JP3832533B2 - Method for producing ammonium persulfate - Google Patents
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- JP3832533B2 JP3832533B2 JP09470098A JP9470098A JP3832533B2 JP 3832533 B2 JP3832533 B2 JP 3832533B2 JP 09470098 A JP09470098 A JP 09470098A JP 9470098 A JP9470098 A JP 9470098A JP 3832533 B2 JP3832533 B2 JP 3832533B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、過硫酸アンモニウムの製造方法に関する。過硫酸アンモニウムはポリ塩化ビニルや、ポリアクリロニトリルの重合開始剤として、或いはプリント配線板処理剤として広く工業的に用いられている。
【０００２】
【従来の技術】
過硫酸アンモニウムの一般的な製造方法としては、硫酸及び硫酸アンモニウムを含有した水溶液、即ち硫酸水素アンモニウム水溶液を原料とした電解製法が知られている。この方法では、硫酸水素アンモニウムを原料とし過硫酸アンモニウムを電解法によって製造し、生成した過硫酸アンモニウムを真空晶析・遠心分離等により濃縮・分離・乾燥し、製品化している。この時、結晶を含有していた溶液（通常晶析母液と呼ばれる）は、陰極の生成液と混合され、陽極原料として使用される。
【０００３】
例えば、特開昭５５−３４７００号公報には、プロトン、アルカリ金属イオンまたはアンモニウムイオンを伴った硫酸イオンの水溶液を隔膜電解槽中で陽極酸化することによる過硫酸アルカリ塩またはアンモニウム塩の製造方法が記載されているが、この方法では、最終的な電流効率は約８０％にとどまり経済的な製法ではない。また、特開昭５７−１９８２７５号公報には硫酸水素アンモニウムと電解促進剤を原料とする過硫酸アンモニウムの製造方法が記載されているが、この方法でも電流効率は約８０％であり経済的に有利な方法とは言えない。
【０００４】
【発明が解決しようとする課題】
本発明は、従来技術に述べられた過硫酸アンモニウムの製造方法に於ける問題点を解決し、且つ工業的に有利な方法で過硫酸アンモニウムを製造する方法を提供するものである。
【０００５】
【課題を解決するための手段】
本発明者らは、これらの欠点を克服するため鋭意研究を行った結果、陽極原料の硫酸イオンとして硫酸アンモニウムのみを用いることにより過硫酸アンモニウム製造時の電流効率が著しく向上することを見出し、本発明を完成させるに至った。すなわち、本発明は、硫酸アンモニウムを陽極原料として用い、電解することにより過硫酸アンモニウムを製造する方法において、陽極原料の硫酸イオンとして硫酸アンモニウムのみを用いることを特徴とする過硫酸アンモニウムの製造方法に関するものである。
【０００６】
【発明の実施の形態】
本発明の電解工程は、陽極原料として、硫酸アンモニウム３０〜４４重量％、好ましくは硫酸アンモニウム４０〜４４重量％の水溶液を用いる。この陽極原料は、必要量の分極剤を含むが、分極剤としては、チオシアン酸塩、シアン化物、シアン酸塩、フッ化物などが用いられる。陰極原料として、０〜３５重量％の濃度の硫酸アンモニウムを含有する１０〜８０重量％の硫酸水溶液が用いられる。上述した濃度範囲以外では、低い電流効率しか得られず、得策ではない。
【０００７】
電解槽は、アルミナ隔膜等で仕切られた広く工業的に用いられている箱型電槽、または、イオン交換膜等で仕切られたフィルタープレス型電槽でも良い。陽極は、好ましくは白金であるが炭素電極等の化学的に耐性を持つ材料も用いることができる。陰極は、鉛或いはジルコニウムが好ましいが、ステンレス等酸耐性のある金属電極も用いることができる。陽極の電流密度は、少なくとも４０Ａ／ｄｍ2 である。電解槽内温度は、１５〜４０℃である。これより低いと溶液中の塩類が析出する恐れがあり、また、溶液の温度が高くなるほど塩類の溶解度は上昇するが、高温では生成した過硫酸塩の加水分解反応が起こりやすく好ましくない。
【０００８】
電解後の陽極液は、濃縮晶析される。濃縮晶析処理する時の晶析槽は、広く一般に使用される晶析槽が用いられる。晶析温度は、１５〜６０℃好ましくは２０〜５０℃である。これ以下の温度では、コンデンサー部の温度が低くなり過ぎ経済的に得策ではなくなるし、これ以上の温度では、過硫酸アンモニウムが分解し、結果的に低収率となる。晶析圧力は、先の温度範囲に於いて、水が沸騰するような圧力が適用される。晶析後の過硫酸アンモニウム含有スラリーは、遠心分離器等の固液分離器により結晶と晶析母液とに分離される。得られた結晶は、粉体乾燥機を用いて乾燥・製品化される。分離された晶析母液及び陰極生成液は、アンモニアにより中和された後、電解原料として再利用される。
【０００９】
【実施例】
以下に実施例を挙げて本発明を更に詳しく説明するが、本発明はこれらの実施例に限定されるものではない。尚、実施例中の電流効率は（生成した過硫酸イオン（ｍｏｌ）×２）／通電量（Ｆ）×１００％で表され、単位通電量当たりに生成した過硫酸イオンの割合を表す。また、電解電圧は、電極間の電位差であり、濃度の表示は全て重量％である。
【００１０】
実施例１
電解槽は、透明塩化ビニル製を使用した。槽の陽極室と陰極室はシリコーンゴムシール剤を用いて固定した多孔質中性アルミナ隔膜板で仕切った。各室には、バッファータンク兼冷却タンクを設け、バッファータンクから電解室へチューブポンプにより送液を行い、電解室出口よりバッファータンクへの液戻りは、オーバーフローにより行った。バッファータンク内には、ガラス冷却管を挿入し冷却水を循環させた。陽極は、幅１．８ｃｍ×長さ１６ｃｍ（面積２８．８ｃｍ2 ）の白金箔２枚を用いた。陰極は、鉛板を用いた。陽極と陰極は隔膜よりそれぞれ約０．５ｃｍ離してセットした。電解用の直流は、可変整流器より得た。
【００１１】
陽極原料１３９５．２ｇは、硫酸アンモニウム４３．０％（６００．０ｇ）、チオシアン酸アンモニウム０．０３％（０．４２ｇ）の水溶液であった。陰極原料１３３３．６ｇは、硫酸１８．９％（２５２．４ｇ）、硫酸アンモニウム２８．４％（３７８．８ｇ）の水溶液であった。電解は、電流値３４．５Ａにて４時間行った。
【００１２】
電解後、陽極生成液１３３３．８ｇ、陰極生成液１３９１．０ｇを得た。液組成を滴定により分析したところ、陽極生成液組成は、過硫酸アンモニウム３８．３％（５１１．２ｇ）、硫酸アンモニウム７．５０％（１００．０ｇ）、硫酸１．５１％（２０．２ｇ）であった。また、陰極生成液組成は、硫酸アンモニウム４１．９％（５８３．２ｇ）、硫酸０．９１％（１２．６ｇ）であった。この時の電流効率は８７．０％であり、電解電圧は６．０Ｖ、陽極液平均温度２８．７℃、陰極液平均温度２９．２℃であった。
【００１３】
実施例２
実施例１と同じ電解槽を用いた。陽極原料１６７７．５ｇは、過硫酸アンモニウム３．２５％（５４．５ｇ）、硫酸アンモニウム３７．０％（６２１．２ｇ）、チオシアン酸アンモニウム０．０３％（０．５０ｇ）の水溶液であった。陰極原料９５３．４ｇは、硫酸２６．５％（２５２．５ｇ）の水溶液であった。電解は、電流値３４．５Ａにて４時間行った。
【００１４】
電解後、陽極生成液１６１５．９ｇ、陰極生成液１０１０．４ｇを得た。液組成を滴定により分析したところ、陽極生成液組成は、過硫酸アンモニウム３５．０％（５６５．６ｇ）、硫酸アンモニウム７．５０％（１２１．２ｇ）、硫酸１．２５％（２０．２ｇ）であった。また、陰極生成液組成は、硫酸アンモニウム２０．２％（２０４．１ｇ）、硫酸１．２５％（１２．６ｇ）であった。この時の電流効率は８７．０％であり、電解電圧は６．０Ｖ、陽極液平均温度２８．９℃、陰極液平均温度２９．７℃であった。
【００１５】
陽極生成液の全量を撹拌機、コンデンサーを付した晶析槽へ導き、真空度２０ｍｍＨｇ、温度３０℃にて真空晶析を行い、過硫酸アンモニウムを析出させた。得られたスラリーを遠心分離器に導き結晶と晶析母液を分離した。得られた結晶５２６．８ｇを完全に乾燥したところ、純度９９．９％の過硫酸アンモニウム結晶５１１．０ｇが得られた。晶析工程での過硫酸アンモニウム結晶の回収率は９９．９％であった。
【００１６】
また、結晶と分離された晶析母液は４０３．９ｇであり、その組成は、過硫酸アンモニウム１３．５％（５４．５ｇ）、硫酸アンモニウム３０．０％（１２１．２ｇ）、硫酸５．００％（２０．２ｇ）であった。この晶析母液と先の電解で得られた陰極生成液を混合し、更に硫酸アンモニウム２５１．７ｇ、チオシアン酸アンモニウム０．５０ｇを溶解した。その後、混合液中の硫酸をアンモニアガス１１．４ｇで中和し、陽極原料として使用した。陰極原料は別途調製した。
【００１７】
晶析母液及び陰極生成液のリサイクルにより調製された陽極原料１６７７．９ｇは、過硫酸アンモニウム３．２５％（５４．５ｇ）、硫酸アンモニウム３７．０％（６２１．２ｇ）、チオシアン酸アンモニウム０．０３％（０．５０ｇ）の水溶液であった。陰極原料９５３．４ｇは、硫酸２６．５％（２５２．５ｇ）の水溶液であった。電解は、電流値３４．５Ａにて４時間行った。
【００１８】
電解後、陽極生成液１６１５．５ｇ、陰極生成液１０１０．９ｇを得た。液組成を滴定により分析したところ、陽極生成液組成は、過硫酸アンモニウム３５．０％（５６５．６ｇ）、硫酸アンモニウム７．５０％（１２１．２ｇ）、硫酸１．２５％（２０．２ｇ）であった。また、陰極生成液組成は、硫酸アンモニウム２０．２％（２０４．１ｇ）、硫酸１．２５％（１２．６ｇ）であった。この時の電流効率は８７．２％であり、電解電圧は６．０Ｖ、陽極液平均温度２８．３℃、陰極液平均温度２９．５℃であった。
【００１９】
比較例１
実施例１と同じ電解槽を用いた。陽極原料１８１７．８ｇは、過硫酸アンモニウム７．１８％（１３０．６ｇ）、硫酸アンモニウム３３．７％（６１２．８ｇ）、硫酸５．８１％（１０５．７ｇ）、チオシアン酸アンモニウム０．０３％（０．５５ｇ）であった。陰極原料１５２６．７ｇは、硫酸１４．６％（２２３．３ｇ）の水溶液であった。電解は、電流値３４．５Ａにて４時間電解を行った。
【００２０】
電解後、陽極生成液１７１４．６ｇ、陰極生成液１６１６．８ｇを得た。液組成を滴定により分析したところ、陽極生成液組成は、過硫酸アンモニウム３５．４％（６０６．４ｇ）、硫酸アンモニウム５．７９％（９９．２ｇ）、硫酸５．５８％（９５．６ｇ）であった。また、陰極生成液組成は、硫酸アンモニウム１４．７％（２３８．１ｇ）、硫酸１．７９％（２８．９ｇ）であった。この時の電流効率は８１．０％であり、電解電圧は６．２Ｖ、陽極平均温度２７．１℃、陰極平均温度２８．１℃であった。この方法では、電流効率は本発明に比べ約６％低い結果となった。
【００２１】
【発明の効果】
本発明の方法によれば、電解の電流効率が高く、安価に過硫酸アンモニウムを製造することが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing ammonium persulfate. Ammonium persulfate is widely used industrially as a polymerization initiator for polyvinyl chloride or polyacrylonitrile, or as a printed wiring board treating agent.
[0002]
[Prior art]
As a general method for producing ammonium persulfate, an electrolytic production method using an aqueous solution containing sulfuric acid and ammonium sulfate, that is, an aqueous solution of ammonium hydrogen sulfate, as a raw material is known. In this method, ammonium persulfate is produced using ammonium hydrogen sulfate as a raw material by an electrolytic method, and the produced ammonium persulfate is concentrated, separated and dried by vacuum crystallization, centrifugation, etc., and commercialized. At this time, a solution containing crystals (usually called a crystallization mother liquor) is mixed with a cathode production solution and used as an anode raw material.
[0003]
For example, JP-A-55-34700 discloses a method for producing an alkali persulfate or ammonium salt by anodizing an aqueous solution of sulfate ions accompanied by protons, alkali metal ions or ammonium ions in a diaphragm electrolytic cell. Although described, this method has a final current efficiency of only about 80% and is not an economical process. Japanese Patent Application Laid-Open No. 57-198275 describes a method for producing ammonium persulfate using ammonium hydrogen sulfate and an electrolysis accelerator as raw materials, but this method also has an economically advantageous current efficiency of about 80%. It's not a good way.
[0004]
[Problems to be solved by the invention]
The present invention solves the problems in the method for producing ammonium persulfate described in the prior art and provides a method for producing ammonium persulfate by an industrially advantageous method.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to overcome these drawbacks, the present inventors have found that the current efficiency during the production of ammonium persulfate is significantly improved by using only ammonium sulfate as the sulfate ion of the anode material. It came to complete. That is, the present invention relates to a method for producing ammonium persulfate, characterized in that ammonium sulfate is used as an anode raw material, and ammonium persulfate is produced by electrolysis.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
In the electrolysis step of the present invention, an aqueous solution containing 30 to 44% by weight ammonium sulfate, preferably 40 to 44% by weight ammonium sulfate is used as the anode material. The anode material includes a necessary amount of a polarizing agent, and as the polarizing agent, thiocyanate, cyanide, cyanate, fluoride, or the like is used. As the cathode material, a 10 to 80 wt% aqueous sulfuric acid solution containing 0 to 35 wt% ammonium sulfate is used. Outside the concentration range described above, only low current efficiency is obtained, which is not a good idea.
[0007]
The electrolytic cell may be a box type battery case widely used industrially partitioned by an alumina diaphragm or a filter press type battery case partitioned by an ion exchange membrane or the like. The anode is preferably platinum, but a chemically resistant material such as a carbon electrode can also be used. The cathode is preferably lead or zirconium, but an acid resistant metal electrode such as stainless steel can also be used. The anode current density is at least 40 A / dm 2 . The temperature in the electrolytic cell is 15 to 40 ° C. If the temperature is lower than this, the salt in the solution may be precipitated, and the solubility of the salt increases as the temperature of the solution increases. However, the hydrolysis of the persulfate produced tends to occur at a high temperature, which is not preferable.
[0008]
The anolyte after electrolysis is concentrated and crystallized. A widely used crystallization tank is used as the crystallization tank for the concentration crystallization treatment. The crystallization temperature is 15-60 ° C, preferably 20-50 ° C. If the temperature is lower than this, the temperature of the condenser part becomes too low to be economically advantageous, and if the temperature is higher than this, ammonium persulfate decomposes, resulting in a low yield. As the crystallization pressure, a pressure at which water boils in the above temperature range is applied. The ammonium persulfate-containing slurry after crystallization is separated into crystals and a crystallization mother liquor by a solid-liquid separator such as a centrifugal separator. The obtained crystals are dried and commercialized using a powder dryer. The separated crystallization mother liquor and cathode production liquid are neutralized with ammonia and then reused as an electrolytic raw material.
[0009]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The current efficiency in the examples is expressed by (generated persulfate ions (mol) × 2) / energization amount (F) × 100%, and represents the ratio of persulfate ions generated per unit energization amount. Moreover, the electrolysis voltage is a potential difference between the electrodes, and all the concentration indications are by weight.
[0010]
Example 1
The electrolytic cell was made of transparent vinyl chloride. The anode chamber and cathode chamber of the tank were partitioned by a porous neutral alumina diaphragm plate fixed using a silicone rubber sealant. Each chamber was provided with a buffer tank / cooling tank, and the solution was fed from the buffer tank to the electrolysis chamber by a tube pump. The liquid return from the electrolysis chamber outlet to the buffer tank was performed by overflow. A glass cooling tube was inserted into the buffer tank to circulate the cooling water. As the anode, two platinum foils having a width of 1.8 cm and a length of 16 cm (area: 28.8 cm 2 ) were used. A lead plate was used as the cathode. The anode and cathode were set about 0.5 cm apart from the diaphragm. The direct current for electrolysis was obtained from a variable rectifier.
[0011]
The anode raw material 1395.2 g was an aqueous solution of ammonium sulfate 43.0% (600.0 g) and ammonium thiocyanate 0.03% (0.42 g). The cathode raw material 1333.6 g was an aqueous solution of 18.9% (252.4 g) sulfuric acid and 28.4% (378.8 g) ammonium sulfate. The electrolysis was performed at a current value of 34.5 A for 4 hours.
[0012]
After the electrolysis, 1333.8 g of an anode generating solution and 1391.0 g of a cathode generating solution were obtained. When the liquid composition was analyzed by titration, the composition of the anode production liquid was ammonium persulfate 38.3% (511.2 g), ammonium sulfate 7.50% (100.0 g), and sulfuric acid 1.51% (20.2 g). It was. Moreover, the cathode production liquid composition was ammonium sulfate 41.9% (583.2g) and sulfuric acid 0.91% (12.6g). The current efficiency at this time was 87.0%, the electrolysis voltage was 6.0 V, the average anolyte temperature was 28.7 ° C., and the average catholyte temperature was 29.2 ° C.
[0013]
Example 2
The same electrolytic cell as in Example 1 was used. The anode raw material 1677.5 g was an aqueous solution of ammonium persulfate 3.25% (54.5 g), ammonium sulfate 37.0% (621.2 g), and ammonium thiocyanate 0.03% (0.50 g). The cathode raw material 953.4 g was an aqueous solution of 26.5% (252.5 g) sulfuric acid. The electrolysis was performed at a current value of 34.5 A for 4 hours.
[0014]
After electrolysis, 1615.9 g of an anode generating solution and 1010.4 g of a cathode generating solution were obtained. When the liquid composition was analyzed by titration, the anode production liquid composition was 35.0% (565.6 g) ammonium persulfate, 7.50% (121.2 g) ammonium sulfate, and 1.25% (20.2 g) sulfuric acid. It was. The composition of the cathode generation liquid was 20.2% (204.1 g) ammonium sulfate and 1.25% (12.6 g) sulfuric acid. The current efficiency at this time was 87.0%, the electrolysis voltage was 6.0 V, the anolyte average temperature was 28.9 ° C., and the catholyte average temperature was 29.7 ° C.
[0015]
The total amount of the anode production liquid was guided to a crystallization tank equipped with a stirrer and a condenser, and vacuum crystallization was performed at a vacuum degree of 20 mmHg and a temperature of 30 ° C. to precipitate ammonium persulfate. The resulting slurry was guided to a centrifuge to separate crystals and crystallization mother liquor. When 526.8 g of the obtained crystals were completely dried, 511.0 g of ammonium persulfate crystals having a purity of 99.9% were obtained. The recovery rate of ammonium persulfate crystals in the crystallization step was 99.9%.
[0016]
The crystallized mother liquor separated from the crystals was 403.9 g, and its composition was ammonium persulfate 13.5% (54.5 g), ammonium sulfate 30.0% (121.2 g), sulfuric acid 5.00% ( 20.2 g). This crystallization mother liquor and the cathode production liquid obtained in the previous electrolysis were mixed, and further 251.7 g of ammonium sulfate and 0.50 g of ammonium thiocyanate were dissolved. Thereafter, sulfuric acid in the mixed solution was neutralized with 11.4 g of ammonia gas and used as an anode raw material. The cathode material was prepared separately.
[0017]
The anode raw material 1677.9 g prepared by recycling the crystallization mother liquor and the cathode production liquid was 3.25% (54.5 g) ammonium persulfate, 37.0% ammonium sulfate (621.2 g), 0.03% ammonium thiocyanate. (0.50 g) of an aqueous solution. The cathode raw material 953.4 g was an aqueous solution of 26.5% (252.5 g) sulfuric acid. The electrolysis was performed at a current value of 34.5 A for 4 hours.
[0018]
After electrolysis, 1615.5 g of an anode generating solution and 1010.9 g of a cathode generating solution were obtained. When the liquid composition was analyzed by titration, the anode production liquid composition was 35.0% (565.6 g) ammonium persulfate, 7.50% (121.2 g) ammonium sulfate, and 1.25% (20.2 g) sulfuric acid. It was. The composition of the cathode generation liquid was 20.2% (204.1 g) ammonium sulfate and 1.25% (12.6 g) sulfuric acid. The current efficiency at this time was 87.2%, the electrolysis voltage was 6.0 V, the anolyte average temperature was 28.3 ° C., and the catholyte average temperature was 29.5 ° C.
[0019]
Comparative Example 1
The same electrolytic cell as in Example 1 was used. Anode raw materials 1817.8 g were ammonium persulfate 7.18% (130.6 g), ammonium sulfate 33.7% (612.8 g), sulfuric acid 5.81% (105.7 g), ammonium thiocyanate 0.03% (0 .55 g). The cathode raw material 1526.7 g was an aqueous solution of sulfuric acid 14.6% (223.3 g). The electrolysis was performed at a current value of 34.5 A for 4 hours.
[0020]
After electrolysis, 1714.6 g of an anode generating solution and 1616.8 g of a cathode generating solution were obtained. When the liquid composition was analyzed by titration, the composition of the anode production liquid was 35.4% (606.4 g) ammonium persulfate, 5.79% (99.2 g) ammonium sulfate, and 5.58% (95.6 g) sulfuric acid. It was. The composition of the cathode generation liquid was ammonium sulfate 14.7% (238.1 g) and sulfuric acid 1.79% (28.9 g). The current efficiency at this time was 81.0%, the electrolysis voltage was 6.2 V, the anode average temperature was 27.1 ° C., and the cathode average temperature was 28.1 ° C. With this method, the current efficiency was about 6% lower than that of the present invention.
[0021]
【The invention's effect】
According to the method of the present invention, ammonium persulfate can be produced at a low cost with high current efficiency of electrolysis.
Claims (5)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09470098A JP3832533B2 (en) | 1998-04-07 | 1998-04-07 | Method for producing ammonium persulfate |
| TW088103936A TW416997B (en) | 1998-03-30 | 1999-03-15 | Process for producing persulfate |
| US09/275,026 US6214197B1 (en) | 1998-03-30 | 1999-03-24 | Process for producing persulfate |
| DE19913820A DE19913820B4 (en) | 1998-03-30 | 1999-03-26 | Process for the preparation of ammonium persulphate and its use for the preparation of sodium or potassium persulphate |
| CNB991045076A CN1197765C (en) | 1998-03-30 | 1999-03-30 | Process for producing persulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09470098A JP3832533B2 (en) | 1998-04-07 | 1998-04-07 | Method for producing ammonium persulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11293484A JPH11293484A (en) | 1999-10-26 |
| JP3832533B2 true JP3832533B2 (en) | 2006-10-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09470098A Expired - Fee Related JP3832533B2 (en) | 1998-03-30 | 1998-04-07 | Method for producing ammonium persulfate |
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| JP (1) | JP3832533B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5320173B2 (en) | 2008-06-30 | 2013-10-23 | クロリンエンジニアズ株式会社 | Sulfuric acid electrolysis method |
| KR101377428B1 (en) * | 2011-12-13 | 2014-03-26 | (주) 휴브글로벌 | Continuous operating method for producing ammonium persulfate |
| CN102828197B (en) * | 2012-08-31 | 2014-12-10 | 云浮市银利化工有限公司 | Full-sealed type ammonium persulfate electrolysis system and method |
| CN104152943B (en) * | 2014-08-15 | 2017-05-10 | 东南大学 | Device and method for preparing ammonium persulphate with ammonia and urea solution flue gas purified absorption solution |
| KR102260402B1 (en) | 2017-01-13 | 2021-06-03 | 도레이 카부시키가이샤 | Method for producing ammonium persulfate |
| CN113174604B (en) * | 2021-04-13 | 2022-12-06 | 浙江工业大学 | Method for preparing sodium persulfate through direct electrooxidation |
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| JPH11293484A (en) | 1999-10-26 |
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