JP7407024B2 - Waste liquid treatment method - Google Patents
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- JP7407024B2 JP7407024B2 JP2020038970A JP2020038970A JP7407024B2 JP 7407024 B2 JP7407024 B2 JP 7407024B2 JP 2020038970 A JP2020038970 A JP 2020038970A JP 2020038970 A JP2020038970 A JP 2020038970A JP 7407024 B2 JP7407024 B2 JP 7407024B2
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- 239000007788 liquid Substances 0.000 title claims description 99
- 239000002699 waste material Substances 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 53
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims description 39
- 239000011574 phosphorus Substances 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000000706 filtrate Substances 0.000 claims description 19
- 229920002678 cellulose Polymers 0.000 claims description 15
- 239000001913 cellulose Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002121 nanofiber Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 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 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000002351 wastewater Substances 0.000 description 13
- 229910019142 PO4 Inorganic materials 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- -1 aluminum compound Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002506 iron compounds Chemical class 0.000 description 4
- 150000002681 magnesium compounds Chemical class 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 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 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 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
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Removal Of Specific Substances (AREA)
Description
本発明は、リンを有効に除去することのできる廃液処理方法に関する。 The present invention relates to a waste liquid treatment method that can effectively remove phosphorus.
水質汚濁防止法による排水基準には、有害物質に関する排水基準と生活環境項目に関する排水基準があり、生活環境項目に関する排水基準の１つとしてリンの含有量が規制され、国のリンの排水基準は８ｍｇ／Ｌとされている。
栄養塩類であるリンが存在することにより、植物プランクトンとなる藻類が発生して水中の酸素が消費され、嫌気性雰囲気となって水質の悪化が引き起こされる。特に、湖沼や内湾等の閉鎖性水域では、かかるリンによる水質の悪化が生じやすいため、総量規制や上乗せ基準等、水質汚濁防止法による一律排水基準よりも一層厳しい規制が課されている。
The wastewater standards under the Water Pollution Control Law include wastewater standards for hazardous substances and wastewater standards for living environment items.The content of phosphorus is regulated as one of the wastewater standards for living environment items, and the national wastewater standards for phosphorus are It is said to be 8 mg/L.
The presence of phosphorus, a nutrient, causes algae, which become phytoplankton, to grow and consume oxygen in the water, creating an anaerobic atmosphere and deteriorating water quality. In particular, in closed water bodies such as lakes and inner bays, water quality is likely to deteriorate due to phosphorus, so regulations such as total volume regulations and additional standards are imposed that are even stricter than the uniform wastewater standards under the Water Pollution Control Law.
こうしたなか、従来より、廃液を処理するための種々の方法が開発されている。例えば、特許文献１には、廃水に鉄系の凝集剤を添加し、生成されるフロックが破壊されるのに十分な高速で攪拌する廃水の脱リン方法が開示されている。また、特許文献２には、リン酸塩の以外の無機塩類を高濃度で含む工業廃液に、マグネシウム塩を添加して、リン含有不溶性塩を形成させ、これを除去するリンの除去方法が開示されている。
一方、特許文献３～４には、廃水に植物由来のカチオン性又はアニオン性ナノフィブリル状セルロースを所定量添加し、廃水中に含まれる金属イオンのナノフィブリル状セルロースへの吸着を含む浄化処理を行い、これを分離する方法が開示されている。
Under these circumstances, various methods for treating waste liquid have been developed. For example, Patent Document 1 discloses a method for dephosphorizing wastewater in which an iron-based flocculant is added to wastewater and the mixture is stirred at a high enough speed to destroy the generated flocs. Additionally, Patent Document 2 discloses a phosphorus removal method in which a magnesium salt is added to industrial wastewater containing a high concentration of inorganic salts other than phosphates to form a phosphorus-containing insoluble salt, and this is removed. has been done.
On the other hand, Patent Documents 3 and 4 disclose that a predetermined amount of plant-derived cationic or anionic nanofibrillar cellulose is added to wastewater, and a purification treatment including adsorption of metal ions contained in the wastewater to the nanofibrillar cellulose is performed. A method for performing and separating the same is disclosed.
このような排水処理は、水質環境の変動等に応じて、今後益々厳しい基準値や規制対象地域が拡大されることも充分に予想されるため、より高度な技術が求められる。 In this type of wastewater treatment, more advanced technology is required because it is expected that stricter standards and areas subject to regulations will be expanded in the future in response to changes in the water quality environment.
しかしながら、例えば廃液中のリンを１ｍｇ／Ｌ未満の含有量に減じようとするにあたり、上記特許文献１～２に記載の方法であると、凝集剤やマグネシウム塩の添加量を過度に増大させる必要が生じたり、汚泥発生量が不要に増大したりするおそれがある。また、上記特許文献３～４に記載の方法であると、リン酸イオンを選択的に吸着・除去することができず、廃水にリン以外の他のイオンが含まれていると、益々困難を伴う状況にある。 However, in order to reduce the phosphorus content in waste liquid to less than 1 mg/L, for example, the methods described in Patent Documents 1 and 2 require excessively increasing the amount of flocculant or magnesium salt added. or the amount of sludge generated may increase unnecessarily. Furthermore, the methods described in Patent Documents 3 and 4 cannot selectively adsorb and remove phosphate ions, and if the wastewater contains ions other than phosphorus, it becomes even more difficult. I am in a situation where
したがって、本発明の課題は、廃液中のリンの含有量を効果的に低減し、リンを選択的かつ有効に除去することのできる廃液処理方法を提供することにある。 Therefore, an object of the present invention is to provide a waste liquid treatment method that can effectively reduce the phosphorus content in waste liquid and selectively and effectively remove phosphorus.
そこで本発明者は、上記課題を解決すべく鋭意検討を行った結果、特定のｐＨ環境下、セルロースナノファイバーを用いつつ、特定の金属化合物をリンに対して特定のモル比で添加することにより、廃液中のリンの含有量を選択的かつ効果的に低減することのできる廃液処理方法を見出した。 Therefore, as a result of intensive studies to solve the above problems, the present inventors found that by adding a specific metal compound to phosphorus at a specific molar ratio while using cellulose nanofibers in a specific pH environment, discovered a wastewater treatment method that can selectively and effectively reduce the phosphorus content in wastewater.
すなわち、本発明は、次の工程（Ｉ）～（II）：
（Ｉ）少なくとも１０ｐｐｍ～２０００ｐｐｍのリンを含む廃液Ｘに、セルロースナノファイバーと金属（Ｍ）化合物（Ｍは、Ａｌ、Ｆｅ又はＭｇを示す）とを添加して、リンと金属（Ｍ）とのモル比（Ｍ／Ｐ）が０．８～６であり、かつｐＨが１．５～９．５である処理液Ｙを得る工程
（II）得られた処理液Ｙをろ過して沈殿物を除去し、ろ液Ｚを得る工程
を備える廃液処理方法を提供するものである。
That is, the present invention provides the following steps (I) to (II):
(I) Cellulose nanofibers and a metal (M) compound (M represents Al, Fe, or Mg) are added to waste liquid Step of obtaining a treatment liquid Y having a molar ratio (M/P) of 0.8 to 6 and a pH of 1.5 to 9.5 (II) Filtering the obtained treatment liquid Y to remove precipitates. The present invention provides a waste liquid treatment method comprising a step of removing the filtrate and obtaining a filtrate Z.
本発明の廃液処理方法によれば、例え硫黄やナトリウム等が残存する廃液であっても、リンを選択的に除去し、その含有量を有効に減じることができる。したがって、今後予想される厳しい基準値や規制等にも十分対応可能な、汎用性の高い廃液処理方法である。 According to the waste liquid treatment method of the present invention, even if sulfur, sodium, etc. remain in the waste liquid, phosphorus can be selectively removed and the content thereof can be effectively reduced. Therefore, it is a highly versatile waste liquid treatment method that can fully meet the strict standards and regulations expected in the future.
以下、本発明について詳細に説明する。
本発明の廃液処理方法は、次の工程（Ｉ）～（II）：
（Ｉ）少なくとも１０ｐｐｍ～２０００ｐｐｍのリンを含む廃液Ｘに、セルロースナノファイバーと金属（Ｍ）化合物（Ｍは、Ａｌ、Ｆｅ又はＭｇを示す）とを添加して、リンと金属（Ｍ）とのモル比（Ｍ／Ｐ）が０．８～６であり、かつｐＨが１．５～９．５である処理液Ｙを得る工程
（II）得られた処理液Ｙをろ過して沈殿物を除去し、ろ液Ｚを得る工程
を備える。
The present invention will be explained in detail below.
The waste liquid treatment method of the present invention includes the following steps (I) to (II):
(I) Cellulose nanofibers and a metal (M) compound (M represents Al, Fe, or Mg) are added to waste liquid Step of obtaining a treatment liquid Y having a molar ratio (M/P) of 0.8 to 6 and a pH of 1.5 to 9.5 (II) Filtering the obtained treatment liquid Y to remove precipitates. A step of removing the filtrate Z to obtain a filtrate Z is provided.
このような工程を備える本発明の廃液処理方法を用いることにより、まずは工程（Ｉ）において、廃液Ｘ（処理前の廃液）中に含まれるリンと金属（Ｍ）化合物とにより、得られる処理液Ｙ中で金属（Ｍ）リン酸塩が生成し、かかる金属（Ｍ）リン酸塩がセルロースナノファイバーに担持されてなる複合物が形成される。次いで工程（II）において、形成された複合物が沈殿物として効率的に除去され、リン含有量が有効に減じられたろ液Ｚ（処理後の廃液Ｘ）を得ることができる。
すなわち、工程（Ｉ）～（II）を経ることにより、処理の対象とする廃液Ｘが処理液Ｙへと、次いでろ液Ｚへと変遷して、リンが選択的かつ有効に減じられた、処理後の廃液Ｘであるろ液Ｙを得ることができる。
By using the waste liquid treatment method of the present invention comprising such steps, first, in step (I), the treated liquid obtained by using phosphorus and metal (M) compounds contained in waste liquid X (waste liquid before treatment) A metal (M) phosphate is generated in Y, and a composite is formed in which the metal (M) phosphate is supported on cellulose nanofibers. Next, in step (II), the formed composite is efficiently removed as a precipitate, and a filtrate Z (waste liquid X after treatment) in which the phosphorus content is effectively reduced can be obtained.
That is, through steps (I) to (II), the waste liquid X to be treated is transformed into a treated liquid Y, and then into a filtrate Z, and phosphorus is selectively and effectively reduced. A filtrate Y, which is the waste liquid X after the treatment, can be obtained.
工程（Ｉ）は、少なくとも１０ｐｐｍ～２０００ｐｐｍのリンを含む廃液Ｘに、セルロースナノファイバーと金属（Ｍ）化合物（Ｍは、Ａｌ、Ｆｅ又はＭｇを示す）とを添加して、リンと金属（Ｍ）とのモル比（Ｍ／Ｐ）が０．８～６であり、かつｐＨが１．５～９．５である処理液Ｙを得る工程である。
本発明において、処理の対象とする廃液Ｘは、少なくとも１０ｐｐｍ～２０００ｐｐｍのリンを含む。このように、リンを低濃度から高濃度の広範囲にわたって含む廃液が処理の対象であっても、本発明の廃液処理方法であれば、かかるリンの含有量を極めて低い値まで有効に減じることができる。
In step (I), cellulose nanofibers and a metal (M) compound (M represents Al, Fe, or Mg) are added to waste liquid ) is a process of obtaining a treatment liquid Y having a molar ratio (M/P) of 0.8 to 6 and a pH of 1.5 to 9.5.
In the present invention, the waste liquid X to be treated contains at least 10 ppm to 2000 ppm of phosphorus. As described above, even if wastewater containing phosphorus in a wide range of concentrations from low to high concentrations is to be treated, the wastewater treatment method of the present invention can effectively reduce the phosphorus content to an extremely low value. can.
かかる廃液Ｘは、その他の成分として、硫黄又はナトリウム、或いは硫黄とナトリウムの双方を含んでいてもよい。本発明の廃液処理方法であれば、廃液Ｘがこれらの成分を含んでいても、リンを選択的に除去することができる。
具体的には、廃液Ｘ中における硫黄の含有量は、１００００ｐｐｍ～２００００ｐｐｍであってもよく、ナトリウムの含有量は、２００ｐｐｍ～３００００ｐｐｍであってもよい。
したがって、本発明において処理の対象とする廃液Ｘとして、上記所定量のリンを含む、種々の原料を取り扱う工場等における廃液を用いることができ、例えばさらに硫黄やナトリウムを含み得る、金属リン酸塩（例えば、リン酸アルミニウム）を製造する工場等における廃液も用いることができる。
Such waste liquid X may contain sulfur or sodium, or both sulfur and sodium as other components. With the waste liquid treatment method of the present invention, even if waste liquid X contains these components, phosphorus can be selectively removed.
Specifically, the sulfur content in the waste liquid X may be 10,000 ppm to 20,000 ppm, and the sodium content may be 200 ppm to 30,000 ppm.
Therefore, as the waste liquid X to be treated in the present invention, waste liquids from factories handling various raw materials containing the above-mentioned predetermined amount of phosphorus can be used, such as metal phosphates that may further contain sulfur and sodium. Waste liquid from factories that manufacture aluminum phosphate (for example, aluminum phosphate) can also be used.
工程（Ｉ）では、廃液Ｘに、セルロースナノファイバーと金属（Ｍ）化合物（Ｍは、Ａｌ、Ｆｅ又はＭｇを示す）とを添加する。
セルロースナノファイバー（ＣＮＦ）とは、全ての植物細胞壁の約５割を占める骨格成分であって、かかる細胞壁を構成する植物繊維をナノサイズまで解繊等することにより得ることができる軽量高強度繊維であり、水への良好な分散性も有している。
また、ＣＮＦを構成するセルロース分子鎖では、炭素による周期的構造が形成されていることから、廃液Ｘ中のリンと金属（Ｍ）化合物により生成される金属（Ｍ）リン酸塩が、ＣＮＦに絡みつつ効率的に担持されて沈殿物の生成に大きく寄与するものと考えられる。
In step (I), cellulose nanofibers and a metal (M) compound (M represents Al, Fe, or Mg) are added to the waste liquid X.
Cellulose nanofiber (CNF) is a skeletal component that accounts for about 50% of all plant cell walls, and is a lightweight, high-strength fiber that can be obtained by fibrillating the plant fibers that make up the cell wall to nano-size. It also has good dispersibility in water.
In addition, since the cellulose molecular chains constituting CNF have a periodic structure made of carbon, metal (M) phosphates generated from phosphorus and metal (M) compounds in waste liquid It is thought that the particles are efficiently supported while being entangled and greatly contribute to the formation of precipitates.
ＣＮＦの平均繊維径は、好ましくは１０μｍ以下であり、より好ましくは１μｍ以下であり、さらに好ましくは１００ｎｍ以下である。下限値については特に制限はないが、通常１ｎｍ以上である。
また、ＣＮＦの平均長さは、廃液Ｘ中のリンと金属（Ｍ）化合物により生成される金属（Ｍ）リン酸塩をＣＮＦに効率的に担持させる観点から、好ましくは１００ｎｍ～１００μｍであり、より好ましくは１μｍ～１００μｍであり、さらに好ましくは５μｍ～１００μｍである。
The average fiber diameter of CNF is preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 100 nm or less. There is no particular restriction on the lower limit, but it is usually 1 nm or more.
Further, the average length of the CNF is preferably 100 nm to 100 μm from the viewpoint of efficiently supporting the metal (M) phosphate generated by the phosphorus and metal (M) compound in the waste liquid X on the CNF, More preferably 1 μm to 100 μm, still more preferably 5 μm to 100 μm.
ＣＮＦの添加量は、生成される金属（Ｍ）リン酸塩のＣＮＦへの担持を有効に促進する観点から、１Ｌの廃液Ｘに対し、好ましくは０．１ｇ～２０．０ｇであり、より好ましくは０．１３ｇ～１５．０ｇであり、さらに好ましくは０．１５ｇ～１０．０ｇである。 The amount of CNF added is preferably 0.1 g to 20.0 g, more preferably 0.1 g to 20.0 g, per 1 L of waste liquid X, from the viewpoint of effectively promoting the support of the generated metal (M) phosphate on CNF. is 0.13g to 15.0g, more preferably 0.15g to 10.0g.
金属（Ｍ）化合物（Ｍは、Ａｌ、Ｆｅ又はＭｇを示す）は、廃液Ｘ中のリンを効率的かつ有効に除去する観点から、水溶性塩であるのが好ましい。具体的には、金属（Ｍ）の硫酸塩、金属（Ｍ）の硝酸塩、又は金属（Ｍ）の塩化物であるのが好ましく、これら１種を単独で用いてもよく、２種以上組み合わせて用いてもよい。なかでも、金属（Ｍ）の硫酸塩、又は金属（Ｍ）の塩化物であるのがより好ましい。
より具体的には、硫酸アルミニウム、硫酸鉄、硫酸マグネシウムの硫酸塩；塩化アルミニウム、塩化鉄、塩化マグネシウムの塩化物；硝酸アルミニウム、硝酸鉄、硝酸マグネシウムの硝酸塩が好ましく、硫酸アルミニウム、硫酸鉄、硫酸マグネシウムの硫酸塩；塩化アルミニウム、塩化鉄、塩化マグネシウムの塩化物がより好ましい。
なお、廃液Ｘへ金属（Ｍ）化合物を添加するにあたり、かかる金属（Ｍ）化合物の形態は、粉体のままであってもよく、水溶液としてもよい。なかでも、廃液Ｘ中において、ＣＮＦと金属（Ｍ）化合物とを良好に分散させて沈殿物の生成を促進させる観点から、水溶液として用いるのが好ましい。
The metal (M) compound (M represents Al, Fe, or Mg) is preferably a water-soluble salt from the viewpoint of efficiently and effectively removing phosphorus in the waste liquid X. Specifically, sulfates of metal (M), nitrates of metal (M), or chlorides of metal (M) are preferable, and these may be used alone or in combination of two or more. May be used. Among these, sulfates of metal (M) or chlorides of metal (M) are more preferable.
More specifically, sulfates of aluminum sulfate, iron sulfate, and magnesium sulfate; chlorides of aluminum chloride, iron chloride, and magnesium chloride; nitrates of aluminum nitrate, iron nitrate, and magnesium nitrate are preferred; Magnesium sulfate; chlorides of aluminum chloride, iron chloride, and magnesium chloride are more preferred.
Note that when adding the metal (M) compound to the waste liquid X, the metal (M) compound may be in the form of a powder or may be an aqueous solution. Among these, it is preferable to use an aqueous solution from the viewpoint of dispersing the CNF and the metal (M) compound well in the waste liquid X and promoting the formation of a precipitate.
廃液ＸへのＣＮＦと金属（Ｍ）化合物の添加順序は、特に制限されず、いずれを先に添加してもよく、双方を一括して添加してもよい。なかでも、廃液Ｘ中において、ＣＮＦと金属（Ｍ）化合物とを良好に分散させて沈殿物の生成を促進させる観点から、先にＣＮＦを廃液Ｘへ添加した後、金属（Ｍ）化合物を添加するのが好ましい。 The order of adding CNF and the metal (M) compound to the waste liquid X is not particularly limited, and either one may be added first, or both may be added at once. Among these, from the viewpoint of dispersing CNF and the metal (M) compound well in the waste liquid X and promoting the formation of precipitates, CNF is first added to the waste liquid X, and then the metal (M) compound is added. It is preferable to do so.
工程（Ｉ）では、上記廃液Ｘに、ＣＮＦと金属（Ｍ）化合物とを添加して、リンと金属（Ｍ）とのモル比（Ｍ／Ｐ）が０．８～６であり、かつｐＨが１．５～９．５である処理液Ｙを得る。
すなわち、処理液Ｙにおけるリンと金属（Ｍ）とのモル比（Ｍ／Ｐ）が上記範囲となるよう、廃液Ｘへの金属（Ｍ）化合物の添加量を調整すればよい。処理液Ｙにおけるリンと金属（Ｍ）とのモル比（Ｍ／Ｐ）は、０．８～６であって、好ましくは１．３～５であり、より好ましくは１．８～４である。
In step (I), CNF and a metal (M) compound are added to the waste liquid X so that the molar ratio of phosphorus to metal (M) (M/P) is 0.8 to 6 and the pH is A processing liquid Y having a value of 1.5 to 9.5 is obtained.
That is, the amount of the metal (M) compound added to the waste liquid X may be adjusted so that the molar ratio (M/P) of phosphorus to metal (M) in the treatment liquid Y falls within the above range. The molar ratio (M/P) of phosphorus and metal (M) in the treatment liquid Y is 0.8 to 6, preferably 1.3 to 5, and more preferably 1.8 to 4. .
また、処理液ＹにおけるｐＨは、１．５～９．５であるが、金属（Ｍ）化合物の種類に応じて変動させるのが望ましい。
具体的には、金属（Ｍ）化合物としてアルミニウム化合物を単独で用いる場合、処理液ＹにおけるｐＨは、好ましくは５～８であり、より好ましくは５．５～７．５であり、さらに好ましくは６～７である。
金属（Ｍ）化合物として鉄化合物を単独で用いる場合、処理液ＹにおけるｐＨは、好ましくは１．５～８であり、より好ましくは３～７であり、さらに好ましくは４～６である。
金属（Ｍ）化合物としてマグネシウム化合物を単独で用いる場合、処理液ＹにおけるｐＨは、好ましくは５～９．５であり、より好ましくは５．５～８であり、さらに好ましくは６～７である。
Further, the pH of the treatment liquid Y is 1.5 to 9.5, but it is desirable to vary it depending on the type of metal (M) compound.
Specifically, when an aluminum compound is used alone as the metal (M) compound, the pH of the treatment liquid Y is preferably 5 to 8, more preferably 5.5 to 7.5, and even more preferably It is 6-7.
When an iron compound is used alone as the metal (M) compound, the pH of the treatment liquid Y is preferably 1.5 to 8, more preferably 3 to 7, and still more preferably 4 to 6.
When a magnesium compound is used alone as the metal (M) compound, the pH of the treatment liquid Y is preferably 5 to 9.5, more preferably 5.5 to 8, and even more preferably 6 to 7. .
また、金属（Ｍ）化合物としてアルミニウム化合物と鉄化合物とを組み合わせて用いる場合、処理液ＹにおけるｐＨは、好ましくは５～８であり、より好ましくは５．３～７であり、さらに好ましくは５．５～６．５である。
金属（Ｍ）化合物としてアルミニウム化合物とマグネシウム化合物とを組み合わせて用いる場合、処理液ＹにおけるｐＨは、好ましくは５～８であり、より好ましくは５．５～７．５であり、さらに好ましくは６～７である。
金属（Ｍ）化合物として鉄化合物とマグネシウム化合物とを組み合わせて用いる場合、処理液ＹにおけるｐＨは、好ましくは５～８であり、より好ましくは５．３～７であり、さらに好ましくは５．５～６．５である。
金属（Ｍ）化合物として、アルミニウム化合物、鉄化合物、及びマグネシウム化合物全てを用いる場合、処理液ＹにおけるｐＨは、好ましくは５～８であり、より好ましくは５．５～７であり、さらに好ましくは６～６．５である。
なお、かかるｐＨは、２０℃における測定値を基準とする値を意味する。
Further, when an aluminum compound and an iron compound are used in combination as the metal (M) compound, the pH of the treatment liquid Y is preferably 5 to 8, more preferably 5.3 to 7, and even more preferably 5. .5 to 6.5.
When using a combination of an aluminum compound and a magnesium compound as the metal (M) compound, the pH of the treatment liquid Y is preferably 5 to 8, more preferably 5.5 to 7.5, and even more preferably 6. ~7.
When using a combination of an iron compound and a magnesium compound as the metal (M) compound, the pH of the treatment liquid Y is preferably 5 to 8, more preferably 5.3 to 7, and even more preferably 5.5. ~6.5.
When using all of an aluminum compound, an iron compound, and a magnesium compound as the metal (M) compound, the pH of the treatment liquid Y is preferably 5 to 8, more preferably 5.5 to 7, and even more preferably It is 6 to 6.5.
In addition, this pH means the value based on the measured value at 20 degreeC.
処理液ＹのｐＨをかかる範囲に調整するにあたり、工程（Ｉ）が、塩酸、硫酸、水酸化ナトリウム、及び水酸化カリウムから選ばれるｐＨ調整剤を用いてｐＨを調整する工程を含むのが好ましい。具体的には、かかるｐＨ調整剤を用いてｐＨを調整する工程は、廃液ＸへのＣＮＦと金属（Ｍ）化合物の添加前であってもよく、廃液ＸへのＣＮＦと金属（Ｍ）化合物の添加後であってもよく、さらに廃液ＸへのＣＮＦと金属（Ｍ）化合物の添加と同時であってもよい。
なかでも、ｐＨを調整する工程は、ＣＮＦと金属（Ｍ）化合物とが良好に分散されてなる処理液Ｙを得る観点、及び金属（Ｍ）リン酸塩の生成を促進させる観点から、少なくとも金属（Ｍ）化合物の添加前であるのが好ましい。或いは、さらに金属（Ｍ）リン酸塩がＣＮＦに担持されてなる沈殿物の生成を促進させる観点から、ＣＮＦと金属（Ｍ）化合物の添加前に、予め廃液ＸにｐＨ調整剤を添加してｐＨを調整する工程を経るのがより好ましい。
In adjusting the pH of the treatment liquid Y to such a range, step (I) preferably includes a step of adjusting the pH using a pH adjuster selected from hydrochloric acid, sulfuric acid, sodium hydroxide, and potassium hydroxide. . Specifically, the step of adjusting the pH using such a pH adjuster may be performed before adding CNF and the metal (M) compound to the waste liquid X. It may be after the addition of CNF and the metal (M) compound to the waste liquid X, or at the same time as the addition of CNF and the metal (M) compound to the waste liquid X.
Among these, the step of adjusting the pH is carried out in order to obtain a treatment liquid Y in which CNF and metal (M) compounds are well dispersed, and to promote the production of metal (M) phosphate. (M) Preferably, this is before the addition of the compound. Alternatively, from the viewpoint of promoting the formation of a precipitate in which metal (M) phosphate is supported on CNF, a pH adjuster may be added to waste liquid X in advance before adding CNF and metal (M) compound. It is more preferable to go through a step of adjusting the pH.
工程（Ｉ）では、廃液ＸへのＣＮＦと金属（Ｍ）化合物の添加後、また必要に応じてｐＨ調整剤を添加した後、後述する工程（II）へ移行する前に、攪拌処理を行って処理液Ｙを得るのがよい。具体的には、好ましくは５℃～６０℃、より好ましくは１５℃～４０℃の温度にて、好ましくは５分間～６０分間、より好ましくは１５分間～４５分間の攪拌処理を行うのがよい。 In step (I), after adding CNF and the metal (M) compound to waste liquid X, and after adding a pH adjuster as necessary, a stirring treatment is performed before proceeding to step (II) described later. It is preferable to obtain the treatment liquid Y by Specifically, the stirring treatment is preferably carried out at a temperature of preferably 5°C to 60°C, more preferably 15°C to 40°C, preferably for 5 minutes to 60 minutes, more preferably 15 minutes to 45 minutes. .
工程（II）は、工程（Ｉ）で得られた処理液Ｙをろ過して沈殿物を除去し、ろ液Ｚを得る工程である。かかる工程（II）において、廃液Ｘに含まれるリンと金属（Ｍ）化合物とから効率的に生成された金属（Ｍ）リン酸塩がＣＮＦに有効に担持されてなる沈殿物を除去することにより、廃液Ｘ中におけるリンが選択的かつ効果的に減じられたろ液Ｙを得ることができる。
処理液Ｙをろ過する際、処理液Ｙにろ過助剤を添加してもよい。用い得るろ過助剤としては、例えば、金属（Ｍ）のリン酸塩、炭酸塩、水酸化物、酸化物、又はこれらとＣＮＦとの複合化物；珪藻土；パーライト；ＣＮＦ以外のセルロース；高分子凝集剤等が挙げられる。
用い得る装置としては、例えば、吸引ろ過、フィルタープレス、及び遠心脱水等が挙げられる。
Step (II) is a step in which a filtrate Z is obtained by filtering the treatment liquid Y obtained in step (I) to remove precipitates. In this step (II), by removing a precipitate formed by effectively supporting CNF with metal (M) phosphate efficiently generated from phosphorus and metal (M) compound contained in waste liquid X. , it is possible to obtain a filtrate Y in which phosphorus in the waste liquid X is selectively and effectively reduced.
When filtering the treatment liquid Y, a filter aid may be added to the treatment liquid Y. Examples of filter aids that can be used include metal (M) phosphates, carbonates, hydroxides, oxides, or complexes of these with CNF; diatomaceous earth; perlite; cellulose other than CNF; polymer aggregates. agents, etc.
Examples of devices that can be used include suction filtration, filter press, and centrifugal dehydration.
以下、本発明について、実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be specifically explained based on Examples, but the present invention is not limited to these Examples.
［実施例１］
リン含有量が１０００ｍｇ／Ｌの廃液Ｘ １Ｌを処理対象とし、塩酸を用いて２０℃におけるｐＨを５に調整した。次いで、廃液Ｘを攪拌しながら、セルロースナノファイバー（ＣＮＦ）水溶液（ダイセルファインケム社製、ＰＣ１１０Ａ、固形分３５％）２．８ｇを添加した後、Ｍ／Ｐモル比が１．０となる量の塩化アルミニウム（３５％水溶液）を添加し、そのまま３０分間攪拌を継続して、処理液Ｙを得た。
得られた処理液Ｙをブフナー漏斗、５Ｃのろ紙を用いてろ過し、沈殿物を除去した。得られたろ液Ｚ（処理後の廃液Ｘ）中のリン含有量をＩＣＰ発光分析により測定した。
[Example 1]
1 L of waste liquid X having a phosphorus content of 1000 mg/L was treated, and its pH at 20° C. was adjusted to 5 using hydrochloric acid. Next, while stirring the waste liquid X, 2.8 g of cellulose nanofiber (CNF) aqueous solution (manufactured by Daicel FineChem, PC110A, solid content 35%) was added, and then an amount such that the M/P molar ratio was 1.0 was added. Aluminum chloride (35% aqueous solution) was added, and stirring was continued for 30 minutes to obtain treatment liquid Y.
The obtained treated solution Y was filtered using a Buchner funnel and 5C filter paper to remove the precipitate. The phosphorus content in the obtained filtrate Z (waste liquid X after treatment) was measured by ICP emission spectrometry.
［実施例２、４～９］
ＣＮＦの添加量、用いる金属（Ｍ）化合物（３５％水溶液）、Ｍ／Ｐモル比、及びｐＨを表１に示す値又は化合物とした以外、実施例１と同様にして廃液Ｘを処理して、ろ液を得るとともに、ろ液Ｚ（処理後の廃液Ｘ）中のリン含有量を測定した。
[Example 2, 4-9]
Waste liquid A filtrate was obtained, and the phosphorus content in the filtrate Z (waste liquid X after treatment) was measured.
［実施例３］
実施例１と同様の廃液Ｘ １Ｌを用い、これを攪拌しながらセルロースナノファイバー（ＣＮＦ）水溶液（ダイセルファインケム社製、ＰＣ１１０Ａ、固形分３５％）２．８ｇを添加した後、Ｍ／Ｐモル比が５．０となる量の硫酸アルミニウム水溶液（３５％水溶液）を添加した。次いで、塩酸を用いて２０℃におけるｐＨを８に調整し、そのまま３０分間攪拌を継続して、処理液Ｙを得た。
次いで、実施例１と同様にして、得られた処理液Ｙからろ液を得るとともに、ろ液Ｚ（処理後の廃液Ｘ）中のリン含有量を測定した。
[Example 3]
Using 1 L of the same waste liquid An aqueous aluminum sulfate solution (35% aqueous solution) was added in an amount such that . Next, the pH at 20° C. was adjusted to 8 using hydrochloric acid, and stirring was continued for 30 minutes to obtain a treatment liquid Y.
Next, in the same manner as in Example 1, a filtrate was obtained from the obtained treated liquid Y, and the phosphorus content in the filtrate Z (waste liquid X after treatment) was measured.
［比較例１］
実施例１と同様の廃液Ｘ １Ｌを用い、塩酸を用いて２０℃におけるｐＨを５に調整した。次いで、廃液Ｘを攪拌しながら、Ｍ／Ｐモル比が１．０となる量の塩化アルミニウム（３５％水溶液）を添加し、そのまま３０分間攪拌を継続して、処理液Ｙを得た。
次いで、実施例１と同様にして、得られた処理液Ｙからろ液を得るとともに、ろ液Ｚ（処理後の廃液Ｘ）中のリン含有量を測定した。
[Comparative example 1]
Using 1 L of the same waste liquid X as in Example 1, the pH at 20° C. was adjusted to 5 using hydrochloric acid. Next, while stirring the waste liquid X, aluminum chloride (35% aqueous solution) was added in an amount such that the M/P molar ratio was 1.0, and stirring was continued for 30 minutes to obtain a treated liquid Y.
Next, in the same manner as in Example 1, a filtrate was obtained from the obtained treated liquid Y, and the phosphorus content in the filtrate Z (waste liquid X after treatment) was measured.
［比較例２］
実施例１と同様の廃液Ｘ １Ｌを用い、塩酸を用いて２０℃におけるｐＨを５に調整した。次いで、廃液Ｘを攪拌しながら、セルロースナノファイバー（ＣＮＦ）水溶液（ダイセルファインケム社製、ＰＣ１１０Ａ、固形分３５％）２．８ｇを添加し、そのまま３０分間攪拌を継続して、処理液Ｙを得た。
次いで、実施例１と同様にして、得られた処理液Ｙからろ液を得るとともに、ろ液（処理後の廃液Ｘ）中のリン含有量を測定した。
これらの結果を表１に示す。
[Comparative example 2]
Using 1 L of the same waste liquid X as in Example 1, the pH at 20° C. was adjusted to 5 using hydrochloric acid. Next, while stirring the waste liquid X, 2.8 g of cellulose nanofiber (CNF) aqueous solution (manufactured by Daicel FineChem, PC110A, solid content 35%) was added, and stirring was continued for 30 minutes to obtain a treated liquid Y. Ta.
Next, in the same manner as in Example 1, a filtrate was obtained from the obtained treated liquid Y, and the phosphorus content in the filtrate (waste liquid X after treatment) was measured.
These results are shown in Table 1.
Claims (4)
（Ｉ）塩酸、硫酸、水酸化ナトリウム、及び水酸化カリウムから選ばれるｐＨ調整剤を用いてｐＨを調整する工程を含み、
１０ｐｐｍ～２０００ｐｐｍのリンを含む廃液Ｘに、１Ｌの廃液Ｘに対するセルロースナノファイバーの添加量を０．１ｇ～２０．０ｇとし、リンと金属（Ｍ）とのモル比（Ｍ／Ｐ）が０．８～６となるよう、セルロースナノファイバーと金属（Ｍ）化合物（Ｍは、Ａｌ、Ｆｅ又はＭｇを示す）とを添加して、リンと金属（Ｍ）とのモル比（Ｍ／Ｐ）が０．８～６であり、かつｐＨが１．５～９．５である処理液Ｙを得る工程
（II）得られた処理液Ｙをろ過して沈殿物を除去し、ろ液Ｚを得る工程
を備える廃液処理方法。 Next steps (I) to (II):
(I) a step of adjusting the pH using a pH adjuster selected from hydrochloric acid, sulfuric acid, sodium hydroxide, and potassium hydroxide;
1. To waste liquid X containing 0 ppm to 2000 ppm of phosphorus, the amount of cellulose nanofibers added to 1 L of waste liquid X is 0.1 g to 20.0 g, and the molar ratio of phosphorus to metal (M) (M/P) is 0. Add cellulose nanofibers and a metal (M) compound (M represents Al, Fe, or Mg) so that the molar ratio of phosphorus to metal (M) (M/P) is 8 to 6. is 0.8 to 6 and pH is 1.5 to 9.5. (II) The obtained treated liquid Y is filtered to remove the precipitate, and the filtrate Z is A waste liquid treatment method comprising a step of obtaining.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003238278A (en) | 2002-02-12 | 2003-08-27 | Seihachiro Miura | Method of composting sewer sludge |
| JP2005246175A (en) | 2004-03-02 | 2005-09-15 | Seihachiro Miura | Dephosphorizing agent and dephosphorizing method using the same |
| JP2005248337A (en) | 2004-03-01 | 2005-09-15 | Seihachiro Miura | Highly active cellulose fiber, method for producing the same, and dehydrating auxiliary using the same |
| JP2012223673A (en) | 2011-04-15 | 2012-11-15 | Toshiba Corp | Phosphorus adsorbent, phosphorus adsorption system, and method for using the phosphorus adsorbent |
| US20150183641A1 (en) | 2012-06-15 | 2015-07-02 | Regents Of The University Of Minnesota | Hydrothermal carbonization of sewage wastes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003238278A (en) | 2002-02-12 | 2003-08-27 | Seihachiro Miura | Method of composting sewer sludge |
| JP2005248337A (en) | 2004-03-01 | 2005-09-15 | Seihachiro Miura | Highly active cellulose fiber, method for producing the same, and dehydrating auxiliary using the same |
| JP2005246175A (en) | 2004-03-02 | 2005-09-15 | Seihachiro Miura | Dephosphorizing agent and dephosphorizing method using the same |
| JP2012223673A (en) | 2011-04-15 | 2012-11-15 | Toshiba Corp | Phosphorus adsorbent, phosphorus adsorption system, and method for using the phosphorus adsorbent |
| US20150183641A1 (en) | 2012-06-15 | 2015-07-02 | Regents Of The University Of Minnesota | Hydrothermal carbonization of sewage wastes |
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