JPH06191852A - Production of inorganic pigment from waste water sludge - Google Patents
Production of inorganic pigment from waste water sludgeInfo
- Publication number
- JPH06191852A JPH06191852A JP15183993A JP15183993A JPH06191852A JP H06191852 A JPH06191852 A JP H06191852A JP 15183993 A JP15183993 A JP 15183993A JP 15183993 A JP15183993 A JP 15183993A JP H06191852 A JPH06191852 A JP H06191852A
- Authority
- JP
- Japan
- Prior art keywords
- sludge
- water
- dehydrated
- inorganic pigment
- main component
- 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.)
- Pending
Links
- 239000010802 sludge Substances 0.000 title claims abstract description 87
- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- 239000001023 inorganic pigment Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013535 sea water Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 238000010304 firing Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 20
- 238000001914 filtration Methods 0.000 abstract description 10
- 239000013505 freshwater Substances 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000001223 reverse osmosis Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Treatment Of Sludge (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は鉄分を主成分とする廃水
スラッジ、特に逆浸透膜法による海水淡水化の前処理装
置である二層ろ過装置から排出される廃水スラッジを処
理して酸化第二鉄を主成分とする酸化けい素及び酸化ア
ルミニウム含有の無機顔料を製造する方法に関する。BACKGROUND OF THE INVENTION The present invention treats and oxidizes wastewater sludge containing iron as a main component, particularly wastewater sludge discharged from a two-layer filtration device which is a pretreatment device for seawater desalination by the reverse osmosis membrane method. The present invention relates to a method for producing an inorganic pigment containing silicon oxide and aluminum oxide, which is mainly composed of diiron.
【０００２】[0002]
【従来の技術】従来、逆浸透膜法による海水淡水化の前
処理装置である砂−アンスラサイト（無煙炭）からなる
二層ろ過装置から排出される鉄分を主成分とする廃水ス
ラッジは廃棄物としてろ過機でろ過処理した後に処分す
るか、処理することなくそのまま海水へ排出していた。2. Description of the Related Art Conventionally, wastewater sludge containing iron as a main component discharged from a two-layer filtration device composed of sand-anthracite (anthracite) which is a pretreatment device for seawater desalination by a reverse osmosis membrane method is treated as waste. It was either filtered after being treated with a filter and then discarded, or it was directly discharged to seawater without treatment.
【０００３】[0003]
【発明が解決しようとする課題】逆浸透膜法による海水
淡水化装置では、膜性能維持のため二層ろ過装置での前
処理装置により海水中の汚濁物質（コロイド性の有機物
及び無機物やウイルス、細菌など）を除去する必要があ
り、そのために凝集剤として塩化第二鉄溶液を添加して
上記汚濁物質を凝集してろ過除去している。二層ろ過装
置に堆積した汚濁物質は逆洗の際に廃水スラッジとして
排出される。その主成分は凝集目的で添加される塩化第
二鉄より生成する水酸化第二鉄〔Ｆｅ（ＯＨ）3 〕であ
るが、他にも酸化けい素（ＳｉＯ2 ）、酸化アルミニウ
ム（Ａｌ2 Ｏ3 ）、炭酸カルシウム（ＣａＣＯ3 ）など
が混在し、かつかなりの有機物及び微生物によるスライ
ムが付着している。この廃水スラッジをろ過、圧搾など
の処理により固形物として廃棄処分する方法もあるが、
大型プラントになるにつれ、そのスラッジ量は大容量と
なり処理コスト上適用は難しい。また廃水スラッジを処
理することなく、そのまま海水へ排出したのでは環境問
題を引き起こす可能性が大きいため、その適正処理対策
が課題とされている。In the seawater desalination apparatus by the reverse osmosis membrane method, the pretreatment device in the two-layer filtration apparatus is used to maintain the membrane performance, and the pollutants in the seawater (organic and inorganic substances such as colloidal substances and viruses, It is necessary to remove bacteria, etc.), and for that purpose, a ferric chloride solution is added as a coagulant to coagulate and remove the contaminants by filtration. The pollutants deposited on the two-layer filter are discharged as wastewater sludge during backwashing. Its main component is ferric hydroxide [Fe (OH) 3 ] produced from ferric chloride added for the purpose of agglomeration. Besides, silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3) 3 ), calcium carbonate (CaCO 3 ) and the like are mixed, and a considerable amount of organic matter and slime due to microorganisms are attached. There is also a method to dispose of this wastewater sludge as solid matter by processing such as filtration and compression,
As it becomes a large plant, the amount of sludge becomes large and it is difficult to apply it due to the treatment cost. Further, if wastewater sludge is not directly treated and discharged into seawater as it is, there is a great possibility that it will cause environmental problems.
【０００４】本発明は上記技術水準に鑑み、鉄分を主成
分とする廃水スラッジを処理して酸化第二鉄を主成分と
する酸化けい素及び酸化アルミニウム含有の鋼材、木材
などの防腐塗料の原料として、また舗装用着色原料とし
て有用な赤色の無機顔料を製造する方法を提供しようと
するものである。In view of the above-mentioned state of the art, the present invention treats wastewater sludge containing iron as a main component to obtain a raw material for antiseptic paints such as steel and wood containing silicon oxide and aluminum oxide containing ferric oxide as a main component. The present invention also aims to provide a method for producing a red inorganic pigment useful as a coloring material for paving.
【０００５】[0005]
【課題を解決するための手段】本発明は（１）鉄分を主
成分とする濃厚廃水スラッジに塩酸を添加してｐＨ３．
５〜４に調整し、十分に攪拌した後、高分子凝集剤を添
加し、これをろ過機に通して脱水したスラッジを水洗し
て混在している海水塩分を除去する第１工程と、第１工
程で得られたスラッジ分を脱水乾燥した後、空気気流中
５００〜８００℃で焼成して酸化第二鉄を主成分とする
酸化けい素及び酸化アルミニウム含有の無機顔料を生成
し、粉砕機で微粉砕する第二工程よりなることを特徴と
する廃水スラッジから無機顔料を製造する方法（以下第
１発明という）及び（２）鉄分を主成分とする濃厚廃水
スラッジに塩酸を添加してｐＨ３．５〜４に調整し、空
気吹込みによる攪拌によってスラッジ中の炭酸カルシウ
ムを溶出分解した後、スラッジを水洗して混在している
酸及び海水塩分を除去したスラッジを脱水機で脱水する
第１工程と、第１工程で得られたスラッジを焼成炉で脱
水乾燥し、次いで同焼成炉で空気気流中５００〜８００
℃で焼成して酸化第二鉄を主成分とする酸化けい素及び
酸化アルミニウム含有の無機顔料を生成し、更に粉砕機
で微粉砕する第２工程よりなることを特徴とする廃水ス
ラッジから無機顔料を製造する方法（以下第２発明とい
う）である。Means for Solving the Problems According to the present invention, (1) hydrochloric acid is added to concentrated wastewater sludge containing iron as a main component to adjust the pH to 3.
5 to 4, after sufficiently stirring, a polymer flocculant is added, and the sludge dehydrated by passing this through a filter is washed with water to remove the mixed seawater salt content. The sludge obtained in one step is dehydrated and dried, and then calcined in an air stream at 500 to 800 ° C. to produce an inorganic pigment containing silicon oxide and aluminum oxide containing ferric oxide as a main component, and a pulverizer. A method for producing an inorganic pigment from wastewater sludge (hereinafter referred to as the first invention), which comprises a second step of finely pulverizing with, and (2) adding hydrochloric acid to concentrated wastewater sludge containing iron as a main component to adjust the pH to 3 5 to 4 and elute and decompose calcium carbonate in the sludge by stirring by blowing air, and then wash the sludge with water to remove the mixed acid and seawater salt, and dehydrate the sludge with a dehydrator No. 1 Process and first The sludge obtained in the extent dehydrated and dried in a firing furnace, and then a flow of air at the same sintering furnace 500 to 800
Inorganic pigment from wastewater sludge, characterized by comprising a second step of calcination at ℃ to produce an inorganic pigment containing silicon oxide and aluminum oxide containing ferric oxide as a main component, and further finely pulverizing with a pulverizer. (Hereinafter referred to as the second invention).
【０００６】[0006]
【作用】本発明の第１発明は鉄分を主成分とする濃厚廃
水スラッジを脱水乾燥した後に、空気気流中５００〜８
００℃で焼成して酸化第二鉄（αＦｅ2 Ｏ3 ）を主成分
とする酸化けい素（ＳｉＯ2 ）及び酸化アルミニウム
（Ａｌ2 Ｏ3 ）含有の無機顔料（赤色）を生成させるも
のであるが、そのままでは無機顔料中に水可溶性の不純
物としてスラッジ中からの炭酸カルシウム（ＣａＣ
Ｏ3 ）や海水からの塩分（ナトリウム，カリウム，カル
シウム，マグネシウム塩）が後述の表１の参考例に示す
如く６．８％も混在してくるため、このままの品質では
無機顔料としての商品価値はなくなる。According to the first aspect of the present invention, the concentrated wastewater sludge containing iron as the main component is dehydrated and dried, and then 500 to 8 in the air stream.
It is fired at 00 ° C. to produce an inorganic pigment (red) containing ferric oxide (αFe 2 O 3 ) as a main component and containing silicon oxide (SiO 2 ) and aluminum oxide (Al 2 O 3 ). However, as it is, calcium carbonate (CaC) from the sludge is added as a water-soluble impurity in the inorganic pigment.
O 3 ) and salt (sodium, potassium, calcium, magnesium salts) from seawater are mixed in as much as 6.8% as shown in the reference example of Table 1 below, so that the quality as it is is a commercial value as an inorganic pigment. Disappears.
【０００７】そこで先ず第１工程としてスラッジ中に混
在しているＣａＣＯ3 を溶解するため濃厚廃水スラッジ
に塩酸を添加攪拌してＣａＣＯ3 をＣａＣＯ3 ＋２ＨＣ
ｌ→ＣａＣｌ2 ＋Ｈ2 Ｏ＋ＣＯ2 ↑の反応によって炭酸
塩を溶解、分解するもので、塩酸の添加濃度はｐＨ：
３．５未満では鉄分が若干溶出し、またｐＨ：４を超え
るとＣａＣＯ3 の溶解が悪くなるのでｐＨ３．５〜４の
範囲にする。溶解時の温度及び時間は常温及び１時間程
度が好ましい。また溶解時の攪拌を十分にするため、エ
アバブリングを行うことが好ましい。Therefore, in the first step, in order to dissolve CaCO 3 mixed in the sludge, hydrochloric acid is added to the concentrated wastewater sludge and stirred to convert CaCO 3 into CaCO 3 + 2HC.
l → CaCl 2 + H 2 O + CO 2 ↑ It dissolves and decomposes carbonate, and the concentration of hydrochloric acid added is pH:
If it is less than 3.5, the iron content is slightly eluted, and if it exceeds pH: 4, the dissolution of CaCO 3 becomes poor, so the pH is set to a range of 3.5 to 4. It is preferable that the temperature and the time during the dissolution are room temperature and about 1 hour. Further, it is preferable to perform air bubbling in order to sufficiently stir at the time of dissolution.
【０００８】ＣａＣＯ3 を溶解した後に添加する高分子
凝集剤は鉄分〔Ｆｅ（ＯＨ）3 〕を主成分とする廃水ス
ラッジに対し効果あるものであればよく、特に選定する
必要はないが、一例を上げればポリアクリル酸ナトリウ
ムなどがあげられる。The polymer coagulant added after dissolving CaCO 3 is not particularly limited as long as it is effective for the wastewater sludge containing iron [Fe (OH) 3 ] as a main component, but one example is If it is raised, sodium polyacrylate and the like can be mentioned.
【０００９】次にろ過機に通して脱水したスラッジを水
洗して混在している海水塩分を効果的に除去する方法に
ついて述べると、スラッジ１容に対し水１０容を添加し
て空気を吹き込んで十分に攪拌し、１時間程度静置して
スラッジ分を沈降させ、その上澄液を排出した後に再度
スラッジ１容に対し水５容を添加して空気を吹き込んで
十分に攪拌し、１時間程度静置してスラッジ分を沈降さ
せ、その上澄液を排出することによってスラッジ中の水
可溶性不純物はほぼ完全に除去される。Next, a method for effectively removing the mixed seawater salt by washing the sludge dehydrated through a filter with water will be described. To 1 volume of sludge, 10 volumes of water were added and air was blown into the sludge. Stir well, let stand for about 1 hour to settle the sludge, discharge the supernatant, add 5 volumes of water to 1 volume of sludge again, blow air and stir for 1 hour. The water-soluble impurities in the sludge are almost completely removed by allowing the sludge to settle by allowing it to stand for a while and discharging the supernatant.
【００１０】次は第１工程で得られた水可溶性不純物除
去後のスラッジ液を第２工程で脱水乾燥した後、スラッ
ジ中の全有機物を発火焼却させるため、５００〜８００
℃の空気気流中で焼成〔２Ｆｅ（ＯＨ）3 →Ｆｅ2 Ｏ3
＋３Ｈ2 Ｏ↑〕して酸化けい素（ＳｉＯ2 ）及び酸化ア
ルミニウム（Ａｌ2 Ｏ3 ）を含有する酸化第二鉄（αＦ
ｅ2 Ｏ3 ）主成分の無機顔料（赤色）が生成される。焼
成温度５００℃未満では２Ｆｅ（ＯＨ）3 →αＦｅ2 Ｏ
3 ＋３Ｈ2 Ｏの反応が進みにくく、また８００℃を超え
ると顔料が固まる傾向になるため好ましくない。Next, the sludge liquid after removing the water-soluble impurities obtained in the first step is dehydrated and dried in the second step, and then 500 to 800 for burning and burning all the organic substances in the sludge.
Calcination in air stream at ℃ [2Fe (OH) 3 → Fe 2 O 3
+ 3H 2 O ↑] and ferric oxide (αF) containing silicon oxide (SiO 2 ) and aluminum oxide (Al 2 O 3 ).
e 2 O 3 ) The main component of the inorganic pigment (red) is produced. If the firing temperature is less than 500 ° C, 2Fe (OH) 3 → αFe 2 O
It is not preferable because the reaction of 3 + 3H 2 O is difficult to proceed, and when the temperature exceeds 800 ° C., the pigment tends to be solidified.
【００１１】また、本発明の第２発明は鉄分を主成分と
する濃厚廃水スラッジを脱水乾燥した後に、空気気流中
５００〜８００℃で焼成して酸化第二鉄（αＦｅ
2 Ｏ3 ）を主成分とする酸化けい素（ＳｉＯ2 ）及び酸
化アルミニウム（Ａｌ2 Ｏ3 ）含有の無機顔料（赤色）
を生成させるものであるが、そのままでは無機顔料中に
水可溶性の不純物としてスラッジ中からの炭酸カルシウ
ム（ＣａＣＯ3 ）や海水からの塩分（ナトリウム，カリ
ウム，カルシウム，マグネシウム塩）が後述の表２の参
考例に示す如く６．８％も混在してくるため、このまま
の品質では無機顔料としての商品価値はなくなる。According to the second aspect of the present invention, ferric oxide (αFe) is obtained by dehydrating and drying the concentrated wastewater sludge containing iron as a main component and then calcining the sludge in an air stream at 500 to 800 ° C.
2 O 3 ) as the main component Silicon oxide (SiO 2 ) and aluminum oxide (Al 2 O 3 ) containing inorganic pigment (red)
However, calcium carbonate (CaCO 3 ) from the sludge and salt (sodium, potassium, calcium, magnesium salts) from the seawater as water-soluble impurities in the inorganic pigment as shown in Table 2 below. As shown in the reference example, since 6.8% is mixed, the product value as an inorganic pigment is lost with the quality as it is.
【００１２】そこで先ず第１工程としてスラッジ中に混
在しているＣａＣＯ3 を溶解するため、濃厚廃水スラッ
ジに塩酸を添加し、空気吹き込みによりスラッジを攪拌
してＣａＣＯ3 をＣａＣＯ3 ＋２ＨＣｌ→ＣａＣｌ2 ＋
Ｈ2 Ｏ＋ＣＯ2 ↑の化学反応によって溶解、分解するも
ので、塩酸の添加濃度は、ｐＨ：３．５未満では鉄分が
若干溶出し、またｐＨ：４を超えるとＣａＣＯ3 の溶解
が悪くなるのでｐＨ３．５〜４の範囲にする。溶解時の
温度及び時間は常温及び１時間程度が好ましい。[0012] Therefore, first to dissolve the CaCO 3 that are mixed into the sludge as a first step, the addition of hydrochloric acid concentrated waste sludge, the CaCO 3 CaCO stirred sludge by blowing air 3 + 2HCl → CaCl 2 +
It dissolves and decomposes due to the chemical reaction of H 2 O + CO 2 ↑. When the concentration of hydrochloric acid added is less than pH: 3.5, some iron elutes, and when it exceeds pH: 4, the dissolution of CaCO 3 deteriorates. Adjust the pH to a range of 3.5-4. It is preferable that the temperature and the time during the dissolution are room temperature and about 1 hour.
【００１３】次にスラッジ液に混在している海水塩分を
効果的に除去する水洗方法について述べると、スラッジ
液１容に対し水１０容を添加して空気を吹き込んで十分
に攪拌し、１時間程度静置してスラッジ分を沈降させ、
その上澄液を排出する。この水洗操作を３回繰り返した
後の含水スラッジを脱水機（圧搾型または遠心分離型な
ど）で脱水することによってスラッジ中の水可溶性不純
物はほぼ完全に除去される。Next, description will be made on a water washing method for effectively removing seawater salt mixed in the sludge liquid. To 10 parts of water is added to 1 volume of the sludge liquid, air is blown therein, and the mixture is sufficiently stirred for 1 hour. Let stand for about a while to settle the sludge,
The supernatant is discharged. The water-soluble sludge in the sludge is almost completely removed by dehydrating the hydrous sludge after repeating this washing operation three times with a dehydrator (pressing type or centrifugal separation type).
【００１４】次は第１工程で得られた水可溶性不純物除
去後のスラッジを１１０℃前後の焼成炉で脱水乾燥し、
次いで同焼成炉でスラッジ中の全有機物を発火焼却させ
るため、５００〜８００℃の空気気流中で焼成〔２Ｆｅ
（ＯＨ）3 →Ｆｅ2 Ｏ3 ＋３Ｈ2 Ｏ↑〕して酸化けい素
（ＳｉＯ2 ）及び酸化アルミニウム（Ａｌ2 Ｏ3 ）を含
有する酸化第二鉄（αＦｅ2 Ｏ3 ）主成分の無機顔料
（赤色）が生成される。焼成温度５００℃未満では２Ｆ
ｅ（ＯＨ）3 →αＦｅ2 Ｏ3 ＋３Ｈ2 Ｏの反応が進みに
くく、また８００℃を超えると顔料が固まる傾向になる
ため好ましくない。Next, the sludge obtained in the first step, from which water-soluble impurities have been removed, is dehydrated and dried in a firing furnace at about 110 ° C.,
Then, in order to ignite and incinerate all the organic substances in the sludge in the same firing furnace, firing in an air stream of 500 to 800 ° C [2Fe
(OH) 3 → Fe 2 O 3 + 3H 2 O ↑] to contain silicon oxide (SiO 2 ) and aluminum oxide (Al 2 O 3 ) as the main component of ferric oxide (αFe 2 O 3 ) inorganic pigment (Red) is generated. 2F when firing temperature is less than 500 ℃
The reaction of e (OH) 3 → αFe 2 O 3 + 3H 2 O is difficult to proceed, and when the temperature exceeds 800 ° C., the pigment tends to harden, which is not preferable.
【００１５】[0015]
（実施例１）本発明の第１発明の一実施例を図１の工程
図によって説明する。逆浸透膜法による海水淡水化の前
処理装置である二層ろ過装置から排出される廃水スラッ
ジは通常主成分として鉄分〔組成Ｆｅ（ＯＨ）3 〕が、
その他に酸化けい素（ＳｉＯ 2 ）、酸化アルミニウム
（Ａｌ2 Ｏ3 ）及び炭酸カルシウム（ＣａＣＯ3 ）が、
またコロイド状有機物、微生物、スライムなどの夾雑物
が含まれている。ここではスラッジそのものの組成とし
てＦｅ（ＯＨ）3 ：５９．３％、ＳｉＯ2 ：１１．５
％、Ａｌ2 Ｏ3 ：４．３％、ＣａＣＯ3 ：５．１％、そ
の他夾雑物：１９．５％の廃水スラッジを試験液として
用いた。 (Embodiment 1) An embodiment of the first invention of the present invention is shown in FIG.
It will be described with reference to the drawings. Before seawater desalination by reverse osmosis membrane method
Waste water sludge discharged from the two-layer filtration device, which is a treatment device.
Di is usually iron as a main component [composition Fe (OH)3〕But,
In addition, silicon oxide (SiO 2),Aluminum oxide
(Al2O3) And calcium carbonate (CaCO3)But,
Also, contaminants such as colloidal organic matter, microorganisms and slime
It is included. Here, the composition of the sludge itself
Fe (OH)3: 59.3%, SiO211.5
%, Al2O3: 4.3%, CaCO3: 5.1%
Foreign matter: 19.5% wastewater sludge as test liquid
Using.
【００１６】そこで先ず含水率９２％の濃厚廃水スラッ
ジ５００リットルをｐＨ調整タンク２に採り、空気を吹
き込みながら塩酸を添加してｐＨ：３．８に調整し、約
０．５時間攪拌した後に高分子凝集剤（例えばポリアク
リル酸ナトリウム）２０ｐｐｍを添加して、ろ過機３に
通して脱水（含水率７８％）したスラッジを水洗タンク
４へ移してスラッジ１容に対し水１０容を加えて空気を
吹き込んで約１５分間攪拌した後に１時間静置してスラ
ッジ分を沈降させ、その上澄液を水中ポンプで排出した
後、再度スラッジ液１容に対し水５容を加えて上記要領
で水洗して１時間静置後その上澄液を排出した。次いで
上澄液を十分に排出した後のスラッジを乾燥機５で脱水
乾燥し、焼成炉６に送り、空気気流中８００℃で焼成
し、これを微粉砕機７に入れ、平均粒径３μｍ以下の微
粒子とした。Therefore, first, 500 liters of concentrated wastewater sludge having a water content of 92% was taken in the pH adjusting tank 2, hydrochloric acid was added while blowing air to adjust the pH to 3.8, and the mixture was stirred for about 0.5 hour and then raised to a high temperature. Add 20 ppm of a molecular flocculant (for example, sodium polyacrylate), pass through a filter 3 to dehydrate (water content 78%), move the sludge to a washing tank 4, add 10 volumes of water to 1 volume of sludge, and add air. The mixture was blown in and stirred for about 15 minutes, then allowed to stand for 1 hour to allow the sludge to settle, the supernatant liquid was discharged with a submersible pump, and then 5 volumes of water were added to 1 volume of the sludge solution and washed with water as described above. After standing for 1 hour, the supernatant was discharged. Then, the sludge from which the supernatant liquid has been sufficiently discharged is dehydrated and dried by a dryer 5, sent to a firing furnace 6 and fired at 800 ° C. in an air stream, and put into a fine pulverizer 7 to have an average particle diameter of 3 μm or less. Of fine particles.
【００１７】こうして得た高純度の酸化第二鉄を主成分
とする酸化けい素及び酸化アルミニウムを含有する赤色
無機顔料の性状を表１に、また全く処理しない初期スラ
ッジを図１の焼成炉６で直接焼成した無機顔料の性状を
表１の参考例に併せて示した。表１から判るように塩酸
洗浄及び水洗浄によって無機顔料中の水可溶性不純物は
効果的に除去されて無機顔料の純度及び品質は顕著に向
上している。The properties of the thus obtained red inorganic pigment containing silicon oxide and aluminum oxide containing high-purity ferric oxide as a main component are shown in Table 1, and the initial sludge not treated at all is shown in the firing furnace 6 in FIG. The properties of the inorganic pigment directly fired in Table 1 are shown in Table 1 together with the reference example. As can be seen from Table 1, the water-soluble impurities in the inorganic pigment are effectively removed by washing with hydrochloric acid and washing with water, and the purity and quality of the inorganic pigment are remarkably improved.
【００１８】[0018]
【表１】 [Table 1]
【００１９】（実施例２）本発明の第２発明の一実施例
を図２の工程図によって説明する。逆浸透膜法による海
水淡水化の前処理装置である二層ろ過装置から排出され
る廃水スラッジは通常主成分として鉄分〔組成Ｆｅ（Ｏ
Ｈ）3 〕が、その他に酸化けい素（ＳｉＯ 2 ）、酸化ア
ルミニウム（Ａｌ2 Ｏ3 ）及び炭酸カルシウム（ＣａＣ
Ｏ3 ）が、またコロイド状有機物、微生物、スライムな
どの夾雑物が含まれている。ここでは前記実施例１と同
じ廃水スラッジを試験液として用いた。(Embodiment 2) One embodiment of the second invention of the present invention
Will be described with reference to the process chart of FIG. Sea by reverse osmosis method
It is discharged from the two-layer filtration device that is the pretreatment device for water desalination.
Wastewater sludge is usually composed of iron [composition Fe (O
H)3], But in addition, silicon oxide (SiO 2), Oxide
Luminium (Al2O3) And calcium carbonate (CaC
O3), But also colloidal organics, microorganisms, slimes
Which impurities are included. Here, the same as in the first embodiment.
The same wastewater sludge was used as the test liquid.
【００２０】そこで先ず含水率９２％の濃厚廃水スラッ
ジ５００リットルを酸洗浄及び水洗タンク２′に採り、
空気を吹き込みながら塩酸を添加してｐＨ３．６に調整
し、約１時間攪拌した後、スラッジ液１容に対し水１０
容を加えて空気を吹き込んで約１５分間攪拌した後に、
１時間静置してスラッジ分を沈降させ、その上澄液を水
中ポンプで排出した。この水洗操作を３回繰り返した後
の含水スラッジを圧搾型の脱水機３′で脱水した後、焼
成炉４′に送り、先ず１１０℃で脱水乾燥し、次いで同
焼成炉４′で空気気流中７００℃で焼成し、これを微粉
砕機５′に入れ、平均粒径３μｍ以下の微粒子とした。Therefore, first, 500 liters of concentrated wastewater sludge having a water content of 92% was taken in the acid washing and water washing tank 2 ',
Hydrochloric acid was added while blowing air to adjust the pH to 3.6, and the mixture was stirred for about 1 hour.
After adding the volume and blowing air and stirring for about 15 minutes,
The sludge was allowed to settle by standing for 1 hour, and the supernatant was discharged with a submersible pump. After repeating this washing operation three times, the water-containing sludge is dehydrated by a compression type dehydrator 3 ', then sent to a firing furnace 4', first dehydrated and dried at 110 ° C, then in an air stream in the same firing furnace 4 '. It was calcined at 700 ° C. and put into a fine pulverizer 5 ′ to obtain fine particles having an average particle size of 3 μm or less.
【００２１】こうして得た高純度の酸化第二鉄を主成分
とする酸化けい素及び酸化アルミニウムを含有する赤色
無機顔料の性状を表２に、また全く処理しない初期スラ
ッジを図２の焼成炉４′で直接脱水乾燥後７００℃で焼
成した無機顔料の性状を表２の参考例に併せて示した。
表２から判るように塩酸洗浄及び水洗浄によって無機顔
料中の水可溶性不純物は効果的に除去されて無機顔料の
純度及び品質は顕著に向上している。The properties of the thus obtained red inorganic pigment containing silicon oxide and aluminum oxide containing high-purity ferric oxide as a main component are shown in Table 2, and the initial sludge not treated at all is shown in the firing furnace 4 in FIG. The properties of the inorganic pigment which was directly dehydrated and dried at ′ and calcined at 700 ° C. are also shown in the reference example of Table 2.
As can be seen from Table 2, the water-soluble impurities in the inorganic pigment are effectively removed by washing with hydrochloric acid and washing with water, and the purity and quality of the inorganic pigment are remarkably improved.
【００２２】[0022]
【表２】 [Table 2]
【００２３】[0023]
【発明の効果】本発明方法によれば、従来、逆浸透膜法
による海水淡水化前処理装置の二層ろ過装置から排出廃
棄していた鉄分を主成分とする廃水スラッジから高純
度、高品質で微粒子の酸化第二鉄（αＦｅ2 Ｏ3 ）を主
成分とする酸化けい素（ＳｉＯ2）及び酸化アルミニウ
ム（Ａｌ2 Ｏ3 ）含有の無機顔料（赤色）を製造できる
ので、有価資源回収上極めて有益であるばかりでなく、
環境問題上からも大いに貢献できる。EFFECTS OF THE INVENTION According to the method of the present invention, wastewater sludge containing iron as a main component, which has been conventionally discharged and discarded from the two-layer filtration device of the seawater desalination pretreatment device by the reverse osmosis membrane method, has high purity and high quality. Since it is possible to manufacture an inorganic pigment (red) containing fine particles of ferric oxide (αFe 2 O 3 ) as a main component and containing silicon oxide (SiO 2 ) and aluminum oxide (Al 2 O 3 ), it is possible to recover valuable resources. Not only is it extremely beneficial,
It can also make a great contribution to environmental issues.
【図１】本発明の第１発明の工程図。FIG. 1 is a process drawing of the first invention of the present invention.
【図２】本発明の第２発明の工程図。FIG. 2 is a process drawing of the second invention of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浜田 紘 長崎県長崎市飽の浦町１番１号 三菱重工 業株式会社長崎造船所内 (72)発明者 吉田 博明 長崎県長崎市深堀町五丁目717番地１ 長 菱エンジニアリング株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiro Hamada 1-1 1-1 Atsunoura-machi, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd. Nagasaki Shipyard (72) Inventor Hiroaki Yoshida 5-717, Fukahori-cho, Nagasaki-shi, Nagasaki Choryo Engineering Co., Ltd.
Claims (2)
塩酸を添加してｐＨ３．５〜４に調整し、十分に攪拌し
た後、高分子凝集剤を添加し、これをろ過機に通して脱
水したスラッジを水洗して混在している海水塩分を除去
する第１工程と、第１工程で得られたスラッジ分を脱水
乾燥した後、空気気流中５００〜８００℃で焼成して酸
化第二鉄を主成分とする酸化けい素及び酸化アルミニウ
ム含有の無機顔料を生成し、更に粉砕機で微粉砕する第
２工程よりなることを特徴とする廃水スラッジから無機
顔料を製造する方法。1. A hydrochloric acid is added to concentrated wastewater sludge containing iron as a main component to adjust the pH to 3.5 to 4, and after sufficiently stirring, a polymer flocculant is added, and this is passed through a filter. The first step of washing the dehydrated sludge with water to remove the mixed seawater salt content, and the sludge content obtained in the first step are dehydrated and dried, and then calcined in an air stream at 500 to 800 ° C. to oxidize the second A method for producing an inorganic pigment from wastewater sludge, which comprises a second step of producing an inorganic pigment containing iron oxide as a main component and containing silicon oxide and aluminum oxide, and further finely pulverizing with a pulverizer.
塩酸を添加してｐＨ３．５〜４に調整し、空気吹込みに
よる攪拌によってスラッジ中の炭酸カルシウムを溶出分
解した後、スラッジを水洗して混在している酸及び海水
塩分を除去したスラッジを脱水機で脱水する第１工程
と、第１工程で得られたスラッジを焼成炉で脱水乾燥
し、次いで同焼成炉で空気気流中５００〜８００℃で焼
成して酸化第二鉄を主成分とする酸化けい素及び酸化ア
ルミニウム含有の無機顔料を生成し、更に粉砕機で微粉
砕する第２工程よりなることを特徴とする廃水スラッジ
から無機顔料を製造する方法。2. A concentrated wastewater sludge containing iron as a main component is adjusted to pH 3.5 to 4 by adding hydrochloric acid, and calcium carbonate in the sludge is eluted and decomposed by stirring by blowing air, and then the sludge is washed with water. The first step of dehydrating the sludge from which the mixed acid and seawater salt have been removed by a dehydrator, and the sludge obtained in the first step is dehydrated and dried in a firing furnace, and then 500-500 in an air stream in the same firing furnace. Inorganic from wastewater sludge, characterized by comprising a second step of calcination at 800 ° C to produce an inorganic pigment containing silicon oxide and aluminum oxide containing ferric oxide as a main component, and further finely pulverizing with a pulverizer. A method for producing a pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15183993A JPH06191852A (en) | 1992-10-27 | 1993-06-23 | Production of inorganic pigment from waste water sludge |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-288821 | 1992-10-27 | ||
| JP28882192 | 1992-10-27 | ||
| JP15183993A JPH06191852A (en) | 1992-10-27 | 1993-06-23 | Production of inorganic pigment from waste water sludge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06191852A true JPH06191852A (en) | 1994-07-12 |
Family
ID=26480952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15183993A Pending JPH06191852A (en) | 1992-10-27 | 1993-06-23 | Production of inorganic pigment from waste water sludge |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06191852A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6379559B1 (en) | 1997-10-29 | 2002-04-30 | Hideomi Iida | Method of making sludge precipitated in a chromium plating impurity recovery electrolysis tank harmless |
| KR100855064B1 (en) * | 2007-07-05 | 2008-08-29 | 한국신발피혁연구소 | Black Pigment Composition Using Leather Waste Sludge Carbide |
| CN111055602A (en) * | 2019-12-31 | 2020-04-24 | 安徽省粤隆印刷科技有限公司 | Environment-friendly printing process with low migration volume |
| CN113816571A (en) * | 2020-06-19 | 2021-12-21 | 宝山钢铁股份有限公司 | Treatment method of cold rolling acid regeneration desilication sludge |
-
1993
- 1993-06-23 JP JP15183993A patent/JPH06191852A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6379559B1 (en) | 1997-10-29 | 2002-04-30 | Hideomi Iida | Method of making sludge precipitated in a chromium plating impurity recovery electrolysis tank harmless |
| KR100855064B1 (en) * | 2007-07-05 | 2008-08-29 | 한국신발피혁연구소 | Black Pigment Composition Using Leather Waste Sludge Carbide |
| CN111055602A (en) * | 2019-12-31 | 2020-04-24 | 安徽省粤隆印刷科技有限公司 | Environment-friendly printing process with low migration volume |
| CN111055602B (en) * | 2019-12-31 | 2021-09-10 | 安徽省粤隆印刷科技有限公司 | Environment-friendly printing process with low migration volume |
| CN113816571A (en) * | 2020-06-19 | 2021-12-21 | 宝山钢铁股份有限公司 | Treatment method of cold rolling acid regeneration desilication sludge |
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