JP7519054B2 - 製紙スラッジの脱水方法 - Google Patents
製紙スラッジの脱水方法 Download PDFInfo
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- JP7519054B2 JP7519054B2 JP2020124862A JP2020124862A JP7519054B2 JP 7519054 B2 JP7519054 B2 JP 7519054B2 JP 2020124862 A JP2020124862 A JP 2020124862A JP 2020124862 A JP2020124862 A JP 2020124862A JP 7519054 B2 JP7519054 B2 JP 7519054B2
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- 229920000642 polymer Polymers 0.000 claims description 43
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
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- 125000002091 cationic group Chemical group 0.000 claims description 12
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- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
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- DWSMBORYMHSAEA-UHFFFAOYSA-N 3-[(4-amino-4-iminobutan-2-yl)diazenyl]butanimidamide;dihydrochloride Chemical compound Cl.Cl.NC(=N)CC(C)N=NC(C)CC(N)=N DWSMBORYMHSAEA-UHFFFAOYSA-N 0.000 description 2
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- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 2
- PZXSLFQJOZPCJG-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 PZXSLFQJOZPCJG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000013076 target substance Substances 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- VBZBISQOWJYWCC-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)N=NC(C)(C)C(O)=O VBZBISQOWJYWCC-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- KVHAVGCFHDEWNN-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate methanesulfonic acid Chemical compound CS([O-])(=O)=O.CC(=C)C(=O)OCC[NH3+] KVHAVGCFHDEWNN-UHFFFAOYSA-N 0.000 description 1
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 description 1
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- DXLZNKULUVFFFY-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate;hydrochloride Chemical compound Cl.NCCOC(=O)C=C DXLZNKULUVFFFY-UHFFFAOYSA-N 0.000 description 1
- WPKZZIHHLZDJGN-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate;sulfuric acid Chemical compound OS(O)(=O)=O.NCCOC(=O)C=C WPKZZIHHLZDJGN-UHFFFAOYSA-N 0.000 description 1
- RUUHDEGJEGHQKL-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;chloride Chemical compound [Cl-].CC(O)C[N+](C)(C)C RUUHDEGJEGHQKL-UHFFFAOYSA-M 0.000 description 1
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- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Description
そこで、製紙スラッジに適用するPAM系水溶性高分子として種々提案されている。例えば、特許文献1では、無機凝集剤を添加した後、(A)カチオン単量体単位と(B)アニオン単量体単位との合計が13~60モル%、(C)その他の単量体単位が40~87モル%であって且つ前記(A)カチオン単量体単位と(B)アニオン単量体単位とのモル比が0.03<(B)/(A)<0.8である両性PAMを添加する脱水処理方法が提案されている。
特許文献2では、特定の単量体組成を有する単量体と複数のビニル基を有する単量体からなる単量体混合物を重合した架橋性イオン性PAMからなる処理剤を製紙スラッジに添加する脱水方法が提案されている。
特許文献3では、特定の構造を有するカチオン性単量体、非イオン性単量体、及びアニオン性単量体1~8モル%からなる単量体混合物を重合した特定の物性を有する両性PAMを製紙スラッジに添加する方法が開示されている。
しかし、製紙スラッジは余剰汚泥と混合される場合もあり、その性状は不安定であり、これらPAM系水溶性高分子の効果も不安定である。
一方、凝集処理剤として、ポリビニルアミン系水溶性高分子やポリアミジン系水溶性高分子は特異的に脱水ケーキ含水率が低下する場合がありPAM系水溶性高分子とは使い分けが重要なことが知られている。この現象はPAM系水溶性高分子中の三級アミノ基や四級アンモニウム塩と、ポリビニルアミン系水溶性高分子やポリアミジン系水溶性高分子中の一級あるいは二級アミノ基との違いに起因することが示唆される。特にポリアミジン系水溶性高分子はカチオン度が高く特異的な構造から、繊維分の少ない所謂難脱水性汚泥に優れた効果を発揮することが知られている。
そこで、特許文献4では、アミジン系水溶性高分子水溶液に、水に対し非混和性の炭化水素系溶剤と油溶性乳化剤を添加し攪拌することにより調製したアミジン系水溶性高分子エマルジョンを製紙スラッジに添加する脱水方法が開示されている。しかし、これらアミジン系水溶性高分子では一定の効果を得るには添加率が増加する傾向にあり効果も製紙スラッジ性状により限定的である。
特許文献5には、一級アミノ基含有重合体エマルジョン型凝集剤が開示、製紙スラッジへの適用が記載されている。しかし、製紙スラッジ性状の変動に適用できる一級アミノ基含有重合体の組成、物性が最適化されている訳ではない。
そこで、製紙スラッジ性状の変動においても安定して脱水効率の高い凝集処理剤の開発が要望されている。
一般式(1)
R1は水素又はメチル基、Aは酸素原子又はNH、Bは炭素数2~3のアルキレン基又はアルコキシレン基、X-は陰イオンをそれぞれ表わす。
尚、粗浮遊物は下記の測定方法に従い測定したものである。
(製紙スラッジ中の粗浮遊物の測定方法)
(1)汚泥100mLをビーカー500mLにはかり取り、水を加えて200mLとする。
(2)これを標準ふるい(呼び寸法0.075mm)の中央部に静かに移し水洗する。
(3)この残渣を濾紙6種(あらかじめ乾燥して、その質量(Xmg)をはかってあるもの)の上に移して濾過する。
(4)この濾紙をあらかじめ乾燥して質量をはかってある蒸発皿に移し、105℃で2時間加熱乾燥した後デシケーター中で室温まで放冷し、その質量(Ymg)をはかる。
(5)この濾紙をのせた蒸発皿を磁性のふたで覆い、電気炉に入れて600℃で1時間灰化し、デシケーター中で放冷した後、その質量(Zmg)をはかり、次式によって、汚泥中の粗浮遊物の濃度(質量%)を算出する。
製紙スラッジ中の粗浮遊物(質量%)=(Y-X-Z)×1/1000
形態:EM;油中水型エマルジョン
0.2質量%水溶液粘度(mPa・s);0.2質量%高分子水溶液をB型粘度計により測定(25℃)。
0.5質量%塩水溶液粘度(mPa・s);0.5質量%高分子水溶液に4質量%塩化ナトリウムを添加、完全溶解後にB型粘度計により測定(25℃)。
AQV;0.2質量%水溶液粘度(mPa・s)
SLV;0.5質量%塩水溶液粘度(mPa・s)
AQV/SLV;無次元
DMQ;アクリロイルオキシエチルトリメチルアンモニウム塩化物
AAM;アクリルアミド、AAC;アクリル酸
形態:EM;油中水型エマルジョン、P;粉末
0.2質量%水溶液粘度(mPa・s);0.2質量%高分子水溶液をB型粘度計により測定(25℃)。
0.5質量%塩水溶液粘度(mPa・s);0.5質量%高分子水溶液に4質量%塩化ナトリウムを添加、完全溶解後にB型粘度計により測定(25℃)。
AQV;0.2質量%水溶液粘度(mPa・s)
SLV;0.5質量%塩水溶液粘度(mPa・s)
AQV/SLV;無次元
Claims (2)
- M-アルカリ度が1000mg/L以上であり、粗浮遊物が20質量%以下(対スラッジ固形分)である製紙スラッジに、下記一般式(1)で表されるカチオン性単量体として、2-アミノエチルアクリレート、2-アミノエチルメタクリレート、3-アミノプロピルアクリレート、3-アミノプロピルメタクリレートの有機酸及び無機酸の塩から選択される一種以上を含有する単量体あるいは単量体混合物を乳化重合して得た油中水型エマルジョンからなる一級アミノ基含有重合体であり、該一級アミノ基含有重合体の25℃における、0.2質量%水溶液粘度をAQV、0.5質量%の4質量%食塩水溶液中粘度をSLVとすると、AQVとSLVの比が、
10≦AQV/SLV<30であり、SLVが5~70mPa・sの範囲である一級アミノ基含有重合体を添加し脱水処理することを特徴とする製紙スラッジの脱水方法。
一般式(1)
R1は水素またはメチル基、Aは酸素原子またはNH、Bは炭素数2~3のアルキレン基またはアルコキシレン基、X-は陰イオンをそれぞれ表わす。 - 前記一級アミノ基含有重合体が、前記一般式(1)で表されるカチオン性単量体70~100モル%を含有する単量体混合物を乳化重合して得た油中水型エマルジョンであることを特徴とする請求項1に記載の製紙スラッジの脱水方法。
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JP2002166104A (ja) | 2000-09-25 | 2002-06-11 | Hymo Corp | 一級アミノ基含有重合体エマルジョン型凝集剤 |
JP2015051428A (ja) | 2013-08-06 | 2015-03-19 | 三洋化成工業株式会社 | 高分子凝集剤 |
JP2015150534A (ja) | 2014-02-18 | 2015-08-24 | ハイモ株式会社 | 凝集処理剤及びそれを用いた汚泥の脱水方法 |
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JP2002166104A (ja) | 2000-09-25 | 2002-06-11 | Hymo Corp | 一級アミノ基含有重合体エマルジョン型凝集剤 |
JP2015051428A (ja) | 2013-08-06 | 2015-03-19 | 三洋化成工業株式会社 | 高分子凝集剤 |
JP2015150534A (ja) | 2014-02-18 | 2015-08-24 | ハイモ株式会社 | 凝集処理剤及びそれを用いた汚泥の脱水方法 |
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