WO2003004417A1 - An antioxidative aqueous solution of a ferrous halide and its preparing method - Google Patents
An antioxidative aqueous solution of a ferrous halide and its preparing method Download PDFInfo
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- WO2003004417A1 WO2003004417A1 PCT/CN2001/001155 CN0101155W WO03004417A1 WO 2003004417 A1 WO2003004417 A1 WO 2003004417A1 CN 0101155 W CN0101155 W CN 0101155W WO 03004417 A1 WO03004417 A1 WO 03004417A1
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- WIPO (PCT)
- Prior art keywords
- solution
- ferrous
- aqueous
- aqueous solution
- halide
- Prior art date
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- 239000007864 aqueous solution Substances 0.000 title claims abstract description 41
- -1 ferrous halide Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 title abstract 2
- 239000000243 solution Substances 0.000 claims abstract description 39
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims abstract description 20
- 229940046149 ferrous bromide Drugs 0.000 claims abstract description 20
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Chemical group 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011630 iodine Chemical group 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007844 bleaching agent Substances 0.000 claims 2
- 229960002089 ferrous chloride Drugs 0.000 claims 2
- 229940057039 ferrous iodine Drugs 0.000 claims 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 2
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 claims 2
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000003339 best practice Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
- G03C5/44—Bleaching; Bleach-fixing
Definitions
- the present invention relates to a ferrous metal solution and a process for the preparation thereof. More specifically, the present invention relates to an anti- ferrous solution of ferrous iron and a preparation method thereof, and in particular, photographic addition: I: pure bromination of chemicals, 1K aqueous solution of iron; and U: preparation method .
- I pure bromination of chemicals
- U preparation method .
- a stable agent to the aqueous solution of ferrous iron.
- Known stable 3 ⁇ 4 agents can be generally divided into two categories, such as hydroxylamine, tin compounds, ascorbic acid, etc., to prevent the ferrous iron from being oxidized by air or to smash the solution ] 3 ⁇ 4 into ferrous iron, so that the solution remains stable.
- the other type is a complexing agent such as sprinkling acid, lemon acid, etc., and the iron in the solution reacts to form a stable metal chelate or complex to keep the solution stable.
- ⁇ W (Linyi CN1257094A discloses a method of adding 3-10% by weight of ascorbic acid to stabilize the solution in an aqueous solution of ferrous sulfate. In this method, at a temperature of 3 ⁇ 4, the solution can only remain stable in a beaker. 7 m lilj [I. Introduced a large W machine also 3 ⁇ 4 agent.
- H Wood Charter ⁇ ⁇ JP63-274631 3 ⁇ 4 A method of adding 20-100% tartaric acid or citric acid to the aqueous ferrous solution to stabilize the ferrous separation to keep the solution stable. ⁇ The above method phase M, in this method, a large organic acid is also introduced, and the solution is stored for 9 days, and precipitation occurs, and the effect is not good.
- the wood inventor after a long and in-depth study, discovered a method of adding a solution to the aqueous solution of the ferrous compound to keep the aqueous solution stable, without introducing any: H: it is yin (yang-gold) away from, overcoming
- H it is yin (yang-gold) away from, overcoming
- the present invention has been completed by the disadvantages of the prior art. Therefore, the present invention provides an aqueous solution of an anti-oxidizing ferrous iron.
- the wood invention also provides an anti-loaded aqueous solution of ferrous bromide for the production of photographic processing chemicals, which can be stably stored for more than 30 days.
- the wood invention also provides a process for the preparation of the ferrous ferrous solution.
- the invention of the wood invention is a method for preparing an aqueous solution of high-purity ferrous bromide which is resistant to oxidation.
- the present invention is described by taking ferrous iron as an example, and it seems that the present invention is not limited thereto, and J' should be in an aqueous solution of other ferrous compounds.
- the wood invention relates to an aqueous solution of ferrous bromide, and is particularly useful for producing an aqueous solution of iron in a photographic processing product.
- the deuteration of the ferrous iron leaves makes the aqueous solution of ferrous iron extremely unstable.
- the addition of a halide to the aqueous solution of ferrous bromide suppresses the oxidation of ferrous ions and stabilizes the aqueous solution.
- the amount of the halide is added to the aqueous solution of the ferrous bromide in an amount of more than 2 to less than 3, preferably more than 2. 05-2. 95, more preferably more than 2. 15-2. , particularly preferably greater than 2.30-2. 95, wherein X represents fluorine, chlorine, bromine or iodine.
- the halide is selected from the group consisting of halogen, hydrohalic acid or a salt thereof, and combinations thereof.
- the halogen is selected from the group consisting of fluorine, chlorine, bromine or iodine and combinations thereof; the halogen acid is selected from the group consisting of hydrochloric acid, hydrobromic acid or hydroiodic acid; and the hydrohalide is selected from the group consisting of alkali metals, alkaline earth metals or others.
- a soluble halide salt of a metal such as a potassium halide, a sodium halide, a silver halide or a magnesium halide.
- a halogen, a hydrohalic acid or a salt thereof and a mixture thereof to the aqueous ferrous bromide solution can be carried out under reduced pressure, normal pressure or pressure. If it is added in a gaseous form, it is preferably carried out under pressure or reduced pressure; if it is added in a liquid form, it is not particularly limited, and it is preferably added in a countercurrent manner under stirring to facilitate thorough mixing.
- the halide may be added to the aqueous solution of ferrous bromide at a normal temperature or under heating, and is not particularly limited. However, it is preferably carried out under heating. Usually, the temperature is controlled from room temperature to below the boiling point of the aqueous solution, preferably from 20 to 95, more preferably from 30 to 80 °C, and particularly preferably from 35 to 75 °C.
- the pH of the aqueous solution of ferrous bromide is usually less than 7, preferably less than 5, more preferably less than 4, particularly preferably less than 2.
- the ferrous ferrous oxide in the total amount of iron, 70-99. 9 wt%, preferably 85-99. 9 wt%. Best practice of the invention
- the aqueous solution of ferrous bromide prepared according to the method of the present invention is resistant to oxidation and stored in an air atmosphere at a temperature of from room temperature to 9 CTC for 30 days or more, and the color of the aqueous solution is unchanged, and no precipitate is precipitated. Therefore, the aqueous solution of ferrous bromide treated by the method of the present invention is very convenient for transportation, storage and use.
- organic matter and other impurity anions or cations are not introduced, and the original purity of the aqueous solution is maintained for a particular application such as an aqueous solution of ferrous bromide for the production of photographic processing chemicals, which has unique advantages.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to an antioxidative aqueous solution of a ferrous halide and its preparing method, wherein the solution exhibits a X/Fe molar ratio more than 2-3 and X is F, Cl, Br and I. The aqueous solution of a ferrous halide obtained by the process of the present invention has a high antioxidation, and no color changed and no deposit precipitated when it was put in the air atmosphere under room temperature to 90 °C over 30 days. The present invention can maitain the original purity of the solution without adding any organic stabilizers and other impurity anions and cations, and has some special advantages for certain special uses, such as the aqueous solution of ferrous bromide used in the production of photographic chemicals.
Description
〔化的 [^化亚铁水溶液及制备 法 技术领域 [[Chemical ferrous solution and preparation method]
本发明涉及亚铁 化物水溶液及其制备方法。 更 A体地说， 本发明涉及抗 ¼化的 没化亚铁水溶液及其制备方法， 特别¾川于^产照相加: I：化学品的 纯溴化、 1K铁水溶 液及； U:制备方法。 亚铁化合物的水溶液暴露于 ¾气中时， 亚铁离 被氧化成 ^价铁离子， 溶液 ί ι黄 绿色变成棕红色， 并伴随产^沉淀， 这 w为亚铁离 极不稳定 ^化的缘故。 为了 防止 铁离 /·的氧化， 保持其水溶液的稳定性， 人们进行了广泛而深入地研究， 通常 釆川向亚铁水溶液添加稳¾剂的方法。 知的稳¾剂通常可分为两大类， 类^还 ^ 剂， 如羟胺、 锡化合物、 抗坏血酸等， 防止亚铁离 被空气氧化或将溶液屮被 化^ 成的 ^价铁离于还] ¾成亚铁离于，从而使溶液保持稳定。另一类是络合剂， 如洒 酸、 柠樣酸等， 溶液中的铁离于进行反应生成稳 的金属螯合物或配合物， 使溶液保持 稳^。 The present invention relates to a ferrous metal solution and a process for the preparation thereof. More specifically, the present invention relates to an anti- ferrous solution of ferrous iron and a preparation method thereof, and in particular, photographic addition: I: pure bromination of chemicals, 1K aqueous solution of iron; and U: preparation method . When the aqueous solution of the ferrous compound is exposed to 3⁄4 of gas, the ferrous iron is oxidized to a valence iron ion, and the solution ί ι yellow green turns brownish red, accompanied by precipitation, which is ferrous ferrous instability. The reason. In order to prevent the oxidation of iron from /, and to maintain the stability of its aqueous solution, extensive and intensive research has been carried out. Usually, the method of adding a stable agent to the aqueous solution of ferrous iron is carried out. Known stable 3⁄4 agents can be generally divided into two categories, such as hydroxylamine, tin compounds, ascorbic acid, etc., to prevent the ferrous iron from being oxidized by air or to smash the solution ] 3⁄4 into ferrous iron, so that the solution remains stable. The other type is a complexing agent such as sprinkling acid, lemon acid, etc., and the iron in the solution reacts to form a stable metal chelate or complex to keep the solution stable.
屮 W (利屮诸 CN1257094A公开了 硫酸亚铁水溶液中添加 3—10 1^%抗坏血 酸使溶液稳 ¾的方法。在该方法屮，在¾温下，溶液于烧杯屮只能保持稳定 7 m lilj [ I.引入了大^的 W机还 ¾剂。 屮W (Linyi CN1257094A discloses a method of adding 3-10% by weight of ascorbic acid to stabilize the solution in an aqueous solution of ferrous sulfate. In this method, at a temperature of 3⁄4, the solution can only remain stable in a beaker. 7 m lilj [I. Introduced a large W machine also 3⁄4 agent.
H木特许公 Γ· JP63-274631 ¾ 了向亚铁水溶液屮添加 20- 100 ％洒石酸或 柠檬酸以稳定亚铁离 ， 从而保持溶液稳¾的方法。 ^上述方法相 M， 在该方法屮， 也引入了大 的 机酸， 溶液贮 9天 ， 就产生沉淀， 效果不好。 H Wood Charter Γ · JP63-274631 3⁄4 A method of adding 20-100% tartaric acid or citric acid to the aqueous ferrous solution to stabilize the ferrous separation to keep the solution stable. ^ The above method phase M, in this method, a large organic acid is also introduced, and the solution is stored for 9 days, and precipitation occurs, and the effect is not good.
W此， 木发明人经过长期深入地研究， 发现了- 种向亚铁 化物的水溶液屮添加 化物使其水溶液保持稳定的方法， 不引入任何： H:它阴 （阳-金 ) 离于，克服了现^ 技术屮存在的缺点，从而完成了本发明。 所以，本发明提供了- 巾抗氧化的 化亚铁水溶液。 W, the wood inventor, after a long and in-depth study, discovered a method of adding a solution to the aqueous solution of the ferrous compound to keep the aqueous solution stable, without introducing any: H: it is yin (yang-gold) away from, overcoming The present invention has been completed by the disadvantages of the prior art. Therefore, the present invention provides an aqueous solution of an anti-oxidizing ferrous iron.
木发明还提供了- 种抗载化的用于生产照相加工化学品的溴化亚铁水溶液， 它能 够 ：气屮稳定贮 30天以上。 The wood invention also provides an anti-loaded aqueous solution of ferrous bromide for the production of photographic processing chemicals, which can be stably stored for more than 30 days.
木发明也提供了所述肉化亚铁水溶液的制备方法。 The wood invention also provides a process for the preparation of the ferrous ferrous solution.
木发明的¾后 -个^ 的是提供- -种抗氧化的高纯溴化亚铁水溶液的制备方法。 为说明方便起见， 本发明以没化亚铁为例进行说明， 似是， 本发明不受此限制， J '应川于其它的亚铁 ^化物的水溶液。 The invention of the wood invention is a method for preparing an aqueous solution of high-purity ferrous bromide which is resistant to oxidation. For convenience of explanation, the present invention is described by taking ferrous iron as an example, and it seems that the present invention is not limited thereto, and J' should be in an aqueous solution of other ferrous compounds.
简要地说， 木发明涉及 种溴化亚铁水溶液， 特别足用于 ：产照相加工化 ^品的 没化 铁水溶液。众所周知， 山于亚铁离 的 ϋ轼化性，使没化亚铁水溶液极不稳^， Briefly, the wood invention relates to an aqueous solution of ferrous bromide, and is particularly useful for producing an aqueous solution of iron in a photographic processing product. As is known to all, the deuteration of the ferrous iron leaves makes the aqueous solution of ferrous iron extremely unstable.
1 1
确 认 本
其反应如下: Confirmation The response is as follows:
4FeBr2 + 02 + 10H20 4Fe (0H) 3 I + 8HBr (I) 这个反应是可逆反应， 加入溴素或氢溴酸或其盐会发生岐化反应- Br2 + H20 = HBr + HBrO (II) 反应 （II ) 由于生成氢溴酸或次溴酸将抑制氢氧化铁的生成， 使可逆反应 （I ) 向左方向移动， 从而使溴化亚铁水溶液保持稳定。 4FeBr 2 + 0 2 + 10H 2 0 4Fe (0H) 3 I + 8HBr (I) This reaction is a reversible reaction, and the addition of bromine or hydrobromic acid or its salt will cause a deuteration reaction - Br 2 + H 2 0 = HBr + HBrO (II) Reaction (II) The formation of hydrobromic acid or hypobromous acid inhibits the formation of iron hydroxide and moves the reversible reaction (I) to the left to stabilize the aqueous solution of ferrous bromide.
因此，在本发明中，向溴化亚铁水溶液中加入卤化物就可以抑制亚铁离子的氧化， 使其水溶液保持稳定。 向溴化亚铁水溶液中加入的卤化物的量是使水溶液中的 X/Fe 摩尔比为大于 2至小于 3，优选大于 2. 05-2. 95,更优选大于 2. 15-2. 95,特别优选大于 2. 30-2. 95， 所述 X表示氟、 氯、 溴或碘。 所述的卤化物选自卤素、 氢卤酸或其盐及 其组合。 卤素选自氟、 氯、 溴或碘及其组合； 所述的氢卤酸选自氢氯酸、 氢溴酸或氢 碘酸； 所述的氢卤酸盐选自碱金属、 碱土金属或其它金属的可溶性的卤化物盐， 如卤 化钾、 卤化钠、 卤化银或卤化镁等。 优选氯素、 溴素； 氢溴酸、 氢氯酸； 次氢氯酸、 次氢溴酸； 氯化钾、 氯化银； 溴化钾、 溴化银； 碘化钾、 碘化银等。 Therefore, in the present invention, the addition of a halide to the aqueous solution of ferrous bromide suppresses the oxidation of ferrous ions and stabilizes the aqueous solution. The amount of the halide is added to the aqueous solution of the ferrous bromide in an amount of more than 2 to less than 3, preferably more than 2. 05-2. 95, more preferably more than 2. 15-2. , particularly preferably greater than 2.30-2. 95, wherein X represents fluorine, chlorine, bromine or iodine. The halide is selected from the group consisting of halogen, hydrohalic acid or a salt thereof, and combinations thereof. The halogen is selected from the group consisting of fluorine, chlorine, bromine or iodine and combinations thereof; the halogen acid is selected from the group consisting of hydrochloric acid, hydrobromic acid or hydroiodic acid; and the hydrohalide is selected from the group consisting of alkali metals, alkaline earth metals or others. A soluble halide salt of a metal, such as a potassium halide, a sodium halide, a silver halide or a magnesium halide. Preferred are chlorine, bromine; hydrobromic acid, hydrochloric acid; hypochlorous acid, hypohydrobromic acid; potassium chloride, silver chloride; potassium bromide, silver bromide; potassium iodide, silver iodide, and the like.
向溴化亚铁水溶液中加入卤素、 氢卤酸或其盐及其混合物， 可在减压、 常压或加 压下进行。 如果是以气态形式加入， 优选在加压或减压下进行； 如果是以液态形式加 入， 没有特别地限制， 优选在搅拌下以逆流的方式加入， 便于充分混合。 The addition of a halogen, a hydrohalic acid or a salt thereof and a mixture thereof to the aqueous ferrous bromide solution can be carried out under reduced pressure, normal pressure or pressure. If it is added in a gaseous form, it is preferably carried out under pressure or reduced pressure; if it is added in a liquid form, it is not particularly limited, and it is preferably added in a countercurrent manner under stirring to facilitate thorough mixing.
向溴化亚铁水溶液中加入卤化物， 可在常温下进行， 也可在加热下进行， 没有特 别限制。 但是优选在加热下进行， 通常，温度控制在室温至水溶液的沸点以下， 优选 温度为 20-95 ,更优选温度为 30- 80°C，特别优选温度为 35-75°C。 The halide may be added to the aqueous solution of ferrous bromide at a normal temperature or under heating, and is not particularly limited. However, it is preferably carried out under heating. Usually, the temperature is controlled from room temperature to below the boiling point of the aqueous solution, preferably from 20 to 95, more preferably from 30 to 80 °C, and particularly preferably from 35 to 75 °C.
溴化亚铁水溶液的 pH值， 通常为小于 7， 优选小于 5， 更优选小于 4， 特别优选 小于 2。 The pH of the aqueous solution of ferrous bromide is usually less than 7, preferably less than 5, more preferably less than 4, particularly preferably less than 2.
溴化亚铁水溶液中，亚铁离子占铁总量的 70-99. 9重量 %,优选为 85-99. 9重量％。 本发明的最佳 施 式 重量重量。 The ferrous ferrous oxide in the total amount of iron, 70-99. 9 wt%, preferably 85-99. 9 wt%. Best practice of the invention
下面， 用实施例更详细地描述本发明， 这些实施例只是用于更好的描述本发明， 不是对本发明构成限制， 本发明的范围在附属的权利要求书中提出。 In the following, the invention is described in more detail by way of examples, which are set forth to illustrate the invention.
实施例 Example
向 1升溴化亚铁溶液 (32. 4重量 %)分别加入溴素 0克 (对比例）、 15克、 20克、 23 克、 30克、 42克、 50克、 59克、 67克、 80克制取不同 Br / Fe摩尔比的溴化亚铁水 溶液， 将其放置在空气中不同温度下， 目视测定颜色及沉淀变化，结果示于表 1。
表 1不同 Br / Fe摩尔比的溴化亚铁溶液的稳定 To 1 liter of ferrous bromide solution (32.4% by weight), 0 g (comparative ratio), 15 g, 20 g, 23 g, 30 g, 42 g, 50 g, 59 g, 67 g, respectively, were added. 80 g of an aqueous solution of ferrous bromide having a different Br / Fe molar ratio was prepared and placed in air at different temperatures, and the color and precipitation change were visually observed. The results are shown in Table 1. Table 1 Stabilization of ferrous bromide solutions with different Br / Fe molar ratios
按照本发明的方法制备的溴化亚铁水溶液，抗氧化，在空气气氛于室温至 9CTC温 度下， 存放 30天以上水溶液颜色不变， 没有沉淀析出。 因此， 经本发明方法处理的 溴化亚铁水溶液， 运输和贮存、 使用都非常方便。 The aqueous solution of ferrous bromide prepared according to the method of the present invention is resistant to oxidation and stored in an air atmosphere at a temperature of from room temperature to 9 CTC for 30 days or more, and the color of the aqueous solution is unchanged, and no precipitate is precipitated. Therefore, the aqueous solution of ferrous bromide treated by the method of the present invention is very convenient for transportation, storage and use.
按照本发明的方法， 不引入有机物及其它杂质阴离子或阳离子， 对特殊的应用如 用于生产照相加工化学品的溴化亚铁水溶液来说， 保持了水溶液的原有纯度， 具有独 特的优点。
According to the method of the present invention, organic matter and other impurity anions or cations are not introduced, and the original purity of the aqueous solution is maintained for a particular application such as an aqueous solution of ferrous bromide for the production of photographic processing chemicals, which has unique advantages.
Claims
1. 一种抗氧化的卤化亚铁水溶液，其特征是所述水溶液中卤素与铁的摩尔比 (X I Fe摩尔比)大于 2至小于 3， X表示氟、 氯、 溴或碘。 An aqueous solution of an anti-oxidation ferrous halide, characterized in that the molar ratio of halogen to iron (X I Fe molar ratio) in the aqueous solution is more than 2 to less than 3, and X represents fluorine, chlorine, bromine or iodine.
2. 按权利要求 1所述的卤化亚铁水溶液， 其特征是卤化亚铁水溶液是选自氟化亚 铁水溶液、 氯化亚铁水溶液、 溴化亚铁水溶液或碘化亚铁水溶液中的至少一种及其组 合， 卤素是选自氟素、 氯素、 溴素或碘素中的至少一种及其组合。 2. The aqueous ferrous halide solution according to claim 1, wherein the aqueous ferrous halide solution is at least selected from the group consisting of aqueous ferrous fluoride solution, aqueous ferrous chloride solution, aqueous ferrous bromide solution or aqueous ferrous iodine solution. And a combination thereof, the halogen is at least one selected from the group consisting of fluorocarbon, chlorin, bromine or iodine, and combinations thereof.
3. 按权利要求 1所述的卤化亚铁水溶液,其特征是 X / Fe摩尔比为 2. 01-2. 99， X 表示氟、 氯、 溴或碘。 The aqueous ferrous halide solution according to claim 1, wherein the X / Fe molar ratio is 2. 01-2. 99, and X represents fluorine, chlorine, bromine or iodine.
4. 按权利要求 1所述的卤化亚铁水溶液,其特征是卤化亚铁水溶液是溴化亚铁水 溶液， Br / Fe摩尔比为于 2. 05-2. 95。 4. The aqueous ferrous halide solution according to claim 1, wherein the aqueous ferrous halide solution is a ferrous bromine solution having a Br / Fe molar ratio of from 2.05 to 2.95.
5. 按权利要求 1所述的卤化亚铁水溶液,其特征是 Fe2+占总铁量的 70-99. 9重量％。5. The aqueous solution of ferrous halide to claim 1, characterized in that 70 to 99. Fe 2+ 9 wt% of the total amount of iron.
6. 按权利要求 1-5中的任一项所述的卤化亚铁水溶液，其特征是水溶液的 pH值至 少小于 6。 The aqueous ferrous halide solution according to any one of claims 1 to 5, wherein the aqueous solution has a pH of at least less than 6.
7. 按权利要求 6中的任一项所述的卤化亚铁水溶液，其特征是水溶液的 pH值至少 小于 4。 The aqueous ferrous halide solution according to any one of claims 6 to 4, wherein the aqueous solution has a pH of at least less than 4.
8. 权利要求 1-7所述的 ¾化亚铁水溶液的制备方法，其特征是将卤素加入卤化亚 铁水溶液中， 使水溶液中的 X / Fe摩尔比大于 2至小于 3， X表示氟、 氯、 溴或碘。 The method for preparing an aqueous ferrous solution according to any one of claims 1 to 7, wherein a halogen is added to the aqueous solution of ferrous hydride to make the X / Fe molar ratio in the aqueous solution is greater than 2 to less than 3, and X represents fluorine. Chlorine, bromine or iodine.
9. 按权利要求 6所述的方法， 其特征是卤化亚铁水溶液是选自氟化亚铁水溶液、 氯化亚铁水溶液、 溴化亚铁水溶液或碘化亚铁水溶液中的至少一种及其组合，卤素是 选自氟素、 氯素、 溴素或碘素中的至少一种及其组合。 9. The method according to claim 6, wherein the aqueous ferrous halide solution is at least one selected from the group consisting of aqueous ferrous fluoride solution, aqueous ferrous chloride solution, aqueous ferrous bromide solution or aqueous ferrous iodine solution; In combination, the halogen is at least one selected from the group consisting of fluorine, chlorine, bromine or iodine, and a combination thereof.
10. 权利要求 4所述的溴化亚铁水溶液在生产照相加工化学品， 即漂白液和漂白 定影液中应用。
10. The aqueous ferrous bromide solution of claim 4 for use in the production of photographic processing chemicals, i.e., bleach and bleach fixers.
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| CNA018232728A CN1507416A (en) | 2001-07-05 | 2001-07-05 | Antioxidant ferrous halide water solution and its prepn process |
| PCT/CN2001/001155 WO2003004417A1 (en) | 2001-07-05 | 2001-07-05 | An antioxidative aqueous solution of a ferrous halide and its preparing method |
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| PCT/CN2001/001155 WO2003004417A1 (en) | 2001-07-05 | 2001-07-05 | An antioxidative aqueous solution of a ferrous halide and its preparing method |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6241718A (en) * | 1985-08-19 | 1987-02-23 | Tokai Kagaku Kogyosho:Kk | Stabilization of iron compound |
| JPS62221356A (en) * | 1986-03-24 | 1987-09-29 | コスモ石油株式会社 | Deodorant |
| JPS63274631A (en) * | 1987-05-01 | 1988-11-11 | Global Kikaku:Kk | Stabilizing method for ferrous aqueous solution |
| JPH02211240A (en) * | 1989-02-10 | 1990-08-22 | Minato Sangyo Kk | Iron (ii) composition |
| GB2246561A (en) * | 1990-06-11 | 1992-02-05 | Tioxide Group Services Ltd | Aqueous ferric sulphate solutions |
| CN1257094A (en) * | 1998-12-17 | 2000-06-21 | 天津三凌环保技术研究所有限公司 | Method for stabilizing ferrous compound water solution |
-
2001
- 2001-07-05 CN CNA018232728A patent/CN1507416A/en active Pending
- 2001-07-05 WO PCT/CN2001/001155 patent/WO2003004417A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6241718A (en) * | 1985-08-19 | 1987-02-23 | Tokai Kagaku Kogyosho:Kk | Stabilization of iron compound |
| JPS62221356A (en) * | 1986-03-24 | 1987-09-29 | コスモ石油株式会社 | Deodorant |
| JPS63274631A (en) * | 1987-05-01 | 1988-11-11 | Global Kikaku:Kk | Stabilizing method for ferrous aqueous solution |
| JPH02211240A (en) * | 1989-02-10 | 1990-08-22 | Minato Sangyo Kk | Iron (ii) composition |
| GB2246561A (en) * | 1990-06-11 | 1992-02-05 | Tioxide Group Services Ltd | Aqueous ferric sulphate solutions |
| CN1257094A (en) * | 1998-12-17 | 2000-06-21 | 天津三凌环保技术研究所有限公司 | Method for stabilizing ferrous compound water solution |
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