JPS627122B2 - - Google Patents
Info
- Publication number
- JPS627122B2 JPS627122B2 JP14953479A JP14953479A JPS627122B2 JP S627122 B2 JPS627122 B2 JP S627122B2 JP 14953479 A JP14953479 A JP 14953479A JP 14953479 A JP14953479 A JP 14953479A JP S627122 B2 JPS627122 B2 JP S627122B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- wet
- wet phosphoric
- organic matter
- hydrogen sulfide
- 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
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 112
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 24
- 239000005416 organic matter Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 19
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 150000004763 sulfides Chemical class 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 20
- 238000007254 oxidation reaction Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 235000021317 phosphate Nutrition 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003729 cation exchange resin Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002367 phosphate rock Substances 0.000 description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- -1 arsenic Chemical compound 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Removal Of Specific Substances (AREA)
Description
【発明の詳細な説明】
本発明は、湿式法リン酸中の有機物除去法に関
するものである。本発明では、リン鉱石を硫酸、
塩酸、硝酸等の鉱酸で分解して得られるリン酸、
すなわち、湿式リン酸またはこれを出発原料とし
て得られるリン酸を湿式法リン酸と総称する。上
記湿式リン酸には、通常、鉄、アルミニウム、カ
ルシウム等の金属不純物、過剰の鉱酸、フツ素、
シリカ等の不純物のほか、有機物が大量に含まれ
る。上記湿式リン酸は、通常、茶褐色ないし黒褐
色を呈しており、そのまま工業用、医薬用、食品
用等に供することができず、脱色する必要があ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a wet method for removing organic matter from phosphoric acid. In the present invention, phosphate rock is sulfuric acid,
Phosphoric acid obtained by decomposition with mineral acids such as hydrochloric acid and nitric acid,
That is, wet phosphoric acid or phosphoric acid obtained using this as a starting material is collectively referred to as wet phosphoric acid. The above wet phosphoric acid usually contains metal impurities such as iron, aluminum, and calcium, excess mineral acid, fluorine,
In addition to impurities such as silica, it also contains large amounts of organic matter. The above-mentioned wet phosphoric acid usually exhibits a brown to blackish-brown color and cannot be used as is for industrial, pharmaceutical, food, etc. purposes, and must be decolorized.
従来、着色した湿式リン酸の脱色法としては、
活性炭、イオン交換樹脂等による吸着、酸化剤に
よる分解、溶媒による抽出洗浄等多くの処理法が
提案されていた。しかしながら、これらの方法は
脱色については効果的であるが、得られたリン酸
を濃縮などのために加熱する場合は再び着色し、
またリン酸塩合成に際し臭気が発生したり着色し
たりする。このような着色および臭いの原因物質
は、リン酸中の有機物によるものである。 Conventionally, the decolorization method for colored wet phosphoric acid is as follows:
Many treatment methods have been proposed, including adsorption using activated carbon and ion exchange resins, decomposition using oxidizing agents, and extraction and cleaning using solvents. However, although these methods are effective for decolorization, when the obtained phosphoric acid is heated for concentration etc., it becomes colored again.
Also, during phosphate synthesis, odor is generated and coloration occurs. The substances responsible for such coloring and odor are organic substances in phosphoric acid.
また、ｎ−ブタノール等の溶媒で抽出処理され
た抽出リン酸を塩素酸塩などの酸化剤と接触させ
て微量の有機物を酸化分解する方法が知られてい
る（特開昭52−97395）。しかしながら、この方法
では、得られる湿式リン酸中に残留する酸化剤を
除去するための特殊な処理が要求され、且つこの
特殊な処理方法によつて得られた高純度リン酸中
の酸化剤から派生するイオン濃度もH3PO4として
75重量％リン酸濃度の場合で19重量ppmまで低
減するのが限度である。 Furthermore, a method is known in which trace amounts of organic matter are oxidized and decomposed by contacting extracted phosphoric acid extracted with a solvent such as n-butanol with an oxidizing agent such as chlorate (Japanese Patent Laid-Open No. 52-97395). However, this method requires a special treatment to remove the oxidizing agent remaining in the wet phosphoric acid obtained, and the oxidizing agent in the high purity phosphoric acid obtained by this special treatment method is The derived ion concentration is also H 3 PO 4
In the case of a 75% by weight phosphoric acid concentration, the limit is 19 ppm by weight.
本発明の目的は、短い処理時間で少量の酸化剤
によつて湿式法リン酸中の有機物を完全に除去し
再加熱によつて着色することなく且つリン酸塩合
成に際し、臭気の発生および着色のないリン酸を
得る方法を提供することにある。 The purpose of the present invention is to completely remove organic substances in wet phosphoric acid using a small amount of oxidizing agent in a short processing time, and to avoid coloring due to reheating, and to eliminate odor generation and coloring during phosphate synthesis. The object of the present invention is to provide a method for obtaining phosphoric acid free of phosphoric acid.
本発明者は、湿式法リン酸中の有機物を完全に
除去する方法について深く検討した結果、湿式リ
ン酸を硫化水素または硫化物のアルカリ溶液と接
触させたのち析出物を分離し次いで分離液を酸化
剤と接触させれば、有機物を完全に分解除去でき
ることを見いだし本発明の方法に到達した。 As a result of deep studies on a method for completely removing organic matter from wet phosphoric acid, the inventors of the present invention have found that after contacting wet phosphoric acid with hydrogen sulfide or an alkaline solution of sulfide, the precipitate is separated, and then the separated liquid is It was discovered that organic substances can be completely decomposed and removed by contacting with an oxidizing agent, and the method of the present invention was developed.
すなわち、本発明は、湿式リン酸を硫化水素ま
たは硫化物のアルカリ溶液と接触させたのち析出
物を分離し次いで分離液を酸化剤と接触させ、し
かるのち抽出処理する湿式法リン酸中の有機物除
去法であり、これによつて上記の目的は容易に達
成される。 That is, the present invention provides organic matter in phosphoric acid by a wet method, which involves contacting wet phosphoric acid with hydrogen sulfide or an alkaline solution of sulfide, separating precipitates, and then contacting the separated liquid with an oxidizing agent, followed by extraction treatment. This is a removal method, by which the above objectives are easily achieved.
而して、本発明の方法による場合は、析出物の
分離により湿式リン酸中の有機物の70重量％以上
および不純物イオンの一部が除去され、次いで行
なわれる有機物酸化のための酸化剤使用量が低減
する。また、この方法では、酸化剤と接触したリ
ン酸がリン酸塩になり、この塩が抽出処理の洗浄
効率を向上させるため、酸化剤使用量が過剰にな
りリン酸塩濃度が増加しても差支えない。すなわ
ち、分離液中の不純物イオンは、次いで行なわれ
る抽出処理における水相中のリン酸塩とともに溶
媒中のリン酸から殆んど完全に分離することがで
きるからである。この方法によつて得られる高純
度リン酸中の酸化剤から派生するイオン濃度は、
H3PO4として75重量％リン酸濃度の場合で、５重
量ppm程度であり、従来法に比して大きく低減
することが出来る。 Therefore, in the case of the method of the present invention, more than 70% by weight of the organic matter and a part of the impurity ions in the wet phosphoric acid are removed by separating the precipitate, and the amount of oxidizing agent used for the subsequent oxidation of the organic matter is reduced. is reduced. In addition, in this method, the phosphoric acid that comes into contact with the oxidizing agent turns into phosphate, and this salt improves the cleaning efficiency of the extraction process, so even if the oxidizing agent is used in excess and the phosphate concentration increases. No problem. That is, the impurity ions in the separated liquid can be almost completely separated from the phosphoric acid in the solvent together with the phosphate in the aqueous phase in the subsequent extraction process. The concentration of ions derived from the oxidizing agent in the high purity phosphoric acid obtained by this method is:
In the case of a phosphoric acid concentration of 75% by weight as H 3 PO 4 , it is about 5 ppm by weight, which can be significantly reduced compared to conventional methods.
本発明をさらに詳細に説明する。 The present invention will be explained in further detail.
湿式リン酸を硫化水素または硫化物のアルカリ
溶液と接触させる際の温度としては、通常、30℃
以上、好ましくは40〜60℃の範囲が用いられる。
また、処理圧力は、通常、1.0Kg／cm2（ゲージ
圧）以上が用いられる。これは、湿式リン酸中の
硫化水素塩の濃度を上げて反応を促進させるため
の好ましい条件である。 The temperature at which wet phosphoric acid is brought into contact with hydrogen sulfide or an alkaline solution of sulfide is usually 30°C.
Above, preferably a temperature in the range of 40 to 60°C is used.
Further, the processing pressure used is usually 1.0 Kg/cm 2 (gauge pressure) or higher. This is a preferred condition for increasing the concentration of hydrogen sulfide salt in the wet phosphoric acid and promoting the reaction.
湿式リン酸を硫化水素または硫化物のアルカリ
溶液と接触させることにより、好ましくは硫化水
素ナトリウムの水酸化ナトリウム溶液と接触させ
ることにより、湿式リン酸中のアンチモン、銅、
水銀、鉛、ビスマス、スズ、カドミウム、ヒ素等
の硫化物が析出する。この際の硫化水素ナトリウ
ムの濃度は、湿式リン酸に対してNaSHとして
500mg／以上とするのがよい。 The antimony, copper,
Sulfides such as mercury, lead, bismuth, tin, cadmium, and arsenic precipitate. The concentration of sodium hydrogen sulfide at this time is as NaSH for wet phosphoric acid.
It is recommended that the amount be 500mg/or more.
湿式リン酸と硫化水素または硫化物のアルカリ
溶液とを接触させることにより析出した析出物は
通常の分離方法、例えば過法によつて分離され
る。この際用いられる過機は通常の過機で十
分である。この際分離される過ケークは、過
助剤、湿式リン酸中のスラツジ、有機物、アンチ
モン、銅、水銀、鉛、ビスマス、スズ、カドミウ
ム、ヒ素等の硫化物、付着リン酸、付着水等から
構成される。 The precipitate deposited by contacting wet phosphoric acid with hydrogen sulfide or an alkaline solution of sulfide is separated by a conventional separation method, such as a filtration method. A normal filter is sufficient for use in this case. The overcake that is separated at this time is free from super-aids, sludge in wet phosphoric acid, organic matter, antimony, copper, mercury, lead, bismuth, tin, cadmium, sulfides such as arsenic, adhering phosphoric acid, adhering water, etc. configured.
析出物を分離して得られた分離液を酸化剤と接
触させる際の温度は、100℃以上であることが好
ましい。これは、100℃に達しない温度において
は、発生期の酸素の発生速度が小さすぎ、有機物
を完全に酸化分解することができないからであ
る。しかしながら、この温度が160℃をこえると
装置が腐食され易くなる上、リン酸が縮合するお
それがあるので、好ましくは100〜160℃の範囲、
更に好ましくは110〜150℃の範囲が用いられる。
また、この際の処理圧力は、好ましくは1.0Kg／
cm2（ゲージ圧）以上が用いられる。これは、湿式
リン酸中に溶存する発生期の酸素濃度を上げて、
有機物の酸化分解を完全に行なうためである。 The temperature at which the separated liquid obtained by separating the precipitate is brought into contact with the oxidizing agent is preferably 100° C. or higher. This is because at temperatures below 100°C, the rate of oxygen generation during the nascent stage is too slow to completely oxidize and decompose organic matter. However, if this temperature exceeds 160°C, the equipment is likely to be corroded and phosphoric acid may condense, so it is preferably in the range of 100 to 160°C.
More preferably, a temperature range of 110 to 150°C is used.
In addition, the processing pressure at this time is preferably 1.0Kg/
cm 2 (gauge pressure) or higher is used. This increases the nascent oxygen concentration dissolved in the wet phosphoric acid,
This is to completely oxidize and decompose organic matter.
本発明者は、使用する酸化剤について、硝酸、
過塩素酸塩、重クロム酸塩、過マンガン酸塩、塩
素酸塩、次亜塩素酸塩、亜塩素酸塩、過酸化水
素、オゾン等の有機物の分解の効果を検討した結
果、塩素酸塩が特に好ましく有機物をほぼ完全に
分解することを見いだした。而して好適な塩素酸
塩としては、例えば、比較的入手の容易な塩素酸
ナトリウム、塩素酸カリウム、塩素酸カルシウム
等をあげることができる。これらは、固体のま
ま、水溶液、その他いずれの形態で使用してもよ
く、湿式リン酸分離液中のH3PO4に対して0.05重
量％以上添加するのがよい。この際、有機物は短
時間に完全に分解するが、塩素酸塩をも完全に分
解させるためには、処理時間を0.1〜６時間の範
囲とするのがよく、また塩化水素を併用すれば処
理時間の短縮および塩素酸塩の使用量の低減など
の利点が生じる。 The present inventor has determined that the oxidizing agent used is nitric acid,
As a result of examining the effects of decomposing organic substances such as perchlorate, dichromate, permanganate, chlorate, hypochlorite, chlorite, hydrogen peroxide, and ozone, we found that chlorate It has been found that this is particularly preferable and almost completely decomposes organic matter. Suitable chlorates include, for example, relatively easily available sodium chlorate, potassium chlorate, calcium chlorate, and the like. These may be used as a solid, in an aqueous solution, or in any other form, and are preferably added in an amount of 0.05% by weight or more based on H 3 PO 4 in the wet phosphoric acid separation solution. At this time, organic matter is completely decomposed in a short time, but in order to completely decompose chlorate, it is best to set the treatment time in the range of 0.1 to 6 hours, and if hydrogen chloride is used together, the treatment Benefits include time savings and reduced chlorate usage.
湿式リン酸を硫化水素または硫化物のアルカリ
溶液と接触させたのち析出物を分離することによ
り、湿式リン酸の酸化反応液中に残存する有機物
を酸化分解するための酸化剤は著しく少量にな
る。 By contacting wet phosphoric acid with hydrogen sulfide or an alkaline sulfide solution and separating the precipitate, the amount of oxidizing agent needed to oxidize and decompose the organic matter remaining in the wet phosphoric acid oxidation reaction solution is significantly reduced. .
従つて、酸化反応後液中に残留する酸化剤量が
低減するため、酸化反応液の還元処理は必らずし
も必要ではない。しかし乍ら、より高純度の目的
物を得るためには、酸化反応液を活性炭、硫化水
素、亜硫酸ナトリウム、亜硫酸カリウム等の亜硫
酸塩等を用いて還元することが好ましい。この還
元処理は、酸化反応から還元反応完結までに要す
る時間を短縮し且つ装置、機器、配管等の保護に
役立つ。 Therefore, since the amount of oxidizing agent remaining in the liquid after the oxidation reaction is reduced, reduction treatment of the oxidation reaction liquid is not necessarily necessary. However, in order to obtain a target product of higher purity, it is preferable to reduce the oxidation reaction solution using activated carbon, hydrogen sulfide, a sulfite such as sodium sulfite, potassium sulfite, or the like. This reduction treatment shortens the time required from the oxidation reaction to the completion of the reduction reaction, and is useful for protecting equipment, equipment, piping, etc.
かくして得られた酸化反応液中には、なおかな
りの量のイオン、例えば、鉄、マグネシウム、亜
鉛等の陽イオン、塩素、フツ素、硫酸根等の陰イ
オン、等が残留している。これらのイオンの除去
法としては、好ましくは0.05重量％以上のリン酸
塩を含有する溶媒で抽出処理するのがよい。而し
てこのようなリン酸塩の具体例としてはリン酸ソ
ーダ、リン酸マグネシウム、リン酸亜鉛等があげ
られる。また、溶媒の具体例として、メタノー
ル、エタノール、イソプロピルアルコール、ｎ−
ブタノール等のアルコール類、アセトン、エーテ
ル、等をあげることが出来る。抽出処理に際し、
溶媒とリン酸の重量比は、８：１〜１：１の範囲
が好ましい範囲として用いられる。このようなリ
ン酸塩を含有する触媒による抽出処理により酸化
反応液中に存在したイオンの98重量％以上が通常
除去される。 In the oxidation reaction solution thus obtained, a considerable amount of ions, such as cations such as iron, magnesium, and zinc, and anions such as chlorine, fluorine, and sulfate radicals, remain. A method for removing these ions is preferably extraction treatment with a solvent containing 0.05% by weight or more of phosphate. Specific examples of such phosphates include sodium phosphate, magnesium phosphate, zinc phosphate, and the like. Further, specific examples of solvents include methanol, ethanol, isopropyl alcohol, n-
Examples include alcohols such as butanol, acetone, and ether. During the extraction process,
The weight ratio of solvent to phosphoric acid is preferably in the range of 8:1 to 1:1. By such extraction treatment using a catalyst containing phosphate, 98% by weight or more of the ions present in the oxidation reaction solution are usually removed.
ここで、本発明の湿式法リン酸中の有機物除去
法の代表的工程を第１図に示す。湿式リン酸液１
および硫化水素または硫化物のアルカリ溶液２
は、反応装置１２に供給され通常30℃以上の温度
で且つやや加圧された状態で接触させられる。反
応液３はフイルター１３に供給され、、次いで反
応液３から排ガス４および過ケーク５が除去さ
れる。液６および酸化剤７は、酸化反応装置１
４に供給され通常100℃以上の温度で且つやや加
圧された状態で接触させられる。この際、塩素、
ｂ二酸化炭素等を含む排ガス８は装置外へ放出さ
れる。酸化反応液９および還元剤１０は、場合に
より還元装置１５に供給され有機物除去後の湿式
リン酸液１１として装置外へ抜きだされる。 Here, FIG. 1 shows typical steps of the wet method for removing organic matter from phosphoric acid of the present invention. Wet phosphoric acid solution 1
and hydrogen sulfide or sulfide alkaline solution 2
are supplied to the reactor 12 and brought into contact with each other at a temperature of usually 30° C. or higher and under slight pressure. The reaction liquid 3 is supplied to the filter 13, and then the exhaust gas 4 and the overcake 5 are removed from the reaction liquid 3. The liquid 6 and the oxidizing agent 7 are supplied to the oxidation reactor 1
4 and brought into contact at a temperature of usually 100° C. or higher and under slight pressure. At this time, chlorine,
b Exhaust gas 8 containing carbon dioxide and the like is discharged outside the device. The oxidation reaction liquid 9 and the reducing agent 10 are optionally supplied to a reducing device 15 and extracted from the device as a wet phosphoric acid solution 11 after organic matter has been removed.
以下、本発明の実施例および比較例を示す。
〔％〕および〔ppm〕は重量による。 Examples and comparative examples of the present invention are shown below.
[%] and [ppm] are by weight.
実施例 １
リン鉱石〔モロツコ産〕を硫酸で分解して得た
リン酸を濃縮してH3PO4として74.50％の湿式リ
ン酸を得た。この湿式リン酸1000ｇを、
NaSH11.75％、NaOH8.26％、H2O79.99％、なる
組成の液8.5ｇと接触させ、次いで40℃で且つ６
Kg／cm2（ゲージ圧）で25分間反応させた。この反
応液をフイルターで過して液を得た。この
液は、H3PO474.50％、有機物500ppm、金属元素
1.26％であり、褐色を呈していた。Example 1 Phosphoric acid obtained by decomposing phosphate rock (from Morocco) with sulfuric acid was concentrated to obtain 74.50% wet phosphoric acid as H 3 PO 4 . 1000g of this wet phosphoric acid,
It was brought into contact with 8.5 g of a solution having the following composition: NaSH 11.75%, NaOH 8.26%, H 2 O 79.99%, and then heated at 40°C for 6 hours.
The reaction was carried out at Kg/cm 2 (gauge pressure) for 25 minutes. This reaction solution was filtered through a filter to obtain a solution. This liquid contains 74.50% H 3 PO 4 , 500 ppm of organic matter, and metal elements.
It was 1.26% and had a brown color.
この液1000ｇ、塩素酸ナトリウム7.46ｇを１
の撹拌機付フラスコにとり、132℃で且つ３
Kg／cm2（ゲージ圧）で約２時間反応させて、
H3PO4、74.50％、有機物−こん跡、金属元素
1.26％、ＮαClO3こん跡、なる組成の酸化反応液
を得た。この液をH2Sによる還元、ｎ−ブタノー
ルによる抽出洗浄、陽イオン交換樹脂との接触、
次いで粒状活性炭との接触を行なつて得られた液
は、Na3.2ppm、Cl4.7ppmであり、300℃まで加
熱しても着色することなく且つリン酸水素二ナト
リウム、ピロリン酸カリウムの合成の際臭いも着
色も見出されなかつた。 1000g of this liquid, 7.46g of sodium chlorate 1
Place in a flask with a stirrer and heat at 132°C for 30 minutes.
React at Kg/cm 2 (gauge pressure) for about 2 hours,
H 3 PO 4 , 74.50%, organic matter - traces, metallic elements
An oxidation reaction solution having a composition of 1.26% and traces of NαClO 3 was obtained. This solution was reduced with H 2 S, extracted and washed with n-butanol, contacted with a cation exchange resin,
Next, the liquid obtained by contacting with granular activated carbon has Na3.2ppm and Cl4.7ppm, does not become colored even when heated to 300℃, and is suitable for the synthesis of disodium hydrogen phosphate and potassium pyrophosphate. No particular odor or coloring was found.
実施例 ２
リン鉱石（フロリダ産）を硫酸で分解して得た
リン酸を濃縮してH3PO4として75.92％の湿式リ
ン酸を得た。この湿式リン酸1000ｇを、
NaOH18.32％、H2O81.68％、なる組成の液11.59
ｇおよび硫化水素0.91ｇと接触させて、45℃で且
つ5.5Kg／cm2（ゲージ圧）で30分間反応させた。
この反応液をフイルターで過して液を得た。
この液は、H3PO475.92％、有機物450ppm、金
属元素1.06％であり、褐色を呈していた。Example 2 Phosphoric acid obtained by decomposing phosphate rock (from Florida) with sulfuric acid was concentrated to obtain 75.92% wet phosphoric acid as H 3 PO 4 . 1000g of this wet phosphoric acid,
Liquid with a composition of 18.32% NaOH, 81.68% H2O , and 11.59%
g and 0.91 g of hydrogen sulfide to react for 30 minutes at 45° C. and 5.5 Kg/cm 2 (gauge pressure).
This reaction solution was filtered through a filter to obtain a solution.
This liquid contained 75.92% H 3 PO 4 , 450 ppm of organic matter, and 1.06% of metal elements, and was brown in color.
この液1000ｇ、塩素酸ナトリウム6.70ｇを１
の撹拌機付フラスコにとり、135℃で且つ３
Kg／cm2（ゲージ圧）で約２時間反応させて、
H3PO475.92％、有機物−こん跡、金属元素1.06
％、NaClO3こん跡、なる組成の酸化反応液を得
た。この液をNa2SO3による還元、イソプロピル
アルコールによる抽出洗浄、陽イオン交換樹脂と
の接触、次いで粒状活性炭との接触を行なつて得
られた液は、Na3.5ppm、Cl4.5ppmであり、300
℃まで加熱しても着色することなく且つリン酸水
素二ナトリウム、ピロリン酸カリウムの合成の際
臭いも着色も見出されなかつた。 1000g of this liquid, 6.70g of sodium chlorate
Place in a flask with a stirrer and heat at 135°C for 30 minutes.
React at Kg/cm 2 (gauge pressure) for about 2 hours,
H 3 PO 4 75.92%, organic matter - traces, metallic elements 1.06
An oxidation reaction solution was obtained with a composition of % and traces of NaClO3 . This liquid was reduced with Na 2 SO 3 , extracted and washed with isopropyl alcohol, contacted with a cation exchange resin, and then contacted with granular activated carbon, and the resulting liquid contained 3.5 ppm of Na and 4.5 ppm of Cl. 300
Even when heated to ℃, there was no coloration, and neither odor nor coloration was found during the synthesis of disodium hydrogen phosphate and potassium pyrophosphate.
実施例 ３
実施例１において得られた、液1000ｇ、35％
塩酸0.29ｇおよび塩素酸ナトリウム4.48ｇを１
の撹拌機付フラスコにとり、130℃で且つ３Kg／
cm2（ゲージ圧）で約１時間反応させて、
H2PO474.50％、有機物−こん跡、金属元素1.26
％、NaClO3こん跡、なる組成の酸化反応液を得
た。この液をH2Sによる還元、ｎ−ブタノールに
よる抽出洗浄、陽イオン交換樹脂との接触、次い
で粒状活性炭との接触を行なつて得られた液は、
Na3.3ppm、Cl 5ppmであり、300℃まで加熱し
ても着色することなく且つリン酸水素二ナトリウ
ム、ピロリン酸カリウムの合成の際臭いも着色も
見出されなかつた。Example 3 1000 g of liquid obtained in Example 1, 35%
0.29g of hydrochloric acid and 4.48g of sodium chlorate in 1
Transfer to a flask with a stirrer and heat at 130℃ and 3 kg/
React at cm 2 (gauge pressure) for about 1 hour,
H 2 PO 4 74.50%, organic matter - traces, metallic elements 1.26
An oxidation reaction solution was obtained with a composition of % and traces of NaClO3 . The liquid obtained by reducing this liquid with H 2 S, extracting and washing with n-butanol, contacting with a cation exchange resin, and then contacting with granular activated carbon,
The content of Na was 3.3 ppm and Cl was 5 ppm, and there was no coloration even when heated to 300°C, and no odor or coloration was found during the synthesis of disodium hydrogen phosphate and potassium pyrophosphate.
比較例 １
実施例２において採用した湿式リン酸1000ｇ、
塩素酸ナトリウム70.5ｇを１の撹拌機付フラス
コにとり、135℃で且つ３Kg／cm2（ゲージ圧）で
約２時間反応させ、H3PO475.92％、有機物
500ppm、金属元素1.06％、NaClO3こん跡、なる
組成の酸化反応液を得た。この液をフイルターで
過し、次いでNa2SO3による還元、イソプロピ
ルアルコールによる抽出洗浄、陽イオン交換樹脂
との接触、粒状活性炭との接触を行なつて得られ
た液は、Na15ppm、Cl 20ppmであり、300℃ま
で加熱した際着色した。Comparative Example 1 1000g of wet phosphoric acid used in Example 2,
70.5g of sodium chlorate was placed in a flask with a stirrer (No. 1), and reacted at 135°C and 3Kg/cm 2 (gauge pressure) for about 2 hours, resulting in 75.92% of H 3 PO 4 and 75.92% of organic matter.
An oxidation reaction solution with a composition of 500 ppm, 1.06% of metal elements, and traces of NaClO3 was obtained. This liquid was filtered, and then reduced with Na 2 SO 3 , extracted and washed with isopropyl alcohol, contacted with a cation exchange resin, and contacted with granular activated carbon.The resulting liquid contained 15 ppm of Na and 20 ppm of Cl. Yes, it became colored when heated to 300℃.
第１図は、本発明の代表的な実施の態様を示す
工程説明図である。
１……湿式リン酸液、２……硫化水素または硫
化物のアルカリ溶液、３……反応液、４……排ガ
ス、５……過ケーク、６……液、７……酸化
剤、８……排ガス、９……酸化反応液、１０……
還元剤、１１……有機物除去後の湿式リン酸液、
１２……反応装置、１３……フイルター、１４…
…酸化反応装置、１５……還元装置。
FIG. 1 is a process explanatory diagram showing a typical embodiment of the present invention. 1... Wet phosphoric acid solution, 2... Hydrogen sulfide or sulfide alkaline solution, 3... Reaction liquid, 4... Exhaust gas, 5... Percake, 6... Liquid, 7... Oxidizing agent, 8... ...Exhaust gas, 9...Oxidation reaction liquid, 10...
Reducing agent, 11... Wet phosphoric acid solution after organic matter removal,
12... Reactor, 13... Filter, 14...
...Oxidation reactor, 15...Reduction device.
Claims (1)
リ溶液と接触させたのち析出物を分離し次いで分
離液を酸化剤と接触させしかるのち抽出処理する
ことを特徴とする湿式法リン酸中の有機物除去
法。 ２ 湿式リン酸を40〜60℃の温度で硫化水素また
は硫化物のアルカリ溶液と接触させることを特徴
とする特許請求の範囲第１項記載の方法。 ３ 湿式リン酸を硫化水素または硫化物のアルカ
リ溶液と接触させるときの圧力が1.0Kg／cm2（ゲ
ージ圧）以上であることを特徴とする特許請求の
範囲第１又は２項記載の方法。 ４ 湿式リン酸と硫化水素ナトリウムとをNaSH
として500mg／以上の濃度で接触させることを
特徴とする特許請求の範囲第１〜３項のいずれか
１項に記載の方法。 ５ 湿式リン酸の分離液を酸化剤と接触させたの
ち還元剤と接触させ次いで抽出処理することを特
徴とする特許請求の範囲第１〜４項のいずれか１
項に記載の方法。[Claims] 1. A wet method characterized by contacting wet phosphoric acid with hydrogen sulfide or an alkaline solution of sulfide, separating the precipitate, and then contacting the separated liquid with an oxidizing agent, followed by extraction treatment. Method for removing organic matter from phosphoric acid. 2. A method according to claim 1, characterized in that wet phosphoric acid is brought into contact with hydrogen sulfide or an alkaline solution of sulfides at a temperature of 40 to 60°C. 3. The method according to claim 1 or 2, characterized in that the pressure at which wet phosphoric acid is brought into contact with hydrogen sulfide or an alkaline solution of sulfide is 1.0 Kg/cm 2 (gauge pressure) or more. 4 Wet phosphoric acid and sodium hydrogen sulfide are converted into NaSH
The method according to any one of claims 1 to 3, characterized in that the contact is carried out at a concentration of 500 mg/min or more. 5. Any one of claims 1 to 4, characterized in that the wet phosphoric acid separated liquid is brought into contact with an oxidizing agent and then brought into contact with a reducing agent and then subjected to extraction treatment.
The method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14953479A JPS5673608A (en) | 1979-11-20 | 1979-11-20 | Removing method for organic matter in wet process phosphoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14953479A JPS5673608A (en) | 1979-11-20 | 1979-11-20 | Removing method for organic matter in wet process phosphoric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5673608A JPS5673608A (en) | 1981-06-18 |
| JPS627122B2 true JPS627122B2 (en) | 1987-02-16 |
Family
ID=15477232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14953479A Granted JPS5673608A (en) | 1979-11-20 | 1979-11-20 | Removing method for organic matter in wet process phosphoric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5673608A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4457899A (en) * | 1981-11-23 | 1984-07-03 | Mobil Oil Corporation | Process for removal of residual organic matter from purified phosphoric acid |
| JPS63201018A (en) * | 1987-02-10 | 1988-08-19 | Nemoto Masayuki | Method for recovering magnetic powder from magnetic recording medium |
| JP4316946B2 (en) * | 2003-07-01 | 2009-08-19 | 日本化学工業株式会社 | High purity phosphoric acid and method for producing the same |
-
1979
- 1979-11-20 JP JP14953479A patent/JPS5673608A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5673608A (en) | 1981-06-18 |
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