溶存している全セレン13mg/lの248倍モル量)添加して、水酸化ナトリウムを添加することによりpHを10に調節して30分間攪拌混合した。次いで高分子凝集剤を2mg/l添加して10分間攪拌混合し、静置10分後にこの処理液を5種Aのろ紙でろ過した。
上記ろ液を原水1の分析方法により定量を行った。全セレンは0.01mg/lであり、水質汚濁防止法に係る排水基準値の0.1mg/lをクリアした。
To the above filtrate is added 10.2 ml of 1 mol / l ferric chloride hexahydrate (248 times mole amount of 13 mg / l of total selenium dissolved in raw water 1), and sodium hydroxide is added. The pH was adjusted to 10 by mixing for 30 minutes. Subsequently, 2 mg / l of a polymer flocculant was added, and the mixture was stirred and mixed for 10 minutes. After 10 minutes of standing, the treated liquid was filtered with 5 types A filter paper.
The filtrate was quantified by the raw water 1 analysis method. The total selenium was 0.01 mg / l, which cleared the wastewater standard value of 0.1 mg / l according to the Water Pollution Control Law.
(実施例2)
抽気ダスト250gに水2500gを加え、3時間攪拌しスラリー化した。スラリーは1μmの孔径のメンブランフィルターで固液分離を行い、得られたろ液(以下、原水2と称す)のpHは12.0、酸化還元電位は−103mVであった。
(Example 2)
2500 g of water was added to 250 g of extracted dust and stirred for 3 hours to form a slurry. The slurry was subjected to solid-liquid separation with a membrane filter having a pore size of 1 μm. The pH of the obtained filtrate (hereinafter referred to as raw water 2) was 12.0, and the oxidation-reduction potential was −103 mV.
この原水2に含まれる全セレンは、原水1の分析方法で定量した。
全セレン(4価セレンと6価セレン)および6価セレンの含有量は夫々49、4mg/lであった。
The total selenium contained in the raw water 2 was quantified by the raw water 1 analysis method.
The contents of total selenium (tetravalent selenium and hexavalent selenium) and hexavalent selenium were 49 and 4 mg / l, respectively.
上記原水2(250ml)のpHが10になるように水酸化ナトリウムを添加し、硫酸第一鉄・七水和物を、液相の酸化還元電位が−706mVになるまで添加した。その後30分間攪拌混合した。
次いで上記高分子凝集剤を2mg/l添加して10分間攪拌混合し、静置10分後にこの処理液を5種Aのろ紙でろ過した。
Sodium hydroxide was added so that the pH of the raw water 2 (250 ml) was 10, and ferrous sulfate heptahydrate was added until the redox potential of the liquid phase was -706 mV. Thereafter, the mixture was stirred and mixed for 30 minutes.
Next, 2 mg / l of the above polymer flocculant was added and stirred and mixed for 10 minutes. After 10 minutes of standing, this treatment liquid was filtered with 5 types A filter paper.
上記ろ液に1mol/lの塩化第二鉄・六水和物を15.5ml(原水2に溶存している全セレン49mg/lの100倍モル量)添加して、水酸化ナトリウムを添加することによりpHを10に調節して30分間攪拌混合した。次いで高分子凝集剤を1mg/l添加して10分間攪拌混合し、静置10分後にこの処理液を5種Aのろ紙でろ過した。
上記ろ液を原水2の分析方法により定量を行った。全セレンは0.04mg/lであり、水質汚濁防止法に係る排水基準値の0.1mg/lをクリアした。
15.5 ml of 1 mol / l ferric chloride hexahydrate (100 times mole amount of all selenium 49 mg / l dissolved in raw water 2) is added to the filtrate, and sodium hydroxide is added. The pH was adjusted to 10 by mixing for 30 minutes. Subsequently, 1 mg / l of a polymer flocculant was added and stirred and mixed for 10 minutes. After 10 minutes of standing, this treatment liquid was filtered with 5 types A filter paper.
The filtrate was quantified by the raw water 2 analysis method. The total selenium was 0.04 mg / l, which cleared the wastewater standard value of 0.1 mg / l according to the Water Pollution Control Law.
(比較例1)
抽気ダスト250gに水2500gを加え、3時間攪拌しスラリー化した。スラリーは1μmの孔径のメンブランフィルターで固液分離を行い、得られたろ液(以下、原水3と称す)のpHは13.0、酸化還元電位は−114mVであった。
この原水3に含まれる全セレンは、原水1の分析方法で定量した。
全セレン(4価セレンと6価セレン)および6価セレンの含有量は夫々13、12mg/lであった。
上記原水3(250ml)のpHが8になるように水酸化ナトリウムを添加し、硫酸第一鉄・七水和物を、液相の酸化還元電位が−537mVになるまで添加した。その後30分間攪拌混合した。
次いで上記高分子凝集剤を2mg/l添加して10分間攪拌混合し、静置10分後にこの処理液を5種Aのろ紙でろ過した。
(Comparative Example 1)
2500 g of water was added to 250 g of extracted dust and stirred for 3 hours to form a slurry. The slurry was subjected to solid-liquid separation with a membrane filter having a pore size of 1 μm, and the pH of the obtained filtrate (hereinafter referred to as raw water 3) was 13.0 and the oxidation-reduction potential was −114 mV.
The total selenium contained in the raw water 3 was quantified by the raw water 1 analysis method.
The contents of total selenium (tetravalent selenium and hexavalent selenium) and hexavalent selenium were 13, 12 mg / l, respectively.
Sodium hydroxide was added so that the pH of the raw water 3 (250 ml) was 8, and ferrous sulfate heptahydrate was added until the redox potential of the liquid phase became −537 mV. Thereafter, the mixture was stirred and mixed for 30 minutes.
Next, 2 mg / l of the above polymer flocculant was added and stirred and mixed for 10 minutes. After 10 minutes of standing, this treatment liquid was filtered with 5 types A filter paper.
上記ろ液に1mol/lの塩化第二鉄・六水和物を10.2ml(原水1に溶存している全セレン13mg/lの248倍モル量)添加して、水酸化ナトリウムを添加することによりpHを10に調節して30分間攪拌混合した。次いで高分子凝集剤を2mg/l添加して10分間攪拌混合し、静置10分後にこの処理液を5種Aのろ紙でろ過した。
上記ろ液を原水1の分析方法により定量を行った。全セレンは0.22mg/lであり、水質汚濁防止法に係る排水基準値の0.1mg/lをクリアしなかった。
To the above filtrate is added 10.2 ml of 1 mol / l ferric chloride hexahydrate (248 times mole amount of 13 mg / l of total selenium dissolved in raw water 1), and sodium hydroxide is added. The pH was adjusted to 10 by mixing for 30 minutes. Subsequently, 2 mg / l of a polymer flocculant was added, and the mixture was stirred and mixed for 10 minutes. After 10 minutes of standing, the treated liquid was filtered with 5 types A filter paper.
The filtrate was quantified by the raw water 1 analysis method. Total selenium was 0.22 mg / l, which did not clear the wastewater standard value of 0.1 mg / l according to the Water Pollution Control Law.
(比較例2)
抽気ダスト250gに水2500gを加え、3時間攪拌しスラリー化した。スラリーは1μmの孔径のメンブランフィルターで固液分離を行い、得られたろ液(以下、原水4と称す)のpHは12.0、酸化還元電位は−111mVであった。
この原水4に含まれる全セレンは、原水1の分析方法で定量した。
全セレン(4価セレンと6価セレン)および6価セレンの含有量は夫々49、4mg/lであった。
上記原水4(250ml)のpHが10になるように水酸化ナトリウムを添加し、硫酸第一鉄・七水和物を、液相の酸化還元電位が−532mVになるまで添加した。その後30分間攪拌混合した。
次いで上記高分子凝集剤を2mg/l添加して10分間攪拌混合し、静置10分後にこの処理液を5種Aのろ紙でろ過した。
(Comparative Example 2)
2500 g of water was added to 250 g of extracted dust and stirred for 3 hours to form a slurry. The slurry was subjected to solid-liquid separation with a membrane filter having a pore size of 1 μm, and the pH of the obtained filtrate (hereinafter referred to as raw water 4) was 12.0, and the oxidation-reduction potential was −111 mV.
The total selenium contained in the raw water 4 was quantified by the raw water 1 analysis method.
The contents of total selenium (tetravalent selenium and hexavalent selenium) and hexavalent selenium were 49 and 4 mg / l, respectively.
Sodium hydroxide was added so that the pH of the raw water 4 (250 ml) was 10, and ferrous sulfate heptahydrate was added until the redox potential of the liquid phase was −532 mV. Thereafter, the mixture was stirred and mixed for 30 minutes.
Next, 2 mg / l of the above polymer flocculant was added and stirred and mixed for 10 minutes. After 10 minutes of standing, this treatment liquid was filtered with 5 types A filter paper.
上記ろ液に1mol/lの塩化第二鉄・六水和物を15.5ml(原水2に溶存している全セレン49mg/lの100倍モル量)添加して、水酸化ナトリウムを添加することによりpHを10に調節して30分間攪拌混合した。次いで高分子凝集剤を1mg/l添加して10分間攪拌混合し、静置10分後にこの処理液を5種Aのろ紙でろ過した。
上記ろ液を原水1の分析方法により定量を行った。全セレンは0.25mg/lであり、水質汚濁防止法に係る排水基準値の0.1mg/lをクリアしなかった。
15.5 ml of 1 mol / l ferric chloride hexahydrate (100 times mole amount of all selenium 49 mg / l dissolved in raw water 2) is added to the filtrate, and sodium hydroxide is added. The pH was adjusted to 10 by mixing for 30 minutes. Subsequently, 1 mg / l of a polymer flocculant was added and stirred and mixed for 10 minutes. After 10 minutes of standing, this treatment liquid was filtered with 5 types A filter paper.
The filtrate was quantified by the raw water 1 analysis method. The total selenium was 0.25 mg / l, which did not clear the wastewater standard value of 0.1 mg / l according to the Water Pollution Control Law.
1 第1工程
2 第2工程
3 第3工程
4 抽気ダスト
5 セメント原料
6 放流水
1 First process 2 Second process 3 Third process 4 Extracted dust 5 Cement raw material 6 Effluent water
Claims (5)
(1)塩素およびセレンを含むダストに水を加えてスラリー化した後、固液分離する第1工程、
(2)第1工程で得られた固液分離後の液相(以下、原水と称す)に、該液相の酸化還元電位が−600mV以下になるまで第一鉄塩化合物を添加した後、固液分離を行う第2工程。
(3)第2工程で得られた固液分離後の液相に、第二鉄塩化合物を添加し、固液分離を行う第3工程。 A method for treating dust containing chlorine and selenium, comprising the following steps.
(1) A first step in which water is added to a dust containing chlorine and selenium to form a slurry, followed by solid-liquid separation,
(2) After adding the ferrous salt compound to the liquid phase after solid-liquid separation obtained in the first step (hereinafter referred to as raw water) until the oxidation-reduction potential of the liquid phase becomes −600 mV or less, Second step for solid-liquid separation.
(3) A third step in which a ferric salt compound is added to the liquid phase after solid-liquid separation obtained in the second step to perform solid-liquid separation.
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