JP5038587B2 - Dewatering method for sewage digested sludge - Google Patents
Dewatering method for sewage digested sludge Download PDFInfo
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- JP5038587B2 JP5038587B2 JP2004194197A JP2004194197A JP5038587B2 JP 5038587 B2 JP5038587 B2 JP 5038587B2 JP 2004194197 A JP2004194197 A JP 2004194197A JP 2004194197 A JP2004194197 A JP 2004194197A JP 5038587 B2 JP5038587 B2 JP 5038587B2
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- sludge
- meth
- flocculant
- amphoteric polymer
- sewage
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- 239000010802 sludge Substances 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 30
- 239000010865 sewage Substances 0.000 title claims description 16
- 229920000642 polymer Polymers 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 150000003839 salts Chemical group 0.000 claims description 8
- -1 dimethylaminoethyl Chemical group 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 230000029087 digestion Effects 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000523 sample Substances 0.000 description 8
- 208000005156 Dehydration Diseases 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920006317 cationic polymer Polymers 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008394 flocculating agent Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920006318 anionic polymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- WZAPMUSQALINQD-UHFFFAOYSA-M potassium;ethenyl sulfate Chemical compound [K+].[O-]S(=O)(=O)OC=C WZAPMUSQALINQD-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229950003937 tolonium Drugs 0.000 description 2
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Treatment Of Sludge (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Description
本発明は、凝集力及び脱水性に優れ、濾過速度が速く、優れたフロックを得ることができるという各種凝集脱水性能に優れる、下水消化汚泥の脱水方法に関するものである。 The present invention relates to a method for dewatering sewage-digested sludge having excellent cohesive strength and dewaterability, high filtration speed, and excellent various coagulation and dewatering performances such that an excellent floc can be obtained.
下水、し尿処理場及び有機性産業排水等より生じる有機質汚泥は、高分子凝集剤を添加して、スクリュープレス、スクリューデカンター及びベルトプレス等の脱水装置を使用して脱水される。
脱水処理後の汚泥ケーキは、埋め立てや焼却処分されるが、汚泥ケーキ中の含水率を1%低下させることで、焼却で使用する燃料の10%程度をコストダウンすることができるため、汚泥ケーキ中の含水率を低下させるために、種々の検討が行われている。
ところで、下水処理場において、汚泥中に含まれる有機分含有量が多い場合には、有機質汚泥に嫌気性処理がなされる。近年において、有機質汚泥を嫌気性処理して得られる消化汚泥は、繊維分が極端に低いことや、腐敗性粘着性物質を含むため、従来の脱水方法では脱水し難い性状となっている。
Organic sludge generated from sewage, human waste treatment plant, organic industrial wastewater, and the like is dehydrated using a dehydrating device such as a screw press, screw decanter or belt press with the addition of a polymer flocculant.
The sludge cake after dehydration is landfilled or incinerated, but reducing the moisture content in the sludge cake by 1% can reduce the cost of about 10% of the fuel used for incineration, so the sludge cake Various studies have been conducted in order to reduce the moisture content therein.
By the way, in a sewage treatment plant, when there is much organic content contained in sludge, anaerobic treatment is made to organic sludge. In recent years, digested sludge obtained by anaerobic treatment of organic sludge has properties that are extremely difficult to dehydrate by conventional dehydration methods because of its extremely low fiber content and containing a septic sticky substance.
消化汚泥の脱水方法としては、例えば、無機凝集剤としてポリ硫酸鉄を用い、これにノニオン、アニオン、又はカチオン性高分子凝集剤を単独で添加してフロックを形成し脱水する方法(特許文献1)や、無機凝集剤を添加後、pHを5〜8に調節し、これに両性高分子凝集剤を添加する方法(特許文献2)があるが、凝集剤を多量に使用する必要があるため、凝集剤の使用コストが高くなったり、汚泥脱水性能が不十分となることがあった。
最近では、消化汚泥の処理方法として、ポリアミジンを使用する方法(特許文献3)や、無機凝集剤とアクリレート系カチオン高分子凝集剤を併用する方法(特許文献4)が知られている。前者のポリアミジンを使用する方法は、ポリアミジンの高いカチオン性により、前記した汚泥脱水方法に対して優れた方法であり、後者の無機凝集剤とアクリレート系カチオン高分子凝集剤を併用する方法も、前記した汚泥脱水方法に対して優れた方法である。しかしながら、得られるフロックが、凝集性及びろ過性の点で不十分で、脱水ケーキの含水率も不十分であり、かつ凝集剤の使用量を多量にせざるを得ないといった問題を有している。
As a method for dewatering digested sludge, for example, polyiron sulfate is used as an inorganic flocculant, and nonionic, anionic, or cationic polymer flocculants are added alone to form a floc for dehydration (Patent Document 1). ) And after adding an inorganic flocculant, there is a method (Patent Document 2) in which the pH is adjusted to 5 to 8 and an amphoteric polymer flocculant is added thereto, but it is necessary to use a large amount of flocculant. In some cases, the cost of using the flocculant becomes high, or the sludge dewatering performance becomes insufficient.
Recently, as a method for treating digested sludge, a method using polyamidine (Patent Document 3) and a method using an inorganic flocculant and an acrylate cationic polymer flocculant in combination (Patent Document 4) are known. The former method using polyamidine is an excellent method for the sludge dewatering method due to the high cationic property of polyamidine, and the latter method using an inorganic flocculant and an acrylate-based cationic polymer flocculant in combination is also described above. It is an excellent method for the sludge dewatering method. However, the obtained floc is insufficient in terms of cohesiveness and filterability, the moisture content of the dehydrated cake is insufficient, and there is a problem that the amount of coagulant used must be increased. .
本発明者らは、下水消化汚泥に対して、凝集性及びろ過性に優れるフロックを得ることができ、且つ脱水ケーキの含水率を低下させることができる汚泥の脱水方法を見出すため鋭意検討を行ったのである。 The present inventors have intensively studied to find a method for dewatering sludge that can obtain flocs excellent in cohesiveness and filterability and can reduce the moisture content of the dewatered cake with respect to sewage digested sludge. It was.
本発明者は、前記課題を解決するため種々の検討を行った結果、下水消化汚泥に対して、無機凝集剤と、特定のカチオン当量及びアニオン当量を有する両性高分子凝集剤を添加することで、前記課題を解決し得ることを見出し本発明を完成した。
以下に、本発明を詳細に説明する。
尚、本明細書においては、アクリレート又はメタクリレートを(メタ)アクリレートと表し、アクリルアミド又はメタクリルアミドを(メタ)アクリルアミドと表し、アクリル酸又はメタクリル酸を(メタ)アクリル酸と表し、アクリロニトリル又はメタクリロニトリルを(メタ)アクリロニトリルと表す。
As a result of various studies to solve the above problems, the present inventor added an inorganic flocculant and an amphoteric polymer flocculant having a specific cation equivalent and an anion equivalent to sewage digested sludge. The present invention has been completed by finding out that the above problems can be solved.
The present invention is described in detail below.
In this specification, acrylate or methacrylate is represented as (meth) acrylate, acrylamide or methacrylamide is represented as (meth) acrylamide, acrylic acid or methacrylic acid is represented as (meth) acrylic acid, acrylonitrile or methacrylonitrile. Is represented as (meth) acrylonitrile.
本発明は、下水消化汚泥に、無機凝集剤を添加した後、カチオン当量値が3.5meq/g以上でかつアニオン当量値が1.0meq/g以下であり、ジメチルアミノエチル(メタ)アクリレート4級塩単量体単位を80〜99.5モル%、(メタ)アクリル酸及びこのアルカリ金属塩又はアンモニウム塩単量体単位を0.5〜15モル%及び(メタ)アクリルアミド単量体単位を0〜19.5モル%を有する両性高分子凝集剤を添加する汚泥の脱水方法に関する。
以下、それぞれの構成要件について説明する。
In the present invention, after adding an inorganic flocculant to sewage digested sludge, the cation equivalent value is 3.5 meq / g or more and the anion equivalent value is 1.0 meq / g or less , and dimethylaminoethyl (meth) acrylate 4 80 to 99.5 mol% of the grade salt monomer unit, 0.5 to 15 mol% of the (meth) acrylic acid and alkali metal salt or ammonium salt monomer unit, and the (meth) acrylamide monomer unit The present invention relates to a sludge dewatering method in which an amphoteric polymer flocculant having 0 to 19.5 mol% is added.
Hereinafter, each component requirement will be described.
1.下水消化汚泥
本発明が適用できる下水消化汚泥としては、下水処理場で発生する有機質汚泥を嫌気性消化処理したものであれば種々の汚泥に適用可能である。有機質汚泥としては特に制限は無く、具体的には、初沈汚泥と余剰汚泥の混合生汚泥を消化処理したもの等が挙げられる。
1. Sewage Digested Sludge The sewage digested sludge to which the present invention can be applied is applicable to various sludges as long as the organic sludge generated at the sewage treatment plant is subjected to anaerobic digestion. There is no restriction | limiting in particular as organic sludge, Specifically, what digested mixed raw sludge of primary sedimentation sludge and excess sludge etc. are mentioned.
2.無機凝集剤
無機凝集剤としては、汚泥の脱水で通常使用されるものを使用することができる。具体的には、硫酸アルミニウム、ポリ塩化アルミニウム、塩化第二鉄及び硫酸第一鉄及びポリ硫酸鉄等を挙げることができる。
2. Inorganic flocculant As the inorganic flocculant, those usually used in sludge dewatering can be used. Specific examples include aluminum sulfate, polyaluminum chloride, ferric chloride, ferrous sulfate, and polyiron sulfate.
3.両性高分子凝集剤
本発明において、両性高分子凝集剤としては、カチオン当量値(以下「Cv」という)が3.5meq/g以上でかつアニオン当量値(以下「Av」という)が1.0meq/g以下を有する両性高分子(以下単に両性高分子という)を使用する。
Cvとしては、3.8〜5.5meq/gが好ましく、Avとしては、0.1〜0.9meq/gが好ましい。
Cvが3.5meq/g未満では、汚泥の荷電中和が不十分となるため、脱水が不十分となり、且つフロックの造粒性が不足してしまい、Avが1.0meq/gを超えると、フロックの造粒性が乏しく、両性高分子凝集剤を多量に使用せざるを得なくなってしまう。
3. Amphoteric polymer flocculant In the present invention, the amphoteric polymer flocculant has a cation equivalent value (hereinafter referred to as “Cv”) of 3.5 meq / g or more and an anion equivalent value (hereinafter referred to as “Av”) of 1.0 meq. An amphoteric polymer having a / g or less (hereinafter simply referred to as an amphoteric polymer) is used.
Cv is preferably 3.8 to 5.5 meq / g, and Av is preferably 0.1 to 0.9 meq / g.
If Cv is less than 3.5 meq / g, the charge neutralization of sludge becomes insufficient, dehydration becomes insufficient, and floc granulation is insufficient, and Av exceeds 1.0 meq / g. , Floc granulation is poor, and amphoteric polymer flocculants must be used in large amounts.
尚、本発明において、両性高分子のCv及びAvは、以下に示すコロイド滴定法によって求めた値をいう。 In the present invention, Cv and Av of the amphoteric polymer are values determined by the colloid titration method shown below.
1)Cvの測定
(1)滴定法
コニカルビーカーに脱イオン水90mlをとり、試料500ppm溶液10mlを加え、塩酸水溶液でpHを3.0とし、約1分間攪拌する。次に、トルイジンブルー指示薬を
2〜3滴加え、N/400ポリビニル硫酸カリウム試薬(以下N/400PVSKという)で滴定する。
滴定速度は2ml/分とし、検水が青から赤紫色に変色、10秒間以上保持する時点を終点とする。
1) Cv measurement
(1) Titration method Take 90 ml of deionized water in a conical beaker, add 10 ml of a 500 ppm sample solution, bring the pH to 3.0 with an aqueous hydrochloric acid solution, and stir for about 1 minute. Next, 2-3 drops of toluidine blue indicator is added and titrated with N / 400 potassium potassium sulfate reagent (hereinafter referred to as N / 400 PVSK).
The titration rate is 2 ml / min, and the end point is the time when the sample water changes from blue to magenta for 10 seconds or longer.
(2)試料500ppm水溶液の調製
試料0.2g(乾品換算しない)を精秤し、共栓付三角コルベンにとり、脱イオン水100mlで溶解する。この25mlを100mlメスフラスコにて脱イオン水でメスアツプする。
(2) Preparation of sample 500 ppm aqueous solution 0.2 g (not converted to dry product) of sample is precisely weighed, taken into a triangular corben with a stopper, and dissolved in 100 ml of deionized water. The 25 ml is made up with deionized water in a 100 ml volumetric flask.
(3)計算法 (3) Calculation method
2)Avの測定
(1)滴定法
コニカルビーカーに脱イオン水90mlをとり、試料500ppm溶液10mlを加え、苛性ソーダ水溶液でpHを7.0とし、約1分間攪拌する。次に、トルイジンブルー指示薬を2〜3滴加え、N/400ポリビニル硫酸カリウム試薬(以下N/400PVSKという)で滴定する。
滴定速度は2ml/分とし、検水が青から赤紫色に変色、10秒間以上保持する時点を終点とする。
2) Measurement of Av
(1) Titration method Take 90 ml of deionized water in a conical beaker, add 10 ml of a 500 ppm sample, adjust the pH to 7.0 with aqueous caustic soda, and stir for about 1 minute. Next, 2-3 drops of toluidine blue indicator is added and titrated with N / 400 potassium potassium sulfate reagent (hereinafter referred to as N / 400 PVSK).
The titration rate is 2 ml / min, and the end point is the time when the sample water changes from blue to magenta for 10 seconds or longer.
(2)試料500ppm水溶液の調製
試料0.2g(乾品換算しない)を精秤し、共栓付三角コルベンにとり、脱イオン水100mlで溶解する。この25mlを100mlメスフラスコにて脱イオン水でメスアツプする。
(2) Preparation of sample 500 ppm aqueous solution 0.2 g (not converted to dry product) of sample is precisely weighed, taken into a triangular corben with a stopper, and dissolved in 100 ml of deionized water. The 25 ml is made up with deionized water in a 100 ml volumetric flask.
(3)計算法 (3) Calculation method
両性高分子としては、ジメチルアミノエチル(メタ)アクリレート4級塩単量体単位を80〜99.5モル%、(メタ)アクリル酸及びこのアルカリ金属塩又はアンモニウム塩単量体単位を0.5〜15モル%及び(メタ)アクリルアミド単量体単位を0〜19.5モル%を有する両性高分子が使用できる。 As the amphoteric polymer, dimethylaminoethyl (meth) acrylate quaternary salt monomer unit is 80 to 99.5 mol% , (meth) acrylic acid and alkali metal salt or ammonium salt monomer unit is 0.5. Amphoteric polymers having ˜15 mol% and (meth) acrylamide monomer units of 0 to 19.5 mol% can be used.
カチオン性単量体としては、ジメチルアミノエチル(メタ)アクリレート4級塩単量体である。 The cationic monomer is a dimethylaminoethyl (meth) acrylate quaternary salt monomer .
アニオン性単量体としては、(メタ)アクリル酸及びこのナトリウム塩等のアルカリ金属塩又
はアンモニウム塩である。
Examples of the anionic monomer include (meth) acrylic acid and alkali metal salts such as sodium salts or ammonium salts .
両性高分子としては、必要に応じてノニオン性単量体が使用できる。 As the amphoteric polymer, a nonionic monomer can be used as necessary.
両性高分子の製造方法については特に制限はなく、前記した単量体を使用して、一般的な重合方法を採用することができる。例えば、水溶液重合であれば、重合開始剤として過硫酸カリウム、過硫酸アンモニウム、2,2'−アゾビス(2−アミジノプロパン)二塩酸塩や、レドックス系の重合開始剤等を用いて、熱ラジカル重合を行なう方法や、ベンゾイン及びアセトフェノン型の光重合開始剤を用いて紫外線照射により光ラジカル重合を行なうこともできる。又、逆相のエマルション重合であれば、前記重合開始剤以外に、アゾビスイソブチロニトリルや過酸化ベンゾイル等の水不溶性開始剤を用いて重合を行っても良い。 There is no restriction | limiting in particular about the manufacturing method of an amphoteric polymer, A general polymerization method can be employ | adopted using the above-mentioned monomer. For example, in the case of aqueous solution polymerization, thermal radical polymerization using potassium persulfate, ammonium persulfate, 2,2′-azobis (2-amidinopropane) dihydrochloride, a redox polymerization initiator or the like as a polymerization initiator. Or radical photopolymerization by ultraviolet irradiation using a benzoin and acetophenone type photopolymerization initiator. In the case of reverse phase emulsion polymerization, the polymerization may be carried out using a water-insoluble initiator such as azobisisobutyronitrile or benzoyl peroxide in addition to the polymerization initiator.
得られたゲル状の重合体は、その後、公知の方法で切断・細断する。細断した重合体は、バンド式乾燥機、回転式乾燥機、遠赤外線式乾燥機及び振動流動式乾燥機等の乾燥機を
使用し、温度60〜150℃程度で乾燥し、ロール式粉砕機等で粉砕して粉末状の共重合体とされ、粒度調整される。
本発明の両性高分子としては、粉末状品のものが好ましく使用される。
The obtained gel polymer is then cut and chopped by a known method. The chopped polymer is dried at a temperature of about 60 to 150 ° C. using a dryer such as a band dryer, a rotary dryer, a far-infrared dryer, or a vibratory fluid dryer, and a roll mill. Etc. to obtain a powdery copolymer, and the particle size is adjusted.
As the amphoteric polymer of the present invention, a powdery product is preferably used.
本発明における両性高分子は、分子量の指標である0.5%塩粘度が10〜120mPa・sのものが好ましく、安定した脱水処理を達成するためには、15〜90mPa・sがより好ましい。
本発明において0.5%塩粘度とは、4%塩化ナトリウム水溶液に両性高分子を0.5%溶解した試料を25℃で、B型粘度計にて、ローターNo.1又は2を用いて、60rpmで測定した値をいう。
The amphoteric polymer in the present invention preferably has a 0.5% salt viscosity of 10 to 120 mPa · s, which is an index of molecular weight, and more preferably 15 to 90 mPa · s in order to achieve a stable dehydration treatment.
In the present invention, 0.5% salt viscosity means that a sample obtained by dissolving 0.5% of an amphoteric polymer in a 4% sodium chloride aqueous solution at 25 ° C. using a B-type viscometer, rotor No. The value measured at 60 rpm using 1 or 2.
本発明の両性高分子凝集剤としては、前記両性高分子に加え、硫酸水素ナトリウム、硫酸ナトリウム及びスルファミン酸等、脱水処理に悪影響がでないかぎり公知の添加剤と混合して使用しても良い。 As the amphoteric polymer flocculant of the present invention, in addition to the amphoteric polymer, sodium bisulfate, sodium sulfate, sulfamic acid and the like may be mixed with known additives as long as they do not adversely affect the dehydration treatment.
4.汚泥の脱水方法
本発明は、下水消化汚泥に、無機凝集剤を添加した後、前記両性高分子凝集剤を添加する汚泥の脱水方法である。
フロックの形成方法は、公知の方法に従えば良い。
4). TECHNICAL FIELD The present invention is a sludge dewatering method in which an inorganic flocculant is added to sewage digested sludge and then the amphoteric polymer flocculant is added.
The flock formation method may be a known method.
無機凝集剤の汚泥に対する添加割合としては、500〜50,000ppmが好ましく、TSに対しては0.01〜20質量%が好ましい。 As an addition ratio with respect to the sludge of an inorganic flocculant, 500-50,000 ppm is preferable and 0.01-20 mass% is preferable with respect to TS.
本発明においては、無機凝集剤を添加した後、pHを4〜8とすることが、より効果的に汚泥の処理を行うことができるため好ましい。
pHの調整方法としては、無機凝集剤を添加した後、当該pH値を満たす場合は、特にpH調整の必要はないが、本発明で限定する範囲を満たさない場合は、酸又はアルカリを添加して調整する。
酸としては、塩酸、硫酸、酢酸及びスルファミン酸等を挙げることができる。又、アルカリとしては、苛性ソーダ、苛性カリ、消石灰及びアンモニア等が挙げられる。
In the present invention, it is preferable to adjust the pH to 4 to 8 after adding the inorganic flocculant because the sludge can be treated more effectively.
As a method for adjusting pH, after adding an inorganic flocculant, if the pH value is satisfied, pH adjustment is not particularly required, but if the range limited by the present invention is not satisfied, acid or alkali is added. Adjust.
Examples of the acid include hydrochloric acid, sulfuric acid, acetic acid and sulfamic acid. Examples of the alkali include caustic soda, caustic potash, slaked lime, and ammonia.
両性高分子凝集剤の汚泥に対する添加割合としては、50〜1,000ppmが好ましく、TSに対しては0.1〜5質量%が好ましい。両性高分子凝集剤と後記するその他の高分子凝集剤を併用する場合は、全高分子凝集剤の合計量が前記添加割合を満たすことが好ましい。 The addition ratio of the amphoteric polymer flocculant to the sludge is preferably 50 to 1,000 ppm, and preferably 0.1 to 5% by mass with respect to TS. When the amphoteric polymer flocculant and other polymer flocculants described later are used in combination, it is preferable that the total amount of all the polymer flocculants satisfies the addition ratio.
本発明においては、無機凝集剤及び両性高分子凝集剤の他、必要に要に応じて、有機カチオン性化合物、カチオン性高分子凝集剤及びアニオン性高分子凝集剤を併用することができる。 In the present invention, in addition to the inorganic flocculant and the amphoteric polymer flocculant, an organic cationic compound, a cationic polymer flocculant and an anionic polymer flocculant can be used in combination as necessary.
有機カチオン性化合物としては、ポリマーポリアミン、ポリアミジン及びカチオン性界面活性剤等を例示できる。 Examples of organic cationic compounds include polymer polyamines, polyamidines, and cationic surfactants.
カチオン性高分子凝集剤としては、前記したカチオン性単量体の単独重合体及び前記したカチオン性単量体及びノニオン性単量体の共重合体等を挙げることができる。 Examples of the cationic polymer flocculant include a homopolymer of the aforementioned cationic monomer and a copolymer of the aforementioned cationic monomer and nonionic monomer.
アニオン性高分子凝集剤としては、前記したアニオン性単量体の単独重合体及び前記したアニオン性単量体及びノニオン性単量体の共重合体等を挙げることができる。 Examples of the anionic polymer flocculant include a homopolymer of the aforementioned anionic monomer and a copolymer of the aforementioned anionic monomer and nonionic monomer.
汚泥脱水剤を添加した後の攪拌速度及び攪拌時間等は、従来行われている脱水条件に従えば良い。 The stirring speed and stirring time after adding the sludge dehydrating agent may follow the conventional dehydrating conditions.
このようにして形成したフロックは、公知の手段を用いて脱水し、脱水ケーキとする。 The flocs thus formed are dehydrated using a known means to obtain a dehydrated cake.
脱水装置としては、スクリュープレス型脱水機、ベルトプレス型脱水機、フィルタープレス型脱水機及びスクリューデカンター等を例示することができる。 Examples of the dehydrator include a screw press dehydrator, a belt press dehydrator, a filter press dehydrator, a screw decanter, and the like.
又、本発明の汚泥脱水剤は、濾過部を有する造粒濃縮槽を使用する脱水方法にも適用可能である。
具体的には、汚泥に、無機凝集剤を添加し、さらに汚泥脱水剤を添加した後、又は汚泥脱水剤と共に、該汚泥を濾過部を有する造粒濃縮槽に導入し、該濾過部からろ液を取り出すと共に造粒し、この造粒物を脱水機で脱水処理する方法等が挙げられる。
The sludge dewatering agent of the present invention can also be applied to a dewatering method using a granulation concentration tank having a filtration part.
Specifically, after adding an inorganic flocculant to the sludge and further adding a sludge dewatering agent, or together with the sludge dewatering agent, the sludge is introduced into a granulation concentration tank having a filtration part, and filtered from the filtration part. Examples include a method of taking out the liquid and granulating, and dehydrating the granulated product with a dehydrator.
本発明の汚泥の脱水方法によれば、下水消化汚泥に対して、凝集性及びろ過性に優れたフロックを得ることができ、且つ脱水ケーキの含水率を低下させることが可能となる。 According to the sludge dewatering method of the present invention, flocs excellent in cohesiveness and filterability can be obtained with respect to sewage digested sludge, and the water content of the dewatered cake can be reduced.
本発明は、下水消化汚泥に、無機凝集剤を添加した後、前記両性高分子からなる両性高分子凝集剤を添加する汚泥の脱水方法である。 The present invention, in sewage digestion sludge, after adding an inorganic flocculant, Ru dehydration process der sludge adding an amphoteric polymer flocculant comprising the amphoteric polymer.
<実施例1、2及び比較例1、2>
高分子凝集剤としては、下記表1に示す単量体を水溶液重合し、得られたゲル状重合体を切断・細断し、乾燥したものを使用した。
尚、表1のDACはジメチルアミノエチルアクリレートのメチルクロライド4級塩、AAはアクリル酸、AMはアクリルアミドを意味する。
<Examples 1 and 2 and Comparative Examples 1 and 2>
As the polymer flocculant, a monomer shown in Table 1 below was polymerized in an aqueous solution, and the resulting gel polymer was cut, chopped and dried.
In Table 1, DAC means methyl chloride quaternary salt of dimethylaminoethyl acrylate, AA means acrylic acid, and AM means acrylamide.
300mlビーカーに入れた下水消化汚泥(TS=1.8質量%)200mlに対しポリ硫酸鉄1,000ppmを添加して攪拌機を用い150rpmにて30秒間攪拌した。続いて表1に記載の高分子凝集剤の0.2%水溶液を固形分換算で200ppm添加し、同様に180秒間攪拌して汚泥フロックを生成させその粒径を測定した。
その後、80メッシュの網をフィルターとして用い、前記汚泥フロック分散液を重力濾過した。10秒後の濾液容量を測定しこれを濾過速度とした。
得られたケーキをミニベルトプレス機にて圧搾脱水し(面圧0.5kg/cm、3段)、含水率を測定した。これらの結果を表2に示す。
To 200 ml of sewage digested sludge (TS = 1.8 mass%) placed in a 300 ml beaker, 1,000 ppm of polysulfate was added and stirred at 150 rpm for 30 seconds using a stirrer. Subsequently, a 0.2% aqueous solution of a polymer flocculant shown in Table 1 was added at 200 ppm in terms of solid content, and similarly stirred for 180 seconds to produce sludge flocs, and the particle size was measured.
Thereafter, the sludge floc dispersion was gravity filtered using an 80 mesh net as a filter. The filtrate volume after 10 seconds was measured and used as the filtration rate.
The obtained cake was squeezed and dehydrated with a mini belt press (surface pressure 0.5 kg / cm, 3 stages), and the moisture content was measured. These results are shown in Table 2.
実施例と比較例から明らかな様に、いずれの実施例の汚泥脱水方法も、Avが本願発明で規定する範囲を超えるの両性凝集剤を用いた場合(比較例1)、及びアニオン基を有しないカチオン性高分子凝集剤(比較例2)と比較し、フロック粒径が大きく、濾過速度にすぐれ且つ含水率も減少している。 As is clear from the examples and comparative examples, the sludge dewatering method of any of the examples uses an amphoteric flocculant whose Av exceeds the range specified in the present invention (Comparative Example 1) and has an anionic group. Compared with the cationic polymer flocculant that does not (Comparative Example 2), the floc particle size is large, the filtration rate is excellent, and the water content is also reduced.
本発明の汚泥の脱水方法は、下水消化汚泥の脱水方法として有用である。
The sludge dewatering method of the present invention is useful as a method for dewatering sewage digested sludge.
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