JPH0440201A - Manufacture of aluminum sulfate crystal according to continuous crystallization process - Google Patents
Manufacture of aluminum sulfate crystal according to continuous crystallization processInfo
- Publication number
- JPH0440201A JPH0440201A JP14665390A JP14665390A JPH0440201A JP H0440201 A JPH0440201 A JP H0440201A JP 14665390 A JP14665390 A JP 14665390A JP 14665390 A JP14665390 A JP 14665390A JP H0440201 A JPH0440201 A JP H0440201A
- Authority
- JP
- Japan
- Prior art keywords
- aluminum sulfate
- crystallization
- tank
- crystallizing
- crystallization tank
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 56
- 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 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000002425 crystallisation Methods 0.000 title claims description 71
- 230000008025 crystallization Effects 0.000 title claims description 67
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 18
- 230000003028 elevating effect Effects 0.000 abstract 1
- 239000012527 feed solution Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000009738 saturating Methods 0.000 abstract 1
- 238000000502 dialysis Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000010812 mixed waste Substances 0.000 description 2
- 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 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野１
本発明は硫酸アルミニウム溶液から連続的に硫酸アルミ
ニウム結晶な晶析、分離する方法に関するもので、特に
、アルミニウム電解コンデンサー、アルミニウムサツシ
等のアルミニウムまたはアルミニウム合金を硫酸または
塩酸と硫酸の混酸で表面処理する際に発生するアルミニ
ウムを含有する廃酸液から六角板状の硫酸アルミニウム
結晶を分離すると共に回収酸を分離し、それぞれを有効
に再利用する無公害クローズドシステムの処理方法であ
って、六角板状の硫酸アルミニウム結晶を連続方式で晶
析する製造方法に係るものである。Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a method for continuously crystallizing and separating aluminum sulfate crystals from an aluminum sulfate solution. Separate hexagonal plate-shaped aluminum sulfate crystals from the aluminum-containing waste acid solution generated when surface treating aluminum alloys with sulfuric acid or a mixed acid of hydrochloric acid and sulfuric acid, separate recovered acid, and reuse each effectively. The present invention is a pollution-free closed system treatment method, and relates to a production method in which hexagonal plate-shaped aluminum sulfate crystals are continuously crystallized.
従来、硫酸アルミニウムの結晶化は、硫酸アルミニウム
溶液の粘度が高いのと準安定領域が広いために困難とさ
れていた。そのために多くの研究者はアンモニウム明パ
ン法を利用するかアルコール添加によって粘度を下げる
方法な採る方式を試みていたが、いずれも硫酸アルミニ
ウム結晶を工業的に得ることができなかった。Conventionally, crystallization of aluminum sulfate has been considered difficult due to the high viscosity of aluminum sulfate solutions and the wide metastable region. For this purpose, many researchers have tried methods such as using the ammonium light bread method or reducing the viscosity by adding alcohol, but in either case it was not possible to obtain aluminum sulfate crystals industrially.
本発明者らは先に特公昭４８−４１）５７号、特公昭４
９−２９８２１号、特公昭５１−６０３４号、特公昭５
１−６０３５号および特開平１−１５３５１７号公報で
、六角板状の硫酸アルミニウム結晶の製造方法、および
含アルミニウム廃硫酸または塩酸と硫酸との廃混合酸を
これら酸液中に含まれる硫酸アルミニウム結晶を晶析す
ることによって処理する方法を提案した。The present inventors previously published Japanese Patent Publication No. 48-41) No. 57, Japanese Patent Publication No. 48-41
No. 9-29821, Special Publication No. 51-6034, Special Publication No. 5
No. 1-6035 and JP-A No. 1-153517 disclose a method for producing hexagonal plate-shaped aluminum sulfate crystals, and aluminum-containing waste sulfuric acid or waste mixed acid of hydrochloric acid and sulfuric acid to produce aluminum sulfate crystals contained in these acid solutions. We proposed a method to treat it by crystallizing it.
上記各公報に記載の方法は、硫酸アルミニウム結晶の晶
析工程中で、結晶析出後温度上昇を与え晶へきを変化さ
せる工程を１回以上繰り返して、硫酸アルミニウム結晶
を六角板状の厚みのある結晶として母液との分離を容易
とすると共に結晶の高純度化を行ったものである。また
、前記温度上昇な晶析工程中に与える回数を減らすため
には六角板状結晶を種晶として添加することが必要であ
り、実操業にあたってより容易な方式が望まれていた。The method described in each of the above publications involves repeating the step of increasing the temperature after crystal precipitation and changing the crystal cleavage one or more times during the crystallization process of aluminum sulfate crystals to form aluminum sulfate crystals into hexagonal plate-like thick sheets. It is made into crystals that can be easily separated from the mother liquor, and the crystals are highly purified. Furthermore, in order to reduce the number of times of crystallization during the temperature-increasing crystallization step, it is necessary to add hexagonal plate-shaped crystals as seed crystals, and an easier method for actual operation has been desired.
〔発明が解決しようとする課題］
アルミニウムまたはアルミニウム合金の表面処理工場よ
り排出されるアルミニウムを含む廃硫酸、塩酸と硫酸と
の混合廃酸は、その大部分は中和処理されて廃棄されて
おり、一部が製紙工場の排水処理用として利用されてい
る程度にすぎない、しかしながら、これら廃酸液には多
量の硫酸アルミニウムが含まれていることから、硫酸ア
ルミニウムを結晶として分離すれば有効に利用できるこ
とは明らかである。しがるに、硫酸アルミニウムは上記
したように準安定領域が広いため通常の方法ではノリ状
ないし針状結晶として析出するため分離が困難であった
。また、分離が容易な六角板状結晶体を得るには、温度
上昇を晶析工程中に繰り返し与えなければならないなど
煩雑な手段が必要であった。[Problem to be solved by the invention] Most of the waste sulfuric acid containing aluminum and the mixed waste acid of hydrochloric acid and sulfuric acid discharged from factories for surface treatment of aluminum or aluminum alloys are neutralized and disposed of. However, since these waste acid solutions contain a large amount of aluminum sulfate, it would be effective to separate the aluminum sulfate as crystals. It is clear that it can be used. However, as mentioned above, aluminum sulfate has a wide metastable region, so it is difficult to separate it by conventional methods because it precipitates as glue-like or needle-like crystals. Furthermore, in order to obtain hexagonal plate-shaped crystals that are easy to separate, complicated measures such as having to repeatedly increase the temperature during the crystallization process are required.
このような状況下で取扱性、保管性、貯蔵性にすぐれて
おり、使用時の溶解性も良好である六角板状の硫酸アル
ミニウム結晶と分離酸とを回収する方法で、人手のかか
らない簡単な方法が望まれている。Under these circumstances, it is a simple method that does not require much labor to recover hexagonal plate-shaped aluminum sulfate crystals and separated acid, which are easy to handle, store, and store, and have good solubility during use. A method is desired.
本発明は、連続晶析法で温度上昇工程を特別に設けるこ
となしにクローズドシステムで操業が可能な硫酸アルミ
ニウム結晶の製造方法を提供するものである。The present invention provides a method for producing aluminum sulfate crystals that can be operated in a closed system using a continuous crystallization method without providing a special temperature raising step.
〔課題を解決するための手段］
本発明者らは硫酸アルミニウムの晶析法について鋭意検
討した結果、晶析温度を順次低くした晶析槽を２個以上
設け、第１の晶析槽のスラリーを第２の晶析槽に供給し
硫酸アルミニウム結晶を析出させるに当たり、第２の晶
析槽のスラリーの一部を第１の晶析槽に循環させること
によって六角板状の硫酸アルミニウム結晶が連続的に製
造できることを見出して本発明を完成させた。[Means for Solving the Problems] As a result of intensive studies on the crystallization method of aluminum sulfate, the present inventors have provided two or more crystallization tanks in which the crystallization temperature is successively lowered, and the slurry in the first crystallization tank is When supplying the slurry to the second crystallization tank to precipitate aluminum sulfate crystals, a part of the slurry in the second crystallization tank is circulated to the first crystallization tank to form continuous hexagonal plate-shaped aluminum sulfate crystals. The present invention was completed by discovering that it can be manufactured in a similar manner.
従って、本発明の多槽式連続晶析方式による硫酸アルミ
ニウム結晶の製造方法は、アルミニウムを含む硫酸単独
または塩酸と硫酸との混合酸液をほぼ飽和濃度に濃縮し
、該濃縮液を晶析温度に保持した第１晶析槽に供給し、
次いで第１晶析槽よりも低温とした第２晶析槽に移行さ
せて硫酸アルミニウム結晶を析出させるにあたり、第２
晶析槽中のスラリーの一部を第１晶析槽へ循環せしめる
ことを特徴とする。Therefore, the method for producing aluminum sulfate crystals by the multi-vessel continuous crystallization method of the present invention involves concentrating aluminum-containing sulfuric acid alone or a mixed acid solution of hydrochloric acid and sulfuric acid to a nearly saturated concentration, and then bringing the concentrated solution to the crystallization temperature. and supplied to the first crystallization tank held at
Next, in transferring to the second crystallization tank, which was set at a lower temperature than the first crystallization tank, to precipitate aluminum sulfate crystals, the second crystallization tank was heated.
It is characterized in that a part of the slurry in the crystallization tank is circulated to the first crystallization tank.
本発明でのアルミニウムを含む硫酸単独または塩酸と硫
酸との混合酸液（以下単に酸液という）の濃縮はどのよ
うな方式によってもよいが、その後の晶析を考えると減
圧濃縮方式が好ましい、また、晶析原液となる濃縮酸液
の飽和温度は第１晶析槽での晶析温度、および最終晶析
時のスラリー濃度を考えると６５℃〜５０℃が好ましい
。In the present invention, the sulfuric acid containing aluminum alone or the mixed acid solution of hydrochloric acid and sulfuric acid (hereinafter simply referred to as acid solution) may be concentrated by any method, but in consideration of subsequent crystallization, a vacuum concentration method is preferable. Further, the saturation temperature of the concentrated acid solution which becomes the crystallization stock solution is preferably 65°C to 50°C, considering the crystallization temperature in the first crystallization tank and the slurry concentration during the final crystallization.
したがって、第１晶析槽の液温は６５℃〜５０℃付近の
温度から選択するとよい、第１晶析槽と第２晶析槽との
温度差は２〜５℃が好ましく、これ以上の差があるとノ
リ状物質が発生し易く、操作が困難になる。また、第２
晶析槽から第１晶析槽への循環量は供給液量の２〜ｌＯ
倍が好ましく、２倍以下ではノリ状物質の発生が多く最
終の分離工程での分離が悪くなる。また、１０倍以上と
すると供給液の温度と第１晶析槽との温度差を２０〜５
０℃以上とする必要があり、これも実用化が困難となる
。もしこのバランスを破ると第１晶析槽の温度が低下す
るので、加熱操作が必要となるしノリ状物質の発生も多
くなる。Therefore, the liquid temperature in the first crystallization tank is preferably selected from a temperature around 65°C to 50°C, and the temperature difference between the first crystallization tank and the second crystallization tank is preferably 2 to 5°C, and the temperature difference above this is preferably selected. If there is a difference, a paste-like substance is likely to be generated, making operation difficult. Also, the second
The amount of circulation from the crystallization tank to the first crystallization tank is 2 to 1O of the amount of supplied liquid.
The ratio is preferably twice as much, and if it is less than 2 times, a lot of paste-like substances will be generated and the separation in the final separation step will be poor. In addition, if the temperature is 10 times or more, the temperature difference between the temperature of the supply liquid and the first crystallization tank will be 20 to 5 times.
The temperature must be 0° C. or higher, which also makes it difficult to put it into practical use. If this balance is broken, the temperature of the first crystallization tank will drop, requiring heating operations and increasing the generation of glue-like substances.
本発明で使用する循環ポンプは六角板状の結晶を破損し
ない物が好ましい、第２晶析槽と第３晶析槽の温度差は
５℃以上でもよいが余り大きいことは好ましくない。The circulation pump used in the present invention is preferably one that does not damage the hexagonal plate-shaped crystals.The temperature difference between the second crystallization tank and the third crystallization tank may be 5°C or more, but it is not preferable that it is too large.
本発明において晶析槽内での新規結晶発生量は、槽から
オーバーフローにて流出する量以上とすることが結晶成
長の点で好ましい。In the present invention, from the viewpoint of crystal growth, it is preferable that the amount of new crystals generated in the crystallization tank be equal to or greater than the amount that overflows from the tank.
得られる六角板状結晶は結晶水を含む１６水塩であるた
め、結晶成長にしたがって酸液中の水分は結晶中にとり
込まれ酸濃度は増大し、晶析を容易とする。Since the obtained hexagonal plate-shaped crystal is a 16-hydrate salt containing crystal water, as the crystal grows, water in the acid solution is incorporated into the crystal, increasing the acid concentration and facilitating crystallization.
晶析した結晶の分離は、通常の分離方法、例えば遠心分
離機、加圧フィルター等によって行うことができる。な
お、酸液中に含まれるアルミニウム以外の金属等の不純
物は結晶の表面に付着して系外に排出される。Separation of the crystallized crystals can be carried out by a conventional separation method, such as a centrifuge or a pressure filter. Note that impurities such as metals other than aluminum contained in the acid solution adhere to the surface of the crystal and are discharged from the system.
結晶分離後の酸液（濾過液）は、イオン交換膜による拡
散透析槽またはイオン交換樹脂による方法等によって遊
離酸分を回収し、残渣は必要に応じ晶析槽の前の工程に
循環させて再利用する。The free acid content of the acid solution (filtrate) after crystal separation is recovered using a diffusion dialysis tank using an ion exchange membrane or a method using an ion exchange resin, and the residue is circulated to the process before the crystallization tank as necessary. Reuse.
［実施例］
以下、本発明を実施例により説明するが、本発明はこれ
に限られるものではない。[Example] The present invention will be described below with reference to Examples, but the present invention is not limited thereto.
実施例１
アルミニウム箔を電解処理した酸洗液（Ａｌ８ ｇ／ｌ
、 ＨＣＩ ６０ｇ／ｌ 、 Ｈ，５Ｏ４２５０ｇ／
ｌ ）を１０ｇ／ｈの流量で連続的に真空濃縮工程へ仕
込み、ドレンな６Ｉ２／ｈ流出させた時、真空度３１０
Ｔｏｒ、沸点９０℃の濃縮度で濃縮液（Ａｌ ２１ ｇ
／ｌ 、 Ｈに１）９ ｇ／ｌ、ＨｚＳ０４６１０ ｇ
／ｌ ）を４β／ｈ得た。Example 1 Pickling solution for electrolytically treating aluminum foil (Al8 g/l
, HCI 60g/l, H,5O4250g/
l) was continuously fed into the vacuum concentration process at a flow rate of 10 g/h, and when drained 6I2/h, the degree of vacuum was 310.
Tor, concentrated liquid (Al 21 g
/l, H to 1) 9 g/l, HzS04610 g
/l) was obtained at 4β/h.
この濃縮液を晶析原液として、液温を晶出点近くの５３
℃に保持するように設定した第１晶析槽に供給し、次ぎ
に第１晶析槽中の結晶を含むスラリーを液温４８℃に設
定した第２晶析槽に供給し、同温度に冷却して更に結晶
を析出させた。この間、下記容量の循環ポンプで第２晶
析槽のスラリーの一部を第１晶析槽へ循環させた。その
後第３晶析槽にて最終冷却液温２５℃まで冷却した。循
環ポンプで循環させる以外の各晶析槽から晶析槽等への
スラリーの移動は、オーバーフロ一方式によった。This concentrated liquid was used as the crystallization stock solution, and the liquid temperature was adjusted to 53°C near the crystallization point.
The slurry containing the crystals in the first crystallizer was then supplied to the second crystallizer whose liquid temperature was set to 48°C, and the slurry was then heated to the same temperature. Further crystals were precipitated by cooling. During this time, a part of the slurry in the second crystallization tank was circulated to the first crystallization tank using a circulation pump having the capacity shown below. Thereafter, it was cooled to a final cooling liquid temperature of 25° C. in a third crystallization tank. The movement of the slurry from each crystallization tank to the crystallization tank, etc., other than circulation using a circulation pump, was carried out using an overflow method.
本実施例で用いた晶析装置の概略は図に示すとおり、調
整槽ｌ、真空濃縮装置２および晶析原液槽３の前調整工
程（第１工程）段階と、第１晶析槽４、第２晶析槽５お
よび循環ポンプ６の循環工程（第２工程）段階と、第３
晶析槽７、スラリー槽８および遠心分離機９の結晶分離
工程（第３工程）段階およびその後の拡散透析槽１０の
酸回収工程（第４工程）段階とからなる。なお、各装置
の仕様は、第１晶析槽ｌβ、第２晶析槽１）、第３晶析
槽３２Ｉ２、循環ポンプ１７β／ｈである。第３晶析槽
７からオーバーフローしたスラリーを貯めるスラリー槽
８は結晶の分離が遠心分離機９による回分操作であるた
めクツションタンクとして使用する。As shown in the figure, the outline of the crystallizer used in this example includes the pre-conditioning step (first step) of the adjustment tank 1, the vacuum concentrator 2, and the crystallization stock tank 3, the first crystallization tank 4, The circulation process (second process) of the second crystallization tank 5 and the circulation pump 6, and the third
It consists of a crystal separation step (third step) using a crystallization tank 7, a slurry tank 8, and a centrifugal separator 9, and a subsequent acid recovery step (fourth step) using a diffusion dialysis tank 10. The specifications of each device are a first crystallization tank lβ, a second crystallization tank 1), a third crystallization tank 32I2, and a circulation pump 17β/h. Slurry tank 8, which stores the slurry overflowing from third crystallization tank 7, is used as a cushion tank because the separation of crystals is a batch operation using centrifuge 9.
遠心分離機９からは硫酸アルミニウム結晶が０．７１
Ｋｇ／Ｈｒ得られた。また、分離された濾過液（Ａｌ
７ ｇ／ｌ、ＩＣ１２１ｇ／ｌ、Ｈ＊５０４６００ ｇ
／ｌ ）は３．５Ｊ２／ｈであった。Aluminum sulfate crystals from centrifuge 9 are 0.71
Kg/Hr was obtained. In addition, the separated filtrate (Al
7 g/l, IC121g/l, H*504600 g
/l) was 3.5 J2/h.
濾過液中の濃度アップされた遊離酸分は拡散透析槽１０
にて透析され回収される。この回収工程で回収酸（Ａｌ
０．４ ｇ／１． ＭＣＩ １９ ｇ／ｌ、 ８２Ｓ
Ｏ−４７２ｇ／ｌ ） ３．５Ｌ／ｈと透析残渣（Ａ
１６．６ ｇ／ｌ、ＭＣＩ ２ ｇ／ｌ 、 ＨａＳ
０４１２８ ｇ／ｌ ） ３．５℃／ｈを得た０回
収工程で得た透析残渣は第１工程へ循環させて使用した
。２０回循環させて繰り返し使用したが得られた硫酸ア
ルミニウム結晶に変化はなかった。The increased concentration of free acid in the filtrate is transferred to the diffusion dialysis tank 10.
It is dialyzed and collected. In this recovery process, recovered acid (Al
0.4 g/1. MCI 19 g/l, 82S
O-472g/l) 3.5L/h and dialysis residue (A
16.6 g/l, MCI 2 g/l, HaS
04128 g/l) The dialysis residue obtained in the zero recovery step, which yielded 3.5° C./h, was recycled to the first step and used. The aluminum sulfate crystals obtained did not change even after repeated use by cycling 20 times.
得られた硫酸アルミニウム結晶は付着水７％で、脱水性
のよい六角板状結晶であり、晶析時間は４９氾／ ４
Ｉ２／ｈ＝ １２．３ ｈであった。The aluminum sulfate crystals obtained were hexagonal plate-shaped crystals with 7% attached water and good dehydration properties, and the crystallization time was 49/4.
I2/h=12.3 h.
実施例２
アルミサツシの電解処理酸廃液（Ａｌ １５ｇ／ｌ、Ｈ
ｇＳＯ４２５０ｇ／ｌ ）を実施例１と同一装置にｌＯ
β／ｈの流量で仕込み、ドレンな５．２Ｉ２／ｈ流出さ
せた時、真空度２６０ Ｔａｒ、沸点９２℃の濃縮度で
濃縮液（ＡＩ ３１ ｇ／ｌ 、 Ｈ，５０４５２４ｇ
／ｌ ）の濃縮液を４１’ｈ得た。Example 2 Acid waste solution from electrolytic treatment of aluminum sash (Al 15g/l, H
gSO4250g/l) was added to the same apparatus as in Example 1.
When charged at a flow rate of β/h and drained at 5.2 I2/h, a concentrated liquid (AI 31 g/l, H, 504524 g
/l) was obtained for 41'h.
この濃縮液を晶析原液として、実施例１と同一装置で液
温を、第１晶析槽５３℃、第２晶析槽４８℃、第３晶析
槽２５℃に設定した装置に供給して、実施例１と同条件
で循環させ、分離して硫酸アルミニウム結晶１．１ Ｋ
ｇ／ｈ 、濾過液（Ａ１）４ ｇ／ｌ Ｈ，３０，
４８２ｇ／ｌ ） ４．２５１２／ｈを得た。This concentrated solution was used as a crystallization stock solution and was supplied to the same device as in Example 1, with the liquid temperature set at 53°C in the first crystallization tank, 48°C in the second crystallization tank, and 25°C in the third crystallization tank. Then, it was circulated under the same conditions as in Example 1 and separated to give aluminum sulfate crystals of 1.1 K.
g/h, filtrate (A1) 4 g/l H, 30,
482g/l) 4.2512/h was obtained.
濾過液の遊離酸分を拡散透析槽で回収して回収酸（Ａｌ
Ｏ，７ｇ／ｌ、Ｈ，ＳＧ４３３０ ｇ／ｌ ） ４
．２５Ｉ２／ｈと透析残渣（Ａｌ １３．４ ｇ／ｌ
、 Ｈ，５０４１５３ｇ／ｌ ） ４．２５ Ｉ２／
ｈを得た。The free acid content of the filtrate is collected in a diffusion dialysis tank and recovered acid (Al
O, 7g/l, H, SG4330 g/l) 4
．． 25I2/h and dialysis residue (Al 13.4 g/l
, H, 504153g/l) 4.25 I2/
I got h.
本実施例の場合も透析残渣は第１工程へ循環させ、２０
回循環させて繰り返し使用したが得られた硫酸アルミニ
ウム結晶に変化はなかった。In the case of this example as well, the dialysis residue was circulated to the first step and
Although the aluminum sulfate crystals obtained were repeatedly used by circulation, there was no change in the obtained aluminum sulfate crystals.
得られた硫酸アルミニウム結晶は付着水７％で、脱水性
のよい六角板状結晶であり、晶析時間は４１／４．８１
！、／ｈ＝１０．２ ｈであった。The aluminum sulfate crystals obtained were hexagonal plate-shaped crystals with 7% attached water and good dehydration properties, and the crystallization time was 41/4.81.
! ,/h=10.2 h.
〔発明の効果］
本発明は、多槽式連続方式によるアルミニウムを含む廃
硫酸または塩酸と硫酸との混合廃酸より六角板状の硫酸
アルミニウム結晶な晶析製造する方法で、昇温の工程を
特に設置せず、スラリー循環によってこれを行うので人
手がかからない上に装置の設置面積が少なくて済むので
実用上の効果は大である。[Effects of the Invention] The present invention is a method for crystallizing hexagonal plate-shaped aluminum sulfate crystals from aluminum-containing waste sulfuric acid or a mixed waste acid of hydrochloric acid and sulfuric acid using a multi-tank continuous method, and the process of increasing the temperature is performed. Since this is done by circulating the slurry without any special installation, it does not require much manpower and the installation area of the device is small, so it has great practical effects.
【図面の簡単な説明】 図は本発明で使用する装置の一例を示す配置図である。 図中、 ｌ ・・・ 調整槽 真空濃縮装置 晶析原液槽 第１晶析槽 ・・・ 第２晶析槽 ・・・ 循環ポンプ 第３晶析槽 ・・・ スラリー槽 遠心分離機 ・・・ 拡散透析槽[Brief explanation of drawings] The figure is a layout diagram showing an example of a device used in the present invention. In the figure, l...Adjustment tank vacuum concentrator Crystallization bulk solution tank 1st crystallization tank ...Second crystallization tank ...Circulation pump Third crystallization tank ...Slurry tank centrifuge ... Diffusion dialysis tank
Claims (2)
の混合酸液をほぼ飽和濃度に濃縮し、該濃縮液を晶析温
度に保持した第１晶析槽に供給し、次いで第１晶析槽よ
りも低温とした第２晶析槽に移行させて硫酸アルミニウ
ム結晶を析出させるにあたり、第２晶析槽中のスラリー
の一部を第１晶析槽へ循環せしめることを特徴とする多
槽式連続晶析方式による硫酸アルミニウム結晶の製造方
法。(1) Concentrate sulfuric acid alone or a mixed acid solution of hydrochloric acid and sulfuric acid containing aluminum to almost saturated concentration, supply the concentrated solution to the first crystallization tank maintained at the crystallization temperature, and then A multi-tank type characterized in that a part of the slurry in the second crystallization tank is circulated to the first crystallization tank when the aluminum sulfate crystals are precipitated in the second crystallization tank at a lower temperature than the second crystallization tank. A method for producing aluminum sulfate crystals using a continuous crystallization method.
酸を更に分離回収し、その残渣を濃縮前の工程に循環す
るクローズド化方式による請求項第１項記載の硫酸アル
ミニウム結晶の製造方法。(2) The method for producing aluminum sulfate crystals according to claim 1, which is a closed method in which the free acid in the filtrate after separating the aluminum sulfate crystals is further separated and recovered, and the residue is recycled to a step before concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2146653A JPH067882B2 (en) | 1990-06-05 | 1990-06-05 | Method for producing aluminum sulfate crystal by continuous crystallization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2146653A JPH067882B2 (en) | 1990-06-05 | 1990-06-05 | Method for producing aluminum sulfate crystal by continuous crystallization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0440201A true JPH0440201A (en) | 1992-02-10 |
| JPH067882B2 JPH067882B2 (en) | 1994-02-02 |
Family
ID=15412593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2146653A Expired - Fee Related JPH067882B2 (en) | 1990-06-05 | 1990-06-05 | Method for producing aluminum sulfate crystal by continuous crystallization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH067882B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008036545A (en) * | 2006-08-07 | 2008-02-21 | Sumitomo Chemical Co Ltd | Crystallization method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5333313A (en) * | 1976-09-10 | 1978-03-29 | Toyo Electric Mfg Co Ltd | Method of controlling a plurality of speed controllable aac motors |
| JPS5755442A (en) * | 1980-09-18 | 1982-04-02 | Fujitsu Ltd | Data input device |
-
1990
- 1990-06-05 JP JP2146653A patent/JPH067882B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5333313A (en) * | 1976-09-10 | 1978-03-29 | Toyo Electric Mfg Co Ltd | Method of controlling a plurality of speed controllable aac motors |
| JPS5755442A (en) * | 1980-09-18 | 1982-04-02 | Fujitsu Ltd | Data input device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008036545A (en) * | 2006-08-07 | 2008-02-21 | Sumitomo Chemical Co Ltd | Crystallization method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH067882B2 (en) | 1994-02-02 |
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