JP6565268B2 - Method and apparatus for treating inorganic carbon-containing water - Google Patents
Method and apparatus for treating inorganic carbon-containing water Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 95
- 229910052799 carbon Inorganic materials 0.000 title claims description 95
- 238000000034 method Methods 0.000 title claims description 25
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- 125000002091 cationic group Chemical group 0.000 claims description 59
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- 238000004220 aggregation Methods 0.000 claims description 21
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- VNCYATOBAGQGFF-UHFFFAOYSA-N 2-methylpropane;sulfuric acid Chemical compound CC(C)C.OS(O)(=O)=O VNCYATOBAGQGFF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000001112 coagulating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- -1 diallyl ammonium salts Chemical class 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical class C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
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- 239000005416 organic matter Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Description
本発明は、無機炭素を５０ｍｇ／Ｌ以上含み、無機炭素による凝集阻害の問題のある無機炭素含有水を効率的に凝集処理して固液分離する方法と装置に関する。 The present invention relates to a method and apparatus for efficiently aggregating inorganic carbon-containing water containing inorganic carbon in an amount of 50 mg / L or more and having a problem of agglomeration inhibition due to inorganic carbon to solid-liquid separation.
被処理水に含まれる有機炭素や濁質を除去するには、沈殿槽や濾過器、除濁膜で固液分離処理することが一般的である。また、この際、固液分離効率を高めるために、固液分離に先立ち凝集処理が一般的に行われる。 In order to remove organic carbon and turbidity contained in the water to be treated, it is common to perform a solid-liquid separation treatment using a precipitation tank, a filter, or a turbidity removal membrane. At this time, in order to increase the solid-liquid separation efficiency, agglomeration is generally performed prior to the solid-liquid separation.
従来、凝集処理薬品（凝集剤）としては、鉄塩やアルミニウム塩といった無機凝集剤が代表的である。 Conventionally, as the aggregating chemical (aggregating agent), inorganic aggregating agents such as iron salts and aluminum salts are typical.
しかしながら、水中に無機炭素を多く含む場合、凝集ｐＨ領域であるｐＨ５．５〜８．５では、無機炭素由来の炭酸イオンが無機凝集剤と濁質ないしは有機物との反応を阻害し、凝集不良を引き起こす。 However, when a lot of inorganic carbon is contained in water, in the aggregation pH range of pH 5.5 to 8.5, the carbonate ion derived from inorganic carbon inhibits the reaction between the inorganic flocculant and the turbidity or organic matter, resulting in poor aggregation. cause.
一般的な日本国内の河川水、湖水の無機炭素濃度は１０ｍｇ／Ｌ前後であり、無機凝集剤を阻害するには至らない。また、一般的な工場排水でも無機炭素濃度は５０ｍｇ／Ｌを超えないため、上記の無機炭素による凝集不良が問題になることはない。
しかし、工場排水には、製造過程で添加される薬品や特有の工程によっては、無機炭素濃度が５０ｍｇ／Ｌ以上に上昇したものがある。
Generally, the inorganic carbon concentration in river water and lake water in Japan is around 10 mg / L, and does not inhibit the inorganic flocculant. Moreover, since the concentration of inorganic carbon does not exceed 50 mg / L even in general factory effluent, the above-mentioned poor aggregation due to inorganic carbon does not become a problem.
However, some industrial wastewaters have an inorganic carbon concentration increased to 50 mg / L or more depending on chemicals added during the manufacturing process and specific processes.
通常の排水処理では、凝集不良を改善するためには、凝集剤を大量に添加する方法が一般的だが、汚泥が大量に発生するなどの問題がある。また、無機炭素を多く含む排水に、このように凝集剤を大量に添加しても、本来除去すべき有機炭素や濁質の除去性が悪化し、例えば沈殿槽や濾過器で除去し得なくなる。
後段で除去できなかった濁質や有機炭素などは、これを系外に排出する際に環境汚染を引き起こす要因となる。また、例えば沈殿槽や濾過器の後段に除濁膜や逆浸透（ＲＯ）膜がある場合、それらの汚染にも繋がる。
後段の濾過器等で除去し得ない有機炭素などを低減する方法として、オゾン処理なども提案されているが、電力コストがかかるため、前段の凝集、固液分離処理で極力有機炭素濃度を低減することが効果的である。
In ordinary wastewater treatment, a method of adding a large amount of a flocculant is common to improve agglomeration failure, but there is a problem that a large amount of sludge is generated. Moreover, even if a large amount of a flocculant is added to wastewater containing a large amount of inorganic carbon, the organic carbon and turbidity that should be removed are deteriorated and cannot be removed by, for example, a precipitation tank or a filter. .
Turbidity, organic carbon, etc. that could not be removed in the latter stage cause environmental pollution when discharged outside the system. Further, for example, when there is a turbidity removal membrane or a reverse osmosis (RO) membrane in the subsequent stage of the settling tank or the filter, it also leads to contamination thereof.
Ozone treatment is also proposed as a method to reduce organic carbon that cannot be removed by a subsequent filter, etc., but it costs power, so the organic carbon concentration is reduced as much as possible by coagulation and solid-liquid separation treatment in the previous stage. It is effective to do.
従来、排水中の有機炭素や濁質の除去効率を高めるために、無機凝集剤と共にカチオン性有機凝集剤と併用することは公知であり、例えば、特許文献１には、製紙工場排水等の排水に、水溶性カチオン系重合体を添加混合した後、無機凝集剤を添加混合し、次いで、アニオン系高分子凝集剤を添加して凝集処理する方法が提案されている。
特許文献２には、アニオン系染料廃水に、極限粘度が０．４〜１．４のポリジアリルジメチルアンモニウムクロライドと無機凝集剤を添加して所定のｐＨで凝集処理する方法が提案されている。
また、特許文献３には、カチオン性有機凝集剤と無機凝集剤とを混合してなる凝集剤組成物が提案されている。
Conventionally, it is known to use together with an inorganic flocculant and a cationic organic flocculant in order to increase the removal efficiency of organic carbon and turbidity in wastewater. For example,
しかし、従来技術は、いずれも、排水中の有機炭素や濁質の除去率を向上させるために、無機凝集剤と共にカチオン性有機凝集剤を併用するものであり、無機炭素による凝集阻害に着目した凝集処理技術は提案されていない。 However, all of the conventional techniques use a cationic organic flocculant together with an inorganic flocculant in order to improve the removal rate of organic carbon and turbidity in wastewater, and focused on aggregation inhibition by inorganic carbon. No agglomeration technique has been proposed.
本発明は、無機炭素を５０ｍｇ／Ｌ以上含み、無機炭素による凝集阻害の問題のある無機炭素含有水を効率的に凝集処理して固液分離する方法と装置を提供することを課題とする。 An object of the present invention is to provide a method and an apparatus for efficiently coagulating inorganic carbon-containing water containing inorganic carbon in an amount of 50 mg / L or more and having a problem of aggregation inhibition due to inorganic carbon to solid-liquid separation.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、無機炭素含有水に、無機凝集剤とカチオン基を有する有機凝結剤とを併用して添加することにより、好ましくは所定のコロイド当量のカチオン基を有する有機凝結剤を用いることにより、無機炭素含有水を効率的に凝集処理し、有機炭素や濁質を高度に除去することができることを見出した。
本発明はこのような知見に基づいて達成されたものであり、以下を要旨とする。
As a result of intensive studies to solve the above-mentioned problems, the present inventors preferably added a combination of an inorganic flocculant and an organic coagulant having a cationic group to inorganic carbon-containing water. It has been found that by using an organic coagulant having a colloidal equivalent cationic group, inorganic carbon-containing water can be efficiently coagulated and organic carbon and turbidity can be removed to a high degree.
The present invention has been achieved based on such findings, and the gist thereof is as follows.
［１］ 無機炭素５０ｍｇ／Ｌ以上を含む被処理水に、無機凝集剤とカチオン基を有する有機凝結剤とを添加して凝集処理した後、固液分離することを特徴とする無機炭素含有水の処理方法。 [1] Inorganic carbon-containing water characterized by solid-liquid separation after adding an inorganic flocculant and an organic coagulant having a cationic group to water to be treated containing 50 mg / L or more of inorganic carbon and aggregating it. Processing method.
［２］ ［１］において、前記被処理水にカチオン基を有する有機凝結剤を添加した後、無機凝集剤を添加して凝集処理することを特徴とする無機炭素含有水の処理方法。 [2] A method for treating inorganic carbon-containing water according to [1], wherein an organic coagulant having a cationic group is added to the water to be treated, and then an inorganic flocculant is added to perform the coagulation treatment.
［３］ ［１］又は［２］において、前記カチオン基を有する有機凝結剤のコロイド当量が１ｍｅｑ／ｇ以上であることを特徴とする無機炭素含有水の処理方法。 [3] The method for treating inorganic carbon-containing water according to [1] or [2], wherein the organic coagulant having the cationic group has a colloid equivalent of 1 meq / g or more.
［４］ ［１］ないし［３］のいずれかにおいて、前記被処理水の無機炭素濃度に応じて、前記カチオン基を有する有機凝結剤の添加量を制御することを特徴とする無機炭素含有水の処理方法。 [4] The inorganic carbon-containing water according to any one of [1] to [3], wherein the amount of the organic coagulant having a cationic group is controlled according to the inorganic carbon concentration of the water to be treated. Processing method.
［５］ ［１］ないし［４］のいずれかにおいて、更に、アニオン基を有する有機凝集剤を前記被処理水に添加して凝集処理することを特徴とする無機炭素含有水の処理方法。 [5] The method for treating inorganic carbon-containing water according to any one of [1] to [4], further comprising adding an organic flocculant having an anion group to the water to be treated for aggregation treatment.
［６］ ［１］ないし［５］のいずれかにおいて、前記固液分離で得られた分離水を除濁膜または逆浸透膜分離処理することを特徴とする無機炭素含有水の処理方法。 [6] The method for treating inorganic carbon-containing water according to any one of [1] to [5], wherein the separated water obtained by the solid-liquid separation is subjected to a turbidity membrane or reverse osmosis membrane separation treatment.
［７］ 無機炭素５０ｍｇ／Ｌ以上を含む被処理水を凝集処理した後固液分離する無機炭素含有水の処理装置であって、該被処理水に無機凝集剤とカチオン基を有する有機凝結剤を添加して凝集処理する凝集処理手段と、凝集処理水を固液分離する固液分離手段とを有することを特徴とする無機炭素含有水の処理装置。 [7] A treatment apparatus for inorganic carbon-containing water that coagulates and treats water to be treated containing 50 mg / L or more of inorganic carbon and then solid-liquid separates the organic coagulant having an inorganic flocculant and a cationic group in the water to be treated. An apparatus for treating inorganic carbon-containing water, characterized by comprising a coagulation treatment means for performing coagulation treatment by adding water and a solid-liquid separation means for solid-liquid separation of the coagulation treated water.
［８］ ［７］において、前記凝集処理手段は、前記被処理水にカチオン基を有する有機凝結剤を添加した後無機凝集剤を添加して凝集処理する手段であることを特徴とする無機炭素含有水の処理装置。 [8] In the inorganic carbon according to [7], the aggregation treatment means is a means for adding an organic coagulant having a cationic group to the water to be treated and then adding an inorganic flocculant to perform the aggregation treatment. Water treatment equipment.
［９］ ［７］又は［８］において、前記カチオン基を有する有機凝結剤のコロイド当量が１ｍｅｑ／ｇ以上であることを特徴とする無機炭素含有水の処理装置。 [9] An apparatus for treating inorganic carbon-containing water according to [7] or [8], wherein the organic coagulant having the cationic group has a colloid equivalent of 1 meq / g or more.
［１０］ ［７］ないし［９］のいずれかにおいて、前記被処理水の無機炭素濃度を測定する無機炭素濃度測定手段と、この測定値に基づいて、前記カチオン基を有する有機凝結剤の添加量を制御する制御手段とを有することを特徴とする無機炭素含有水の処理装置。 [10] In any one of [7] to [9], the inorganic carbon concentration measuring means for measuring the inorganic carbon concentration of the water to be treated, and the addition of the organic coagulant having the cationic group based on the measured value And a control means for controlling the amount of the inorganic carbon-containing water treatment apparatus.
［１１］ ［１］ないし［４］のいずれかにおいて、前記凝集処理手段は、前記被処理水に更にアニオン基を有する有機凝集剤を添加して凝集処理する手段であることを特徴とする無機炭素含有水の処理装置。 [11] In any one of [1] to [4], the aggregating treatment means is a means for aggregating by further adding an organic flocculant having an anion group to the water to be treated. Carbon-containing water treatment equipment.
［１２］ ［７］ないし［１１］のいずれかにおいて、前記固液分離手段で得られた分離水が導入される除濁膜または逆浸透膜分離手段を有することを特徴とする無機炭素含有水の処理装置。 [12] The inorganic carbon-containing water according to any one of [7] to [11], comprising a turbidity membrane or reverse osmosis membrane separation means into which the separated water obtained by the solid-liquid separation means is introduced. Processing equipment.
本発明によれば、無機炭素を５０ｍｇ／Ｌ以上含み、無機炭素による凝集阻害の問題のある無機炭素含有水を効率的に凝集処理して水中の有機炭素や濁質を高度に固液分離することができる。
本発明によれば、無機炭素による凝集阻害を防止して濁質や有機炭素を高度に除去することができるため、固液分離水にこれらが残留することによる、後段の除濁膜やＲＯ膜等の膜汚染を防止することができ、膜の洗浄頻度を低減することができる。また、オゾン処理等の後段の処理装置の負荷を軽減して処理コストを低減することができる。
According to the present invention, inorganic carbon-containing water containing inorganic carbon in an amount of 50 mg / L or more and having a problem of aggregation inhibition due to inorganic carbon is efficiently agglomerated to highly solid-liquid-separate organic carbon and turbidity in water. be able to.
According to the present invention, turbidity and organic carbon can be removed to a high degree by preventing the inhibition of aggregation by inorganic carbon. Film contamination such as the above can be prevented, and the frequency of cleaning the film can be reduced. Moreover, the processing cost can be reduced by reducing the load on the subsequent processing apparatus such as ozone treatment.
以下に、本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜メカニズム＞
カチオン基を有する有機凝結剤（以下、「カチオン性有機凝結剤」と称す場合がある。）と無機凝集剤とを併用添加する本発明による凝集性の向上効果のメカニズムは、以下の通りである。
<Mechanism>
The mechanism of the coagulation-improving effect according to the present invention in which an organic coagulant having a cationic group (hereinafter sometimes referred to as “cationic organic coagulant”) and an inorganic coagulant are added together is as follows. .
カチオン性有機凝結剤を添加するのみでは、被処理水中の濁質や有機炭素を十分に凝集処理することができない。
無機凝集剤を添加することで、濁質や有機炭素を凝集処理することができるが、前述の通り、無機炭素濃度の高い被処理水の場合、無機炭素由来の炭酸イオンが無機凝集剤と濁質や有機炭素との反応を阻害する。
このような被処理水にカチオン性有機凝結剤を添加すると、水中の無機炭素とカチオン性有機凝結剤とが反応することで、無機炭素による凝集阻害を抑制し、無機凝集剤と濁質や有機炭素との反応性を向上させることができる。
Only by adding a cationic organic coagulant, turbidity and organic carbon in the water to be treated cannot be sufficiently coagulated.
By adding an inorganic flocculant, turbidity and organic carbon can be agglomerated, but as described above, in the case of water to be treated with a high inorganic carbon concentration, carbonate ions derived from inorganic carbon and turbidity with the inorganic flocculant. Impedes reaction with quality and organic carbon.
When a cationic organic coagulant is added to such water to be treated, the inorganic carbon in the water reacts with the cationic organic coagulant to suppress aggregation inhibition by the inorganic carbon, and the inorganic coagulant and turbid or organic The reactivity with carbon can be improved.
本発明においては、カチオン性有機凝結剤と無機凝集剤との併用で良好な凝集効果を得ることができるが、更にアニオン基を有する有機凝集剤（以下、「アニオン性有機凝集剤」と称す場合がある。）を併用してもよく、アニオン性有機凝集剤の併用で、凝集フロックを粗大化させて、固液分離水の水質をより良好なものとすることができる。 In the present invention, a combination of a cationic organic coagulant and an inorganic flocculant can provide a good flocculation effect. However, an organic flocculant having an anionic group (hereinafter referred to as “anionic organic flocculant”) In combination with an anionic organic flocculant, the aggregate flocs can be coarsened to improve the quality of the solid-liquid separation water.
＜被処理水＞
本発明において処理する被処理水は、無機炭素濃度が５０ｍｇ／Ｌ以上で、無機炭素による無機凝集剤の凝集阻害が起こり易い水である。
このような無機炭素濃度の多い被処理水が発生する要因は定かではないが、工場等に特有の工程が存在している場合が想定される。
これらの水のＳＳ濃度は１０ｍｇ／Ｌ以上である場合が多く、電気伝導率は１００ｍＳ／ｍ以上である。なお、通常河川水や湖水を水源として凝集、沈殿、濾過処理等をする場合、無機炭素濃度は１０ｍｇ／Ｌ前後であり、２ｍｇ／Ｌ以下の場合もある。
<Treatment water>
The water to be treated in the present invention is water that has an inorganic carbon concentration of 50 mg / L or more and easily inhibits the aggregation of the inorganic flocculant by inorganic carbon.
The cause of the generation of water to be treated with such a high inorganic carbon concentration is not clear, but it is assumed that there are processes unique to factories and the like.
The SS concentration of these waters is often 10 mg / L or more, and the electrical conductivity is 100 mS / m or more. In addition, when performing agglomeration, precipitation, filtration treatment, etc., usually using river water or lake water as a water source, the inorganic carbon concentration is around 10 mg / L, and may be 2 mg / L or less.
＜カチオン性有機凝結剤＞
カチオン性有機凝結剤としては、特に制限はなく、従来より使用されているものまたはこれらと類似のものが使用でき、例えばポリエチレンイミン、ジシアンジアミド−ホルマリン縮合物、アルキレンポリアミン−アルキレンジハライド縮合物、ポリジメチルジアリルアンモニウム塩、ポリアクリルアミドのマンニッヒ変性物、ポリアクリルアミドのホフマン分解物、エピハロヒドリシ−アミン縮合物、カチオン化デンプン、カチオン化グアガム、キトサン、アミノアルキル（メタ）アクリレート（三級、四級化物も含む）の単独重合体またはアクリルアミドもしくは他のモノマーとの共重合体などが例示できるが、特に、エピハロヒドリシ−アミン縮合物、ポリエチレンイミン、ジシアンジアミド−ホルマリン縮合物、アルキレンポリアミン−アルキレンジハライド縮合物、ポリジメチルジアリルアンモニウム塩が好ましい。これらは１種のみを用いてもよく、２種以上を混合して用いてもよい。
<Cationic organic coagulant>
The cationic organic coagulant is not particularly limited, and those conventionally used or similar can be used. For example, polyethyleneimine, dicyandiamide-formalin condensate, alkylene polyamine-alkylene dihalide condensate, poly Dimethyldiallylammonium salt, polyacrylamide Mannich modified product, polyacrylamide Hofmann degradation product, epihalohydric-amine condensate, cationized starch, cationized guar gum, chitosan, aminoalkyl (meth) acrylate (including tertiary and quaternized products) ) Homopolymers or copolymers with acrylamide or other monomers, and in particular, epihalohydric-amine condensates, polyethyleneimines, dicyandiamide-formalin condensates, alkylenepolyamides, etc. - alkylene dihalide condensates, polydimethyl diallyl ammonium salts are preferred. These may use only 1 type and may mix and
カチオン性有機凝結剤としては、カチオン基による無機炭素との反応性の高いものが好ましく、コロイド当量が１ｍｅｑ／ｇ以上、特に５ｍｅｑ／ｇ以上であるものを用いることが、無機凝集剤にカチオン性有機凝結剤を併用することによる凝集性の向上効果に優れる点において好ましい。カチオン性有機凝結剤のコロイド当量の上限については特に制限はないが、通常２０ｍｅｑ／ｇ以下である。 As the cationic organic coagulant, those having high reactivity with inorganic carbon due to a cation group are preferable, and those having a colloidal equivalent of 1 meq / g or more, particularly 5 meq / g or more are used as the inorganic flocculant. The organic coagulant is preferred in that it is excellent in the effect of improving the cohesiveness due to the combined use. Although there is no restriction | limiting in particular about the upper limit of the colloid equivalent of a cationic organic coagulant, Usually, it is 20 meq / g or less.
被処理水へのカチオン性有機凝結剤の添加量は、被処理水の水質、カチオン性有機凝結剤の種類等によっても異なるが、２〜３０ｍｇ／Ｌ、特に５〜１０ｍｇ／Ｌ程度とすることが好ましい。カチオン性有機凝結剤の添加量が少な過ぎると、カチオン性有機凝結剤を添加することによる凝集性の改善効果を十分に得ることができず、多過ぎると、例えば、後段に膜処理がある場合に、それ自体が汚染される可能性がある。 The amount of the cationic organic coagulant added to the water to be treated varies depending on the quality of the water to be treated and the type of the cationic organic coagulant, but should be 2 to 30 mg / L, particularly about 5 to 10 mg / L. Is preferred. If the amount of the cationic organic coagulant added is too small, the effect of improving the cohesiveness by adding the cationic organic coagulant cannot be obtained sufficiently. In addition, it can become contaminated.
カチオン性有機凝結剤は、特に、被処理水中の無機炭素濃度に応じてその添加量を制御することが、カチオン性有機凝結剤の過不足を防止して良好な凝集効果を得る上で好ましい。従って、被処理水の無機炭素濃度をＧＥ製Ｓｉｅｖｅｒｓ９００などで測定し、その測定結果に基づいて、カチオン性有機凝結剤を薬注制御することが好ましい。この場合、カチオン性有機凝結剤は、被処理水の無機炭素濃度（ｍｇ／Ｌ）に対して、１〜５重量％程度の添加量（ｍｇ／Ｌ）となるように薬注制御することが好ましい。なお、被処理水の無機炭素濃度は、連続的に計測してもよく、間欠的に計測してもよい。 In particular, it is preferable to control the addition amount of the cationic organic coagulant in accordance with the inorganic carbon concentration in the water to be treated in order to prevent the cationic organic coagulant from being excessive or insufficient and to obtain a good coagulation effect. Therefore, it is preferable to measure the inorganic carbon concentration of the water to be treated with GE Sievers 900 or the like, and to control the injection of the cationic organic coagulant based on the measurement result. In this case, the cationic organic coagulant can be controlled so as to have an addition amount (mg / L) of about 1 to 5% by weight with respect to the inorganic carbon concentration (mg / L) of the water to be treated. preferable. In addition, the inorganic carbon concentration of to-be-processed water may be measured continuously and may be measured intermittently.
＜無機凝集剤＞
無機凝集剤としては、アルミニウム系ないし鉄系の無機凝集剤を用いることができる。これらは１種のみを用いてもよく、２種以上を混合して用いてもよい。具体的には、アルミニウム系無機凝集剤としては、硫酸アルミニウム（硫酸バンド）、ポリ塩化アルミニウム（ＰＡＣ）、塩化アルミニウムが例示できる。また、鉄系無機凝集剤としては、塩化第二鉄、塩化第一鉄、硫酸第一鉄、硫酸第二鉄、ポリ硫酸鉄等が例示できる。
<Inorganic flocculant>
As the inorganic flocculant, aluminum-based or iron-based inorganic flocculants can be used. These may use only 1 type and may mix and
被処理水への無機凝集剤の添加量は、被処理水の水質、無機凝集剤の種類等によっても異なるが、５０〜５００ｍｇ／Ｌ、特に１００〜３００ｍｇ／Ｌ程度とすることが好ましい。無機凝集剤の添加量が少な過ぎると、被処理水中の濁質や有機炭素を十分に凝集処理して良好な水質の固液分離水を得ることができないが、本発明はカチオン性有機凝結剤を併用することで、無機凝集剤の必要添加量を低減するものであり、無機凝集剤の添加量を過度に多くすることは、汚泥発生量の増加につながり、また薬剤コストの面でも好ましくない。 The amount of the inorganic flocculant added to the water to be treated varies depending on the quality of the water to be treated, the type of the inorganic flocculant, etc., but is preferably about 50 to 500 mg / L, particularly about 100 to 300 mg / L. If the amount of the inorganic flocculant added is too small, turbidity and organic carbon in the water to be treated cannot be sufficiently agglomerated to obtain solid water-liquid separated water with good water quality, but the present invention is a cationic organic coagulant. In combination, the required amount of the inorganic flocculant is reduced, and excessive addition of the inorganic flocculant leads to an increase in the amount of sludge generated, and is not preferable in terms of chemical cost. .
＜アニオン性有機凝集剤＞
アニオン性有機凝集剤としては、ポリアクリル酸ナトリウム、ポリアクリルアミド部分加水分解物、部分スルホメチル化ポリアクリルアミド、ポリ（２−アクリルアミド）−２−メチルプロパン硫酸塩などの１種又は２種以上を使用することができる。
<Anionic organic flocculant>
As an anionic organic flocculant, 1 type (s) or 2 or more types, such as sodium polyacrylate, a polyacrylamide partial hydrolyzate, a partial sulfomethylation polyacrylamide, a poly (2-acrylamide) 2-methylpropane sulfate, are used. be able to.
アニオン性有機凝集剤を併用する場合、その添加量は被処理水の水質や用いるアニオン性有機凝集剤の種類によっても異なるが、通常０．１〜５ｍｇ／Ｌ程度である。 When an anionic organic flocculant is used in combination, the amount added varies depending on the quality of the water to be treated and the type of anionic organic flocculant used, but is usually about 0.1 to 5 mg / L.
＜凝集処理＞
無機炭素を含有する被処理水にカチオン性有機凝結剤と無機凝集剤とを添加して凝集処理する際、カチオン性有機凝結剤と無機凝集剤とは同時に添加しても別々に添加してもよいが、カチオン性有機凝結剤の添加による無機炭素に起因する無機凝集剤の凝集阻害を防止する観点から、予めカチオン性有機凝結剤を添加した後、無機凝集剤を添加して凝集処理することが好ましい。この場合、被処理水にカチオン性有機凝結剤を添加して１〜２０分程度撹拌して凝集処理した後、無機凝集剤を添加して３〜２０分程度撹拌して凝集処理することが好ましい。
<Aggregation treatment>
When a cationic organic coagulant and an inorganic flocculant are added to the water to be treated containing inorganic carbon for coagulation treatment, the cationic organic coagulant and the inorganic flocculant may be added simultaneously or separately. Although it is good, from the viewpoint of preventing the aggregation of the inorganic flocculant caused by inorganic carbon due to the addition of the cationic organic coagulant, after adding the cationic organic coagulant in advance, the inorganic flocculant is added and the coagulation treatment is performed. Is preferred. In this case, after adding a cationic organic coagulant to the water to be treated and stirring for about 1 to 20 minutes, it is preferable to add an inorganic flocculant and stir for about 3 to 20 minutes for aggregation. .
アニオン性有機凝集剤を併用する場合、アニオン性有機凝集剤は、無機凝集剤添加後に添加することが好ましい。 When an anionic organic flocculant is used in combination, the anionic organic flocculant is preferably added after the inorganic flocculant is added.
凝集処理時のｐＨは、用いる無機凝集剤に応じた好適なｐＨであることが好ましく、アルミニウム系無機凝集剤であれば、ｐＨ５．８〜７．０程度、鉄系無機凝集剤であればｐＨ５．８〜７．５程度にそれぞれ必要に応じて酸又はアルカリを添加してｐＨ調製することが好ましい。但し、本処理方法であれば、特段のｐＨ調整を行うことなく処理をすることが可能である。 The pH during the flocculation treatment is preferably a suitable pH according to the inorganic flocculant to be used. If it is an aluminum-based inorganic flocculant, the pH is about 5.8 to 7.0, and if it is an iron-based inorganic flocculant, the pH is 5 It is preferable to adjust the pH by adding acid or alkali to about 8 to 7.5 as necessary. However, with this treatment method, it is possible to carry out the treatment without special pH adjustment.
＜固液分離＞
凝集処理後の固液分離手段としては特に制限はなく、沈殿槽、加圧浮上槽、膜分離装置、濾過器等を用いることができる。
<Solid-liquid separation>
The solid-liquid separation means after the coagulation treatment is not particularly limited, and a precipitation tank, a pressure levitation tank, a membrane separation device, a filter and the like can be used.
＜後段処理＞
固液分離手段の後段、特に、固液分離手段として沈殿槽を用いた場合は、固液分離水のＳＳをより高度に除去するために、後段に濾過器や除濁膜装置等を設けてもよい。また、逆浸透（ＲＯ）膜分離装置を設けて脱塩処理を行ったり、オゾン処理で残留有機物を処理してもよい。この場合において、本発明によれば、凝集性の改善で、濁質や有機炭素が十分に低減された良好な水質の固液分離水を得ることができるため、これらの後段の処理手段の処理コストを削減すると共に安定運転を行うことが可能となる。
<Post-processing>
In the latter stage of the solid-liquid separation means, particularly when a precipitation tank is used as the solid-liquid separation means, a filter, a turbidity membrane device, etc. are provided in the latter stage in order to remove the solid-liquid separation water SS to a higher degree. Also good. Moreover, a reverse osmosis (RO) membrane separation apparatus may be provided to perform a desalting treatment or to treat residual organic substances by ozone treatment. In this case, according to the present invention, it is possible to obtain solid water-liquid separated water having a good water quality in which turbidity and organic carbon are sufficiently reduced by improving the cohesiveness. It is possible to reduce costs and perform stable operation.
＜無機炭素含有水の処理装置＞
以下、図１を参照して本発明の無機炭素含有水の処理装置を説明する。
図１は、本発明の無機炭素含有水の処理装置の実施の形態の一例を示す系統図である。
<Inorganic carbon-containing water treatment device>
Hereinafter, the treatment apparatus for inorganic carbon-containing water of the present invention will be described with reference to FIG.
FIG. 1 is a system diagram showing an example of an embodiment of an apparatus for treating inorganic carbon-containing water according to the present invention.
原水槽１内の原水は、配管１１より第１凝集槽２に送給される過程でカチオン性有機凝結剤が添加された後、第１凝集槽２で所定時間凝集処理される。
第１凝集槽２の凝集処理水は、配管１２より第２凝集槽３に送給される過程で無機凝集剤が添加された後、第２凝集槽３で所定時間凝集処理される。
第２凝集槽３の凝集処理水は、配管１３を経て沈殿槽３に送給される過程でアニオン性有機凝集剤が添加された後、沈殿槽４で固液分離される。
沈殿槽４の分離水は、配管１４より除濁膜装置５に送給されて更に除濁処理された後、配管１５よりＲＯ膜分離装置６に送給されＲＯ膜分離処理され、透過水が処理水として配管１６より系外へ排出される。
The raw water in the
The aggregating water in the first aggregating
The agglomerated water in the second aggregating
The separation water in the settling tank 4 is supplied to the
なお、図１は本発明の無機炭素含有水の処理装置の一例を示すものであって、本発明は何ら図示のものに限定されるものではない。
カチオン性有機凝結剤や無機凝集剤は配管注入ではなく、凝集槽に添加してもよく、更にアニオン性有機凝集剤を添加して凝集処理するための凝集槽を設けてもよい。
FIG. 1 shows an example of the treatment apparatus for inorganic carbon-containing water of the present invention, and the present invention is not limited to the illustrated one.
The cationic organic coagulant and the inorganic coagulant may be added to the coagulation tank instead of pipe injection, and an anionic organic coagulant may be added and a coagulation tank for coagulation treatment may be provided.
以下に実施例及び比較例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
［凝集処理剤］
以下の実施例及び比較例において用いた凝集処理剤は以下の通りである。
無機凝集剤：塩化第二鉄（昭和化学工業社製）
カチオン性有機凝結剤Ａ：エピクロルヒドリン−ジメチルアミン縮合物、コロイド当量６．５ｍｅｑ／ｇ
カチオン性有機凝結剤Ｂ：ポリジメチルジアリルアンモニウムクロライド、コロイド当量０．５ｍｅｑ／ｇ
アニオン性有機凝集剤：アクリル酸ナトリウムとアクリルアミドとの共重合体
[Aggregating agent]
The aggregation treatment agents used in the following examples and comparative examples are as follows.
Inorganic flocculant: Ferric chloride (manufactured by Showa Chemical Industry Co., Ltd.)
Cationic organic coagulant A: epichlorohydrin-dimethylamine condensate, colloid equivalent 6.5 meq / g
Cationic organic coagulant B: polydimethyldiallylammonium chloride, colloidal equivalent 0.5 meq / g
Anionic organic flocculant: copolymer of sodium acrylate and acrylamide
［原水］
下記の実施例及び比較例で凝集処理に供した原水は、Ａ工場の排水（無機炭素濃度５５〜２５０ｍｇ／Ｌ）を生物処理して得られる下記水質のものである。生物処理を施しても無機炭素濃度は変化しない。
[Raw water]
The raw water subjected to the flocculation treatment in the following Examples and Comparative Examples is of the following water quality obtained by biological treatment of the wastewater (inorganic carbon concentration 55 to 250 mg / L) of the A factory. Inorganic carbon concentration does not change even after biological treatment.
［凝集性能の評価］
以下の実施例及び比較例においては、凝集槽と沈殿槽と除濁膜装置がこの順で連結された水処理装置を用い、７日間連続処理を行って、以下の評価項目で凝集性能を評価した。
[Evaluation of aggregation performance]
In the following Examples and Comparative Examples, using a water treatment apparatus in which a coagulation tank, a precipitation tank, and a turbidity removing film apparatus are connected in this order, continuous treatment is performed for 7 days, and the aggregation performance is evaluated using the following evaluation items. did.
固液分離水の濁度：沈殿槽の分離水を採取して濁度（ＮＴＵ）を濁度計で測定した。
沈殿汚泥量比：沈殿槽で分離された汚泥量を計量し、実施例１の場合を１として、相対評価した。
濾過水ＳＤＩ：沈殿槽の分離水を採取し、Ｎｏ．５Ａ濾紙で濾過して得られた濾過水のＳＤＩをＡＳＴＭ Ｄ４１８９−９５（２００２）に則り測定した。
ＭＦ膜差圧上昇速度：沈殿槽の後段の除濁膜（旭化成社製 孔径０．１μｍのＰＶＤＦ製ＭＦ膜）装置に、沈殿槽の分離水を、流量２ｍ３／ｍ２／ｄａｙで連続通水したときの供給水側と処理水側の圧力を計測し、差圧の上昇速度（ｋＰａ／ｄａｙ）を算出した。
Turbidity of solid-liquid separation water: The separation water of the precipitation tank was collected and turbidity (NTU) was measured with a turbidimeter.
Sediment sludge ratio: The amount of sludge separated in the sedimentation tank was weighed, and relative evaluation was made with the case of Example 1 being 1.
Filtered water SDI: The separated water collected in the settling tank was collected. The SDI of filtered water obtained by filtering with 5A filter paper was measured according to ASTM D4189-95 (2002).
MF membrane differential pressure increase rate: Separation water in the sedimentation tank is continuously passed through the turbidity membrane (PVDF MF membrane with a pore size of 0.1 μm manufactured by Asahi Kasei Co., Ltd.) in the latter stage of the precipitation tank at a flow rate of 2 m 3 / m 2 / day The pressure on the supply water side and the treated water side when water was measured was measured, and the rate of increase in differential pressure (kPa / day) was calculated.
［実施例１］
凝集槽にカチオン性有機凝結剤Ａ５ｍｇ／Ｌと無機凝集剤２００ｍｇ／Ｌを添加してｐＨを調整せず、１０分間凝集処理した後、沈殿槽、除濁膜装置に通水した。
[Example 1]
The cationic
［実施例２］
凝集槽を２槽設け、第１凝集槽でカチオン性有機凝結剤Ａ５ｍｇ／Ｌを添加して５分間凝集処理した後、第２凝集槽で無機凝集剤を２００ｍｇ／Ｌ添加して１０分間凝集処理したこと以外は、実施例１と同様に行った。
[Example 2]
Two agglomeration tanks are provided. After adding 5 mg / L of the cationic organic coagulant A in the first agglomeration tank and aggregating for 5 minutes, adding 200 mg / L of inorganic aggregating agent in the second agglomeration tank and aggregating for 10 minutes Except that, the same procedure as in Example 1 was performed.
［実施例３］
実施例２において、１時間に１回、原水の無機炭素濃度をＧＥ製Ｓｉｅｖｅｒｓ９００により測定し、無機炭素濃度（ｍｇ／Ｌ）に対して１０重量％となるように、カチオン性有機凝結剤Ａの添加量（ｍｇ／Ｌ）を制御して添加したこと以外は実施例２と同様に行った。
[Example 3]
In Example 2, the inorganic carbon concentration of the raw water was measured with a GE Sievers 900 once an hour, so that the cationic organic coagulant A was 10% by weight with respect to the inorganic carbon concentration (mg / L). The same operation as in Example 2 was conducted except that the addition amount (mg / L) was controlled.
［実施例４］
実施例２において、第２凝集槽の流出水にアニオン性有機凝集剤を２ｍｇ／Ｌ添加したこと以外は実施例２と同様に行った。
[Example 4]
In Example 2, it carried out like Example 2 except having added 2 mg / L of anionic organic flocculants to the effluent of the 2nd flocculent tank.
［実施例５］
実施例３において、カチオン性有機凝結剤Ａの代りにカチオン性有機凝結剤Ｂを用いたこと以外は実施例３と同様に行った。
[Example 5]
In Example 3, it carried out like Example 3 except having used the cationic organic coagulant B instead of the cationic organic coagulant A.
［比較例１］
実施例１において、カチオン性有機凝結剤Ａも無機凝集剤も添加しなかったこと以外は実施例１と同様に行った。
[Comparative Example 1]
In Example 1, it carried out like Example 1 except having added neither the cationic organic coagulant A nor an inorganic flocculant.
［比較例２］
実施例１において、カチオン性有機凝結剤Ａを添加しなかったこと以外は実施例１と同様に行った。
[Comparative Example 2]
In Example 1, it carried out like Example 1 except not having added cationic organic coagulant A.
［比較例３］
実施例１において、カチオン性有機凝結剤Ａを添加せず、無機凝集剤添加量を２倍の４００ｍｇ／Ｌとしたこと以外は実施例１と同様に行った。
[Comparative Example 3]
Example 1 was carried out in the same manner as Example 1 except that the cationic organic coagulant A was not added and the inorganic flocculant addition amount was doubled to 400 mg / L.
実施例１〜５及び比較例１〜３の結果を表１に示す。 Table 1 shows the results of Examples 1 to 5 and Comparative Examples 1 to 3.
表１より次のことが分かる。
凝集剤を用いていない比較例１や、無機凝集剤のみで凝集処理した比較例２では、固液分離水の濁度が高い。
無機凝集剤添加量を２倍とした比較例３では、固液分離水濁度や、濾過水のＳＤＩは、良好な値であったが、汚泥量が実施例１の約１．８９倍となった。
Table 1 shows the following.
In Comparative Example 1 in which no flocculant is used and in Comparative Example 2 in which flocculation treatment is performed using only the inorganic flocculant, the turbidity of the solid-liquid separated water is high.
In Comparative Example 3 in which the amount of inorganic flocculant added was double, the solid-liquid separation water turbidity and the SDI of filtered water were good values, but the amount of sludge was about 1.89 times that of Example 1. became.
これに対して、カチオン性有機凝結剤と無機凝集剤とを併用した実施例１〜５では良好な結果が得られた。
特に、カチオン性有機凝結剤を添加した後無機凝集剤を添加した実施例２では、実施例１に比べて固液分離水の濁度が低く、濾過水のＳＤＩ値も低い値を示し、ＭＦ膜の差圧上昇速度も低下した。
原水の無機炭素濃度に応じてカチオン性有機凝結剤添加量を制御した実施例３では、実施例２よりも更に固液分離水の濁度が低く、変動幅も小さくなり、濾過水のＳＤＩ、ＭＦ膜の差圧上昇速度も更に改善された。
更に、アニオン性有機凝集剤を添加した実施例４では、凝集フロックが大きくなり、固液分離水濁度が低減した。
実施例５は、コロイド当量が低いカチオン性有機凝結剤を用いたものであり、固液分離水の濁度や濾過水ＳＤＩ、ＭＦ膜の差圧上昇速度が他の実施例に比べて劣るものの、比較例１，２に比べて良好な結果が得られ、比較例３に比べて汚泥量を少なくすることができる。
On the other hand, the favorable result was obtained in Examples 1-5 which used together the cationic organic coagulant and the inorganic flocculant.
In particular, in Example 2 in which an inorganic flocculant was added after adding a cationic organic coagulant, the turbidity of solid-liquid separated water was lower than that in Example 1, and the SDI value of filtered water was also low. The rate of increase in the differential pressure of the membrane also decreased.
In Example 3 where the addition amount of the cationic organic coagulant was controlled according to the inorganic carbon concentration of the raw water, the turbidity of the solid-liquid separated water was lower than that of Example 2, and the fluctuation range was smaller. The differential pressure increase rate of the MF membrane was further improved.
Furthermore, in Example 4 to which the anionic organic flocculant was added, the flocs flocs increased and the solid-liquid separation water turbidity decreased.
Example 5 uses a cationic organic coagulant having a low colloidal equivalent, and the turbidity of solid-liquid separation water and the rate of increase in the differential pressure of filtered water SDI and MF membrane are inferior to those of other examples. Favorable results are obtained as compared with Comparative Examples 1 and 2, and the amount of sludge can be reduced as compared with Comparative Example 3.
１ 原水槽
２ 第１凝集槽
３ 第２凝集槽
４ 沈殿槽
５ 除濁膜装置
６ ＲＯ膜分離装置
DESCRIPTION OF
Claims (9)
前記被処理水の無機炭素濃度を測定する無機炭素濃度測定手段と、この測定値に基づいて、前記カチオン基を有する有機凝結剤の添加量を制御する制御手段とを有することを特徴とする無機炭素含有水の処理装置。 An inorganic flocculant and an organic coagulant having a cationic group with a colloidal equivalent of 1 meq / g or more are added to water to be treated containing 50 mg / L or more of inorganic carbon, and agglomeration is performed at pH 5.5 to 8.5. a flocculation treatment unit, a processing device for a continuously machine the carbon-containing water that have a and solid-liquid separation means for solid-liquid separation aggregation process water,
An inorganic carbon concentration measuring means for measuring the inorganic carbon concentration of the water to be treated, and a control means for controlling the addition amount of the organic coagulant having the cationic group based on the measured value Carbon-containing water treatment equipment .
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