JPH0483710A - Production of high-purity phosphoric acid - Google Patents
Production of high-purity phosphoric acidInfo
- Publication number
- JPH0483710A JPH0483710A JP19697090A JP19697090A JPH0483710A JP H0483710 A JPH0483710 A JP H0483710A JP 19697090 A JP19697090 A JP 19697090A JP 19697090 A JP19697090 A JP 19697090A JP H0483710 A JPH0483710 A JP H0483710A
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- urea
- acid
- aqueous solution
- nitric acid
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 54
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004202 carbamide Substances 0.000 claims abstract description 34
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 claims abstract description 19
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000003016 phosphoric acids Chemical class 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は金属カチオン、無機アニオン、有機物などの不
純物が極めて少く、且つ残存尿素がｌｐｐｍ以下、残存
硝酸がｌｐｐｍ以下で、高純度のリン酸の製造法に関す
る。この高純度リン酸は電子工業用エツチング剤等に利
用可能である。Detailed Description of the Invention [Industrial Application Field] The present invention is a highly pure phosphoric acid with extremely low impurities such as metal cations, inorganic anions, and organic substances, and with residual urea of 1 ppm or less and residual nitric acid of 1 ppm or less. Concerning the manufacturing method. This high purity phosphoric acid can be used as an etching agent for the electronic industry.
リン鉱石と硫酸から製造される湿式リン酸は多量の不純
物を含有しているためにブラック・アシド（Ｂｌａｃｋ
−Ａｃｉｄ）とも呼ばれる。この酸から有機物・コロイ
ド状の不溶物・浮遊物および溶存している硫酸イオンを
除去するのにケイソウ土、消石灰、高分子凝集剤、活性
炭等の使用による濾過、または傾斜等の操作を経て緑色
透明なグリーン・アンド （Ｇｒｅｅｎ−Ａｃｉｄ）を
得ることができる。このグリーン・アシドを５０〜８０
°Ｃに加温して尿素を溶解反応させるとリン酸尿素が生
成する。リン酸尿素の溶解度は温度と共に増加するので
リン酸尿素の収率を向上させるためには晶析温度を下げ
る必要がある。このような晶析法により製造されたリン
酸尿素はｐＨが低い状態で結晶化されるので原理的には
金属カチオンは母液中に残り、結晶中に含有されない。Wet phosphoric acid, which is manufactured from phosphate rock and sulfuric acid, contains a large amount of impurities and is known as black acid.
-Acid). In order to remove organic matter, colloidal insoluble matter, suspended matter, and dissolved sulfate ions from this acid, it is necessary to remove the organic matter, colloidal insoluble matter, suspended matter, and dissolved sulfate ions by filtration using diatomaceous earth, slaked lime, polymer flocculants, activated carbon, etc., or through operations such as tilting. Transparent Green-Acid can be obtained. 50 to 80 of this green acid
When heated to °C to cause a dissolution reaction of urea, urea phosphate is produced. Since the solubility of urea phosphate increases with temperature, it is necessary to lower the crystallization temperature in order to improve the yield of urea phosphate. Since urea phosphate produced by such a crystallization method is crystallized at a low pH, in principle, metal cations remain in the mother liquor and are not contained in the crystals.
しかしながら母液が結晶の表面に付着するため０〜５°
Ｃの純水で結晶表面を洗浄したり、更に不純物を除去す
るために純水中で再結晶されることもある。このような
方法で得られた高純度のリン酸尿素の結晶またはこれの
水溶液と精製された硝酸との反応から硝酸尿素とリン酸
が生成される。次に硝酸尿素をろ過により分離してリン
酸水溶液を得る。しかしこのリン酸水溶液中には飽和溶
解度分の硝酸尿素か存在する。However, since the mother liquor adheres to the surface of the crystal, the
The crystal surface may be washed with C pure water, or recrystallized in pure water to further remove impurities. Urea nitrate and phosphoric acid are produced by the reaction of the highly purified urea phosphate crystals obtained by this method or an aqueous solution thereof with purified nitric acid. Next, urea nitrate is separated by filtration to obtain an aqueous phosphoric acid solution. However, this phosphoric acid aqueous solution contains urea nitrate equivalent to the saturated solubility.
硝酸尿素のリン酸中の溶解度はリン酸水溶液中のリン酸
濃度を高くしたり、リン酸水溶液の温度を下げることに
より減少できる。The solubility of urea nitrate in phosphoric acid can be decreased by increasing the phosphoric acid concentration in the phosphoric acid aqueous solution or lowering the temperature of the phosphoric acid aqueous solution.
以上の工程の詳細は特公昭５４−４００７５公報、米国
特許３，９６７．９４８号公報等に論じられている通り
である。The details of the above steps are as discussed in Japanese Patent Publication No. 54-40075, US Pat. No. 3,967.948, etc.
従来技術により硝酸尿素から得られたリン酸水溶液には
飽和溶解度分に相当する多量の硝酸尿素が存在するため
に肥料用の酸として利用されているに過ぎない。このリ
ン酸水溶液の用途を工業用、電子工業用等に拡大するた
めには、さらに硝酸・尿素を除去しなければならない。A phosphoric acid aqueous solution obtained from urea nitrate according to the prior art contains a large amount of urea nitrate corresponding to the saturated solubility, so it is only used as an acid for fertilizers. In order to expand the use of this phosphoric acid aqueous solution to industrial and electronic industries, it is necessary to further remove nitric acid and urea.
本発明者等はこの残存硝酸・尿素の除去方法について鋭
意研究し本発明を完成した。The present inventors conducted intensive research on a method for removing residual nitric acid and urea and completed the present invention.
即ち、本発明は湿式リン酸を出発原料として、リン酸尿
素晶析、硝酸尿素晶析の工程を経て得られるリン酸水溶
液中に溶存する尿素、硝酸を除去し高純度のリン酸を得
るにあたり、溶存する尿素に対して２倍モル以上の硝酸
及び４倍モル以上の塩酸を添加し、残留尿素を分解する
ことを特徴とする高純度リン酸の製造法に関する。That is, the present invention uses wet phosphoric acid as a starting material and removes urea and nitric acid dissolved in a phosphoric acid aqueous solution obtained through the steps of urea phosphate crystallization and urea nitrate crystallization to obtain highly pure phosphoric acid. , relates to a method for producing high-purity phosphoric acid, characterized in that nitric acid or more and hydrochloric acid are added in an amount of twice or more moles to dissolved urea to decompose residual urea.
リン酸中の尿素は、以下のように反応して窒素と水に分
解するものと思われる。It is thought that urea in phosphoric acid reacts as follows and decomposes into nitrogen and water.
２ＨＮ０３＋６ＨＣ１；≧−２ＮＯＣ１２（Ｊ’ ２
＋４Ｈ２０■２ＮＯ（Ｊ’ ＋ ２Ｈ２０＝２ＨＮＯ２
＋ ２ＨＣｆｆ ■２ＨＮ０２＋ＣＯ（Ｎｌ
２）２→２Ｎ２ ＋ ＣＯ２＋３Ｈ２０■■十 ■十
■
２ＨＮＯ３＋４ＨＣ１＋ ＣＯ（Ｎｌ２）２ −
〉 ■２Ｎ２ 十ＣＯ２＋ ５Ｈ２０
＋ ２（Ｊ’ ２これらの反応は反応水溶液中のリン酸
濃度か増大するほど促進される傾向にある。常圧下にお
ける尿素の分解反応はリン酸濃度が６０〜７０重量％の
範囲なら４０°Ｃ付近で速やかに分解するか、リン酸濃
度が４０重量％以下の場合には反応温度を１２０°Ｃ付
近まで上昇させる必要かある。2HN03+6HC1; ≧-2NOC12 (J' 2
+4H20■2NO(J' + 2H20=2HNO2
+ 2HCff ■2HN02+CO(Nl
2) 2→2N2 + CO2+3H20■■10 ■10
■ 2HNO3+4HC1+ CO(Nl2)2 −
〉 ■2N2 10CO2+ 5H20
+ 2 (J' 2 These reactions tend to be accelerated as the phosphoric acid concentration in the reaction aqueous solution increases.The decomposition reaction of urea under normal pressure occurs at 40° if the phosphoric acid concentration is in the range of 60 to 70% by weight. If the phosphoric acid concentration is below 40% by weight, it is necessary to either rapidly decompose at around C or raise the reaction temperature to around 120°C.
Ｎ０Ｃｊ７はＮＯｘガスと塩酸、硝酸、塩素によって下
記のように生成するので、この生成ガスを直接リン酸水
溶液に添加してもよいし、あらかじめ塩酸を添加したリ
ン酸水溶液にＮＯｘガスを吹き込んでもよい。Since N0Cj7 is generated as shown below from NOx gas, hydrochloric acid, nitric acid, and chlorine, this generated gas may be added directly to the phosphoric acid aqueous solution, or the NOx gas may be blown into the phosphoric acid aqueous solution to which hydrochloric acid has been added in advance. .
４ＮＯ＋ ４ＨＣＡ ＋
２ＮＯ＋３ＭＣｌ！＋
ＮＯ＋ ２Ｈ（Ｊ’ ＋
４ＮＯ＋ ６ＨＣＩ！＋
２ＮＯ＋Ｃｆ２
０□ →４ＮＯ（Ｊ’
ＨＮＯａ →３ＮＯＣｆ
ＮＯ□ →２ＮＯＣＩ！
Ｎ２０． →６ＮＯＣＡ
→２ＮＯＣｆ
＋ ２Ｈ２０
＋ ２Ｈ２０
十 Ｎ２０
＋ ３Ｈ２０
しかしながら、これらの方法では、溶存尿素との反応性
が本発明方法のリン酸に塩酸と硝酸を直接添加してＮｏ
（ｌを生成させた場合に比較して小さい。このことは反
応系におけるＮｏ（ｌの溶解量か分解反応に大きく関与
しているためであると思われる。4NO+ 4HCA + 2NO+3MCl! + NO+ 2H(J' + 4NO+ 6HCI!+ 2NO+Cf2 0□ →4NO(J' HNOa →3NOCf NO□ →2NOCI! N20. →6NOCA →2NOCf + 2H20 + 2H20 10 N20 + 3H20 However, these methods Basic By directly adding hydrochloric acid and nitric acid to phosphoric acid in the method of the present invention, the reactivity with No.
(It is small compared to the case where No(l) is produced. This is thought to be because the amount of dissolved No(l) in the reaction system is largely involved in the decomposition reaction.
本発明方法の原料である粗リン酸は、湿式リン酸を出発
原料として、リン酸尿素晶析、硝酸尿素晶析の工程を経
て得られる粗リン酸である。通常この粗リン酸を得る際
に、リン酸尿素結晶に６０〜７０重量％の硝酸を加えて
硝酸尿素とリン酸を生成させた後、硝酸尿素をろ過等に
より分離して４０〜６０重量％の粗リン酸が得る方法が
適用される。この粗リン酸中での尿素濃度は硝酸尿素分
離時の温度により変化するが常温では３〜５重量％であ
る。本発明方法では上述した粗リン酸を出発原料として
、尿素除去のために、溶存する尿素に対して２倍モル以
上の硝酸及び４倍モル以上の塩酸を添加する。硝酸の量
は好ましくは２〜４倍モル、塩酸の量は４〜８倍モルで
ある。この時、反応水溶液中のリン酸濃度は２０〜３０
重量％となる。したがってこのようなリン酸濃度の場合
は粗リン酸水溶液を濃縮し、リン酸濃度を８５％以上と
した後、塩酸と硝酸を添加して反応させることが好まし
い。この際に、塩酸と硝酸を添加後、加熱濃縮して分解
反応と残存する塩酸と硝酸を除去する方法か好ましい。Crude phosphoric acid, which is a raw material for the method of the present invention, is crude phosphoric acid obtained through the steps of urea phosphate crystallization and urea nitrate crystallization using wet phosphoric acid as a starting material. Normally, when obtaining this crude phosphoric acid, 60 to 70% by weight of nitric acid is added to urea phosphate crystals to produce urea nitrate and phosphoric acid, and then urea nitrate is separated by filtration etc. to 40 to 60% by weight. The method for obtaining crude phosphoric acid is applied. The urea concentration in this crude phosphoric acid varies depending on the temperature at which urea nitrate is separated, but is 3 to 5% by weight at room temperature. In the method of the present invention, the above-mentioned crude phosphoric acid is used as a starting material, and in order to remove urea, nitric acid and hydrochloric acid are added in an amount of at least twice the mole of dissolved urea and at least four times the amount of dissolved urea. The amount of nitric acid is preferably 2 to 4 times the mole, and the amount of hydrochloric acid is preferably 4 to 8 times the mole. At this time, the phosphoric acid concentration in the reaction aqueous solution was 20 to 30
% by weight. Therefore, in the case of such a phosphoric acid concentration, it is preferable to concentrate the crude phosphoric acid aqueous solution to a phosphoric acid concentration of 85% or more, and then add hydrochloric acid and nitric acid to react. At this time, it is preferable to add hydrochloric acid and nitric acid and then heat and concentrate to cause a decomposition reaction and remove the remaining hydrochloric acid and nitric acid.
また、硝酸尿素の分離温度を十分低くして、あらかじめ
硝酸尿素の溶解量を減少させておけば尿素分解条件を有
利にてきる。Further, if the separation temperature of urea nitrate is set sufficiently low to reduce the amount of urea nitrate dissolved in advance, the conditions for urea decomposition can be made advantageous.
このような条件下で反応したリン酸水溶液中の尿素はｌ
ｐｐｍ以下にすることができる。Urea in the phosphoric acid aqueous solution reacted under these conditions is l
It can be made less than ppm.
硝酸、塩酸の残存量が多い場合は、リン酸に純水を添加
し加熱濃縮を繰り返し残存する硝酸と塩酸を除去する。If there is a large amount of nitric acid or hydrochloric acid remaining, add pure water to the phosphoric acid and repeat heating and concentration to remove the remaining nitric acid and hydrochloric acid.
この際に、リン酸水溶液中の硝酸及び塩酸濃度が各々０
．１重量％程度であれば、リン酸水溶液中の水の濃度を
５０重量％に調整して加熱濃縮すればリン酸水溶液中の
硝酸及び塩酸濃度はｌｐｐｍ以下にすることかできる。At this time, the nitric acid and hydrochloric acid concentrations in the phosphoric acid aqueous solution are each 0.
．． If it is about 1% by weight, the concentration of nitric acid and hydrochloric acid in the phosphoric acid aqueous solution can be reduced to 1 ppm or less by adjusting the concentration of water in the phosphoric acid aqueous solution to 50% by weight and heating and concentrating it.
このようにして得られた本発明の高純度リン酸は電子工
業用エツチング剤等に利用できる。The high purity phosphoric acid of the present invention thus obtained can be used as an etching agent for the electronic industry.
本発明をさらに説明するためにその実施例を以下に記載
する。Examples are provided below to further illustrate the invention.
実施例１
次の不純物を含むブラック・アシッドの湿式リン酸（た
たし、重量パーセント組成）をＨ３ＰＯ４６２，１％
ＣａＯ，３Ｆｅ ｏ、 ４ ５Ｏ
４５，９Ｍｇ ０．３
１０００ｇに消石灰４５ｇ、ケイソウ土５０ｇ、活性炭
１０ｇを添加し、混合撹拌後不溶物を遠心分離したのち
、得られたケーキを純水１５０ｇで洗浄して９９６ｇの
緑色透明なリン酸水溶液、いわゆるグリーン・アシッド
を得た。得られたリン酸水溶液の分析値は次の通りであ
る。Example 1 Black acid wet phosphoric acid (weight percent composition) containing the following impurities was mixed with H3PO462.1%.
CaO, 3Fe o, 4 5O
45,9Mg 0.3 Add 45g of slaked lime, 50g of diatomaceous earth, and 10g of activated carbon to 1000g of slaked lime, mix and stir, centrifuge to remove insoluble matter, and wash the resulting cake with 150g of pure water to obtain 996g of green transparent phosphorus. An aqueous acid solution, so-called green acid, was obtained. The analytical values of the obtained phosphoric acid aqueous solution are as follows.
重量パーセント組成
Ｈ３ＰＯ４６１，１％ Ｃａ２．３Ｆｅ
Ｏ，４５Ｏ４０，３
Ｍｇ ０．３
このリン酸水溶液に尿素３７２ｇを添加し、６０°Ｃで
撹拌溶解し、その後２０°Ｃまて撹拌しながら冷却して
リン酸尿素の結晶を晶析させた。得られた結晶は遠心機
によりろ過し、６４４ｇのリン酸尿素の結晶を得た。Weight percent composition H3PO461, 1% Ca2.3Fe
O,45O40,3 Mg 0.3 372g of urea was added to this phosphoric acid aqueous solution, stirred and dissolved at 60°C, and then cooled to 20°C with stirring to crystallize urea phosphate crystals. . The obtained crystals were filtered using a centrifuge to obtain 644 g of urea phosphate crystals.
この結晶６４４ｇを６０°Ｃに加温された超純水２５１
ｇに溶解し２０°Ｃまて冷却し再結晶させ遠心分離によ
り３８５ｇのリン酸尿素の結晶を得た。644g of these crystals were heated to 60°C with 251g of ultrapure water.
385 g of phosphate urea crystals were obtained by dissolving the solution in 100 g and cooling to 20° C., recrystallizing, and centrifuging.
この結晶３８５ｇを、再度６０°Ｃに加温した超純水１
５０ｇに溶解し２０°Ｃまて冷却晶析させ遠心分離によ
り２３１ｇのリン酸尿素の結晶を得た。385g of this crystal was heated to 60°C again with ultrapure water 1
The solution was dissolved in 50 g, cooled to 20° C., crystallized, and centrifuged to obtain 231 g of urea phosphate crystals.
得られたリン酸尿素は非常に高純度であり、前記各々の
金属カチオンの含有率は０．５ ｐｐｍ以下であった。The obtained urea phosphate had extremely high purity, and the content of each of the metal cations was 0.5 ppm or less.
この高純度リン酸尿素の結晶２３１ｇに精製された６７
．５重量％硝酸１３６ｇ、超純水１５０ｇを２０°Ｃで
混合撹拌した。この硝酸尿素スラリーを遠心分離するこ
とにより硝酸尿素の結晶１５８ｇ、リン酸水溶液３５８
ｇを得た。得られたリン酸水溶液の分析値は、リン酸４
０．０重量％、硝酸２．９２重量％、尿素３．０７重量
％であった。This 67 was purified into 231g of crystals of high purity urea phosphate.
．． 136 g of 5% by weight nitric acid and 150 g of ultrapure water were mixed and stirred at 20°C. By centrifuging this urea nitrate slurry, 158 g of urea nitrate crystals and 358 g of phosphoric acid aqueous solution were obtained.
I got g. The analytical value of the obtained phosphoric acid aqueous solution was phosphoric acid 4
0.0% by weight, nitric acid 2.92% by weight, and urea 3.07% by weight.
上記の過程により得られたリン酸水溶液２００ｇに６７
．５重量％硝酸１８．４ ｇ、３６重量％塩酸７６、６
ｇを添加し、常圧下１２０°Ｃの条件で加熱濃縮させ
９２ｇのリン酸水溶液を得た。このリン酸水溶液の分析
値は、リン酸８６．９重量％、塩酸８．７重量％、硝酸
３．８重量％、尿素ｌｐｐｍ以下であった。67 to 200g of the phosphoric acid aqueous solution obtained by the above process.
．． 5 wt% nitric acid 18.4 g, 36 wt% hydrochloric acid 76.6
g was added thereto, and the mixture was heated and concentrated at 120° C. under normal pressure to obtain 92 g of an aqueous phosphoric acid solution. The analytical values of this phosphoric acid aqueous solution were 86.9% by weight of phosphoric acid, 8.7% by weight of hydrochloric acid, 3.8% by weight of nitric acid, and 1 ppm or less of urea.
さらにリン酸水溶液中の硝酸、塩酸を除去するために上
記リン酸水溶液に純水６０ｇを添加して常圧下１５０°
Ｃて加熱し６０ｇまで濃縮した。塩酸０．８重量％、硝
酸１．２重量％であった。Furthermore, in order to remove nitric acid and hydrochloric acid in the phosphoric acid aqueous solution, 60 g of pure water was added to the above phosphoric acid aqueous solution and heated to 150° under normal pressure.
The mixture was heated to 60 g and concentrated to 60 g. The contents were 0.8% by weight of hydrochloric acid and 1.2% by weight of nitric acid.
この操作を更に２度繰り返し５６ｇのリン酸水溶液を得
た。得られたリン酸水溶液の分析値はリン酸９３．０重
量％、尿素ｌｐｐｍ以下、硝酸ｌｐｐｍ以下、塩酸ｌｐ
ｐｍ以下であった。This operation was repeated twice more to obtain 56 g of phosphoric acid aqueous solution. The analytical values of the obtained phosphoric acid aqueous solution were phosphoric acid 93.0% by weight, urea lppm or less, nitric acid lppm or less, hydrochloric acid lp
It was below pm.
実施例２
実施例１の方法で得られたリン酸尿素の結晶３００ｇに
６７．５重量％の高純度硝酸１７８ｇと超純水５９４ｇ
を混合撹拌し２０°Ｃの状態てこの硝酸尿素スラリーを
遠心分離し１４２ｇの硝酸尿素の結晶と９３０ｇのリン
酸水溶液を得た。得られたリン酸水溶液の分析値は、リ
ン酸２０．０重量％、硝酸５．１２重量％、尿素４．８
７重量％であった。Example 2 178 g of 67.5% by weight high-purity nitric acid and 594 g of ultrapure water were added to 300 g of urea phosphate crystals obtained by the method of Example 1.
The urea nitrate slurry was mixed and stirred at 20°C and centrifuged to obtain 142 g of urea nitrate crystals and 930 g of an aqueous phosphoric acid solution. The analytical values of the obtained phosphoric acid aqueous solution were 20.0% by weight of phosphoric acid, 5.12% by weight of nitric acid, and 4.8% by weight of urea.
It was 7% by weight.
上記の過程により得られたリン酸水溶液３００ｇを常圧
下１００°Ｃの条件で１５０ｇまで濃縮した。この濃縮
液に６７．５重量％硝酸６８．４ ｇ、３６重量％塩酸
１９１．７ｇを添加し、常圧下１２０°Ｃの条件で加熱
濃縮し７５ｇのリン酸水溶液を得たこのリン酸水溶液の
分析値はリン酸８０．０重量％、塩酸６．５重量％、硝
酸１３．０重量％、尿素１ｐｐｍＪ）、下であった。300 g of the phosphoric acid aqueous solution obtained through the above process was concentrated to 150 g under normal pressure and 100°C. To this concentrated solution, 68.4 g of 67.5% by weight nitric acid and 191.7g of 36% by weight hydrochloric acid were added, and the mixture was heated and concentrated under normal pressure at 120°C to obtain 75g of a phosphoric acid aqueous solution. The analytical values were 80.0% by weight of phosphoric acid, 6.5% by weight of hydrochloric acid, 13.0% by weight of nitric acid, and 1 ppmJ of urea.
上記リン酸水溶液５０ｇに純水５０ｇを添加して常圧下
１５０°Ｃて加熱し５０ｇまで濃縮した。50 g of pure water was added to 50 g of the above phosphoric acid aqueous solution, heated at 150° C. under normal pressure, and concentrated to 50 g.
この操作を更に２度繰り返し５６ｇのリン酸水溶液を得
た。得られたリン酸水溶液の分析値はリン酸９５．０重
量％、尿素０．０００１重量％以下、硝酸ｌｐｐｍ以下
、塩酸ｌｐｐｍ以下であった。This operation was repeated twice more to obtain 56 g of phosphoric acid aqueous solution. The analytical values of the obtained phosphoric acid aqueous solution were 95.0% by weight of phosphoric acid, 0.0001% by weight or less of urea, 1 ppm or less of nitric acid, and 1 ppm or less of hydrochloric acid.
Claims (2)
硝酸尿素晶析の工程を経て得られるリン酸水溶液中に溶
存する尿素、硝酸を除去し高純度のリン酸を得るにあた
り、溶存する尿素に対して２倍モル以上の硝酸及び４倍
モル以上の塩酸を添加し、残留尿素を分解することを特
徴とする高純度リン酸の製造法。(1) Urea phosphate crystallization using wet phosphoric acid as a starting material,
In order to remove urea and nitric acid dissolved in the phosphoric acid aqueous solution obtained through the process of urea nitrate crystallization to obtain high-purity phosphoric acid, nitric acid in an amount of 2 times the mole or more and 4 times the mole or more of dissolved urea are added. A method for producing high-purity phosphoric acid, which is characterized by adding hydrochloric acid to decompose residual urea.
分解した後、純水を加え減圧濃縮を繰り返し適用するこ
とによりリン酸水溶液の尿素、硝酸を除去する請求項１
記載の高純度リン酸の製造法。(2) Urea and nitric acid remaining in the phosphoric acid aqueous solution are removed by decomposing the urea remaining in the phosphoric acid aqueous solution with hydrochloric acid and nitric acid, then adding pure water and repeatedly applying vacuum concentration.Claim 1
The method for producing high purity phosphoric acid as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19697090A JPH0483710A (en) | 1990-07-25 | 1990-07-25 | Production of high-purity phosphoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19697090A JPH0483710A (en) | 1990-07-25 | 1990-07-25 | Production of high-purity phosphoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0483710A true JPH0483710A (en) | 1992-03-17 |
Family
ID=16366678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19697090A Pending JPH0483710A (en) | 1990-07-25 | 1990-07-25 | Production of high-purity phosphoric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0483710A (en) |
-
1990
- 1990-07-25 JP JP19697090A patent/JPH0483710A/en active Pending
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