JPH049598B2 - - Google Patents
Info
- Publication number
- JPH049598B2 JPH049598B2 JP61128363A JP12836386A JPH049598B2 JP H049598 B2 JPH049598 B2 JP H049598B2 JP 61128363 A JP61128363 A JP 61128363A JP 12836386 A JP12836386 A JP 12836386A JP H049598 B2 JPH049598 B2 JP H049598B2
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- treated
- zeolite
- phosphorus
- raw water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 74
- 239000010457 zeolite Substances 0.000 claims description 46
- 229910021536 Zeolite Inorganic materials 0.000 claims description 40
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 37
- 229910021529 ammonia Inorganic materials 0.000 claims description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims description 37
- 239000011574 phosphorus Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 238000005342 ion exchange Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 235000019645 odor Nutrition 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 10
- 229910001603 clinoptilolite Inorganic materials 0.000 description 10
- 229910052680 mordenite Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- -1 that is Substances 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
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Description
〔技術の分野〕
本発明は、リン、アンモニアの同時除去方法に
関する。更に詳しくは、リン酸塩と難溶性塩を生
成し得る特定の金属塩を担持またはイオン交換処
理させたゼオライトを用いて原水すなわちリン酸
塩及びアンモニアを低濃度で含む水を処理する該
除去方法に関する。
〔従来の技術〕
近年各地の湖沼で、流入水等に起因するリン酸
塩とアンモニアによる湖沼水の富栄養化とその進
行が著しく問題視されている。かかる富栄養化し
た湖沼水からリン酸塩およびアンモニアを除去す
る方法としては、前者に対しては、凝集沈殿法、
生物処理および晶析法が、後者に対しては生物処
理、ゼオライトその他の陽イオン交換剤処理およ
び、ストリツピング法が一般的に用いられてい
る。しかし、これ等の公知方法には、次のような
問題点がある。すなわち、除去設備が大規模とな
ること、原水が低濃度の場合は除去効率が低い、
処理に際してスラツジが発生する、およびリン除
去とアンモニア除去とで夫々別個のプラントを必
要とするなどである。
〔発明の目的〕
本発明者等は、上述の問題点を解決すべく研究
の結果、ゼオライトに特定の金属塩を担持または
イオン交換処理により保持せしめたゼオライトを
用いて原水を処理すると、上述の４つの問題点が
凡て解決できることを知つて本発明を完成した。
すなわち、本発明の目的は、小規模のかつ単一の
設備であつても、原水からリンとアンモニアを同
時に除去できる方法を提供することである。
〔発明の構成・効果〕
本発明は、下記(1)の主要構成と(2)〜(3)の実施態
様的構成を有する。
(1) リン酸と難溶性塩を生成する硝酸（第一、第
二）鉄、硫酸（第一、第二）鉄、過塩素酸（第
一、第二）鉄、臭化鉄または、ニツケル、カル
シウム、アルミニウムおよび銀から選ばれたい
づれか一以上の塩を用いてゼオライトを担持ま
たはイオン交換処理して、処理体を得、該処理
体で低濃度のリンとアンモニアを含有する原水
を処理することにより、リンとアンモニアを同
時除去することを特徴とするリン、アンモニア
の同時除去方法。
(2) 原水をPH３〜13で処理することを特徴とする
前記第１項に記載の方法。
(3) 処理体中の被担持物又は被イオン交換処理物
の濃度を被処理原水中のリンおよびアンモニア
の濃度に適合する如くゼオライトを担持処理ま
たはイオン交換処理した処理体を用いる前記第
１項に記載の方法。
本発明の構成と効果につき以下に詳述する。
本発明に使用する担持体またはイオン交換処理
体（以下両者を担持・処理体と総称することがあ
る）は、ゼオライト（担持）を特定の金属塩すな
わちリン酸と難溶性塩を生成し得る金属化合物
（FeCl2、FeCl3を除く）を用いて担持処理または
イオン交換処理して製造する。
上述の担持・処理体を製造するためのゼオライ
トの種類、形状は限定されない。ゼオライトの種
類としては、例えばゼオライトＸ、ゼオライト
Ａ、モルデナイト、クリプチロライトを挙げるこ
とができる。また、その形状は微粒品、粒品、ペ
レツト又はビーズのいづれでもよい。
本発明に使用するリン酸と難溶性塩を生成しう
る金属化合物としては、鉄（FeCl2、FeCl3を除
く）、ニツケル、カルシウム、アルミニウムおよ
び銀の塩をあげることができる。塩の種類は限定
されないが、ゼオライトを処理するためには溶解
度の大きいものが好ましく、ハロゲン塩（特に塩
化物）、硝酸塩などが推奨される。該塩の具体例
としては、銀塩の場合は、過塩素酸銀、硝酸郡お
よびふつ化銀であり、アルミニウム塩の場合は、
硫酸アルミニウム、硝酸アルミニウムおよび塩化
アルミニウムであり、カルシウム塩の場合は、臭
化カルシウム、塩化カルシウム、過塩素酸カルシ
ウム、塩素酸カルシウム、ヨウ化カルシウム、亜
硝酸カルシウムおよび硝酸カルシウムであり、ニ
ツケル塩の場合は、臭化ニツケル、塩化ニツケ
ル、過塩素酸ニツケル、硝酸ニツケルおよび硫酸
ニツケルを挙げることができる。
本発明に係るイオン交換処理はつぎのように行
う。すなわち、上述の金属塩を水に溶解すること
により得られる金属イオンを含む溶液
（0.001mol／以上）に所定量のゼオライトを添
加し、室温〜150℃で0.5〜200時間、好ましくは
１〜100時間処理する。処理後は水溶液を濾別し、
必要な乾燥を行つてイオン交換処理体を得る。
また、本発明に係る担持処理はつぎのように行
う。すなわち、上述の金属イオンを含む溶液にア
ルカリ物質を溶解させ、この溶液にゼオライトの
所定量を添加して以後上述のイオン交換処理と同
様に行う。
本発明に係る担持・処理体が、原水（被処理
水）のリンとアンモニアを同時に除去できるの
は、前者（リン）については、被担持物（金属イ
オン）によるのであり、後者（アンモニア）につ
いては、ゼオライト本来の除去能力によるのであ
る。したがつて、ゼオライトを特定の金属イオン
処理することにより、ゼオライト本来のアンモニ
ア除去能が喪失し若しくは減退しないようにする
ことが大切である。本発明に係る金属化合物は、
この目的に合致するよう研究された結果見出され
たものであつて、リン酸と難溶性塩を形成しうる
という物性からのみでは予測できるものではな
い。
本発明の対象物である低濃度のリンとアンモニ
アを含有する原水（以下単に原水という）は、実
用的見地からは、農業用廃水又は都市下水（生活
廃水）若しくはそれらの流入した河川水である
が、これ等以外の原水であつてもリンおよびアン
モニアの除去を必要とする限り対象となる。原水
と処理剤すなわち本発明に係る担持・処理体との
接触方法は公知方法と同様であり、原水と該担
持・処理体とを除去プラント中で必要かつ十分な
程度（温度、時間）に接触せしめる。本発明の方
法の処理対象となる低濃度のリンとアンモニアを
含有する原水中における該リンとアンモニアの濃
度は、それぞれ0.5〜100mg／好ましくは１〜10
mg／ならびに0.1〜200mg／好ましくは0.1〜
10mg／である。
本発明の方法によれば、原水からリン、アンモ
ニアを除去することに関し、次の効果がある。
処理体の除去能力が大きいので、従来のもの
と比較して小規模の設備で比較的大量の原水を
処理することができる。
原水中のリン又はアンモニアの濃度が低濃度
（例えば10mg／程度）であつても良好な除去
率（例えば80〜90％）を達成できる。
処理によつてスラツジが発生することがな
い。
リンの除去とアンモニアの除去を同一の設備
で行うことができるので、設備の維持、管理及
び償却の面で経済的である。
以下試験例および実施例によつて本発明を説明
する。
試験例 １
（イオン交換処理、担持処理）
４種の金属塩および４種のゼオライトを用い、
本発明に使用する担持・処理体を製造した。製造
条件（温度、時間）と結果（担持量、陽イオン交
換容量［Cation Exchange Capacity：CEC］）
を表−１に示す。
[Field of Technology] The present invention relates to a method for simultaneously removing phosphorus and ammonia. More specifically, the removal method involves treating raw water, that is, water containing low concentrations of phosphate and ammonia, using zeolite that supports or undergoes ion exchange treatment with a specific metal salt that can generate phosphate and poorly soluble salts. Regarding. [Prior Art] In recent years, eutrophication of lake waters due to phosphates and ammonia caused by inflow water and the like has become a serious problem in lakes and marshes throughout the country. Methods for removing phosphates and ammonia from such eutrophic lake water include coagulation-sedimentation method,
Biological treatment and crystallization methods are commonly used for the latter, biological treatment, treatment with zeolites and other cation exchange agents, and stripping methods. However, these known methods have the following problems. In other words, the removal equipment will be large-scale, and if the raw water has a low concentration, the removal efficiency will be low.
Sludge is generated during processing, and separate plants are required for phosphorus removal and ammonia removal. [Purpose of the Invention] As a result of research to solve the above-mentioned problems, the present inventors have found that when raw water is treated with zeolite in which a specific metal salt is supported or retained through ion exchange treatment, the above-mentioned problems occur. The present invention was completed knowing that all four problems could be solved.
That is, an object of the present invention is to provide a method that can simultaneously remove phosphorus and ammonia from raw water even if it is small-scale and uses a single facility. [Configuration/Effects of the Invention] The present invention has the following main configuration (1) and embodiment configurations (2) to (3). (1) Ferrous (ferrous or ferric) nitrate, iron (ferrous or ferric) sulfate, iron (ferrous or ferric) perchlorate, iron bromide or nickel, which form poorly soluble salts with phosphoric acid. A treated body is obtained by supporting or ion-exchanging zeolite using one or more salts selected from calcium, aluminum, and silver, and raw water containing low concentrations of phosphorus and ammonia is treated with the treated body. A method for simultaneously removing phosphorus and ammonia, characterized by simultaneously removing phosphorus and ammonia. (2) The method according to item 1 above, wherein the raw water is treated at a pH of 3 to 13. (3) Using a treated body that has been subjected to zeolite support treatment or ion exchange treatment so that the concentration of the supported substance or ion exchange treated substance in the treated body matches the concentration of phosphorus and ammonia in the raw water to be treated. The method described in. The configuration and effects of the present invention will be explained in detail below. The support or ion-exchange treated body (hereinafter both may be collectively referred to as the supported/treated body) used in the present invention is a zeolite (supported) with a specific metal salt, that is, a metal that can form a poorly soluble salt with phosphoric acid. Manufactured by supporting treatment or ion exchange treatment using compounds (excluding FeCl 2 and FeCl 3 ). The type and shape of the zeolite for producing the above-mentioned supported/treated body are not limited. Examples of the types of zeolite include zeolite X, zeolite A, mordenite, and cryptilolite. Further, the shape thereof may be any of fine particles, grains, pellets, or beads. Examples of metal compounds that can form poorly soluble salts with phosphoric acid used in the present invention include salts of iron (excluding FeCl 2 and FeCl 3 ), nickel, calcium, aluminum, and silver. Although the type of salt is not limited, salts with high solubility are preferred for treating zeolite, and halogen salts (especially chlorides), nitrates, etc. are recommended. Specific examples of the salt include silver perchlorate, nitrate, and silver fluoride, and aluminum salts include:
Aluminum sulfate, aluminum nitrate and aluminum chloride; for calcium salts, calcium bromide, calcium chloride, calcium perchlorate, calcium chlorate, calcium iodide, calcium nitrite and calcium nitrate; for nickel salts may include nickel bromide, nickel chloride, nickel perchlorate, nickel nitrate and nickel sulfate. The ion exchange treatment according to the present invention is performed as follows. That is, a predetermined amount of zeolite is added to a solution containing metal ions (0.001 mol/or more) obtained by dissolving the above-mentioned metal salt in water, and the mixture is heated at room temperature to 150°C for 0.5 to 200 hours, preferably 1 to 100 mol/min. Process time. After treatment, the aqueous solution is filtered,
Perform necessary drying to obtain an ion exchange treated body. Further, the supporting treatment according to the present invention is performed as follows. That is, an alkaline substance is dissolved in a solution containing the metal ions described above, a predetermined amount of zeolite is added to this solution, and the subsequent ion exchange treatment is carried out in the same manner as the ion exchange treatment described above. The reason why the supporting/processing body according to the present invention can simultaneously remove phosphorus and ammonia from raw water (water to be treated) is that the former (phosphorus) depends on the supported material (metal ions), and the latter (ammonia) This is due to the inherent removal ability of zeolite. Therefore, it is important to treat zeolite with specific metal ions so that the inherent ammonia removal ability of zeolite is not lost or diminished. The metal compound according to the present invention is
This was discovered as a result of research to meet this objective, and it cannot be predicted solely from the physical property that it can form a sparingly soluble salt with phosphoric acid. From a practical standpoint, raw water containing low concentrations of phosphorus and ammonia (hereinafter simply referred to as raw water), which is the object of the present invention, is agricultural wastewater, urban sewage (domestic wastewater), or river water into which they flow. However, raw water other than these is also covered as long as it requires removal of phosphorus and ammonia. The method of contacting the raw water with the treatment agent, that is, the supported/treated body according to the present invention, is the same as the known method, and the raw water and the supported/treated body are brought into contact with each other to a necessary and sufficient degree (temperature, time) in the removal plant. urge The concentrations of phosphorus and ammonia in the raw water containing low concentrations of phosphorus and ammonia to be treated by the method of the present invention are each 0.5 to 100 mg/preferably 1 to 10 mg.
mg/and 0.1~200mg/preferably 0.1~
It is 10mg/. According to the method of the present invention, the following effects are achieved regarding the removal of phosphorus and ammonia from raw water. Since the removal capacity of the treatment body is large, a relatively large amount of raw water can be treated with a small-scale facility compared to conventional ones. A good removal rate (for example, 80 to 90%) can be achieved even if the concentration of phosphorus or ammonia in the raw water is low (for example, about 10 mg/). No sludge is generated during processing. Since phosphorus removal and ammonia removal can be performed with the same equipment, it is economical in terms of equipment maintenance, management, and depreciation. The present invention will be explained below using test examples and examples. Test example 1 (ion exchange treatment, support treatment) Using 4 types of metal salts and 4 types of zeolites,
A supporting/processing body used in the present invention was manufactured. Manufacturing conditions (temperature, time) and results (supported amount, cation exchange capacity [CEC])
are shown in Table-1.
【表】【table】
【表】
試験例 ２
試験例１で得られた担持・処理体を用いてアン
モニアの除去処理を行つた。結果を図−１ １〜
４に示す。
各図は、夫々担体としてモルデナイト（Md）、
クリノプチロライト（Cp）、ゼオライトＡ（Ａ）
およびゼオライトＸ（Ｘ）を用い、被担持物とし
てNiCl2（Ni）、CaCl2（Ca）、Fe（NO3）2、Fe
（NO3）3、Al（NO3）3およびAgNO3（Ag）を用い
ている。
各図から明らかなように、担持体モルデナイト
（Md）およびクリノプチロライト（Cp）の場合
は、処理によつてもアンモニアの除去能はかわら
ず、およそ100mep／100ｇであつた。またゼオラ
イトＸ、ゼオライトＡの場合については、該担持
処理したものは処理前の原試料より除去能は低下
するものの、該低下後の除去能として上述のモル
デナイトやクリノプチロライトと同等の除去量を
示した。
以上の事実から、担体（ゼオライト）に本発明
に係る金属塩を担持せしめても、ゼオライトが本
来保有するアンモニアの除去能力は、有用な程度
に維持されていることがわかる。
試験例 ３
試験例１で得られた担持・処理体を用いてリン
の除去処理を行つた。結果を図−２〜−６に示
す。
図−２は、上述の４種のゼオライトにつきPH３
〜13の範囲内でリンの吸着量（meq／100ｇ）を
調べたものである。
その結果、ゼオライトＡとゼオライトＸとは、
どのPH条件においてもリンの除去能力を示さなか
つた。一方、モルデナイトとクリノプチロライト
とは、PH３で共に約5meq／100ｇ、PH13でモルデ
ナイトは10meq／100ｇの除去を示した。
これらのゼオライトに上述の塩処理を行うと、
得られた担持・処理体は図−３〜−６のような結
果を示した。
図−３はゼオライトＡとゼオライトＸを処理し
たときのPHとリンの除去量の関係を示した。同図
において、銀で処理したゼオライトＡ、ゼオライ
トＸはともにPH12で180meq／100ｇ、カルシウム
で処理したものはPH13で200meq／100ｇ（ゼオラ
イトＸの場合）および150meq／100ｇ（ゼオライ
トＡの場合）の除去を示した。また、PH７におい
ても、ニツケル、アルミニウムおよび銀で処理し
たゼオライトＸおよびゼオライトＡは、ともに
50meq／100ｇの除去を示した。
図−４では、モルデナイトおよびクリノプチロ
ライトを処理したときのPHとリンの除去量の関係
を示す。特に銀で処理したものの除去量が多く、
PH12では、モルデナイト、クリノプチロライト共
に70meq／100ｇの除去を示し、PH７においても
クリノプチロライトは20meq／100ｇの除去を示
した。
図−５は、鉄でイオン交換処理した上述４種の
ゼオライトのPHとリン除去量の関係を、図−６
は、鉄で担持処理した上述４種のゼオライトのPH
とリン除去量の関係を示した。いづれの場合も原
試料（註、未処理ゼオライト）に比べ高い除去量
を示した。とくに担持処理したモルデナイトとク
リノプチロライトは、それぞれPH３で30meq／
100ｇ、35meq／100ｇと高い除去量を示した。
実施例
以上の試験例２、３の結果にもとづき、試験例
１の被処理ゼオライト（下記５種）を用いて、PH
７でリンとアンモニアの同時除去を行つた。
原水に代える試験水としては、リン10mg／、
アンモニア10mg／の模擬水を用いた。
（被処理ゼオライトの種類）
Fe−Cp−１：鉄で担持処理したクリノプチロラ
イト
Fe−Ａ−１：鉄で担持処理したゼオライトＡ
Fe−Md−２：鉄でイオン交換処理したモルデナ
イト
Al−Md：アルミニウムでイオン交換処理したモ
ルデナイト
Ca−Ａ：カルシウムでイオン交換処理したゼオ
ライトＡ
Ni−Ｘ−１：ニツケルでイオン交換処理したゼ
オライトＸ
結果を図−７に示す。同図にあきらかなよう
に、鉄で担持処理したクリノプチロライトは、リ
ンを40％、アンモニアを85％除去した。ニツケル
でイオン交換処理したゼオライトＸは、リンを
100％、アンモニアを45％除去した。このように
ゼオライトにイオン交換処理または担持処理を行
うことによつて、リンとアンモニアの同時除去が
可能になる。さらにこの同時除去を原水のPH調整
なしで行うことができる。
試験例 ４
前述のように、イオン交換処理または担持処理
されたゼオライトによる被処理水からのリンおよ
びアンモニアの除去量は、該処理に係る鉄、ニツ
ケル、カルシウム、アルミニウムおよび銀の処理
量によつて定まる。該処理量は、リンの除去量と
比例し、アンモニア除去量と反比例する。この事
実を定量的に把握するために、前述表−１に示さ
れた鉄で処理された４種のゼオライトにおける鉄
含有量とリン、アンモニアの除去量の関係を該ゼ
オライトを用いて原水を処理することによつて求
めた。結果を表−２に示す。[Table] Test Example 2 The supported and treated body obtained in Test Example 1 was used to perform ammonia removal treatment. The results are shown in Figure 1.
4. Each figure shows mordenite (Md) as the carrier,
Clinoptilolite (Cp), Zeolite A (A)
NiCl 2 (Ni), CaCl 2 (Ca), Fe(NO 3 ) 2 , Fe
(NO 3 ) 3 , Al(NO 3 ) 3 and AgNO 3 (Ag). As is clear from each figure, in the case of the supports mordenite (Md) and clinoptilolite (Cp), the ammonia removal ability remained unchanged regardless of the treatment, and was approximately 100 mep/100 g. In addition, in the case of zeolite showed that. From the above facts, it can be seen that even when the metal salt according to the present invention is supported on the carrier (zeolite), the ammonia removal ability originally possessed by the zeolite is maintained at a useful level. Test Example 3 The supported and treated body obtained in Test Example 1 was used to perform phosphorus removal treatment. The results are shown in Figures-2 to -6. Figure 2 shows the PH3 of the four types of zeolites mentioned above.
The adsorption amount of phosphorus (meq/100g) was investigated within the range of ~13. As a result, zeolite A and zeolite
It did not show any ability to remove phosphorus under any PH conditions. On the other hand, mordenite and clinoptilolite both showed removal of about 5meq/100g at PH3, and mordenite showed removal of 10meq/100g at PH13. When these zeolites are subjected to the above salt treatment,
The obtained supported and treated bodies showed the results shown in Figures 3 to 6. Figure 3 shows the relationship between pH and the amount of phosphorus removed when zeolite A and zeolite X were treated. In the same figure, zeolite A and zeolite showed that. Also, at PH7, both zeolite X and zeolite A treated with nickel, aluminum and silver
It showed a removal of 50meq/100g. Figure 4 shows the relationship between PH and the amount of phosphorus removed when mordenite and clinoptilolite are treated. In particular, the removal amount of those treated with silver is large,
At PH12, mordenite and clinoptilolite both showed a removal of 70meq/100g, and even at PH7, clinoptilolite showed a removal of 20meq/100g. Figure 5 shows the relationship between the PH and the amount of phosphorus removed for the four types of zeolites mentioned above treated with iron ion exchange.
are the pH values of the above four types of zeolites supported with iron.
The relationship between the amount of phosphorus removed and the amount of phosphorus removed was shown. In all cases, the removal amount was higher than that of the original sample (note: untreated zeolite). In particular, supported mordenite and clinoptilolite each have 30 meq/clinoptilolite at PH3.
It showed a high removal amount of 100g and 35meq/100g. Example Based on the results of Test Examples 2 and 3 above, the PH
In step 7, phosphorus and ammonia were removed simultaneously. As test water to replace raw water, phosphorus 10mg/,
Simulated water containing 10 mg of ammonia was used. (Types of zeolite to be treated) Fe-Cp-1: Clinoptilolite supported with iron Fe-A-1: Zeolite A supported with iron Fe-Md-2: Mordenite Al- treated with ion exchange treatment with iron Md: Mordenite treated with ion exchange treatment with aluminum Ca-A: Zeolite A treated with ion exchange treatment with calcium Ni-X-1: Zeolite X treated with ion exchange treatment with nickel The results are shown in Figure 7. As is clear from the figure, iron-supported clinoptilolite removed 40% of phosphorus and 85% of ammonia. Zeolite
100% and 45% of ammonia removed. By subjecting zeolite to ion exchange treatment or support treatment in this manner, it becomes possible to simultaneously remove phosphorus and ammonia. Furthermore, this simultaneous removal can be performed without adjusting the pH of the raw water. Test Example 4 As mentioned above, the amount of phosphorus and ammonia removed from water to be treated by zeolite subjected to ion exchange treatment or support treatment depends on the amount of iron, nickel, calcium, aluminum and silver treated in the treatment. Determined. The amount of treatment is proportional to the amount of phosphorus removed and inversely proportional to the amount of ammonia removed. In order to quantitatively understand this fact, we investigated the relationship between the iron content and the amount of phosphorus and ammonia removed in the four types of zeolite treated with iron shown in Table 1 above, and examined the relationship between the iron content and the amount of phosphorus and ammonia removed when raw water was treated with the zeolite. It was found by doing. The results are shown in Table-2.
【表】
試験例４の結果からも明らかなように、処理対
象となる原水のPHやリンおよびアンモニアの濃度
に応じて、ゼオライトを本発明に係る適切な金属
塩溶液で処理することにより、該原水に適応した
除去性能の良好な処理体を設計できる。[Table] As is clear from the results of Test Example 4, by treating zeolite with an appropriate metal salt solution according to the present invention, depending on the pH of the raw water to be treated and the concentrations of phosphorus and ammonia, It is possible to design a treatment body with good removal performance that is suitable for raw water.
第１〜７図は、それぞれ本発明方法の実施態様
を示すための説明図である。
1 to 7 are explanatory diagrams each showing an embodiment of the method of the present invention.
Claims (1)
二）鉄、硫酸（第一、第二）鉄、過塩素酸、（第
一、第二）鉄、臭化鉄または、ニツケル、カルシ
ウム、アルミニウムおよび銀から選ばれたいづれ
か一以上の塩を用いてゼオライトを担持またはイ
オン交換処理して、処理体を得、該処理体で低濃
度のリンとアンモニアを含有する原水を処理する
ことにより、リンとアンモニアを同時除去するこ
とを特徴とするリン、アンモニアの同時除去方
法。 ２ 原水をPH３〜13で処理することを特徴とする
特許請求の範囲第１項に記載の方法。 ３ 処理体中の被担持物又は被イオン交換処理物
の濃度を被処理原水中のリンおよびアンモニアの
濃度に適合する如くゼオライトを担持処理または
イオン交換処理した処理体を用いる特許請求の範
囲第１項に記載の方法。[Claims] 1. Iron (ferrous and ferric) nitrates, iron (ferrous and ferric) sulfates, perchloric acid, iron (ferrous and ferric), and odors that form poorly soluble salts with phosphoric acid. Zeolite is supported or ion-exchanged using iron chloride or one or more salts selected from nickel, calcium, aluminum, and silver to obtain a treated body, and the treated body contains low concentrations of phosphorus and ammonia. A method for simultaneously removing phosphorus and ammonia, characterized by simultaneously removing phosphorus and ammonia by treating raw water. 2. The method according to claim 1, characterized in that raw water is treated at a pH of 3 to 13. 3. Claim 1 using a treated body that has been subjected to zeolite carrying treatment or ion exchange treatment so that the concentration of the supported substance or ion-exchanged substance in the treated body matches the concentration of phosphorus and ammonia in the raw water to be treated. The method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12836386A JPS62286589A (en) | 1986-06-03 | 1986-06-03 | Simultaneous removal of phosphorus and ammonia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12836386A JPS62286589A (en) | 1986-06-03 | 1986-06-03 | Simultaneous removal of phosphorus and ammonia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62286589A JPS62286589A (en) | 1987-12-12 |
| JPH049598B2 true JPH049598B2 (en) | 1992-02-20 |
Family
ID=14982968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12836386A Granted JPS62286589A (en) | 1986-06-03 | 1986-06-03 | Simultaneous removal of phosphorus and ammonia |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62286589A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1001479C2 (en) * | 1995-10-23 | 1997-04-25 | Holding Company Belgie Nv | Modified zeolite production |
| CN102658086A (en) * | 2012-05-08 | 2012-09-12 | 北京大学 | Modified clinoptilolite composite material and preparation method as well as application thereof |
| CN104230131A (en) * | 2014-09-12 | 2014-12-24 | 哈尔滨工业大学深圳研究生院 | Method for synchronously controlling release of nitrogen and phosphorus as well as smell-causing substances in polluted sediment |
| JP6674344B2 (en) * | 2016-07-11 | 2020-04-01 | 太平洋セメント株式会社 | Water treatment material and method for producing the same |
| JP7287813B2 (en) * | 2019-03-27 | 2023-06-06 | 太平洋セメント株式会社 | Water purification material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4964253A (en) * | 1972-10-21 | 1974-06-21 |
-
1986
- 1986-06-03 JP JP12836386A patent/JPS62286589A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4964253A (en) * | 1972-10-21 | 1974-06-21 |
Also Published As
| Publication number | Publication date |
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| JPS62286589A (en) | 1987-12-12 |
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