JPH0458415B2 - - Google Patents
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- Publication number
- JPH0458415B2 JPH0458415B2 JP24478188A JP24478188A JPH0458415B2 JP H0458415 B2 JPH0458415 B2 JP H0458415B2 JP 24478188 A JP24478188 A JP 24478188A JP 24478188 A JP24478188 A JP 24478188A JP H0458415 B2 JPH0458415 B2 JP H0458415B2
- Authority
- JP
- Japan
- Prior art keywords
- chromium hydroxide
- liquid
- chromium
- exchange resin
- water
- 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
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
〔産業上の利用分野〕
本発明は高純度水酸化クロムの製造方法に係
り、特にイオン交換樹脂を使用して不純物のきわ
めて少ない水酸化クロムの製造方法に関し、触
媒、高純度金属クロム等の製造分野に利用され
る。
〔従来の技術〕
従来の高純度水酸化クロムの製造方法は、通常
精製された硫酸クロムもしくは塩化クロムを原料
とし、その水溶液を苛性ソーダもしくはアンモニ
ア水で中和し、得られた水酸化クロムのスラリー
液から沈澱物を濾過分離した後、複数回の水洗、
濾過を繰返して水酸化クロム沈澱に付着している
Na+、NH+ 4、SO4 2-等の不純物イオンを除去す
る方法にて製造されて来た。しかし水酸化クロム
はゲル状のため難濾過性であり、水洗、濾過の繰
返しによつても不純物の除去は極めて困難であ
る。特にSO4 2-はCr（OH）ｘ・（SO4）ｙ・ZH2O
なる錯塩を形成しているものと考えられ、その錯
核に入り込んでいるために特に除去が困難である
ほか、工業的にも水洗、濾過の繰返しは、きわめ
て効率が悪い方法である。
本発明者が上記水洗、濾過の繰返しによる従来
法にて不純物の除去実験を行つた結果について説
明する、本発明者は硫酸クロム〔Cr2（SO4）3・
4H2O〕の水溶液を苛性ソーダで中和し、水酸化
クロムを生成させ、得られた水酸化クロムの沈澱
を濾過し、次に沈澱物を容積比にて沈澱物１部に
対し150部の水で懸濁して水洗、濾過を繰返して
得られた水酸化クロム中の不純物の除去状況を示
すと第１表のとおりである。
[Industrial Application Field] The present invention relates to a method for producing high-purity chromium hydroxide, and in particular to a method for producing chromium hydroxide with extremely low impurities using an ion exchange resin, and for producing catalysts, high-purity metallic chromium, etc. Used in the field. [Prior art] Conventional methods for producing high-purity chromium hydroxide usually use purified chromium sulfate or chromium chloride as raw materials, neutralize the aqueous solution with caustic soda or aqueous ammonia, and produce a slurry of chromium hydroxide. After filtering and separating the precipitate from the liquid, washing with water multiple times,
Adhered to chromium hydroxide precipitate after repeated filtration
It has been produced by a method that removes impurity ions such as Na + , NH + 4 and SO 4 2- . However, since chromium hydroxide is gel-like, it is difficult to filter, and it is extremely difficult to remove impurities even by repeated washing with water and filtration. In particular, SO 4 2- is Cr(OH)x・(SO 4 )y・ZH 2 O
It is thought to form a complex salt, which is particularly difficult to remove because it is embedded in the complex nucleus.In addition, repeated washing and filtration is an extremely inefficient method from an industrial perspective. The present inventor will explain the results of an experiment to remove impurities using the conventional method by repeating the above-mentioned water washing and filtration .
4H 2 O] is neutralized with caustic soda to produce chromium hydroxide, the resulting chromium hydroxide precipitate is filtered, and then the precipitate is mixed in a volume ratio of 150 parts to 1 part of the precipitate. Table 1 shows the removal of impurities from chromium hydroxide obtained by repeatedly suspending the suspension in water, washing with water, and filtration.
【表】
第１表より明らかな如く、不純物S4 2-の除去に
関しては中和PH値が高い方がよいが、PH値が高く
なるほど水酸化クロム中に含まれるNa含有量が
増加し、水洗によるNeイオンの除去効率が低下
する。またPH値が余り高いと過剰のアルカリによ
つて水酸化クロムが再溶解し亜クロム酸塩を生じ
るので、中和PHは９〜10が適切である。この実験
においてはPH値が10.0にて５回の水洗、濾過を繰
返すことによつてようやくNa：0.002％以下、
SO4：0.05％以下の水準に達し得ることが判明し
た。
第２表は、硫酸クロム〔Cr2（SO4）3・4H2O〕
の水溶液を苛性ソーダで中和して水酸化クロムを
生成させ、得られた水酸化クロムの沈澱を濾過
し、次いで、該沈澱物を容積比にて沈澱物１部に
対し150部の水で懸濁水洗した後濾過する操作を
繰返した場合における水酸化クロムスラリー液の
上澄液中の不純物NaおよびSO4濃度および該ス
ラリー液を濾過して得られた水酸化クロム中の不
純物Na、SO4含有量を示したものである。[Table] As is clear from Table 1, the higher the neutralization PH value is, the better the removal of the impurity S 4 2- , but the higher the PH value, the more the Na content contained in chromium hydroxide increases. The removal efficiency of Ne ions by water washing decreases. Furthermore, if the pH value is too high, chromium hydroxide will be redissolved by excess alkali to produce chromite, so a neutralization pH of 9 to 10 is appropriate. In this experiment, by repeating water washing and filtration five times at a pH value of 10.0, Na: 0.002% or less was finally achieved.
SO 4 : It was found that it could reach a level of 0.05% or less. Table 2 shows chromium sulfate [Cr 2 (SO 4 ) 3・4H 2 O]
The aqueous solution of is neutralized with caustic soda to produce chromium hydroxide, the resulting chromium hydroxide precipitate is filtered, and the precipitate is suspended in a volume ratio of 1 part of precipitate to 150 parts of water. Concentrations of impurities Na and SO 4 in the supernatant liquid of the chromium hydroxide slurry when the operation of washing with cloudy water and filtration is repeated, and impurities Na and SO 4 in the chromium hydroxide obtained by filtering the slurry. This shows the content.
高純度水酸化クロムを製造する上記従来方法
は、水酸化クロムの沈澱を懸濁、水洗、濾過を繰
返すのみで、この方法によりNa、SO4等の不純
物を除去して高純度水酸化クロムとすることが、
きわめて困難であり、かつ著しく非能率である現
状に鑑み、本発明の目的は、上記従来技術の問題
点を解決して、Na、SO4等の不純物のきわめて
少ない高純度水酸化クロムを容易な方法により得
ることのできる効果的な製造方法を提供するにあ
る。
〔問題点を解決するための手段および作用〕
本発明の要旨とするところは次の如くである。
すなわち、３価のクロム塩を原料とする高純度水
酸化クロムの製造方法において、前記３価のクロ
ム塩水溶液を苛性ソーダもしくはアンモニア水に
て中和し、得られた水酸化クロムのスラリー液か
ら沈澱物を濾過分離する工程と、前記分離した沈
澱物を水に懸濁させてスラリー液とする工程と、
前記スラリー液をイオン交換樹脂塔に通液して水
可溶性の不純物を吸着分離する工程と、を有して
成ることを特徴とする高純度水酸化クロムの製造
方法である。
しかして、前記３価のクロム塩水溶液を苛性ソ
ーダもしくはアンモニア水にて中和して水酸化ク
ロムを生成する反応の最終PHを9.0〜11.0と限定
する。
また、前記水に懸濁したスラリー液をイオン交
換樹脂塔に通液するに際し該スラリー液を先ず強
塩基性陰イオン交換樹脂塔に、続いて強酸性陽イ
オン交換樹脂塔に通液する順序にて、かつ上昇流
で通液する通液方法をも限定するものである。
本発明の詳細を添附図面を参照して説明する。
第１図は本発明による高純度水酸化クロムの製造
方法を示す模式工程図である。
本発明による高純度水酸化クロムを製造する原
料としては、通常の工業生産による硫酸クロム
〔Cr2（SO4）3・4H2O〕、塩基性硫酸クロム〔Cr
（OH）・SO4〕等の３価のクロム塩が好適である。
特に３価のクロム塩と限定する必要がなく、すべ
てのクロム塩は原料として使用可能であるが、３
価のクロム塩を使用した方が還元その他の工程を
省略できるので好ましい。
原料の硫酸クロム、塩基性硫酸クロム等の３価
のクロム塩の水溶液を苛性ソーダ、もしくはアン
モニア水にて中和して水酸化クロム〔Cr（OH）3〕
の沈澱を生成する。この工程のPHは9.0〜11.0と
限定する。かくの如くこの反応のPH値を高く限定
した理由は、先に第１表にて示した如く、PHが高
いほど水酸化クロム中に含まれるSO4含有量が少
ないが、一方PHが高くなるほど水酸化クロム中に
含まれるNa含有量が増加する傾向があるので、
双方を勘案してPHを9.0〜11.0と限定した。好ま
しくは9.5〜10.5の範囲である。得られた水酸化
クロムのスラリー液から沈澱物を濾過分離する。
この分離した沈澱物２に水を加えてスラリー液と
し、第１図で示す給液槽４に入れ攪拌機６を作動
せしめ十分攪拌しながらポンプ８によつて、先ず
Ｒ−OH型強塩基性陰イオン交換樹脂塔１０に、
続いてＲ−Ｈ型強酸性陽イオン交換樹脂塔１２
に、それぞれイオン交換樹脂塔の下部より上昇流
で通液し、処理液を受液槽１４で受ける。この操
作によつて沈澱物２中の水可溶性不純物をイオン
交換樹脂に吸着せしめる。
通常のイオン交換樹脂塔による脱塩操作は、第
１塔に陽イオン交換樹脂塔、第２塔に陰イオン交
換樹脂塔に通液し、通液は下降流で行うが、本発
明においては、全くその逆の操作を行うことを特
徴としている。その理由は、第１塔に陽イオン交
換樹脂塔を使用すると、水酸化クロムスラリー液
中のNaイオンが吸着され、水酸化クロムスラリ
ー液のPHが低下し、水酸化クロムの沈澱２が溶解
する。また下降流で通液すると、イオン交換樹脂
が圧密状態となり、水酸化クロムのスラリー液の
通液が不能となるからである。そのため、本発明
では第１塔に陰イオン交換樹脂塔を使用し、SO4
イオンを吸着除去し、第２塔の陽イオン交換樹脂
塔におけるPH低下を防止するものである。
なお、水酸化クロムスラリー液の第１塔および
第２塔のイオン交換樹脂塔への通液回数は、本発
明者の実験によれば１回だけの処理でNaおよび
SO4等の不純物が確実に除去され、Na：0.002乾
重量％以下、SO4：0.05乾重量％以下の高純度水
酸化クロムが得られることが判明した。
〔実施例〕
実施例 １
硫酸クロム〔Cr2（SO4）3・4H2O〕30ｇに水500
mlを加えて加熱溶解した。No.5B濾紙で濾過後濾
液に水300mlを加え、液量を800mlとした。次に、
この濾液をスターラーで攪拌しながら10％
NaOH水溶液を滴加しPHを10に調節し、水を加
えて総液量を１とし、更に10分間攪拌後、約30
分放置した。放置後、この液をNo.5A濾紙で吸
引濾過し、濾液は捨てる。ケークは２のビーカ
ーに移し約500mlの水を加え、スターラーで十分
攪拌しケークをよく懸濁させた後、水を加えて液
量を２とし、再び10％NaOH水溶液を滴加し
PHを10に調節した。このようにして得られた水酸
化クロムのスラリー液を第１図で示した給液槽４
に入れ、攪拌機６で攪拌しながらポンプ８を使用
して、最初にＲ−OH型強塩基性陰イオン交換樹
脂塔１０に、続いてＲ−Ｈ型強酸性陽イオン交換
樹脂塔１２に、ぞれぞれのイオン交換樹脂塔の下
部から通液速度SV15で上昇流で通液し、処理液
は受液槽１４で受けた。給液槽４の液を全部処理
した後、受液槽１４の処理液を給液槽４に移し、
再び同じ操作を繰返した。この操作を３回繰返し
て各回における給液槽４、陰イオン塔１０の出口
および受液槽１４における上澄液のPHおよび不純
物濃度、ならび水酸化クロム中の不純物量を測定
した結果は第３表に示すとおりである。
The above conventional method for producing high-purity chromium hydroxide simply involves repeating suspension, water washing, and filtration of precipitated chromium hydroxide. This method removes impurities such as Na and SO 4 and produces high-purity chromium hydroxide. What you can do is
In view of the current situation where it is extremely difficult and extremely inefficient, the purpose of the present invention is to solve the problems of the prior art described above and to easily produce high-purity chromium hydroxide with extremely low impurities such as Na and SO 4 . An object of the present invention is to provide an effective manufacturing method. [Means and effects for solving the problems] The gist of the present invention is as follows.
That is, in a method for producing high-purity chromium hydroxide using trivalent chromium salt as a raw material, the trivalent chromium salt aqueous solution is neutralized with caustic soda or aqueous ammonia, and the resulting slurry of chromium hydroxide is precipitated. a step of separating the substance by filtration; a step of suspending the separated precipitate in water to make a slurry liquid;
This is a method for producing high-purity chromium hydroxide, comprising the step of passing the slurry liquid through an ion exchange resin tower to adsorb and separate water-soluble impurities. Therefore, the final pH of the reaction for producing chromium hydroxide by neutralizing the trivalent chromium salt aqueous solution with caustic soda or aqueous ammonia is limited to 9.0 to 11.0. Further, when passing the slurry liquid suspended in water through the ion exchange resin column, the slurry liquid is first passed through the strong basic anion exchange resin column and then through the strong acid cation exchange resin column in the order of passing the slurry liquid through the ion exchange resin column. In addition, it also limits the method of passing the liquid in an upward flow. The details of the invention will be explained with reference to the accompanying drawings.
FIG. 1 is a schematic process diagram showing a method for producing high-purity chromium hydroxide according to the present invention. The raw materials for producing high-purity chromium hydroxide according to the present invention include chromium sulfate [Cr 2 (SO 4 ) 3.4H 2 O] and basic chromium sulfate [Cr
Trivalent chromium salts such as (OH).SO 4 ] are suitable.
There is no need to limit it to trivalent chromium salts; all chromium salts can be used as raw materials, but
It is preferable to use a valent chromium salt because reduction and other steps can be omitted. An aqueous solution of trivalent chromium salts such as raw chromium sulfate and basic chromium sulfate is neutralized with caustic soda or aqueous ammonia to produce chromium hydroxide [Cr(OH) 3 ].
produces a precipitate. The pH of this step is limited to 9.0 to 11.0. The reason for limiting the PH value of this reaction to such a high value is that, as shown in Table 1 above, the higher the PH, the lower the SO 4 content contained in chromium hydroxide; Since the Na content in chromium hydroxide tends to increase,
Considering both factors, the pH was limited to 9.0 to 11.0. Preferably it is in the range of 9.5 to 10.5. The precipitate is separated by filtration from the obtained slurry of chromium hydroxide.
Add water to this separated precipitate 2 to make a slurry liquid, put it into the liquid supply tank 4 shown in FIG. In the ion exchange resin tower 10,
Subsequently, the R-H type strong acidic cation exchange resin tower 12
The liquid is passed upwardly from the bottom of the ion exchange resin tower, and the treated liquid is received in the liquid receiving tank 14. Through this operation, water-soluble impurities in the precipitate 2 are adsorbed onto the ion exchange resin. In a normal desalination operation using an ion exchange resin tower, liquid is passed through the first column to the cation exchange resin column and the second column to the anion exchange resin column, and the liquid is passed in a downward flow, but in the present invention, It is characterized by performing the exact opposite operation. The reason is that when a cation exchange resin column is used in the first column, Na ions in the chromium hydroxide slurry are adsorbed, the pH of the chromium hydroxide slurry decreases, and the chromium hydroxide precipitate 2 is dissolved. . Furthermore, if the liquid is passed in a downward flow, the ion exchange resin becomes compressed, making it impossible to pass the chromium hydroxide slurry liquid through the resin. Therefore, in the present invention, an anion exchange resin column is used as the first column, and SO 4
It adsorbs and removes ions and prevents the pH from decreasing in the cation exchange resin tower of the second tower. According to the inventor's experiments, Na and Na and Na and
It was found that impurities such as SO 4 were reliably removed and high purity chromium hydroxide containing Na: 0.002% by dry weight or less and SO 4 : 0.05% by dry weight or less was obtained. [Example] Example 1 30 g of chromium sulfate [Cr 2 (SO 4 ) 3・4H 2 O] and 500 g of water
ml and heated to dissolve. After filtration with No. 5B filter paper, 300 ml of water was added to the filtrate to make a liquid volume of 800 ml. next,
While stirring this filtrate with a stirrer, 10%
Add NaOH aqueous solution dropwise to adjust the pH to 10, add water to bring the total liquid volume to 1, stir for another 10 minutes, and then adjust the pH to 10.
I left it for a minute. After standing, this liquid is suction filtered using No. 5A filter paper, and the filtrate is discarded. Transfer the cake to beaker 2, add about 500ml of water, stir thoroughly with a stirrer to suspend the cake well, then add water to make the liquid volume 2, and add dropwise 10% NaOH aqueous solution again.
The pH was adjusted to 10. The slurry liquid of chromium hydroxide thus obtained is fed to the liquid supply tank 4 shown in FIG.
using the pump 8 while stirring with the stirrer 6. The liquid was passed in an upward flow from the bottom of each ion exchange resin column at a passing rate of SV15, and the treated liquid was received in the liquid receiving tank 14. After processing all the liquid in the liquid supply tank 4, transfer the treated liquid in the liquid receiving tank 14 to the liquid supply tank 4,
The same operation was repeated again. This operation was repeated three times, and the PH and impurity concentration of the supernatant liquid in the supply tank 4, the outlet of the anion tower 10, and the receiving tank 14, and the amount of impurities in the chromium hydroxide were measured each time. As shown in the table.
【表】
第３表より明らかなとおり、１回の処理で水酸
化クロム中の不純物が
Na：0.002乾重量％以下
SO4：0.05乾重量％以下
に低減しており、Na、SO4の不純物が少くとも
１回のイオン交換樹脂塔への通液により確実に除
去され、高純度の水酸化クロムが得られることが
判明した。
実施例 ２
重クロム酸ソーダー（Na2Cr2O7）を亜硫酸ガ
スで還元して得た芒硝を含む塩基性硫酸クロム
〔Cr（OH）SO4〕30ｇを原料とし、これに水500
mlを加えて加熱溶解した。この溶液をNo.5B濾紙
で濾過後、濾液に水300mlを加え液量を800mlとし
た。次にこの濾液をスターラーで攪拌しながら10
％NaOH水溶液を滴加しPHを10に調節し、水を
加えて総液量を１とし、更に10分間攪拌後約30
分放置した。放置後、この液をNo.5A濾紙で吸
引濾過し、濾液を捨てる。ケークを２のビーカ
ーに移し、約500mlの水を加え、スターラーで十
分攪拌しケークをよく懸濁させた後、水を加えて
液量を約２とし、再び10％NaOH水溶液を滴
加しPHを10に調節した。このようにして得られた
水酸化クロムスラリー液を、第１図で示した給液
槽４に入れ、攪拌機６で攪拌しながらポンプ８を
使用して、実施例１と同様に最初にＲ−OH型塩
基性陰イオン交換樹脂塔１０に、続いてＲ−Ｈ型
強酸性陽イオン交換樹脂塔１２に、それぞれイオ
ン交換樹脂塔の下部から上昇流として通液速度
SV15で通液し、処理液は受液槽１４で受けた。
かくして給液槽４のスラリー液を全部処理した
後、受液槽１４の処理液を給液槽４に移し、PHを
10に調節して再び同一操作繰を返した、この操作
を３回繰返して各回における給液槽４、陰イオン
塔１０の出口および受液槽１４におけるそれぞれ
の上澄液のPHおよび不純物濃度、ならびに水酸化
クロム中の不純物量を測定した結果は第４表に示
すとおりである。[Table] As is clear from Table 3, impurities in chromium hydroxide are reduced to Na: 0.002% dry weight or less, SO 4 : 0.05% dry weight or less, and impurities of Na and SO 4 are reduced. It has been found that chromium hydroxide can be reliably removed by passing the liquid through the ion exchange resin column at least once, and that highly pure chromium hydroxide can be obtained. Example 2 30 g of basic chromium sulfate [Cr(OH)SO 4 ] containing mirabilite obtained by reducing sodium dichromate (Na 2 Cr 2 O 7 ) with sulfur dioxide gas was used as a raw material, and 500 g of water was added to it.
ml and heated to dissolve. After filtering this solution through No. 5B filter paper, 300 ml of water was added to the filtrate to make a liquid volume of 800 ml. Next, while stirring this filtrate with a stirrer,
% NaOH aqueous solution was added dropwise to adjust the pH to 10, water was added to bring the total liquid volume to 1, and after stirring for another 10 minutes, the pH was adjusted to 10.
I left it for a minute. After standing, this liquid is suction filtered through No. 5A filter paper, and the filtrate is discarded. Transfer the cake to the beaker No. 2, add about 500 ml of water, stir thoroughly with a stirrer to fully suspend the cake, add water to make the liquid volume about 2, and add 10% NaOH aqueous solution dropwise again to adjust the pH. was adjusted to 10. The chromium hydroxide slurry liquid thus obtained was put into the liquid supply tank 4 shown in FIG. The liquid is passed through the OH type basic anion exchange resin tower 10 and then into the R-H type strong acidic cation exchange resin tower 12 as an upward flow from the bottom of the ion exchange resin tower.
The liquid was passed through with SV15, and the treated liquid was received in the liquid receiving tank 14.
After all the slurry liquid in the liquid supply tank 4 has been treated in this way, the treated liquid in the liquid receiving tank 14 is transferred to the liquid supply tank 4, and the pH is adjusted.
10, and the same operation was repeated again. This operation was repeated three times, and the pH and impurity concentration of the supernatant liquid in each of the supply tank 4, the outlet of the anion tower 10, and the receiving tank 14 in each time, The results of measuring the amount of impurities in chromium hydroxide are shown in Table 4.
本発明による高純度水酸化クロムの製造方法
は、硫酸クロム、塩基性硫酸クロム等の３価のク
ロム塩を原料とし、その水溶液を苛性ソーダもし
くはアンモニア水にて中和し、水酸化クロムの沈
澱を生成する反応の最終PHを9.0〜11.0と限定し、
得られた水酸化クロムのスラリー液から沈澱物を
分離し、この沈澱物を水に懸濁させたスラリー液
とし、このスラリー液をイオン交換樹脂塔に通液
して、不純物を吸着除去する方法をとつたが、本
発明ではイオン交換樹脂塔に通液するに際し、先
ず強塩基性陰イオン交換樹脂塔に続いて強酸性陽
イオン交換樹脂塔に通液する順序で、かつ上昇流
で通液する方法をとつたので、次の如き効果を挙
げることができた。
(イ) この製造方法にて得られた水酸化クロムは
Na：0.002乾重量％以下
SO4：0.05乾重量％以下
の著しく不純物の少ない高純度水酸化クロムで
ある。
(ロ) 製造方法はきわめて簡単な方法で、従来の水
洗、濾過を繰返えす方法に比し著しくコストを
低減し得る。
(ハ) 特にイオン交換樹脂塔に通液する工程は、従
来法と逆の、先ず強塩基性陰イオン交換樹脂塔
に、続いて強酸性陽イオン交換樹脂塔に通液
し、かつ上昇流による方法をつとたので１回の
通液でNa、SO4等の不純物がほとんど完全に
吸着除去され目標レベルの製品を得ることがで
きた。
本発明の上記効果により、水酸化クロム触媒と
して、また焙焼することによつて高純度の酸化ク
ロム触媒として活用することができる。特に酸化
クロム触媒については、不純物を焙焼過程で除く
必要がないので、焙焼温度、焙焼時間等の条件を
自由に設定できるため、触媒活性を所望値に収め
た触媒とすることができる。
また金属クロム用酸化クロムについても、本発
明による高純度水酸化クロムから不純物の少い、
特にＳ含有量の極めて少い酸化クロムを単純な焙
焼によつて容易に、かつ経済的に製造できる。
更に、本発明による高純度水酸化クロムは各種
の酸に容易に溶解することにより、硫酸クロム、
塩化クロム、硝酸クロム、酢酸クロム、クロム明
礬等の各種の３価クロム化合物のすぐれた製造原
料としても有効に使用することができる。
The method for producing high-purity chromium hydroxide according to the present invention uses trivalent chromium salts such as chromium sulfate and basic chromium sulfate as raw materials, neutralizes the aqueous solution with caustic soda or aqueous ammonia, and removes the precipitate of chromium hydroxide. The final pH of the reaction produced is limited to 9.0 to 11.0,
A method in which the precipitate is separated from the obtained chromium hydroxide slurry liquid, the precipitate is suspended in water to form a slurry liquid, and this slurry liquid is passed through an ion exchange resin column to adsorb and remove impurities. However, in the present invention, when the liquid is passed through the ion exchange resin column, the liquid is first passed through the strong basic anion exchange resin column, then the strong acidic cation exchange resin column, and in an upward flow. By adopting this method, we were able to achieve the following effects. (a) The chromium hydroxide obtained by this production method is a high-purity chromium hydroxide with extremely few impurities, including Na: 0.002% by dry weight or less and SO 4 : 0.05% by dry weight or less. (b) The manufacturing method is extremely simple and can significantly reduce costs compared to the conventional method of repeating water washing and filtration. (c) In particular, the process of passing the liquid through the ion exchange resin tower is the reverse of the conventional method, in which the liquid is first passed through the strongly basic anion exchange resin tower and then through the strongly acidic cation exchange resin tower, and by upward flow. By using this method, impurities such as Na and SO 4 were almost completely adsorbed and removed in one pass, and a product of the target level could be obtained. Due to the above effects of the present invention, it can be utilized as a chromium hydroxide catalyst, and by roasting, it can be used as a highly purified chromium oxide catalyst. In particular, with regard to chromium oxide catalysts, since there is no need to remove impurities during the roasting process, conditions such as roasting temperature and roasting time can be set freely, making it possible to create a catalyst with catalytic activity within the desired value. . In addition, regarding chromium oxide for metal chromium, we use high-purity chromium hydroxide according to the present invention, which has less impurities.
In particular, chromium oxide with an extremely low S content can be easily and economically produced by simple roasting. Furthermore, the high-purity chromium hydroxide according to the present invention is easily dissolved in various acids, so that it can be easily dissolved into chromium sulfate, chromium sulfate,
It can also be effectively used as an excellent raw material for producing various trivalent chromium compounds such as chromium chloride, chromium nitrate, chromium acetate, and chromium alum.
第１図は本発明による高純度水酸化クロムの製
造工程を示す装置の模式配置図である。
２……水酸化クロム沈澱、４……給液槽、６…
…攪拌機、８……ポンプ、１０……陰イオン交換
樹脂塔（アニオン塔）、１２……陽イオン交換樹
脂塔（カチオン塔）、１４……受液槽。
FIG. 1 is a schematic layout diagram of an apparatus showing the manufacturing process of high-purity chromium hydroxide according to the present invention. 2...Chromium hydroxide precipitation, 4...Liquid supply tank, 6...
... Stirrer, 8 ... Pump, 10 ... Anion exchange resin tower (anion tower), 12 ... Cation exchange resin tower (cation tower), 14 ... Liquid receiving tank.
Claims (1)
ロムの製造方法において、前記３価のクロム塩水
溶液を苛性ソーダもしくはアンモニア水にて中和
し、得られた水酸化クロムのスラリー液から沈澱
物を濾過分離する工程と、前記分離した沈澱物を
水に懸濁させてスラリー液とする工程と、前記ス
ラリー液をイオン交換樹脂塔に通液して水可溶性
の不純物を吸着分離する工程と、を有して成るこ
とを特徴とする高純度水酸化クロムの製造方法。 ２ 前記３価のクロム塩水溶液を苛性ソーダもし
くはアンモニア水にて中和して水酸化クロムを生
成する反応の最終PHを9.0〜11.0とする請求項１
記載の高純度水酸化クロムの製造方法。 ３ 前記水に懸濁したスラリー液をイオン交換樹
脂塔に通液するに際し該スラリー液を先ず強塩基
性陰イオン交換樹脂塔に、続いて強酸性陽イオン
交換樹脂塔に通液する順序にて、かつ上昇流で通
液する請求項１または２記載の高純度水酸化クロ
ムの製造方法。[Claims] 1. In a method for producing high-purity chromium hydroxide using trivalent chromium salt as a raw material, the trivalent chromium salt aqueous solution is neutralized with caustic soda or aqueous ammonia, and the obtained chromium hydroxide a step of filtering and separating a precipitate from a slurry liquid, a step of suspending the separated precipitate in water to obtain a slurry liquid, and passing the slurry liquid through an ion exchange resin column to remove water-soluble impurities. A method for producing high-purity chromium hydroxide, comprising the steps of adsorption and separation. 2. Claim 1: The final pH of the reaction for producing chromium hydroxide by neutralizing the trivalent chromium salt aqueous solution with caustic soda or aqueous ammonia is 9.0 to 11.0.
The method for producing high-purity chromium hydroxide as described. 3. When passing the slurry liquid suspended in water through the ion exchange resin tower, the slurry liquid is first passed through the strong basic anion exchange resin tower and then through the strong acid cation exchange resin tower in the order 3. The method for producing high-purity chromium hydroxide according to claim 1 or 2, wherein the liquid is passed in an upward flow.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24478188A JPH0292828A (en) | 1988-09-29 | 1988-09-29 | Production of highly pure chromium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24478188A JPH0292828A (en) | 1988-09-29 | 1988-09-29 | Production of highly pure chromium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0292828A JPH0292828A (en) | 1990-04-03 |
| JPH0458415B2 true JPH0458415B2 (en) | 1992-09-17 |
Family
ID=17123827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24478188A Granted JPH0292828A (en) | 1988-09-29 | 1988-09-29 | Production of highly pure chromium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0292828A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000039860A (en) * | 1998-12-16 | 2000-07-05 | 이구택 | Preparation method of cr(oh)3 which does not contain so4^2-, cr(oh)3 prepared therefrom, and preparation method of chromium oxide which does not generate sox, using cr(oh)3 |
| JP4667084B2 (en) * | 2005-03-11 | 2011-04-06 | 硬化クローム工業株式会社 | Chromium ion replenishment method for trivalent chromium plating bath |
| CN101795973B (en) * | 2007-04-27 | 2012-07-25 | 日本化学工业株式会社 | Chromium hydroxide, method for producing the same, trivalent chromium-containing solution using the same, and chromium plating method |
| US20110168299A1 (en) * | 2008-09-05 | 2011-07-14 | Nippon Chemical Industrial Co., Ltd. | Process for producing an aqueous solution containing a source of chromium (iii) |
| CN102143916A (en) | 2008-09-05 | 2011-08-03 | 日本化学工业株式会社 | The production method of chromium hydroxide |
| CN102143914A (en) | 2008-09-05 | 2011-08-03 | 日本化学工业株式会社 | Chromium(III) carbonate and process for production of same |
-
1988
- 1988-09-29 JP JP24478188A patent/JPH0292828A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0292828A (en) | 1990-04-03 |
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