JPH10168046A - Production of ferric salt of aminopolycarboxylic acid - Google Patents
Production of ferric salt of aminopolycarboxylic acidInfo
- Publication number
- JPH10168046A JPH10168046A JP32985296A JP32985296A JPH10168046A JP H10168046 A JPH10168046 A JP H10168046A JP 32985296 A JP32985296 A JP 32985296A JP 32985296 A JP32985296 A JP 32985296A JP H10168046 A JPH10168046 A JP H10168046A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- aminopolycarboxylic acid
- iron
- acid
- ferric
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 53
- 150000003839 salts Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 50
- 238000000354 decomposition reaction Methods 0.000 abstract description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 5
- 235000014413 iron hydroxide Nutrition 0.000 abstract description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 35
- 229910052742 iron Inorganic materials 0.000 description 20
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 235000013980 iron oxide Nutrition 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UOMQUZPKALKDCA-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical class [Fe+3].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UOMQUZPKALKDCA-UHFFFAOYSA-K 0.000 description 1
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、写真用薬剤、植物
の微量成分肥料、燃焼助剤等として有用なアミノポリカ
ルボン酸第二鉄塩を、高純度品として効率よく製造する
ことのできる方法に関するものである。TECHNICAL FIELD The present invention relates to a method for efficiently producing ferric aminopolycarboxylic acid salts useful as photographic drugs, plant fertilizers, combustion aids, etc. as high-purity products. It is about.
【０００２】[0002]
【従来の技術】写真用処理剤等として用いられるアミノ
ポリカルボン酸第二鉄塩は、通常水溶液として使用され
るため、製品は水溶液として提供されることが多い。と
ころで、水溶性鉄塩（硫酸第一鉄、硫酸第二鉄、塩化第
二鉄、硝酸鉄など）とアミノポリカルボン酸またはその
アルカリ塩（ナトリウム塩、カリウム塩、アンモニウム
塩、アミン塩など）の水溶液を混合すると、速やかに反
応してアミノポリカルボン酸第二鉄塩が生成することは
周知のことであるが、同時に副生する無機塩が処理設備
の腐食原因となるので、反応液をこのままで使用するこ
とはできない。そこで通常は、塩析、冷却、濃縮などの
手段を経てアミノポリカルボン酸第二鉄塩の結晶を単離
した後、再度水に溶解して提供されている。この水溶液
は、結晶工程で精製されているため高純度であるが、無
機塩の析出混入を防止することの必要上晶析時の濃度を
余り高くすることができないため、濾液と共に流出する
アミノポリカルボン酸第二鉄塩のロスが多く、また晶
析、濾過、水洗等の工程数が多いこともあって、製品コ
ストが高くなるという大きな難点がある。2. Description of the Related Art Ferric aminopolycarboxylate used as a photographic processing agent or the like is usually used as an aqueous solution, so that the product is often provided as an aqueous solution. By the way, water-soluble iron salts (ferrous sulfate, ferric sulfate, ferric chloride, iron nitrate, etc.) and aminopolycarboxylic acid or its alkali salt (sodium salt, potassium salt, ammonium salt, amine salt, etc.) It is well known that when an aqueous solution is mixed, it reacts promptly to produce ferric aminopolycarboxylate, but at the same time, the by-produced inorganic salt causes corrosion of the processing equipment. Can not be used with. Therefore, usually, crystals of ferric aminopolycarboxylate are isolated through means such as salting out, cooling, and concentration, and then provided again after being dissolved in water. This aqueous solution has high purity because it has been purified in the crystallization step, but the concentration at the time of crystallization cannot be made too high because it is necessary to prevent the precipitation and mixing of inorganic salts. There is a large drawback that the cost of the product is increased because the loss of ferric carboxylate is large and the number of steps such as crystallization, filtration and washing is large.
【０００３】上記の様な無機塩を副生しない方法とし
て、特開昭４６−１３１８号公報には四三酸化鉄を原料
として用いる方法も提案されたが、この方法は反応速度
が非常に遅いため、アミノポリカルボン酸を過剰量用い
て高温で反応させる必要があった。この改善策として、
特開昭４９−９３３２５号では金属鉄粉末を併用する方
法、特開昭４９−７６８１６号、特公昭５６−５２３７
号、特公昭５３−３５９２９号では水酸化鉄や四三酸化
鉄と金属鉄を併用して反応速度を高める方法、特開昭５
９−１６７５９５号では、水和酸化鉄と還元剤を併用す
ることによって反応速度を高める方法、などが提案され
た。As a method of not producing the inorganic salt as a by-product as described above, Japanese Patent Application Laid-Open No. 46-1318 has proposed a method using triiron tetroxide as a raw material, but this method has a very low reaction rate. For this reason, it was necessary to use an excess amount of aminopolycarboxylic acid and carry out the reaction at a high temperature. As a remedy,
JP-A-49-93325 discloses a method in which metallic iron powder is used in combination, JP-A-49-76816, and JP-B-56-5237.
And JP-B-53-35929 discloses a method of increasing the reaction rate by using iron hydroxide or iron tetroxide in combination with metallic iron.
No. 9-167595 proposes a method of increasing the reaction rate by using a combination of hydrated iron oxide and a reducing agent.
【０００４】ところが、これらの方法によって得られる
アミノポリカルボン酸第二鉄塩中には、多量の第一鉄塩
が混入してくる。写真漂白用等では第二鉄塩であること
が要求されるので、反応の途中もしくは反応終了後に空
気や酸素を吹き込んで酸化する必要があり、この酸化工
程でアミノポリカルボン酸の酸化分解が起こると言う問
題が生じてくる。事実本発明者らが確認したところによ
ると、酸化処理温度にもよるが、該酸化処理工程で１〜
３重量％程度のアミノポリカルボン酸の分解が生じた。
こうした酸化分解を防止するため、酸化安定剤を添加す
る方法（特開昭６４−７１８４２号）が提案されている
が、この酸化安定剤はそのまま不純物として混入してく
るため推奨されない。However, a large amount of ferrous salt is mixed in the ferric aminopolycarboxylate obtained by these methods. Since it is required to be a ferric salt for photo bleaching or the like, it is necessary to oxidize by blowing air or oxygen during or after the reaction, and oxidative decomposition of aminopolycarboxylic acid occurs in this oxidation step A problem arises. In fact, the present inventors have confirmed that, depending on the oxidation treatment temperature, the oxidation treatment step may have
About 3% by weight of aminopolycarboxylic acid was decomposed.
In order to prevent such oxidative decomposition, a method of adding an oxidation stabilizer (Japanese Patent Application Laid-Open No. 64-71842) has been proposed, but this oxidation stabilizer is not recommended because it is directly mixed as an impurity.
【０００５】特開昭４６−１３１８号には、鉄源として
第二鉄の酸化物である赤鉄鉱を使用し、またドイツ特許
３，６２２，３６４号では鉄源としてＦｅＯ（ＯＨ）を
用いてアミノポリカルボン酸第二鉄塩を製造する方法が
提案されており、更にチェコスロバキア特許２５５４３
５号には、塩化第二鉄と苛性ソーダから得た酸化第二鉄
をアミノポリカルボン酸と反応させる方法も提案されて
いる。ところがこれらの方法は、いずれも反応速度が遅
いため沸点温度あるいはそれ以上の温度に加熱しなけれ
ばならず、また鉄源に対して過剰量のアミノポリカルボ
ン酸を使用しなければならないため効率が非常に悪い。Japanese Patent Application Laid-Open No. 46-1318 uses hematite, which is an oxide of ferric iron, as an iron source, and FeO (OH) as an iron source in German Patent No. 3,622,364. A method for producing ferric aminopolycarboxylic acid salt has been proposed, and further disclosed in Czechoslovakia Patent 25543
No. 5 also proposes a method of reacting ferric oxide obtained from ferric chloride and caustic soda with an aminopolycarboxylic acid. However, all of these methods have a low reaction rate and must be heated to a boiling point or higher, and the efficiency must be increased because an excessive amount of aminopolycarboxylic acid must be used relative to the iron source. Very bad.
【０００６】第二鉄は酸化能力を有しており、高温条件
下でアミノポリカルボン酸を酸化分解して第一鉄に変わ
ることが確認されており、本発明者らの実験によれば１
００℃で１時間当たり１〜１．５重量％のアミノポリカ
ルボン酸が分解すると共にその対応量が第一鉄に変化す
るので、いずれにしろ、高純度のアミノポリカルボン酸
第二鉄塩を得ることができない。Ferric iron has an oxidizing ability, and it has been confirmed that aminopolycarboxylic acid is oxidatively decomposed into ferrous iron under high-temperature conditions.
Since 1 to 1.5% by weight of aminopolycarboxylic acid per hour is decomposed at 00 ° C. and the corresponding amount is changed to ferrous iron, in any case, a highly pure ferric aminopolycarboxylic acid salt is used. I can't get it.
【０００７】[0007]
【発明が解決しようとする課題】例えば写真用漂白剤と
して用いられるアミノポリカルボン酸第二鉄水溶液は、
第二鉄の酸化能力を活用するものであり、性能確保の為
には第一鉄含有量を極力少なく抑えなければならず、前
述の如く事後的に空気酸化等を行なう方法を採用する
と、アミノポリカルボン酸の酸化分解ロスが避けられな
い。従って、鉄源としては、本質的に酸化工程の必要の
ない酸化第二鉄を使用するのが理想であるが、前述の如
く酸化第二鉄は反応速度が極めて遅く、反応速度を高め
るために高温処理を行なうと、アミノポリカルボン酸の
熱分解が避けられなかったのである。For example, an aqueous solution of ferric aminopolycarboxylate used as a photographic bleach is
It utilizes the oxidizing ability of ferric iron, and the ferrous content must be kept as low as possible in order to ensure the performance. Oxidative decomposition loss of polycarboxylic acid is inevitable. Therefore, as an iron source, it is ideal to use ferric oxide which essentially does not require an oxidation step. However, as described above, ferric oxide has a very slow reaction rate, and in order to increase the reaction rate, When high-temperature treatment was performed, thermal decomposition of aminopolycarboxylic acid was inevitable.
【０００８】本発明はこの様な事情に着目してなされた
ものであって、その目的は、アミノポリカルボン酸との
反応工程で分解することがなく、且つアミノポリカルボ
ン酸の分解ロスを招くこともなく、高純度のアミノポリ
カルボン酸第二鉄を効率よく製造することのできる方法
を確立しようとするものである。The present invention has been made in view of such circumstances, and has as its object to prevent decomposition in the step of reacting with aminopolycarboxylic acid and cause loss of aminopolycarboxylic acid decomposition. It is an object of the present invention to establish a method capable of efficiently producing high-purity ferric aminopolycarboxylate without any problems.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決すること
のできた本発明に係る製法とは、アミノポリカルボン酸
にγ−ＦｅＯ（ＯＨ）を反応させるところにその特徴を
有しており、この発明を実施するに当たっては、アミノ
ポリカルボン酸１モルに対し、γ−ＦｅＯ（ＯＨ）を
０．９５〜１．０５モルの範囲で使用するのがよく、ま
たこの反応は、水系溶媒中、ｐＨを５以下に維持し、５
０〜８０℃の温度範囲で行なうことにより、高純度のア
ミノポリカルボン酸第二鉄を効率よく製造することがで
きる。Means for Solving the Problems The manufacturing method according to the present invention which can solve the above problems has a feature in that γ-FeO (OH) is reacted with an aminopolycarboxylic acid. In carrying out the invention, it is preferable to use γ-FeO (OH) in the range of 0.95 to 1.05 mol per mol of aminopolycarboxylic acid, and this reaction is carried out in an aqueous solvent at pH Is maintained at 5 or less, and 5
By performing the reaction in the temperature range of 0 to 80 ° C., high-purity ferric aminopolycarboxylate can be efficiently produced.
【００１０】[0010]
【発明の実施の形態】本発明者らは前述の様な課題の解
決を最終の目的とし、代表的なアミノポリカルボン酸と
してエチレンジアミン四酢酸（ＥＤＴＡ）を使用し、様
々の酸化鉄との反応性について検討した結果、下記の様
な事実を確認した。BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present invention aim at solving the above-mentioned problems and use ethylenediaminetetraacetic acid (EDTA) as a typical aminopolycarboxylic acid to react with various iron oxides. As a result of examining the properties, the following facts were confirmed.
【００１１】α−Ｆｅ2 Ｏ3 やγ−Ｆｅ2 Ｏ3 は、ＥＤ
ＴＡとの反応性が極めて乏しく、６０℃×２４時間でも
全く反応しない。β−ＦｅＯ（ＯＨ）や水酸化鉄(III)
とＥＤＴＡの反応については、製造直後の水酸化鉄を使
用すると６０℃、１〜２時間で反応は完結するが、経時
変化によって反応速度が極端に低下してくる。しかも、
水酸化鉄はコロイド状であって濾過・水洗に多大な労力
を要するばかりでなく、副生する無機塩の除去が困難で
あり、工業的に安定した品質の製品を得ることは容易で
なく、高純度アミノポリカルボン酸第二鉄塩の製造原料
としては適性を欠く。Α-Fe 2 O 3 and γ-Fe 2 O 3 are ED
The reactivity with TA is extremely poor, and it does not react at all even at 60 ° C. for 24 hours. β-FeO (OH) and iron (III) hydroxide
When using iron hydroxide immediately after production, the reaction is completed at 60 ° C. for 1 to 2 hours, but the reaction rate is extremely reduced due to the change with time. Moreover,
Iron hydroxide is colloidal and not only requires a great deal of labor for filtration and washing, but also it is difficult to remove by-product inorganic salts, and it is not easy to obtain industrially stable quality products. It is not suitable as a raw material for producing high-purity ferric aminopolycarboxylic acid salt.
【００１２】またα−ＦｅＯ（ＯＨ）やγ−ＦｅＯ（Ｏ
Ｈ）は、安価な硫酸第一鉄を原料として製造することが
できるのでコスト的にも有利であるが、このうちα−Ｆ
ｅＯ（ＯＨ）は、６０℃で２４時間反応を行なっても、
仕込んだ鉄分のうち３０重量％しか反応しなかった。Further, α-FeO (OH) and γ-FeO (O
H) can be produced from inexpensive ferrous sulfate as a raw material, and is therefore cost-effective. Among them, α-F
eO (OH) reacts at 60 ° C. for 24 hours,
Only 30% by weight of the charged iron reacted.
【００１３】ところがγ−ＦｅＯ（ＯＨ）のみについて
は、６０℃、１〜２時間でＥＤＴＡと全量が反応するこ
とをつきとめた。また、「新実験化学講座」（丸善株式
会社より昭和５１年１２月２０日発行）の製法Ｉでは、
γ−ＦｅＯ（ＯＨ）を得るのに、鉄に対し１２．４モル
のりん酸を添加しており、多量のりん酸は有害となるの
で、その添加量を鉄に対し１モル％に低減したγ−Ｆｅ
Ｏ（ＯＨ）についても反応を試みたところ、６０℃、２
時間で鉄分の１００％が反応することが確認された。更
に驚くべきことに、Ｆｅ3 Ｏ4 を鉄源として用いたＥＤ
ＴＡとの反応（６０℃×２時間）では、この反応工程で
ＥＤＴＡの０．５〜１．０モル％が分解するのに対し、
鉄源としてγ−ＦｅＯ（ＯＨ）を用いたときのＥＤＴＡ
の分解は僅か０．０５〜０．１モル％に過ぎず、第二鉄
源として極めて適していることが確認された。However, it was found that only γ-FeO (OH) reacted with EDTA at 60 ° C. for 1 to 2 hours. Also, in the manufacturing method I of "New Experimental Chemistry Course" (issued by Maruzen Co., Ltd. on December 20, 1977),
To obtain γ-FeO (OH), 12.4 mol of phosphoric acid is added to iron, and a large amount of phosphoric acid is harmful. γ-Fe
When a reaction was attempted on O (OH),
It was confirmed that 100% of the iron content reacted with time. Even more surprisingly, EDs using Fe 3 O 4 as an iron source
In the reaction with TA (60 ° C. × 2 hours), 0.5 to 1.0 mol% of EDTA is decomposed in this reaction step,
EDTA using γ-FeO (OH) as iron source
Was only 0.05 to 0.1 mol%, and it was confirmed that it was extremely suitable as a ferric source.
【００１４】本発明ではこの様な結果を元に、アミノポ
リカルボン酸第二鉄塩の製造に使用する第二鉄化合物と
してγ−ＦｅＯ（ＯＨ）を選択するものであり、使用す
る該γ−ＦｅＯ（ＯＨ）は、もとより前記「新実験化学
講座」に記述された方法によって製造されたものに限定
される訳ではなく、原料となる水溶性無機鉄塩の種類や
ｐＨ調整用アルカリ等の原料の種類や添加順序、添加速
度、反応温度、酸化方法等については適宜変更すること
が可能である。しかもγ−ＦｅＯ（ＯＨ）を製造する際
には、前述の如くりん酸の添加量を減少しても反応速度
は殆んど遅くならないことから、りん酸の添加は必須で
なく、ある種のアミノポリカルボン酸や有機酸等を添加
して得たγ−ＦｅＯ（ＯＨ）を使用することも可能であ
る。In the present invention, based on such a result, γ-FeO (OH) is selected as a ferric compound used for producing a ferric aminopolycarboxylic acid salt, and the γ-FeO (OH) is used. FeO (OH) is not necessarily limited to the one manufactured by the method described in the above-mentioned "New Experimental Chemistry Course", but may be a kind of water-soluble inorganic iron salt as a raw material or a raw material such as an alkali for pH adjustment. , The order of addition, the rate of addition, the reaction temperature, the oxidation method, and the like can be appropriately changed. In addition, when γ-FeO (OH) is produced, the reaction rate hardly decreases even if the amount of phosphoric acid is reduced as described above. It is also possible to use γ-FeO (OH) obtained by adding an aminopolycarboxylic acid or an organic acid.
【００１５】γ−ＦｅＯ（ＯＨ）とアミノポリカルボン
酸を反応させる際の好ましい温度は５０〜８０℃の範囲
であり、反応温度が低くなり過ぎると反応に長時間を要
するため効率が悪く、また温度が高過ぎるとアミノポリ
カルボン酸の分解が起こり易くなる。本発明者らが実験
により確認したところでは、アミノポリカルボン酸の分
解速度は８０℃で１時間当たり０．０７〜０．１モル
％、６０℃で１時間当たり０．００５〜０．０１モル％
であり、本発明で意図するレベルの高純度製品を得るに
は、反応速度と分解量の兼ね合いから６０〜７０℃の範
囲が最も好ましい。The preferred temperature at which γ-FeO (OH) is reacted with aminopolycarboxylic acid is in the range of 50 to 80 ° C. If the reaction temperature is too low, the reaction takes a long time, resulting in poor efficiency. If the temperature is too high, decomposition of the aminopolycarboxylic acid tends to occur. The inventors confirmed by experiments that the decomposition rate of aminopolycarboxylic acid was 0.07 to 0.1 mol% per hour at 80 ° C., and 0.005 to 0.01 mol% per hour at 60 ° C. %
In order to obtain a high-purity product at the level intended in the present invention, the range of 60 to 70 ° C. is most preferable in consideration of the reaction rate and the amount of decomposition.
【００１６】一方、本発明で使用されるアミノポリカル
ボン酸は、鉄をキレート化し得るものであればその種類
の如何は一切問われず、前記ＥＤＴＡの他、ニトロトリ
酢酸、ジエチレントリアミンペンタ酢酸、オルトジアミ
ンシクロヘキサンテトラ酢酸、１，３−プロピレンジア
ミンテトラ酢酸、ヒドロキシエチレンジアミントリ酢酸
なども同様に使用することができ、又これらは単独で使
用し得るほか必要により２種以上を併用することも可能
である。特に本発明では、前述の如く反応後に酸化処理
を行なう必要がないので、酸化安定性の悪いアミノポリ
カルボン酸が有効に使用できる。On the other hand, the aminopolycarboxylic acid used in the present invention is not particularly limited as long as it can chelate iron. In addition to the above EDTA, nitrotriacetic acid, diethylenetriaminepentaacetic acid, orthodiaminecyclohexane Tetraacetic acid, 1,3-propylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid and the like can also be used in the same manner. These can be used alone or in combination of two or more if necessary. In particular, in the present invention, since it is not necessary to perform an oxidation treatment after the reaction as described above, an aminopolycarboxylic acid having poor oxidation stability can be effectively used.
【００１７】尚上記アミノポリカルボン酸とγ−ＦｅＯ
（ＯＨ）の使用比率は、前者１モルに対し後者をＦｅ換
算で０．９５〜１．０５モルの範囲とするのがよく、γ
−ＦｅＯ（ＯＨ）の使用比率が多過ぎても又不足する場
合も、未反応物が不純物として混入することになるの
で、製品純度を下げる原因となる。最も好ましいのは、
両者を等モル比で使用することである。The above aminopolycarboxylic acid and γ-FeO
The use ratio of (OH) is preferably in the range of 0.95 to 1.05 mol in terms of Fe with respect to 1 mol of the former.
If the use ratio of -FeO (OH) is too large or too small, unreacted substances will be mixed in as impurities, which causes a reduction in product purity. Most preferably,
Both are used in an equimolar ratio.
【００１８】上記アミノポリカルボン酸は、部分的に中
和して溶解度を高めてから反応に供するのが一般的であ
るが、元々溶解度の高いアミノカルボン酸の場合は、酸
型のままで使用することも勿論可能である。The aminopolycarboxylic acid is generally partially neutralized to increase the solubility and then subjected to the reaction. However, in the case of an aminocarboxylic acid originally having a high solubility, it is used as it is in the acid form. It is of course possible to do so.
【００１９】γ−ＦｅＯ（ＯＨ）とアミノポリカルボン
酸を反応させる際には、反応中および反応終了後のｐＨ
を５以下に保つことが必要であり、反応系のｐＨが高く
なると反応速度が遅くなると共に、反応時におけるアミ
ノポリカルボン酸第二鉄塩の熱分解も起こり易くなり、
純度低下の原因となる。例えば、ＥＤＴＡ第二鉄塩の８
０℃における分解速度は、ｐＨ４で０．０９モル％／時
間であるのに対し、ｐＨ７．６では０．８％／時間に増
大する。従って反応系のｐＨは低い方が有利であるが、
場合によっては反応中にアミノポリカルボン酸第二鉄塩
の結晶が析出してくることがあるので、この様な場合
は、濾過によって不純物を除去する際に、反応液に少量
のアルカリを添加し、アミノポリカルボン酸第二鉄塩の
溶解度を高めてから濾過することが有利となることもあ
る。When γ-FeO (OH) is reacted with aminopolycarboxylic acid, the pH during and after the reaction is
Is required to be kept at 5 or less, and when the pH of the reaction system increases, the reaction rate decreases, and the thermal decomposition of the aminopolycarboxylic acid ferric salt during the reaction also easily occurs,
This may cause a decrease in purity. For example, ferric EDTA salt 8
The decomposition rate at 0 ° C. is 0.09 mol% / h at pH 4, whereas it increases to 0.8% / h at pH 7.6. Therefore, it is advantageous that the pH of the reaction system is low,
In some cases, crystals of ferric aminopolycarboxylate may precipitate during the reaction.In such a case, a small amount of alkali is added to the reaction solution when removing impurities by filtration. It may be advantageous to increase the solubility of the aminopolycarboxylic acid ferric salt before filtering.
【００２０】先に説明した様に従来法では、反応時にお
けるアミノカルボン酸の分解が避けられず、且つアミノ
ポリカルボン酸を酸化鉄に対して過剰量使用しなければ
ならず、用途によっては未反応のアミノポリカルボン酸
や過剰量の鉄分が嫌われるため、反応終了後あるいは酸
化終了後に反応液中の鉄分とアミノポリカルボン酸の量
を個々に分析し、いずれか一方を添加することによって
両者のモル数を一致させる必要があった。ところが本発
明では、反応時におけるアミノポリカルボン酸の分解が
極めて少なく、且つ反応後の酸化処理も不要で酸化によ
りアミノポリカルボン酸の分解が起こる余地もないの
で、仕込み量で酸化鉄とアミノポリカルボン酸のモル比
を調整しておくだけで、反応後に前述の様なモル比を調
整する必要は全くない。また用途により、もし鉄分ある
いはアミノポリカルボン酸のいずれかを過剰にしたいと
きは、仕込みモル比で調整することによって自由にコン
トロールできる。As described above, in the conventional method, the decomposition of the aminocarboxylic acid during the reaction is unavoidable, and the aminopolycarboxylic acid must be used in an excessive amount relative to the iron oxide. Since the aminopolycarboxylic acid and excessive amount of iron in the reaction are disliked, the amount of iron and aminopolycarboxylic acid in the reaction solution are individually analyzed after completion of the reaction or after completion of oxidation. Had to be matched. However, in the present invention, decomposition of aminopolycarboxylic acid during the reaction is extremely small, and oxidation treatment after the reaction is unnecessary, and there is no room for decomposition of aminopolycarboxylic acid by oxidation. It is not necessary to adjust the molar ratio as described above after the reaction only by adjusting the molar ratio of the carboxylic acid. Depending on the application, if it is desired to increase either the iron content or the aminopolycarboxylic acid, it can be freely controlled by adjusting the charged molar ratio.
【００２１】また、溶解度の低いアミノポリカルボン酸
を使用する場合でも、その溶解度が最低となるｐＨ領域
（一般的にはｐＨ１．５〜２．５程度）でややアミノポ
リカルボン酸過剰で反応を行なえば、未反応のアミノポ
リカルボン酸が不溶物として遊離するので、これを濾別
して得られる溶液中の鉄分とアミノポリカルボン酸のモ
ル比はほぼ１：１となり、モル比の後調整は不要とな
る。Even when an aminopolycarboxylic acid having a low solubility is used, the reaction is carried out in a pH region where the solubility is the lowest (generally about pH 1.5 to 2.5) and a slight excess of the aminopolycarboxylic acid. If this is done, the unreacted aminopolycarboxylic acid is released as an insoluble matter, so that the molar ratio between the iron content and the aminopolycarboxylic acid in the solution obtained by filtration is approximately 1: 1 and no post-adjustment of the molar ratio is necessary. Becomes
【００２２】上記の様に、本発明によって得られる反応
液中には第一鉄は存在しないので、アミノポリカルボン
酸との反応後は、酸化処理等を要することなくそのまま
で使用できるが、必要によってはアルカリを加えてｐＨ
調整したり、あるいは濃縮して高濃度品として製品化
し、更には濃縮して結晶化させ、必要により精製して結
晶として得ることも勿論可能である。As described above, since ferrous iron does not exist in the reaction solution obtained according to the present invention, after the reaction with aminopolycarboxylic acid, it can be used as it is without the need for oxidation treatment. Depending on the pH, add alkali
It is of course possible to adjust or concentrate and commercialize it as a high-concentration product, further concentrate and crystallize, and if necessary, purify to obtain crystals.
【００２３】[0023]
【実施例】次に実施例を挙げて本発明をより具体的に説
明するが、本発明はもとより下記実施例によって制限を
受けるものではなく、前・後記の趣旨に適合し得る範囲
で適当に変更を加えて実施することも可能であり、それ
らは全て本発明の技術的範囲に包含される。EXAMPLES Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, but may be appropriately adjusted within a range that can conform to the purpose of the preceding and following examples. Modifications can be made and all are included in the technical scope of the present invention.
【００２４】実施例１ ２０５ｇのＦｅＳＯ4 ・７Ｈ2 Ｏを１０リットルの水に
溶解し、これに１００．２ｇのアンモニア水（２５％）
を加え、更に１．０５ｇのＮａ2 ＨＰＯ4 を加えた後、
４０℃に加熱しつつ散気管から空気を吹き込んで３時間
酸化を行なう。その間、生成する沈殿は一旦濃緑青色を
経て、黄色で微細な針状のγ−ＦｅＯ（ＯＨ）に変化す
る。この沈殿をヌッチェで濾過し、更に純水で十分に洗
浄してから５０℃で１０時間乾燥した。得られた結晶の
重量は７０．９ｇで、Ｆｅ含有量は５８．０重量％であ
った。[0024] was dissolved FeSO 4 · 7H 2 O in Example 1 205g of 10 liters of water, to which 100.2g of aqueous ammonia (25%)
Was added, and 1.05 g of Na 2 HPO 4 was added.
While heating to 40 ° C., air is blown from the air diffuser to perform oxidation for 3 hours. In the meantime, the generated precipitate once passes through dark green blue, and then changes to yellow fine needle-like γ-FeO (OH). The precipitate was filtered with a Nutsche, further thoroughly washed with pure water, and dried at 50 ° C. for 10 hours. The weight of the obtained crystal was 70.9 g, and the Fe content was 58.0% by weight.
【００２５】得られたγ−ＦｅＯ（ＯＨ）７０．９ｇを
４９９．８ｇの水に添加し、更に２１５．２ｇのＥＤＴ
Ａと５０．１ｇのアンモニア水（２５％）を加え、６０
℃に昇温して攪拌を続けると、約２時間で反応液は透明
となる。冷却してから反応液をＮｏ．５Ｃの濾紙で濾過
したところ、濾過残は全く認められなかった。得られた
反応液からサンプルを採取し、乾燥・焼成して鉄分濃度
を分析したところ、Ｆｅ換算濃度で４．９２重量％であ
り、またサンプルをアルカリで処理しＦｅ分を除去して
からＥＤＴＡ分析を行なったところ、２５．７重量％で
あることが確認された。70.9 g of the obtained γ-FeO (OH) was added to 499.8 g of water, and 215.2 g of EDT was further added.
A and 50.1 g of aqueous ammonia (25%)
When the temperature was raised to ° C. and stirring was continued, the reaction solution became transparent in about 2 hours. After cooling, the reaction solution was no. Filtration with 5C filter paper revealed no filtration residue. A sample was collected from the obtained reaction solution, dried and calcined to analyze the iron concentration. The iron concentration was 4.92% by weight in terms of Fe. The sample was treated with an alkali to remove Fe, and then EDTA was removed. As a result of analysis, it was confirmed that the content was 25.7% by weight.
【００２６】これらの分析値から鉄分（ＭＷ：５５．
８）とＥＤＴＡ（ＭＷ：２９２）のモル比を求めると、
Ｆｅ＝４．９２／５５．８＝０．０８８１７：ＥＤＴＡ
＝２５．７／２９２＝０．０８８０であり、分析誤差範
囲でほぼ等モルであることが確認された。また、高速液
体クロマトグラフィーでＥＤＴＡの分解量を測定したと
ころ、０．０５％（対ＥＤＴＡ）と極めて少なく、反応
液中の第一鉄含有量も０．０１重量％と非常に少ないこ
とが確認された。From these analytical values, the iron content (MW: 55.
8) and the molar ratio of EDTA (MW: 292)
Fe = 4.92 / 55.8 = 0.08817: EDTA
= 25.7 / 292 = 0.0880, and it was confirmed that they were almost equimolar within the analytical error range. In addition, when the amount of EDTA decomposed was measured by high performance liquid chromatography, it was confirmed that the content was extremely low at 0.05% (vs. EDTA), and the ferrous content in the reaction solution was very low at 0.01% by weight. Was done.
【００２７】比較例１ 上記実施例１で得たγ−ＦｅＯ（ＯＨ）を３００℃で加
熱脱水して得たγ−Ｆｅ2 Ｏ3 を使用し、上記実施例１
と同様にしてＥＤＴＡとの反応を試みたところ、６０℃
で２４時間経た後もＦｅの反応は起こらず、反応液は無
色のままであった。Comparative Example 1 The γ-FeO (OH) obtained in Example 1 was heated and dehydrated at 300 ° C., and γ-Fe 2 O 3 was used.
When the reaction with EDTA was attempted in the same manner as in
After 24 hours, the reaction of Fe did not occur, and the reaction solution remained colorless.
【００２８】比較例２ ２０５ｇのＦｅＳＯ4 ・７Ｈ2 Ｏを１６３９ｇの水に溶
解し、これに、４４．２ｇのＮａＯＨを１０６２の水に
溶解した溶液を、３０℃で約２５分間かけて滴下する。
得られる暗緑色の反応液を同温度に保ち、散気管から空
気を５時間吹き込んで酸化を行なうと、反応液は黄色に
変わる。これをヌッチェで濾過して、沈殿を純水で十分
に洗浄し、５０℃で１０時間乾燥した。[0028] was dissolved FeSO 4 · 7H 2 O in Comparative Example 2 205g of water 1639G, this, a solution of NaOH of 44.2g of water 1062, is added dropwise over about 25 minutes at 30 ° C. .
When the resulting dark green reaction solution is kept at the same temperature and oxidized by blowing air from a diffuser for 5 hours, the reaction solution turns yellow. This was filtered with Nutsche, and the precipitate was sufficiently washed with pure water and dried at 50 ° C. for 10 hours.
【００２９】得られた沈殿は、α−ＦｅＯ（ＯＨ）：γ
−ＦｅＯ（ＯＨ）＝約７０：３０重量比の混合物であ
り、この混合物を前記実施例１と同様にしてＥＤＴＡと
反応させたところ、６０℃で２時間反応を行なっても仕
込み酸化鉄の約３０％しか反応せず、約７０重量部のα
−ＦｅＯ（ＯＨ）はＥＤＴＡと全く反応しないことが確
認された。The obtained precipitate is composed of α-FeO (OH): γ
-FeO (OH) = a mixture having a weight ratio of about 70:30. When this mixture was reacted with EDTA in the same manner as in Example 1, the reaction was conducted at 60 ° C. for 2 hours. Reacts only 30%, about 70 parts by weight of α
It was confirmed that -FeO (OH) did not react with EDTA at all.
【００３０】[0030]
【発明の効果】以上の様に本発明によれば、第二鉄塩を
形成する為の第二鉄源としてγ−ＦｅＯ（ＯＨ）を選択
し、これを好ましくは水系溶媒中でｐＨを５以下に維持
しつつ５０〜８０℃で略等モル量のアミノポリカルボン
酸と反応させることにより、アミノポリカルボン酸の分
解ロスを殆んど生じることなく、また鉄分の事後的な酸
化処理等も全く要することなく、極めて高純度のアミノ
ポリカルボン酸第二鉄を効率よく製造し得ることになっ
た。As described above, according to the present invention, .gamma.-FeO (OH) is selected as a ferric source for forming a ferric salt, and is preferably adjusted to pH 5 in an aqueous solvent. By reacting with an aminopolycarboxylic acid in a substantially equimolar amount at 50 to 80 ° C. while maintaining the temperature, the decomposition loss of the aminopolycarboxylic acid hardly occurs, and the post-oxidation treatment of iron can be performed. It is possible to efficiently produce extremely high-purity ferric aminopolycarboxylate without any need.
Claims (4)
Ｈ）を反応させることを特徴とするアミノポリカルボン
酸第二鉄塩の製法。1. An aminopolycarboxylic acid having γ-FeO (O
A method for producing a ferric aminopolycarboxylic acid salt, which comprises reacting H).
−ＦｅＯ（ＯＨ）を０．９５〜１．０５モル反応させる
請求項１記載の製法。2. A method according to claim 1, wherein 1 mol of aminopolycarboxylic acid is
The method according to claim 1, wherein 0.95 to 1.05 mol of -FeO (OH) is reacted.
請求項１または２記載の製法。3. The process according to claim 1, wherein the reaction is carried out in an aqueous solvent at a pH of 5 or less.
３のいずれかに記載の製法。4. The reaction according to claim 1, wherein the reaction is carried out at 50 to 80 ° C.
3. The production method according to any one of 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32985296A JP4024891B2 (en) | 1996-12-10 | 1996-12-10 | Method for producing aminopolycarboxylic acid ferric salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32985296A JP4024891B2 (en) | 1996-12-10 | 1996-12-10 | Method for producing aminopolycarboxylic acid ferric salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10168046A true JPH10168046A (en) | 1998-06-23 |
| JP4024891B2 JP4024891B2 (en) | 2007-12-19 |
Family
ID=18225961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32985296A Expired - Fee Related JP4024891B2 (en) | 1996-12-10 | 1996-12-10 | Method for producing aminopolycarboxylic acid ferric salt |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7034172B1 (en) | 2005-06-07 | 2006-04-25 | Basf Corporation | Ferric and acid complex |
| JP2006518391A (en) * | 2003-02-19 | 2006-08-10 | グロボアジア エルエルシー | Ferric organic compounds, their use, and methods for their production |
-
1996
- 1996-12-10 JP JP32985296A patent/JP4024891B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006518391A (en) * | 2003-02-19 | 2006-08-10 | グロボアジア エルエルシー | Ferric organic compounds, their use, and methods for their production |
| US7034172B1 (en) | 2005-06-07 | 2006-04-25 | Basf Corporation | Ferric and acid complex |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4024891B2 (en) | 2007-12-19 |
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