JPH06100307A - Method for purifying phosphoric acid solution - Google Patents
Method for purifying phosphoric acid solutionInfo
- Publication number
- JPH06100307A JPH06100307A JP25282492A JP25282492A JPH06100307A JP H06100307 A JPH06100307 A JP H06100307A JP 25282492 A JP25282492 A JP 25282492A JP 25282492 A JP25282492 A JP 25282492A JP H06100307 A JPH06100307 A JP H06100307A
- Authority
- JP
- Japan
- Prior art keywords
- sulfide
- phosphoric acid
- acid solution
- arsenic
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は不純な燐酸液の精製法に
関するものであり、とくに、硫化物沈澱法による砒素除
去方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying an impure phosphoric acid solution, and more particularly to a method for removing arsenic by a sulfide precipitation method.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】燐酸の
製造方法には公知の通り、乾式法と湿式法がある。湿式
燐酸は乾式燐酸に比して安価であるが、一方、燐鉱石中
の種々の不純物が可溶化して含まれるため、純度が低
く、このため工業用途に必要とされる純度まで精製する
多くの方法が提示され、とくに、砒素のような有害不純
物の濃度を食品添加用として要求されるレベルまで下げ
る方法として硫化物沈澱法、溶媒抽出法、イオン交換法
等が知られている。2. Description of the Related Art As is well known, a method for producing phosphoric acid includes a dry method and a wet method. Wet phosphoric acid is cheaper than dry phosphoric acid, but on the other hand, various impurities in phosphate rock are solubilized and contained, so the purity is low. Therefore, it is often purified to the purity required for industrial use. In particular, sulfide precipitation method, solvent extraction method, ion exchange method and the like are known as methods for reducing the concentration of harmful impurities such as arsenic to a level required for food addition.
【０００３】しかし溶媒抽出、イオン交換のような方法
は工程および装置を複雑にし処理コストが高くなるので
一般的ではない。代表的な方法である可溶性硫化物を用
いた硫化物沈澱法は簡易な方法であるが、一方、湿式燐
酸のような不純な燐酸液を精製しても得られる砒素濃度
は０．０５重量ｐｐｍ程度が限界とされ、かつ、砒素濃
度０．０５重量ｐｐｍ程度を得るには相当量の可溶性硫
化物の添加が必要なため、砒素除去をした処理液中に含
有する硫化水素の除害設備の増強化およびコストを高く
するという技術的欠点がある。However, methods such as solvent extraction and ion exchange are not common because they complicate the process and equipment and increase the processing cost. The sulfide precipitation method using soluble sulfide, which is a typical method, is a simple method, while the arsenic concentration obtained by purifying an impure phosphoric acid solution such as wet phosphoric acid is 0.05 wt ppm. However, the amount of soluble sulfide must be added to obtain an arsenic concentration of about 0.05 wt ppm. Therefore, equipment for removing hydrogen sulfide contained in the treatment liquid from which arsenic has been removed must be removed. There are technical drawbacks of enhancement and high cost.
【０００４】本発明はこの硫化物沈澱法による不純な燐
酸液中の砒素の除去方法において、砒素濃度０．０５重
量ｐｐｍ以下が容易に得られ、かつ、可溶性硫化物の添
加量を低減させうる簡易な方法を提供することを目的と
するものである。According to the present invention, in the method for removing arsenic in an impure phosphoric acid solution by the sulfide precipitation method, an arsenic concentration of 0.05 ppm by weight or less can be easily obtained, and the amount of soluble sulfide added can be reduced. The purpose is to provide a simple method.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、これの課
題を解決するために硫化物沈澱法による湿式燐酸のよう
な不純な燐酸液からの砒素除去法について検討し、砒素
濃度０．０５重量ｐｐｍ以下の燐酸液が容易に得られ、
かつ可溶性硫化物の添加量を低減させうる簡易な方法を
見出した。In order to solve the above problems, the present inventors have studied a method of removing arsenic from an impure phosphoric acid solution such as wet phosphoric acid by a sulfide precipitation method, and found that the arsenic concentration was 0. A phosphoric acid solution of less than 05 ppm by weight can be easily obtained,
Moreover, a simple method that can reduce the amount of soluble sulfide added was found.
【０００６】即ち、本発明は不純な燐酸液にキレート樹
脂を添加した後、硫化水素または可溶性硫化物を加えて
硫化物を沈澱をさせ、該硫化物沈澱を分離することを特
徴とするものである。That is, the present invention is characterized in that after adding a chelating resin to an impure phosphoric acid solution, hydrogen sulfide or soluble sulfide is added to precipitate sulfide, and the sulfide precipitate is separated. is there.
【０００７】本発明における不純な燐酸液は燐鉱石の鉱
酸分解で得られる湿式燐酸や、湿式燐酸に脱硫酸や脱弗
素のようなある種の予備精製を行ったもの、金属表面処
理等から副生する副生燐酸等、砒素を単独にあるいは他
の不純物と共に含有する燐酸水溶液を意味する。The impure phosphoric acid solution used in the present invention includes wet phosphoric acid obtained by decomposing phosphate rock with mineral acid, wet phosphoric acid which has been subjected to some preliminary purification such as desulfurization and defluorination, and metal surface treatment. It means a phosphoric acid aqueous solution containing arsenic alone or together with other impurities such as by-product phosphoric acid produced as a by-product.
【０００８】一方、本発明で使用されるキレート樹脂
は、市販のポリスチレン系キレート樹脂が好適に使用で
き、例えば、レバチットＴＰ−２０７、ＴＰ−２０８、
ＴＰ−２１４、ＯＣ−１０２６、ＯＣ−１０６０（独、
バイエル社製）、ダイヤイオンＣＲ−１０、ＣＲ−２０
（三菱化成社製）、アンバーライトＩＲＣ−７１８（米
国、ロームアンドハース社製）等の重金属イオンに対し
て選択吸着性を示すものである。On the other hand, as the chelate resin used in the present invention, a commercially available polystyrene-based chelate resin can be preferably used. For example, Levatit TP-207, TP-208,
TP-214, OC-1026, OC-1060 (Germany,
(Made by Bayer), Diaion CR-10, CR-20
(Manufactured by Mitsubishi Kasei Co., Ltd.), Amberlite IRC-718 (manufactured by Rohm and Haas Co., USA), and the like, exhibiting selective adsorption to heavy metal ions.
【０００９】キレート樹脂の添加量は、燐酸液中の砒素
を含めた不純物の含有量にもよるが、通常燐酸液に対す
る重量比で約５００ｐｐｍ以上のキレート樹脂が必要で
あり、好ましくは６００ｐｐｍから８００ｐｐｍの範囲
で用いるとよい。５００ｐｐｍ未満の添加量では従来の
硫化物沈澱法に比し、硫化水素または可溶性硫化物の添
加量を少量にして砒素濃度を低下せしめることができる
が、砒素濃度０．０５重量ｐｐｍ以下までには至らな
い。また、キレート樹脂の添加量が８００ｐｐｍを越え
ることは砒素濃度０．０５重量ｐｐｍ以下を充分満足さ
せることはもちろんのこと、より効果的な結果を示すが
不経済につながるという不都合が生じる。The amount of the chelate resin added depends on the content of impurities including arsenic in the phosphoric acid solution, but usually the chelate resin is required to be about 500 ppm or more by weight ratio to the phosphoric acid solution, preferably 600 to 800 ppm. It is good to use in the range of. When the amount added is less than 500 ppm, the amount of hydrogen sulfide or soluble sulfide added can be reduced and the arsenic concentration can be reduced as compared with the conventional sulfide precipitation method. I can't reach it. Further, if the addition amount of the chelate resin exceeds 800 ppm, it goes without saying that the arsenic concentration of 0.05 wt ppm or less is sufficiently satisfied, and more effective results are shown, but this is uneconomical.
【００１０】又、本発明で用いるキレート樹脂の大きさ
は特に限定するものではないが、粉砕して用いることが
より好ましい。The size of the chelate resin used in the present invention is not particularly limited, but it is more preferable to use it after crushing.
【００１１】燐酸液にキレート樹脂を添加した後、硫化
水素または可溶性硫化物を加えて硫化物を沈澱させる。
本発明でいう可溶性硫化物とは、酸性条件下で硫化水素
を供給しうるものであり、例えば、硫化ソーダ、水硫化
ソーダ、等のものである。After the chelate resin is added to the phosphoric acid solution, hydrogen sulfide or soluble sulfide is added to precipitate the sulfide.
The soluble sulfide as referred to in the present invention is one that can supply hydrogen sulfide under acidic conditions, and is, for example, sodium sulfide, sodium hydrosulfide, or the like.
【００１２】硫化水素または可溶性硫化物の添加量は燐
酸液中の砒素に対し当量以上必要とし、湿式燐酸のよう
に硫黄イオンと反応して不溶性硫化物を生成する砒素以
外の不純物が共存する場合は、それらに対する当量を考
慮して添加量を定める。When hydrogen sulfide or soluble sulfide must be added in an amount equal to or more than the amount of arsenic in the phosphoric acid solution, and impurities other than arsenic that react with sulfur ions to form insoluble sulfide, such as wet phosphoric acid, coexist. Determines the addition amount in consideration of the equivalent amount to them.
【００１３】本発明による前述のキレート樹脂を添加し
た燐酸液に対して、硫化水素または可溶性硫化物の添加
量を明確に述べることはできないものの、例えば、後述
の実施例から明らかな通り従来法に対し大幅な削減をし
ても脱砒素率の向上が示される。Although the amount of hydrogen sulfide or soluble sulfide added to the phosphoric acid solution to which the above-mentioned chelate resin according to the present invention has been added cannot be clearly stated, for example, as will be apparent from the examples described below, the conventional method is used. On the other hand, even with a large reduction, the improvement of the arsenic removal rate is shown.
【００１４】次に、キレート樹脂を添加した後、硫化水
素または可溶性硫化物との反応で生成する硫化物沈澱
は、一般に固液分離で使用される真空濾過機、プレス濾
過機または遠心分離機等従来法で用いられるもので容易
に分離除去される。Next, after adding the chelating resin, the sulfide precipitate formed by the reaction with hydrogen sulfide or soluble sulfide is a vacuum filter, a press filter or a centrifuge which is generally used for solid-liquid separation. It is used in the conventional method and is easily separated and removed.
【００１５】[0015]
【作 用】本発明によれば、従来技術の硫化物沈澱法に
よった湿式燐酸等不純な燐酸液中の砒素の除去方法では
事実上困難であった砒素濃度０．０５重量ｐｐｍ以下の
処理液が容易に得られ、かつ、硫化水素または可溶性硫
化物の添加量を低減させうる簡易で有益な方法が達成で
きる。[Operation] According to the present invention, a treatment with an arsenic concentration of 0.05 ppm by weight or less, which was practically difficult by the prior art method for removing arsenic from impure phosphoric acid solution such as wet phosphoric acid by the sulfide precipitation method. A liquid can be easily obtained, and a simple and useful method capable of reducing the amount of hydrogen sulfide or soluble sulfide added can be achieved.
【００１６】その理由は必ずしも明らかではないが、燐
酸液に対するキレート樹脂の添加量から見ても重金属イ
オンの選択補集機能は極わずかなものであり、この重金
属イオンの選択補集機能とは別に燐酸液と硫化水素また
は可溶性硫化物との反応における硫化物沈澱の生成に対
し、ある種の触媒作用の働きが考えられ結果的に硫化物
沈澱の促進および安定化につながることが推測される。Although the reason for this is not clear, the selective collection and collection function of heavy metal ions is extremely small in view of the amount of the chelate resin added to the phosphoric acid solution, and in addition to this selective collection and collection function of heavy metal ions. It is speculated that some kind of catalytic action may be considered for the formation of sulfide precipitates in the reaction of phosphoric acid solution with hydrogen sulfide or soluble sulfides, resulting in promotion and stabilization of sulfide precipitations.
【００１７】[0017]
【実施例】以下に実施例で本発明を詳細に説明する。
尚、以下において濃度はすべて重量基準である。EXAMPLES The present invention will be described in detail below with reference to examples.
In the following, all concentrations are based on weight.
【００１８】実施例１ Ｐ2 Ｏ5 濃度が５６．５％で、Ａｓ１５ｐｐｍを含む温
度４０℃の湿式燐酸５００ｇにキレート樹脂としてレバ
チットＴＰ−２１４（独、バイエル社製）の粉砕品を燐
酸液に対する重量比で５００ｐｐｍ添加した後、この燐
酸液の入った５００ｍｌポリ製容器内に濃度２５％の水
硫化ソーダ水溶液１．０ｇを入れた１０ｍｌ容器を貼付
し、密栓の後５分間の振盪による反応を行い速やかに真
空濾過器で濾過をしたところＰ2 Ｏ5 濃度が５６．０
％、Ａｓ０．０３ｐｐｍの濾液を得た。Example 1 500 g of wet phosphoric acid having a P 2 O 5 concentration of 56.5% and As of 15 ppm and a temperature of 40 ° C. was ground into a phosphoric acid solution of Levatit TP-214 (manufactured by Bayer, Germany) as a chelating resin. After adding 500 ppm in a weight ratio, a 10 ml container containing 1.0 g of a sodium hydrosulfide solution having a concentration of 25% was attached to a 500 ml poly container containing this phosphoric acid solution, and the reaction was performed by shaking for 5 minutes after sealing. Then, it was immediately filtered with a vacuum filter to find that the P 2 O 5 concentration was 56.0.
%, As 0.03 ppm of filtrate was obtained.
【００１９】比較例１〜６ 実施例１においてキレート樹脂を添加することなしに、
水硫化ソーダの添加量を表１に示すように変更した以外
は実施例１と同様にした。それぞれの濃度２５％の水硫
化ソーダ水溶液の添加量、濾液のＰ2 Ｏ5 濃度とＡｓ濃
度の結果を表１に示す。この結果からキレート樹脂の添
加がなければ、得られる砒素濃度は０．０５ｐｐｍが限
界であり、更に、水硫化ソーダの添加量を増加させて
も、砒素濃度０．０５ｐｐｍ以下にすることは困難なこ
とが示される。Comparative Examples 1 to 6 Without adding a chelating resin in Example 1,
Same as Example 1 except that the addition amount of sodium hydrosulfide was changed as shown in Table 1. Table 1 shows the results of the addition amount of each aqueous solution of sodium hydrosulfide having a concentration of 25%, the P 2 O 5 concentration and the As concentration of the filtrate. From these results, the arsenic concentration obtained without addition of the chelating resin is limited to 0.05 ppm, and it is difficult to reduce the arsenic concentration to 0.05 ppm or less even if the amount of sodium hydrosulfide added is increased. Is shown.
【００２０】[0020]
【表１】 [Table 1]
【００２１】比較例７ レバチットＴＰ−２１４を添加した後、水硫化ソーダ水
溶液を加えることなしに５分間の振盪をした以外は実施
例１と全く同様にした。その結果、濾液はＰ2Ｏ5 濃度
が５６．４％、Ａｓ１５ｐｐｍであり、砒素の除去がな
されていないものであった。Comparative Example 7 The same procedure as in Example 1 was carried out except that the Levatit TP-214 was added and then shaken for 5 minutes without adding the aqueous solution of sodium hydrosulfide. As a result, the filtrate had a P 2 O 5 concentration of 56.4% and As of 15 ppm, indicating that arsenic was not removed.
【００２２】実施例２〜６ キレート樹脂の添加量を表２のように変更した以外は実
施例１と全く同様に実施した。結果を表２に示す（キレ
ート樹脂の添加量は燐酸液に対する重量比で表す）。Examples 2 to 6 The same procedure as in Example 1 was carried out except that the addition amount of the chelate resin was changed as shown in Table 2. The results are shown in Table 2 (the addition amount of the chelate resin is represented by the weight ratio to the phosphoric acid solution).
【００２３】[0023]
【表２】 [Table 2]
【００２４】実施例７〜１１ 表３に掲げるキレート樹脂を使用する以外は、実施例１
と全く同様の操作を行った。結果を表３に示す。濾液中
の砒素濃度は全て０．０５重量ｐｐｍ以下を満足するも
のであった。Examples 7-11 Example 1 except that the chelating resins listed in Table 3 are used.
The same operation was performed. The results are shown in Table 3. The arsenic concentration in the filtrate all satisfied 0.05 ppm by weight or less.
【００２５】[0025]
【表３】 [Table 3]
【００２６】[0026]
【発明の効果】本発明によれば、湿式燐酸等不純な燐酸
液の可溶性硫化物を用いた硫化物沈澱法による砒素除去
において、従来技術では達成されなかった砒素濃度０．
０５重量ｐｐｍ以下の燐酸が容易に得られる有利な方法
が達成される。According to the present invention, in the arsenic removal by the sulfide precipitation method using the soluble sulfide of impure phosphoric acid liquid such as wet phosphoric acid, the arsenic concentration of 0.
An advantageous method is achieved in which less than 05 ppm by weight of phosphoric acid is easily obtained.
【００２７】即ち、不純な燐酸液の可溶性硫化物のみの
添加による硫化物沈澱法の比較例１〜６は、可溶性硫化
物の添加量の増加を行っても得られる燐酸中のの砒素濃
度は０．０５重量ｐｐｍ以下の確保が出来ない。また比
較例７において硫化物沈澱法の利用なくしてはキレート
樹脂の添加だけでは、その添加量が燐酸液に対する重量
比で５００ｐｐｍとした場合、砒素の除去が全くなされ
ない。これに対し、本発明による実施例より砒素濃度
０．０５重量ｐｐｍ以下の処理液が容易に得られる硫化
物沈澱法であることが明らかであり、また従来の硫化物
沈澱法に比して可溶性硫化物の添加量を減少せしめられ
ることにより、砒素除去処理液中の脱硫化水素工程の簡
素化およびコストの低減にもつながるため、本発明の意
義は大きく極めて有益な発明である。That is, in Comparative Examples 1 to 6 of the sulfide precipitation method by adding only the soluble sulfide of the impure phosphoric acid solution, the arsenic concentration in phosphoric acid obtained by increasing the addition amount of the soluble sulfide is It cannot secure 0.05 wtppm or less. Further, in Comparative Example 7, without using the sulfide precipitation method, arsenic is not removed at all when the addition amount of the chelate resin is 500 ppm by weight ratio with respect to the phosphoric acid solution. On the other hand, according to the example of the present invention, it is clear that the treatment liquid having an arsenic concentration of 0.05 ppm by weight or less can be easily obtained, and it is more soluble than the conventional sulfide precipitation method. Since the addition amount of sulfide can be reduced, it also leads to simplification of the desulfurization step in the arsenic removal treatment liquid and reduction of cost, so the present invention has a great significance and is a very useful invention.
Claims (1)
化水素または可溶性硫化物を加えて硫化物を沈澱させ、
該硫化物沈澱を分離することを特徴とする燐酸液の精製
法。1. A chelating resin is added to a phosphoric acid solution, and then hydrogen sulfide or soluble sulfide is added to precipitate the sulfide,
A method for purifying a phosphoric acid solution, which comprises separating the sulfide precipitate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25282492A JPH06100307A (en) | 1992-09-22 | 1992-09-22 | Method for purifying phosphoric acid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25282492A JPH06100307A (en) | 1992-09-22 | 1992-09-22 | Method for purifying phosphoric acid solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06100307A true JPH06100307A (en) | 1994-04-12 |
Family
ID=17242722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25282492A Pending JPH06100307A (en) | 1992-09-22 | 1992-09-22 | Method for purifying phosphoric acid solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06100307A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6861039B1 (en) | 1998-12-28 | 2005-03-01 | Toyo Boeski Kabushiki Kaisha | Method for purification of phosphoric acid high purity polyphosphoric acid |
| CN103979510A (en) * | 2014-04-25 | 2014-08-13 | 防城港博森化工有限公司 | Dearsenization method in production of phosphoric acid |
| CN114455558A (en) * | 2022-03-21 | 2022-05-10 | 东华工程科技股份有限公司 | Arsenic-containing phosphoric acid deep arsenic removal system |
-
1992
- 1992-09-22 JP JP25282492A patent/JPH06100307A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6861039B1 (en) | 1998-12-28 | 2005-03-01 | Toyo Boeski Kabushiki Kaisha | Method for purification of phosphoric acid high purity polyphosphoric acid |
| CN103979510A (en) * | 2014-04-25 | 2014-08-13 | 防城港博森化工有限公司 | Dearsenization method in production of phosphoric acid |
| CN114455558A (en) * | 2022-03-21 | 2022-05-10 | 东华工程科技股份有限公司 | Arsenic-containing phosphoric acid deep arsenic removal system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4233274A (en) | Method of extracting and recovering mercury from gases | |
| US6113868A (en) | Process for treating tungstate solutions to reduce molybdenum impurity and other impurity content | |
| US5023059A (en) | Recovery of metal values and hydrofluoric acid from tantalum and columbium waste sludge | |
| US4601890A (en) | Process for purifying molybdenum trioxide | |
| US4124459A (en) | Process for removing mercury from brine sludges | |
| US4374810A (en) | Recovery of fluorine from pond water of wet process phosphoric acid plants and recycling of defluorinated water | |
| JPH06100307A (en) | Method for purifying phosphoric acid solution | |
| US4514365A (en) | Process for recovering a uranium-containing concentrate and purified phosphoric acid from a wet process phosphoric acid containing uranium | |
| US4311679A (en) | Treatment of sodium tungstate leach liquor containing dissolved silica, phosphorus, and fluorine impurities | |
| US3685964A (en) | Purification of alkali phosphate solution | |
| US5711929A (en) | Purification of elemental sulphur | |
| US4428911A (en) | Method of precipitating uranium peroxide | |
| US3529932A (en) | Process for removing titanium from titanium-containing phosphoric acid | |
| RU2179194C2 (en) | Method of hydrometallurgy preparation of zinc oxide | |
| US4147757A (en) | Method for producing ammonium phosphate which is substantially free of arsenic | |
| JP3503116B2 (en) | Manufacturing method of high concentration free hydroxylamine aqueous solution | |
| US5403571A (en) | Purification of elemental sulphur | |
| US4330509A (en) | Separation of zirconium and uranium | |
| US4448755A (en) | Method for removal of tin from ammonium tungstates | |
| US3259456A (en) | Process for producing basic beryllium material of high purity | |
| JPS6353121B2 (en) | ||
| US3138637A (en) | Process for recovering ethylenediamine-tetraacetic acid (edta) from copper-edta-ion exchange effluent solutions | |
| CN109179617B (en) | Phosphorus removing agent and preparation method and use method thereof | |
| CA2173271C (en) | Purification of elemental sulphur | |
| US4552729A (en) | Method for removing tin from sodium tungstate solution |