JPH0442326B2 - - Google Patents
Info
- Publication number
- JPH0442326B2 JPH0442326B2 JP2293598A JP29359890A JPH0442326B2 JP H0442326 B2 JPH0442326 B2 JP H0442326B2 JP 2293598 A JP2293598 A JP 2293598A JP 29359890 A JP29359890 A JP 29359890A JP H0442326 B2 JPH0442326 B2 JP H0442326B2
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- tank
- steam
- reaction
- temperature
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 174
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 60
- 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 claims description 44
- 239000002699 waste material Substances 0.000 claims description 32
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 239000010802 sludge Substances 0.000 claims description 24
- 238000004381 surface treatment Methods 0.000 claims description 17
- 239000012295 chemical reaction liquid Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000011282 treatment Methods 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000007793 ph indicator Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010979 pH adjustment Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000029219 regulation of pH Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
〔産業上の利用分野〕
本発明は、アルミニウム関係企業のアルマイト
処理工程の排水中から分離してくる水酸化アルミ
ニウムを主成分とするアルミニウムスラツジから
硫酸アルミニウム水溶液を連続的に合成するため
の反応温度制御用装置に関する。
〔従来の技術〕
アルマイト処理工程においては、その前処理と
して、アルミニウム素地表面についたキス等を落
としてアルミニウム表面を滑らかにするためにカ
セイソーダ液でアルミニウムをエツチングするこ
とが行なわれ、また不良アルミニウム製品を再加
工（再着色）するに際し、カセイソーダ液でアル
ミニウム材の酸化皮膜を除去することが行なわれ
る。さらに、硫酸液中でアルミニウムの陽極酸化
処理及び電解着色処理が行なわれるが、これらの
処理時にAlイオンが前記液中に溶出し、このイ
オンが隣接する水洗槽内へ持ち出される。この水
洗水は排水処理工程へ送られ、中和処理される時
に水酸化アルミウニムの白色沈澱物が生じる。
これらの廃液（スラリー）は、通常アクリルア
ミド系等の高分子凝集剤を添加して固形度の高い
フロツクを作り脱水してアルミニウムスラツジ
（以下、単にスラツジと称する）とし、次の処理
（廃棄あるいは回収）に付される。このスラツジ
は、通常、水分83〜87％、Al（OH）38〜12％、不
純物（SiO2、有機物等）６〜３％の組成からな
る。
また、アルミニウム表面処理工程においては、
アルミニウム表面の塗膜及び治具表面に付着した
塗膜を剥離する工程において硫酸水溶液が用いら
れるが、このような塗膜除去工程からは老化廃液
である廃硫酸が生じる。この廃硫酸の組成は、通
常、FreeH2SO475〜90％、Al2（SO4）32〜0.5％で
ある。
上記のようなアルミニウム表面処理工程から生
ずるスラツジ及び廃硫酸は、公害防止及び省資源
の見地から、一般に硫酸アルミニウム水溶液の合
成に利用されている。
しかしながら、硫酸アルミニウムの合成反応は
反応速度が速く、反応速度のコントロールが困難
であり、また、最終製品の硫酸アルミニウムのPH
が用途に応じて規定されることから合成液の最終
PHをこれに合致させる必要があり、このPH調整が
困難であることから、硫酸アルミニウム水溶液を
連続合成法で製造すること困難と考えられてい
た。
そこで、従来のスラツジを用いた硫酸アルミニ
ウム水溶液の合成は、専らいわゆるバツチ方式に
より行なわれており、一般に、合成器に一定量の
廃硫酸を張り込み、これに一定量のスラツジを供
給しながら加熱することにより行なわれていた。
〔発明が解決しようとする課題〕
前記従来法では、合成当初は高濃度廃硫酸の
H2SO4が主成分であるので、耐腐蝕性の優れた
材質から成る合成器が必要であり、例えばグラス
ライニング等の合成器が使用されている。しか
し、この材質は高価で修理、点検等維持管理が難
しい上に、こわれ易いという問題があると共に、
バツチ方式のため合成器が大きく、駆動電力が大
きいと共に、設備が大規模で設置面積も広いた
め、設備費が高くなり、合成器の増設等能力アツ
プが簡単にできない。さらに、バツチ方式のた
め、運転操作が繁雑で作業性が悪く、またジヤケ
ツト方式による加熱のためスケーリングにより熱
効率が下がり、ランニングコストも高くなるとい
う問題がある。
一方、アルミニウム表面処理工程における廃物
としては、前記したスラツジや廃硫酸の他に電解
液の硫酸回収工程で生じる硫酸アルミニウム（以
下、硫バンと略称する）を含有する希薄硫酸水溶
液も問題である。このような硫バン含有硫酸水溶
液は、従来はそれ程生じなかつたため廃水処理で
充分対処できていたが、近年、イオン交換樹脂分
離法、拡散透析膜分離法等電解液処理法の発達に
より、電解液処理が盛んに行なわれ、硫バン含有
硫酸水溶液も大量に発生している。例えば、イオ
ン交換樹脂分離法では、陽極酸化処理、交流着色
処理等の電解槽内の硫酸含有電解液の一部をイオ
ン交換処理し、回収された硫酸は電解槽に戻され
るが、一部の硫酸及び硫バンを含有する処理水が
生じる。また拡散透析膜分離法でも同様に電解槽
内の電解液の一部を拡散透析膜で処理して回収さ
れた硫酸は電解槽に戻されるが、一部の硫酸及び
硫バンを含有する処理水が生じる。これらの硫バ
ンを含有する希薄硫酸水溶液は、通常H2SO43〜
６％、Al2（SO4）37〜９％の組成を有し、近年の
アルミニウム表面処理品質の向上に対応して、電
解処理設備の設置割合の増大に伴ない大量に発生
しており、その処理に困窮しているのが現状であ
る。前記したバツチ方式の硫酸アルミニウム水溶
液合成法に利用することも考えられ、また本出願
人も一部利用しているが、上記硫バン含有硫酸水
溶液は希薄なため、大量に利用することは反応速
度が遅くなり、またバツチ方式のため工業化に適
さないという問題がある。
従つて、本発明の目的は、前記したような問題
点を解消し、アルミニウム表面処理工程で生成し
その処理に困窮しているスラツジ、廃硫酸及び硫
バン含有硫酸水溶液を有効に利用することによ
り、硫酸アルミニウム水溶液を連続的に合成でき
る装置、特にその反応温度制御用装置を提供する
ことにある。
本発明の他の目的は、生産性、作業性、安全性
等に優れ、比較的安価な設備費でしかも高収率で
硫酸アルミニウム水溶液を連続的に合成できる装
置、特にその反応温度制御用装置を提供すること
にある。
本発明のさらに主たる目的は、エネルギー効率
よくしかも低いランニングコストで硫酸アルミニ
ウム水溶液を連続的に合成するための反応温度制
御用装置を提供することにある。
〔課題を解決するための手段〕
本発明者は、前記目的を達成するためには、ア
ルミニウム表面処理工程で生成する水酸化アルミ
ニウムを主成分とするアルミニウムスラツジと、
前記表面処理工程における塗膜除去工程で生じる
廃硫酸と、前記表面処理工程における硫酸回収工
程で生成する硫酸アルミニウムを含有する硫酸水
溶液とを複数の第１槽〜第ｎ槽から成る反応槽へ
供給し、これらを第１槽から第ｎ槽（最終槽）ま
で順次流しながら温度80℃〜反応液の沸点の条件
で反応させると共に、前記硫酸アルミニウムを含
有する硫酸水溶液の一部を第２槽から最終槽まで
の少なくともいずれかの槽に供給し、最終槽の反
応液のPHを1.6〜2.5に調整することにより、アル
ミニウム表面処理工程で生成する副産物から硫酸
アルミニウム水溶液を連続的に製造できることを
見い出した。
上記方法においては反応液のPH調整が一つの重
要な因子になると共に、反応液の温度制御も重要
な因子になる。本発明はこの反応温度制御用装置
を提供するものである。
すなわち、本発明によれば、アルミニウム表面
処理工程で生成する水酸化アルミニウムを主成分
とするアルミニウムスラツジと、前記表面処理工
程における塗膜除去工程で生じる廃硫酸と、前記
表面処理工程における硫酸回収工程で生成する硫
酸アルミニウムを含有する硫酸水溶液をそれぞれ
連続反応させるための第１槽〜第ｎ槽から成る反
応槽と、
該反応槽から得られる反応液の沸点に近い最終
硫酸アルミニウム水溶液と、前記硫酸アルミニウ
ムを含有する硫酸水溶液とを熱交換するための第
１熱交換器と、
前記第１槽内に配設した第１スチーム管と、
該第１槽内に配設した第１温度指示調節記録計
と、
該第１温度指示調節記録計と連動して前記第１
スチーム管内の蒸気流量を調節する第１温度コン
トロールバルブと、
前記第２槽〜第ｎ槽の少なくとも１槽内に配設
した第ｎスチーム管（ｎ＝２以上）及び第ｎ温度
指示記録計（ｎ＝２以上）と、
該第ｎ温度指示記録計と連動して前記第ｎスチ
ーム管内の蒸気流量を手動又は自動にて調節する
第ｎ温度コントロールバルブ（ｎ＝２以上）とを
備えたことを特徴とするアルミニウム表面処理工
程で生成する副産物から硫酸アルミニウム水溶液
を連続的に製造するための反応温度制御用装置が
提供される。
〔発明の作用〕
前記したように、硫酸アルミニウムの合成反応
は80℃〜反応後の沸点（約100℃）、好ましくは90
℃〜約100℃の反応温度に制御しながら行なう必
要がある。
このため、本発明によれば、硫酸アルミニウム
を含有する硫酸水溶液が、まず第１熱交換器にお
いて合成後の沸点近い温度の最終硫酸アルミニウ
ム水溶液と熱交換されて加温され、次いで必要に
応じて第２熱交換器においてスチームと熱交換さ
れた後にアルミニウムスラツジ及びさらに廃硫酸
と混合され、第１反応槽内の反応混合物の温度を
高めるのに供される。
また、第１反応槽内には第１スチーム管及び第
１温度指示調節記録計が配設され、この第１スチ
ーム管に配設された第１温度コントロールバルブ
が前記第１温度指示調節記録計と連動して前記第
１スチーム管内の蒸気流量を調節し、これによつ
て第１反応槽内の混合物の温度を調節する。ま
た、第２槽〜第ｎ槽の少なくとも１槽内に第ｎス
チーム管（ｎ＝２以上）及び第ｎ温度指示記録計
（ｎ＝２以上）を配設し、この第ｎスチーム管に
配設された第ｎ温度コントロールバルブ（ｎ＝２
以上）が前記第ｎ温度指示記録計と連動して前記
第ｎスチーム管内の蒸気流量を手動又は自動にて
調節し、これによつて反応途中の混合物の温度を
調節する。
このようにして、硫酸アルミニウムの合成反応
の反応温度をエネルギー効率よく連続的に調節で
きる。
反応終了後に得られる硫酸アルミニウム合成液
は濾過、濃縮して最終製品の硫酸アルミニウムと
なるが、最終製品の性状は硫酸アルミニウム合成
液の最終PHに左右され、その用途に応じて一定の
範囲に規制される。本発明では反応液のPH調整に
前記した硫バンを含有する希薄硫酸水溶液を利用
するものである。
ところで、硫酸アルミニウムの合成反応は下式
(1)で、計算上の反応式は下式(2)で表わされる。
2Al（OH）3＋3H2SO4
→Al2（SO4）3＋6H2O (1)
AlO3＋3H2SO4
→Al2（SO4）3＋3H2O (2)
上記反応における反応速度定数及びPHの影響に
ついて、下記第１表に示す組成のスラツジ、廃硫
酸及び硫バンを含有する希薄硫酸水溶液を用いて
検討した。
[Industrial Field of Application] The present invention is a reaction method for continuously synthesizing an aqueous aluminum sulfate solution from aluminum sludge, whose main component is aluminum hydroxide, which is separated from wastewater from the alumite treatment process of an aluminum-related company. The present invention relates to a temperature control device. [Prior Art] In the alumite treatment process, as a pretreatment, the aluminum is etched with a caustic soda solution in order to remove the kisses etc. on the surface of the aluminum base material and smooth the aluminum surface. When reprocessing (recoloring) the aluminum material, the oxide film on the aluminum material is removed using a caustic soda solution. Further, aluminum is subjected to anodic oxidation treatment and electrolytic coloring treatment in the sulfuric acid solution, and during these treatments, Al ions are eluted into the solution and carried out into the adjacent washing tank. This washing water is sent to a wastewater treatment process, and when it is neutralized, a white precipitate of aluminum hydroxide is generated. These waste liquids (slurries) are usually added with polymer flocculants such as acrylamide to form highly solid flocs and dehydrated to form aluminum sludge (hereinafter simply referred to as sludge), which is then processed for the next treatment (disposal or collection). This sludge usually has a composition of 83-87% water, 8-12% Al(OH) 3 , and 6-3% impurities (SiO 2 , organic matter, etc.). In addition, in the aluminum surface treatment process,
An aqueous sulfuric acid solution is used in the process of removing the paint film on the aluminum surface and the paint film adhering to the surface of the jig, and waste sulfuric acid, which is an aging waste liquid, is generated from such a paint film removal process. The composition of this waste sulfuric acid is usually 75-90% FreeH 2 SO 4 and 2-0.5% Al 2 (SO 4 ) 3 . The sludge and waste sulfuric acid generated from the above aluminum surface treatment process are generally used to synthesize an aqueous aluminum sulfate solution from the viewpoint of pollution prevention and resource conservation. However, the synthesis reaction of aluminum sulfate has a fast reaction rate, making it difficult to control the reaction rate, and the pH of the final product aluminum sulfate.
The final value of the synthetic liquid is
It is necessary to match the pH to this value, and because this pH adjustment is difficult, it was considered difficult to produce an aqueous aluminum sulfate solution using a continuous synthesis method. Therefore, conventional synthesis of aluminum sulfate aqueous solutions using sludge is carried out exclusively by the so-called batch method, in which a certain amount of waste sulfuric acid is generally charged into a synthesizer, and a certain amount of sludge is supplied to the synthesizer while heating. It was done by this. [Problem to be solved by the invention] In the above conventional method, high concentration waste sulfuric acid is used at the beginning of synthesis.
Since H 2 SO 4 is the main component, a synthesizer made of a material with excellent corrosion resistance is required, and for example, a synthesizer with a glass lining is used. However, this material is expensive, difficult to maintain, such as repair and inspection, and is easily broken.
Due to the batch system, the synthesizer is large and requires a large amount of driving power, and the equipment is large-scale and has a large installation area, which increases the equipment cost and makes it difficult to easily increase the capacity by adding more synthesizers. Furthermore, since it is a batch method, operation is complicated and workability is poor, and heating is performed by a jacket method, which reduces thermal efficiency due to scaling and increases running costs. On the other hand, in addition to the above-mentioned sludge and waste sulfuric acid, a dilute aqueous sulfuric acid solution containing aluminum sulfate (hereinafter abbreviated as sulfuric acid) produced in the sulfuric acid recovery process of the electrolytic solution is also a problem as waste in the aluminum surface treatment process. In the past, such aqueous sulfuric acid solutions containing vanyl sulfate could be adequately dealt with by wastewater treatment because they were not produced to a large extent, but in recent years, with the development of electrolyte treatment methods such as ion exchange resin separation method and diffusion dialysis membrane separation method, electrolyte solution Processing is actively carried out, and a large amount of sulfuric acid aqueous solution containing banium sulfate is also generated. For example, in the ion-exchange resin separation method, a portion of the sulfuric acid-containing electrolyte in the electrolytic cell is subjected to ion-exchange treatment such as anodizing or alternating current coloring, and the recovered sulfuric acid is returned to the electrolytic cell. Processed water containing sulfuric acid and vanium sulfate is produced. Similarly, in the diffusion dialysis membrane separation method, a portion of the electrolyte in the electrolytic cell is treated with a diffusion dialysis membrane and the recovered sulfuric acid is returned to the electrolytic cell, but some of the treated water contains sulfuric acid and sulfur. occurs. These dilute sulfuric acid aqueous solutions containing bansulfate are usually H 2 SO 4 3~
It has a composition of 6% Al 2 (SO 4 ) 3 and 7% to 9% Al 2 (SO 4 ) 3 , and is generated in large quantities as the proportion of electrolytic treatment equipment installed has increased in response to recent improvements in the quality of aluminum surface treatment. , the current situation is that it is difficult to deal with it. It is possible to use it in the above-mentioned batch method aluminum sulfate aqueous solution synthesis method, and the present applicant has also used it in part, but since the ban sulfate-containing sulfuric acid aqueous solution is dilute, it is difficult to use a large amount due to the reaction rate. There are problems in that it is slow and is not suitable for industrialization because it is a batch method. Therefore, an object of the present invention is to solve the above-mentioned problems by effectively utilizing sludge, waste sulfuric acid, and aqueous sulfuric acid solution containing vanyl sulfate, which are generated in the aluminum surface treatment process and are difficult to dispose of. An object of the present invention is to provide an apparatus capable of continuously synthesizing an aqueous aluminum sulfate solution, particularly an apparatus for controlling the reaction temperature thereof. Another object of the present invention is to provide an apparatus that is excellent in productivity, workability, safety, etc. and capable of continuously synthesizing an aqueous aluminum sulfate solution at a high yield with a relatively low equipment cost, and in particular, an apparatus for controlling the reaction temperature thereof. Our goal is to provide the following. A further main object of the present invention is to provide a reaction temperature control device for continuously synthesizing an aqueous aluminum sulfate solution with energy efficiency and low running costs. [Means for Solving the Problems] In order to achieve the above object, the present inventors have proposed an aluminum sludge whose main component is aluminum hydroxide produced in an aluminum surface treatment step,
Supplying waste sulfuric acid generated in the coating film removal step in the surface treatment step and an aqueous sulfuric acid solution containing aluminum sulfate generated in the sulfuric acid recovery step in the surface treatment step to a reaction tank consisting of a plurality of first to nth tanks. Then, while flowing these in order from the first tank to the nth tank (final tank) to react at a temperature of 80°C to the boiling point of the reaction solution, a part of the sulfuric acid aqueous solution containing aluminum sulfate was poured from the second tank. We have discovered that it is possible to continuously produce an aqueous aluminum sulfate solution from the byproducts generated in the aluminum surface treatment process by supplying the solution to at least one of the tanks up to the final tank and adjusting the pH of the reaction solution in the final tank to 1.6 to 2.5. Ta. In the above method, pH adjustment of the reaction solution is an important factor, and temperature control of the reaction solution is also an important factor. The present invention provides a device for controlling this reaction temperature. That is, according to the present invention, aluminum sludge containing aluminum hydroxide as a main component produced in the aluminum surface treatment step, waste sulfuric acid produced in the coating film removal step in the surface treatment step, and sulfuric acid recovered in the surface treatment step a reaction tank consisting of a first tank to an nth tank for continuously reacting the sulfuric acid aqueous solution containing aluminum sulfate produced in the process; a final aluminum sulfate aqueous solution close to the boiling point of the reaction liquid obtained from the reaction tank; a first heat exchanger for exchanging heat with an aqueous sulfuric acid solution containing aluminum sulfate; a first steam pipe disposed within the first tank; and a first temperature indication adjustment disposed within the first tank. a recorder, and the first temperature control recorder in conjunction with the first temperature indication adjustment recorder;
a first temperature control valve that adjusts the flow rate of steam in the steam pipe; an n-th steam pipe (n = 2 or more) and an n-th temperature indicator ( n = 2 or more); and an nth temperature control valve (n = 2 or more) that manually or automatically adjusts the steam flow rate in the nth steam pipe in conjunction with the nth temperature indicator recorder. Provided is a reaction temperature control device for continuously producing an aqueous aluminum sulfate solution from a by-product produced in an aluminum surface treatment process, characterized by: [Operation of the invention] As mentioned above, the synthesis reaction of aluminum sulfate is carried out at a temperature of 80°C to the boiling point after the reaction (approximately 100°C), preferably 90°C.
It is necessary to carry out the reaction while controlling the reaction temperature to about 100°C. Therefore, according to the present invention, the sulfuric acid aqueous solution containing aluminum sulfate is heated by first exchanging heat with the final aluminum sulfate aqueous solution having a temperature close to the boiling point after synthesis in the first heat exchanger, and then heated as necessary. After being heat exchanged with steam in the second heat exchanger, the aluminum sludge and further mixed with waste sulfuric acid are used to raise the temperature of the reaction mixture in the first reactor. Further, a first steam pipe and a first temperature indication adjustment recorder are disposed in the first reaction tank, and a first temperature control valve disposed in the first steam pipe is connected to the first temperature indication adjustment recorder. In conjunction with this, the flow rate of steam in the first steam pipe is adjusted, thereby controlling the temperature of the mixture in the first reaction tank. Further, an n-th steam pipe (n = 2 or more) and an n-th temperature indicator recorder (n = 2 or more) are installed in at least one of the second tank to n-th tank, and the n-th steam pipe is connected to the n-th steam pipe. nth temperature control valve (n=2
The steam flow rate in the n-th steam pipe is adjusted manually or automatically in conjunction with the n-th temperature indicator recorder, thereby adjusting the temperature of the mixture during the reaction. In this way, the reaction temperature of the aluminum sulfate synthesis reaction can be continuously controlled with energy efficiency. The aluminum sulfate synthetic solution obtained after the reaction is filtered and concentrated to become the final product, aluminum sulfate. However, the properties of the final product depend on the final pH of the aluminum sulfate synthetic solution, and are regulated within a certain range depending on its use. be done. In the present invention, the above-mentioned dilute aqueous sulfuric acid solution containing sulfuric acid is used to adjust the pH of the reaction solution. By the way, the synthesis reaction of aluminum sulfate is as follows:
In (1), the calculated reaction formula is expressed by the following formula (2). 2Al(OH) 3 +3H 2 SO 4 →Al 2 (SO 4 ) 3 +6H 2 O (1) AlO 3 +3H 2 SO 4 →Al 2 (SO 4 ) 3 +3H 2 O (2) Reaction rate constant and The influence of PH was investigated using a dilute sulfuric acid aqueous solution containing sludge, waste sulfuric acid, and banyl sulfuric acid having the composition shown in Table 1 below.
以下、添附図面に示す実施例を説明しつつ、本
発明について詳細に説明する。
第１図は、本発明の多段槽式並流反応による硫
酸アルミニウム水溶液の連続合成に適する装置の
一実施例を示すフローシートであり、図中、１は
水酸化アルミニウムを主成分とするスラツジを搬
送するためのベルトコンベヤであり、２は混合
槽、３は第１層乃至第ｎ層よりなる反応層、４は
硫バンを含む希薄硫酸タンク、５は廃硫酸タンク
である。
第１図に示す反応槽は、ｎ＝５の場合を示し、
５槽から成り、第１槽R1と第２槽R2との間は水
面が溢流するように上方に突設された堰状の隔壁
８ａにより分画されており、また第２槽R2と第
３槽R3、第３槽R3と第４槽R4、第４槽R4と第５
槽R5との間は底面部に連通口を有するように上
部から懸垂された隔壁８ｂにより分画されてお
り、各槽には電動機Ｍにより回転駆動される撹拌
機９が配設されている。
スラツジはベルトコンベヤ１により混合槽２に
供給され、一方、希薄硫酸タンク４内の常温の硫
バンを含む希薄硫酸水溶液は、ポンプ１０により
供給ライン１１を経て送られ、第１熱交換器６に
おいて約100℃の生成した硫酸アルミニウム合成
液と熱交換されて約65〜70℃に加温され、次いで
第２熱交換器７において沸点のスチームと熱交換
されて約95〜100℃の高温状態にされた後、第１
供給管１２により混合槽２に、またその一部は第
２供給管１３により最終槽の前の第４槽R4に供
給される。混合槽２内のスラツジと硫バン含有硫
酸水溶液の混合物は約70〜80℃の高温状態にあ
り、撹拌機９により撹拌混合された後第１反応槽
R1に送られる。一方、廃硫酸タンク５内の廃硫
酸はポンプ１４により廃硫酸受槽１５に送られ、
該受槽１５内に配設されたスクリーン１６により
浮遊物質を除去した後、ポンプ１７により第１反
応槽R1に送られる。
反応槽３においては、第１槽R1内のスラツジ、
廃硫酸及び硫バン含有硫酸水溶液の混合物からな
る反応液は、撹拌器９により撹拌下に第１槽R1
から最終の第５槽R5まで流されながら前記反応
式(1)に従つて反応し、第５槽R5から約100℃の硫
酸アルミニウム合成液が得られ、これはポンプ１
８により生成液ライン１９から第１熱交換器６を
経て濾過精製設備（図示せず）に送られる。
次に制御系統について説明する。まず、反応液
のPHの制御について説明すると、第１槽R1及び
第２槽R2内の反応液のPHは約0.8に設定する。ス
ラツジの供給量が変動して理論供給量よりはるか
に少ない場合には、相対的に廃硫酸の供給量が多
くなり、PHが設定値即ちPH0.8より酸性側に移行
する（例えばPH0.2など）ことになるので、PH調
節が必要である。このPH調節は第２槽R2内に配
設された第１PH指示調節記録計（PHICR）２０
により行なわれ、該第１PH指示調節記録計のPH値
がPH0.8以下（強酸性側）の場合には、硫バン含
有希薄硫酸水溶液の第１供給管１２に配設された
上記記録計２０と連動する第１コントロールバル
ブ２１を閉じ、逆にPH0.8以上になると第１コン
トロールバルブ２１を開け、硫バンを含む希薄硫
酸水溶液の供給量によつて初期反応液のPHを0.8
に自動的に調節する。
通常の第１槽のPH調節は上記のとおりである
が、操業再開時等においてあるいは他の要因によ
り第１槽のPH値が設定値より大きく変動した場
合、例えばスラツジの供給量が設定値の範囲を逸
脱して多くなつたときには、当然に第１槽R1の
PH値が設定値の範囲から逸脱することになるが、
このPH値を設定値内に戻すに当り、前記した硫バ
ン含有希薄硫酸水溶液に代えて、これよりPH値が
低い（強酸性側）廃硫酸を使用してもよい。すな
わち、第１PH指示調節記録計２０のPH値がPH0.8
以下の場合には、廃硫酸受槽１５のポンプ１７を
オフにして廃硫酸の供給を止め、逆にPH0.8以上
になるとポンプ１７をオンにして、しかもその容
量を大きく（バルブを開くことにより）して廃硫
酸を第１槽R1に供給してPHを0.8に自動的に調節
する。PH値の低い廃硫酸供給量を加減することに
より、PH値が設定値内に戻る時間が硫バン含有希
薄硫酸水溶液を使用した場合に比べて早くなるの
で、特にPH値が大きく変動した場合のPH調節に有
利である。さらに、硫バン含有希薄硫酸水溶液と
廃硫酸の両方を併用してPH調節を行なうことがで
きるということも、当業者には容易に理解できる
であろう。
なお、第１PH指示調節記録計２０は第１槽R1
内に配設し、第１槽R1の流出側のPHを検出する
ようにしてもよい。反応の進行に伴ない反応液の
PHは弱酸性側に上昇するが、第５槽（最終槽）
R5内の硫酸アルミニウム合成液のPHが所定の値
（1.6〜2.5好ましくは、1.8〜2.0）以下の強酸性側
にある場合には、第５槽R5内に配設された第２
PH指示調節記録計（PHICR）２２の検出器がこ
れを検知して、硫バン含有希薄硫酸水溶液の第２
供給管１３に配設された第２コントロールバルブ
２３を閉じ、逆に所定値以上になつた場合には第
２コントロールバルブ２３を自動的に開ける。な
お、各槽に硫バン含有希薄硫酸水溶液の供給管を
接続し、各槽にPH指示調節記録計を配設し、各槽
の反応液のPHをそれぞれ前記と同様の仕様により
微調節することも可能である。いずれにしても、
反応液のPHは硫バンを含む希薄硫酸水溶液あるい
はそれと共にさらに廃硫酸の供給量の調節により
行なわれ、しかも反応液のPH値は0.8以上であり、
第１槽の反応率が約90％であつて第２槽のPH値は
上記値以下になることはないので、第１槽の材質
はSUS316JIL、第２槽以降の反応槽の材質は
SUS316L程度のステンレス鋼で充分である。
次に反応液の温度制御について説明すると、ま
ず混合槽２内のスラツジと硫バン含有希薄硫酸水
溶液の混合物の温度は、約95〜100℃の硫バン含
有希薄硫酸水溶液の供給により70〜80℃に高めら
れるが、希薄硫酸タンク４内の常温の硫バン含有
希薄硫酸水溶液は前記したように第１熱交換器６
で約65〜70℃に加温した後（温度指示記録計
（TR）２４で検出）、第２熱交換器７で約95〜
100℃に高められる。この温度は硫バン含有希薄
硫酸水溶液の供給ラインの第２熱交換器７の後に
設けた温度指示調節記録計（TRC）２５により
検知し、設定温度以下の場合にはスチーム供給管
２６に設けた上記記録計２５と連動するスチーム
コントールバルブ２７を開け、逆に設定温度以上
の場合にはしぼり、第２熱交換器７に入るスチー
ム量を調節することにより自動的に設定温度に制
御される。各反応槽へはスチーム供給管が接続さ
れており、第１槽R1内の反応液には第１スチー
ム管２８がコイル状、平板状等任意の形態で浸漬
された後廃水溝３２に導かれ、熱交換できるよう
にされており、一方、第２〜第４槽にはスチーム
が導入できるように第２スチーム管２９、第３ス
チーム管３０、第４スチーム管３１がそれぞれ接
続されている。
第１槽R1内の反応液の温度は、該槽にその検
出器が配設された第１温度指示調節記録計
（TRC）３３及び第１スチーム管２８に配設され
た上記記録計３３と連動する第１温度コントロー
ルバルブ３４により調節され、第１槽R1内の反
応液の温度が設定値以上の場合には第１温度コン
トロールバルブ３４をしぼり、設定値以下の場合
には開けて設定温度に自動的に制御される。第３
槽R3及び第５槽R5にはそれぞれ第３及び第５温
度指示記録計（TR）３５及び３６が配設されて
おり、これらの温度指示記録計３５及び３６の検
出温度に応じて第２〜第４温度コントロールバル
ブ３７〜３９を開閉して手動により調節するが、
反応液の温度調節は、各槽に温度指示調節記録計
を配設し、各スチーム管のそれぞれの温度コント
ロールバルブと連動させて自動調節することも可
能である。なお、各槽へスチームを導入して温度
を上げる方式の場合、反応液が希薄になり後の精
製工程で余分なエネルギーが必要となるため、第
１槽の反応液の温度上昇は図示するようなスチー
ム管と反応液との熱交換方式により行なうことが
好ましい。
その他、第１図中符号４０はポンプ１７の電動
機の空運転防止のための廃硫酸受槽１５の液面指
示調節計（LC）であり、ポンプ１４と連動して
廃硫酸受槽１５内の廃硫酸の液面が一定レベル以
下になつたときに自動的にポンプ１４を作動さ
せ、一定レベル以上になつたときに作動を停止さ
せる。符号４１は反応槽３の液面を制御するため
の警報器付液面指示調節計（LICA）を示し、反
応液の液面が設定値以下に下がるとコントロール
バルブ４２を自動的にしぼり、設定値以上に上が
ると開ける。符号４３は硫バンを含む希薄硫酸水
溶液の供給量を示す流量積算指示計（FIQ）であ
る。
前記した第１図に示す装置を用い、以下の条件
で硫酸アルミニウム水溶液の連続合成を行なつ
た。
合成条件
スラツジ：供給量 1429Kg／時間
組成 Al（OH）3 9.5wt％
不純物 3.7 〃
H2O 86.8 〃
廃硫酸：供給量 72.6／時間
組成 Free−H2SO4 90.0wt％
Al2（SO4）3 0.6 〃
比重 1.804（25℃）
硫バン含有硫酸水溶液：供給量3112／時間
組成 Free−H2SO4 5.3wt％
Al2（SO4）3 8.9 〃
H2O 残部
比重 1.134（12℃）
反応温度：99〜100℃
第１槽PH：約0.8
第５槽PH：約2.0
その結果、約98％の反応率で硫酸アルミニウム
水溶液が連続的に合成できた。得られた硫酸アル
ミニウム水溶液を、使用合成液量300ml、濾過温
度20℃、濾過方法−真空方法（助剤なし）、濾過
面積95cm2、使用濾紙−東洋濾紙＃２、濾過圧力
（真空度）120Torrの条件で濾過テストを行なつ
たが、濾過性に問題はなかつた。
第２図は本発明の硫酸アルミニウム水溶液連続
合成装置の他の実施例を示し、第１図に示す装置
の変更個所のみを示し、第２図に示されていない
設備（例えば、廃硫酸タンク、熱交換器等）、計
装（例えばPH指示調節記録計等）及び供給ライン
（例えば硫バン含有硫酸水溶液供給ライン等）は
第１図に示すものと同じである。
第１図に示す装置では混合槽２が設けられてい
るが、これは、既存の設備をそのまま利用した場
合にはベルトコンベアの下に反応槽を設置できな
いために設けられたものであり、混合槽を設ける
ことは必ずしも必要でなく、第２図に示すように
前記原料の三物質を直接、反応槽３の第１槽R1
に投入することができる。第２図では、スラツジ
はポンプで給送されてスラツジ供給管４４により
供給されるが、第１図に示すようにベルトコンベ
アで供給してよいことはもちろんである。第２図
に示す反応槽３では、各槽R1〜R5は堰状の隔壁
８ａ及び上部から懸垂された隔壁８ｂにより交互
に分画され、反応液のシヨートパスが防止される
ように工夫されている。この反応液のシヨートパ
スをさらに有効に防止するために、第３図に示す
ように槽内にじやま板５３を設けてもよい。
また、第１槽R1内の反応液の温度制御は、前
記第１図に示す装置と同様に第１温度指示調節記
録計３３により第１スチーム管２８に設けた第１
温度コントロールバルブ３４の調節により自動的
に行なわれるが、第２〜第４槽R2〜R4内の反応
液の温度制御も、上記と同様にそれぞれ各槽に配
設された第２〜第４温度指示調節記録計（TRC）
４５〜４７及び第２〜第４スチーム管２９〜３１
に設けた第２〜第４温度コントロールバルブ４８
〜５０により自動的に行なわれる。さらに、各槽
の温度制御は、それぞれ各槽内の反応液とこれに
浸漬されたコイル状もしくは平板状の第２〜第４
スチーム管との熱交換方式により行なわれる。
第２図に示す装置においては、合成液排出用の
ポンプ１８の吐出側から第１槽R1に戻る合成液
循環ライン５２が設けられている。これにより、
合成液のPHを示す第２PH指示調節記録計
（PHICR）２２（第１図参照）が異常値（適正範
囲外）を示した時に手動バルブ５１を開き、硫酸
アルミニウム水溶液を第１槽R1に戻すことがで
きる。この循環ラインは第１図に示す装置にも設
けてよいことはもちろんである。
〔発明の効果〕
以上の説明から明らかなように、本発明の反応
温度制御方式によれば、反応槽とは別個の熱交換
方式による加熱のため、スケーリングによる熱効
率の低下がほとんどなく、また自動的に温度制御
ができる。従つて、連続運転の効果と相俟つて、
エネルギー効率がよくまた駆動消費電力も少な
く、ランニングコストが低いという利点が得られ
る。
その他、本発明に係る硫酸アルミニウム水溶液
の製造方法によれば以下のような効果、利点が得
られる。
ａ） 硫酸アルミニウム水溶液の合成を多段槽式
並流反応による連続反応により行なうため、従
来のバツチ式に比べて製造能力が大幅に向上
し、従つて設備も小さなものでよく、設置面積
が狭く屋内設置も可能である。
ｂ） また反応系のPH調節に硫バンを含む希薄硫
酸水溶液を用いるため、PH調節が容易となり、
また一槽目のFree−H2SO4濃度が低く各槽の
反応液のPHを0.8〜2.5に保持することにより、
反応槽の材質としてステンレス鋼が使用でき
る。従つて、反応槽の溶接修理、点検が可能で
維持管理が容易で設備費も安価になると共に、
連続運転により、バルブ、ポンプ、撹拌機等の
切換運転もなく、反応液のPHを連続制御でき、
自動化が容易で作業性、安全性の面でも効果が
ある。
ｃ） さらに、反応速度定数の実験データを基に
小規模の改良で能力アツプが可能である。
本発明の他の利点、効果は前記した説明から明
らかであろう。
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments shown in the accompanying drawings. FIG. 1 is a flow sheet showing an example of an apparatus suitable for continuous synthesis of an aqueous aluminum sulfate solution by a multi-stage co-current reaction of the present invention. 2 is a mixing tank, 3 is a reaction layer consisting of the first layer to the nth layer, 4 is a dilute sulfuric acid tank containing hydrogen sulfur, and 5 is a waste sulfuric acid tank. The reaction tank shown in FIG. 1 shows the case where n=5,
Consisting of 5 tanks, the first tank R 1 and the second tank R 2 are separated by a weir-like bulkhead 8a that protrudes upward so that the water surface overflows, and the second tank R 2 and 3rd tank R 3 , 3rd tank R 3 and 4th tank R 4 , 4th tank R 4 and 5th tank
The tank R5 is separated by a partition wall 8b suspended from the top so as to have a communication port at the bottom, and each tank is provided with an agitator 9 that is rotationally driven by an electric motor M. . The sludge is supplied to a mixing tank 2 by a belt conveyor 1, while a dilute sulfuric acid aqueous solution containing sulfuric acid at room temperature in a dilute sulfuric acid tank 4 is sent via a supply line 11 by a pump 10, and is fed to a first heat exchanger 6. It is heat exchanged with the generated aluminum sulfate synthetic liquid at about 100°C and heated to about 65 to 70°C, and then heat exchanged with steam at the boiling point in the second heat exchanger 7 to reach a high temperature state of about 95 to 100°C. After the first
A supply pipe 12 supplies the mixture to the mixing tank 2, and a part of it is supplied to the fourth tank R 4 before the final tank by a second supply pipe 13. The mixture of the sludge and the aqueous sulfuric acid solution containing vanyl sulfate in the mixing tank 2 is at a high temperature of about 70 to 80°C, and after being stirred and mixed by the stirrer 9, it is transferred to the first reaction tank.
Sent to R1 . On the other hand, the waste sulfuric acid in the waste sulfuric acid tank 5 is sent to the waste sulfuric acid receiving tank 15 by the pump 14.
After removing suspended solids by a screen 16 disposed in the receiving tank 15, the suspended solids are sent to the first reaction tank R1 by a pump 17. In the reaction tank 3, the sludge in the first tank R1 ,
The reaction solution consisting of a mixture of waste sulfuric acid and a sulfuric acid aqueous solution containing banium sulfuric acid is stirred by a stirrer 9 and transferred to the first tank R1 .
The aluminum sulfate synthetic solution at about 100°C is obtained from the fifth tank R5 , which is fed to the pump 1.
8, the product liquid is sent from the product line 19 through the first heat exchanger 6 to a filtration and purification facility (not shown). Next, the control system will be explained. First, to explain the control of the PH of the reaction liquid, the PH of the reaction liquid in the first tank R 1 and the second tank R 2 is set to about 0.8. If the sludge supply amount fluctuates and is much lower than the theoretical supply amount, the amount of waste sulfuric acid supplied will be relatively large, and the PH will shift to the acidic side from the set value of PH 0.8 (for example, PH 0.2). etc.), so PH adjustment is necessary. This PH adjustment is carried out by the first PH indicator control recorder (PHICR) 20 installed in the second tank R2.
When the PH value of the first PH indicating adjustment recorder is PH0.8 or less (strongly acidic side), the recorder 20 disposed in the first supply pipe 12 of the dilute sulfuric acid aqueous solution containing vanium sulfate Close the first control valve 21 that is interlocked with the pH value, and open the first control valve 21 when the pH reaches 0.8 or higher to lower the pH of the initial reaction solution to 0.8 depending on the amount of dilute sulfuric acid aqueous solution containing hydrogen sulfur.
automatically adjusts to The normal PH adjustment of the first tank is as described above, but if the PH value of the first tank fluctuates more than the set value due to restarting operations or other factors, for example, the sludge supply amount may be lower than the set value. When the number exceeds the range, it is natural that the first tank R1
Although the PH value will deviate from the set value range,
In order to return the PH value to within the set value, waste sulfuric acid having a lower PH value (strongly acidic side) may be used instead of the above-mentioned dilute aqueous sulfuric acid solution containing vanyl sulfur. That is, the PH value of the first PH indicator adjustment recorder 20 is PH0.8.
In the following cases, the pump 17 of the waste sulfuric acid receiving tank 15 is turned off to stop the supply of waste sulfuric acid, and conversely, when the pH reaches 0.8 or higher, the pump 17 is turned on and its capacity is increased (by opening the valve). ) and supply waste sulfuric acid to the first tank R1 and automatically adjust the pH to 0.8. By adjusting the supply amount of waste sulfuric acid with a low PH value, the time for the PH value to return to within the set value will be faster than when using a dilute sulfuric acid aqueous solution containing vanium sulfur, so it will be especially effective when the PH value fluctuates greatly. It is advantageous for PH regulation. Furthermore, those skilled in the art will easily understand that pH adjustment can be carried out by using both the dilute aqueous sulfuric acid solution containing vanyl sulfuric acid and waste sulfuric acid in combination. Note that the first PH indicator adjustment recorder 20 is connected to the first tank R1.
Alternatively, the pH on the outflow side of the first tank R1 may be detected. As the reaction progresses, the reaction solution
The PH increases to the weakly acidic side, but in the 5th tank (final tank)
If the pH of the aluminum sulfate synthetic solution in R 5 is on the strongly acidic side below a predetermined value (1.6 to 2.5, preferably 1.8 to 2.0 ), the second
The detector of the PH indicator control recorder (PHICR) 22 detects this, and the second
The second control valve 23 disposed in the supply pipe 13 is closed, and conversely, when the value exceeds a predetermined value, the second control valve 23 is automatically opened. In addition, a supply pipe for a dilute aqueous sulfuric acid solution containing vanyl sulfate should be connected to each tank, a PH indicator adjustment recorder should be installed in each tank, and the PH of the reaction solution in each tank should be finely adjusted according to the same specifications as above. is also possible. In any case,
The pH of the reaction solution is controlled by adjusting the supply amount of a dilute aqueous sulfuric acid solution containing vanyl sulfuric acid or waste sulfuric acid, and the pH value of the reaction solution is 0.8 or more.
Since the reaction rate of the first tank is approximately 90% and the PH value of the second tank will never be lower than the above value, the material of the first tank is SUS316JIL, and the materials of the reaction tanks after the second tank are
Stainless steel of about SUS316L is sufficient. Next, to explain the temperature control of the reaction solution, firstly, the temperature of the mixture of the sludge and the dilute aqueous sulfuric acid solution containing vane sulfate in the mixing tank 2 is controlled to 70 to 80 °C by supplying the dilute aqueous solution of sulfuric acid containing vane sulfate at about 95 to 100 °C. However, as described above, the room temperature dilute sulfuric acid aqueous solution containing vanyl sulfuric acid in the dilute sulfuric acid tank 4 is transferred to the first heat exchanger 6.
After heating to about 65 to 70℃ (detected by temperature indicator recorder (TR) 24), the second heat exchanger 7 heated to about 95 to 70℃.
Raised to 100℃. This temperature is detected by a temperature indicating control recorder (TRC) 25 installed after the second heat exchanger 7 in the supply line of the dilute sulfuric acid aqueous solution containing vanyl sulfate. The steam control valve 27 linked to the recorder 25 is opened, and conversely, when the temperature is higher than the set temperature, the steam control valve 27 is closed, and the amount of steam entering the second heat exchanger 7 is adjusted, thereby automatically controlling the temperature to the set temperature. A steam supply pipe is connected to each reaction tank, and the first steam pipe 28 is immersed in the reaction liquid in the first tank R 1 in an arbitrary shape such as a coil shape or a flat plate shape, and then is led to a waste water groove 32. On the other hand, a second steam pipe 29, a third steam pipe 30, and a fourth steam pipe 31 are respectively connected to the second to fourth tanks so that steam can be introduced thereto. . The temperature of the reaction liquid in the first tank R 1 is determined by the first temperature indication control recorder (TRC) 33 whose detector is installed in the tank and the recorder 33 installed in the first steam pipe 28. When the temperature of the reaction liquid in the first tank R1 is above the set value, the first temperature control valve 34 is closed, and when it is below the set value, it is opened. Automatically controlled to set temperature. Third
A third and a fifth temperature recorder (TR) 35 and 36 are installed in the tank R 3 and the fifth tank R 5 , respectively. It is manually adjusted by opening and closing the second to fourth temperature control valves 37 to 39.
The temperature of the reaction solution can also be automatically adjusted by disposing a temperature indicating control recorder in each tank and linking it with the temperature control valve of each steam tube. In addition, in the case of introducing steam into each tank to raise the temperature, the reaction liquid becomes diluted and extra energy is required in the subsequent purification process, so the temperature rise of the reaction liquid in the first tank is as shown in the diagram. It is preferable to use a heat exchange method between a steam tube and a reaction solution. In addition, reference numeral 40 in FIG. 1 is a liquid level indicating controller (LC) of the waste sulfuric acid receiving tank 15 to prevent the motor of the pump 17 from running dry. When the liquid level falls below a certain level, the pump 14 is automatically operated, and when the liquid level exceeds a certain level, the pump 14 is stopped. Reference numeral 41 indicates a liquid level indicating controller (LICA) with an alarm for controlling the liquid level in the reaction tank 3. When the liquid level of the reaction liquid falls below a set value, the control valve 42 is automatically throttled and the setting is performed. It opens when it rises above the value. Reference numeral 43 is a flow rate integration indicator (FIQ) that indicates the supply amount of the dilute aqueous sulfuric acid solution containing hydrogen sulfur. Using the apparatus shown in FIG. 1 described above, continuous synthesis of an aqueous aluminum sulfate solution was carried out under the following conditions. Synthesis conditions Sludge: Supply amount 1429Kg/hour Composition Al (OH) 3 9.5wt% Impurities 3.7 〃 H 2 O 86.8 〃 Waste sulfuric acid: Supply amount 72.6/hour Composition Free−H 2 SO 4 90.0wt% Al 2 (SO 4 ) 3 0.6 〃 Specific gravity 1.804 (25℃) Aqueous sulfuric acid solution containing vanyl sulfate: Supply rate 3112/hour Composition Free−H 2 SO 4 5.3wt% Al 2 (SO 4 ) 3 8.9 〃 H 2 O Balance Specific gravity 1.134 (12℃) Reaction Temperature: 99-100°C First tank PH: about 0.8 Fifth tank PH: about 2.0 As a result, an aqueous aluminum sulfate solution could be continuously synthesized with a reaction rate of about 98%. The obtained aluminum sulfate aqueous solution was mixed with a synthetic liquid volume of 300 ml, filtration temperature of 20°C, filtration method - vacuum method (no auxiliary agent), filtration area of 95 cm 2 , filter paper used - Toyo Roshi #2, filtration pressure (degree of vacuum) of 120 Torr. A filtration test was conducted under these conditions, and there were no problems with filtration. FIG. 2 shows another embodiment of the apparatus for continuously synthesizing an aqueous aluminum sulfate solution of the present invention, showing only the changes to the apparatus shown in FIG. 1, and equipment not shown in FIG. 2 (for example, a waste sulfuric acid tank, (heat exchanger, etc.), instrumentation (for example, PH indicator adjustment recorder, etc.), and supply lines (for example, a vane sulfate-containing sulfuric acid aqueous solution supply line, etc.) are the same as those shown in FIG. The device shown in Figure 1 is equipped with a mixing tank 2, but this was installed because it would not be possible to install a reaction tank under the belt conveyor if the existing equipment was used as is. It is not necessarily necessary to provide a tank, and as shown in FIG .
can be put into. In FIG. 2, the sludge is fed by a pump and supplied through the sludge supply pipe 44, but it goes without saying that the sludge may be supplied by a belt conveyor as shown in FIG. In the reaction tank 3 shown in FIG. 2, each tank R 1 to R 5 is divided alternately by a weir-like partition wall 8 a and a partition wall 8 b suspended from the upper part, and is designed to prevent the reaction liquid from being shot. ing. In order to more effectively prevent the reaction solution from being shot, a barrier plate 53 may be provided in the tank as shown in FIG. 3. Further, the temperature of the reaction liquid in the first tank R 1 is controlled by a first temperature indication adjustment recorder 33, which is installed in the first steam pipe 28, as in the device shown in FIG.
Although this is automatically performed by adjusting the temperature control valve 34, the temperature control of the reaction liquid in the second to fourth tanks R 2 to R 4 is also performed by adjusting the temperature of the reaction liquid in the second to fourth tanks R 2 to R 4 , respectively. 4 Temperature indication control recorder (TRC)
45 to 47 and second to fourth steam pipes 29 to 31
The second to fourth temperature control valves 48 provided in
~50 is automatically performed. Furthermore, the temperature control of each tank is controlled by controlling the reaction liquid in each tank and the coil-shaped or flat plate-shaped coils immersed in this.
This is done by heat exchange with a steam pipe. In the apparatus shown in FIG. 2, a synthetic liquid circulation line 52 is provided which returns from the discharge side of the synthetic liquid discharge pump 18 to the first tank R1 . This results in
When the second PH indicator control recorder (PHICR) 22 (see Figure 1) indicating the PH of the synthetic solution shows an abnormal value (outside the appropriate range), the manual valve 51 is opened and the aluminum sulfate aqueous solution is poured into the first tank R1 . It can be returned. Of course, this circulation line may also be provided in the apparatus shown in FIG. [Effects of the Invention] As is clear from the above explanation, according to the reaction temperature control method of the present invention, heating is performed by a heat exchange method separate from the reaction tank, so there is almost no decrease in thermal efficiency due to scaling, and automatic Temperature control is possible. Therefore, combined with the effect of continuous operation,
It has the advantages of high energy efficiency, low driving power consumption, and low running costs. In addition, the method for producing an aqueous aluminum sulfate solution according to the present invention provides the following effects and advantages. a) Since the aluminum sulfate aqueous solution is synthesized by a continuous reaction using a multi-stage parallel flow reaction, the production capacity is greatly improved compared to the conventional batch method. Installation is also possible. b) In addition, since a dilute aqueous sulfuric acid solution containing vanyl sulfate is used to adjust the pH of the reaction system, the pH can be adjusted easily.
In addition, the Free-H 2 SO 4 concentration in the first tank is low and the pH of the reaction solution in each tank is maintained at 0.8 to 2.5.
Stainless steel can be used as the material for the reaction tank. Therefore, welding repair and inspection of the reaction tank is possible, maintenance is easy, equipment costs are low, and
Continuous operation allows continuous control of the PH of the reaction solution without switching valves, pumps, stirrers, etc.
It is easy to automate and is effective in terms of workability and safety. c) Furthermore, capacity can be increased by small-scale improvements based on experimental data on reaction rate constants. Other advantages and effects of the present invention will be apparent from the foregoing description.
第１図は本発明の硫酸アルミニウム水溶液の連
続合成に適する装置の一実施例を示すフローシー
ト、第２図は他の実施例を示す部分フローシー
ト、第３図は本発明による反応槽の他の例を示す
部分断面図である。
２は混合槽、３は反応槽、４は硫バンを含む希
薄硫酸タンク、５は廃硫酸タンク、６は第１熱交
換器、７は第２熱交換器、８ａ，８ｂは隔壁、１
２は第１供給管、１３は第２供給管、２０は第１
PH指示調節記録計、２１は第１コントロールバル
ブ、２２は第２PH指示調節記録計、２３は第２コ
ントロールバルブ、２６はスチーム供給管、２８
は第１スチーム管、３３は第１温度指示調節記録
計、３４は第１温度コントロールバルブ、５３は
じやま板。
FIG. 1 is a flow sheet showing one embodiment of an apparatus suitable for continuous synthesis of an aqueous aluminum sulfate solution according to the present invention, FIG. 2 is a partial flow sheet showing another embodiment, and FIG. It is a partial sectional view showing an example. 2 is a mixing tank, 3 is a reaction tank, 4 is a dilute sulfuric acid tank containing van sulfur, 5 is a waste sulfuric acid tank, 6 is a first heat exchanger, 7 is a second heat exchanger, 8a and 8b are partition walls, 1
2 is the first supply pipe, 13 is the second supply pipe, 20 is the first supply pipe.
PH indication adjustment recorder, 21 is a first control valve, 22 is a second PH indication adjustment recorder, 23 is a second control valve, 26 is a steam supply pipe, 28
33 is a first temperature indication adjustment recorder, 34 is a first temperature control valve, and 53 is a board.
Claims (1)
アルミニウムを主成分とするアルミニウムスラツ
ジと、前記表面処理工程における塗膜除去工程で
生じる廃硫酸と、前記表面処理工程における硫酸
回収工程で生成する硫酸アルミニウムを含有する
硫酸水溶液をそれぞれ連続反応させるための第１
槽〜第ｎ槽から成る反応槽と、 該反応槽から得られる反応液の沸点に近い最終
硫酸アルミニウム水溶液と前記硫酸アルミニウム
を含有する硫酸水溶液とを熱交換するための第１
熱交換器と、 前記第１槽内に配設した第１スチーム管と、 該第１槽内に配設した第１温度指示調節記録計
と、 該第１温度指示調節記録計と連動して前記第１
スチーム管内の蒸気流量を調節する第１温度コン
トロールバルブと、 前記第２槽〜第ｎ槽の少なくとも１槽内に配設
した第ｎスチーム管（ｎ＝２以上）及び第ｎ温度
指示記録計（ｎ＝２以上）と、 該第ｎ温度指示記録計と連動して前記第ｎスチ
ーム管内の蒸気流量を手動又は自動にて調節する
第ｎ温度コントロールバルブ（ｎ＝２以上）とを
備えたことを特徴とするアルミニウム表面処理工
程で生成する副産物から硫酸アルミニウム水溶液
を連続的に製造するための反応温度制御用装置。 ２ 硫酸アルミニウム含有硫酸水溶液の供給ライ
ンにおいて前記第１熱交換器の後にさらにスチー
ムと熱交換するための第２熱交換器を設けたこと
を特徴とする特許請求の範囲第１項に記載の装
置。 ３ 前記硫酸アルミニウム含有硫酸水溶液の供給
ラインの前記第２熱交換器の後に温度指示調節記
録計を設け、該記録計と連動して第２熱交換器へ
のスチーム供給量を調節するスチームコントロー
ルバルブを第２熱交換器へのスチーム供給管に設
けたことを特徴とする特許請求の範囲第２項に記
載の装置。[Claims] 1. Aluminum sludge containing aluminum hydroxide as a main component produced in an aluminum surface treatment step, waste sulfuric acid produced in a coating film removal step in the surface treatment step, and a sulfuric acid recovery step in the surface treatment step. The first step is to continuously react the sulfuric acid aqueous solution containing aluminum sulfate produced in
A first reactor for exchanging heat between the final aqueous aluminum sulfate solution, which is close to the boiling point of the reaction liquid obtained from the reactor, and the aqueous sulfuric acid solution containing aluminum sulfate.
a heat exchanger, a first steam pipe disposed in the first tank, a first temperature indication adjustment recorder disposed in the first tank, and interlocking with the first temperature indication adjustment recorder. Said first
a first temperature control valve that adjusts the flow rate of steam in the steam pipe; an n-th steam pipe (n = 2 or more) and an n-th temperature indicator ( n = 2 or more); and an nth temperature control valve (n = 2 or more) that manually or automatically adjusts the steam flow rate in the nth steam pipe in conjunction with the nth temperature indicator recorder. A reaction temperature control device for continuously producing an aqueous aluminum sulfate solution from a byproduct produced in an aluminum surface treatment process, characterized by: 2. The apparatus according to claim 1, wherein a second heat exchanger for further heat exchange with steam is provided after the first heat exchanger in the supply line of the aluminum sulfate-containing sulfuric acid aqueous solution. . 3 A steam control valve that is provided with a temperature indication adjustment recorder after the second heat exchanger in the supply line of the aluminum sulfate-containing sulfuric acid aqueous solution, and that adjusts the amount of steam supplied to the second heat exchanger in conjunction with the recorder. 3. The apparatus according to claim 2, wherein the steam supply pipe to the second heat exchanger is provided with a steam supply pipe.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29359890A JPH03164426A (en) | 1990-11-01 | 1990-11-01 | Reaction temperature controller for continuously producing aqueous aluminum sulfate solution from aluminum hydroxide sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29359890A JPH03164426A (en) | 1990-11-01 | 1990-11-01 | Reaction temperature controller for continuously producing aqueous aluminum sulfate solution from aluminum hydroxide sludge |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61110473A Division JPS62270416A (en) | 1986-05-16 | 1986-05-16 | Method for continuously synthesizing aqueous solution of aluminum sulfate from aluminum hydroxide sludge and device thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03164426A JPH03164426A (en) | 1991-07-16 |
| JPH0442326B2 true JPH0442326B2 (en) | 1992-07-13 |
Family
ID=17796790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29359890A Granted JPH03164426A (en) | 1990-11-01 | 1990-11-01 | Reaction temperature controller for continuously producing aqueous aluminum sulfate solution from aluminum hydroxide sludge |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03164426A (en) |
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| JP2012219002A (en) * | 2011-04-13 | 2012-11-12 | Asahi Kagaku Kogyo Co Ltd | Method of manufacturing aluminum sulfate |
| US11034588B2 (en) | 2018-07-13 | 2021-06-15 | Chameleon Industries, Inc. | Method of preparing aluminum sulfate |
| US10954135B2 (en) * | 2018-07-13 | 2021-03-23 | Chameleon Industries, Inc. | System and method of preparing aluminum sulfate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5347236A (en) * | 1976-10-12 | 1978-04-27 | Fujitsu Ltd | Driving circuit for gas discharge panel |
| JPS5460235A (en) * | 1977-10-22 | 1979-05-15 | Showa Denko Kk | Treatment of electrolytic waste acid in electrolytic oxidation treatment of aluminium plate and moldings |
-
1990
- 1990-11-01 JP JP29359890A patent/JPH03164426A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5347236A (en) * | 1976-10-12 | 1978-04-27 | Fujitsu Ltd | Driving circuit for gas discharge panel |
| JPS5460235A (en) * | 1977-10-22 | 1979-05-15 | Showa Denko Kk | Treatment of electrolytic waste acid in electrolytic oxidation treatment of aluminium plate and moldings |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103101948A (en) * | 2011-11-15 | 2013-05-15 | 沈阳铝镁设计研究院有限公司 | Heating method for sulfuric acid leaching of aluminum-containing material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03164426A (en) | 1991-07-16 |
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