CN113697860A - Green preparation method of potassium ferrate - Google Patents

Green preparation method of potassium ferrate Download PDF

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CN113697860A
CN113697860A CN202111001648.7A CN202111001648A CN113697860A CN 113697860 A CN113697860 A CN 113697860A CN 202111001648 A CN202111001648 A CN 202111001648A CN 113697860 A CN113697860 A CN 113697860A
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ferrate
sodium
potassium ferrate
preparation
solution
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张瑞
张晨晖
雷立
宋扬扬
刘军
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Shaanxi Research Design Institute of Petroleum and Chemical Industry
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/14Alkali metal compounds
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
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Abstract

本申请公开一种高铁酸钾的绿色制备方法,包括以下步骤:(1)制备中间体铁酸钠:将九水合硝酸铁溶于氢氧化钠去离子水溶液中,形成预混料,将预混料和3‑6mol/L的氢氧化钠溶液分别预热,然后混合,通入预热的压缩空气,搅拌,在220‑300℃下反应1‑4小时,冷却,分离沉降,得到的液体为铁酸钠溶液;(2)电解氧化法制备高铁酸钠;(3)制备高铁酸钾:在冰水浴条件下,向高铁酸钠溶液中加入KOH饱和溶液,析出紫黑色固体,过滤、干燥。本发明通过制备中间体铁酸钠,有效规避了现有技术湿式氧化法制备高铁酸钾时氯气(Cl2)和次氯酸盐(ClO)的使用,同时规避高铁酸钾在高温下的分解,为一种绿色制备方法。

Figure 202111001648

The present application discloses a green preparation method of potassium ferrate, comprising the following steps: (1) preparing the intermediate sodium ferrate: dissolving ferric nitrate nonahydrate in a deionized sodium hydroxide aqueous solution to form a premix, The material and the sodium hydroxide solution of 3-6mol/L were preheated respectively, then mixed, fed with preheated compressed air, stirred, reacted at 220-300 ℃ for 1-4 hours, cooled, separated and settled, and the obtained liquid was Sodium ferrate solution; (2) Electrolytic oxidation to prepare sodium ferrate; (3) Preparation of potassium ferrate: Add KOH saturated solution to the sodium ferrate solution under ice-water bath conditions, and a purple-black solid is precipitated, filtered and dried. By preparing the intermediate sodium ferrate, the present invention effectively avoids the use of chlorine (Cl 2 ) and hypochlorite (ClO ) when the prior art wet oxidation method prepares potassium ferrate, and simultaneously avoids the use of potassium ferrate at high temperatures. Decomposition, as a green preparation method.

Figure 202111001648

Description

Green preparation method of potassium ferrate
Technical Field
The invention belongs to the technical field of preparation of chemical water treatment agents, and particularly relates to a green preparation method of potassium ferrate.
Background
Potassium ferrate has strong oxidizing property (E)FeO4 2- /Fe 3+= 2.20V), selectivity and environmentally friendly properties. People find that the potassium ferrate can be used as a high-efficiency and nontoxic environment-friendly multifunctional water treatment agent; the potassium ferrate has good selectivity and can be used for organic synthesis; in addition, potassium ferrate can also be used as an electrode material for high-energy "super-iron" batteries. Therefore, the potassium ferrate has good application prospect in the fields.
At present, the preparation method of potassium ferrate mainly comprises three methods: wet oxidation, electrolytic oxidation, and dry oxidation.
Dry oxidation (also called high-temperature melt oxidation): the alkali metal peroxide and ferric salt or iron oxide are melted and reacted according to a certain proportion under the condition of high temperature and high pressure to generate the potassium ferrate. The peroxide has strong oxidizability, has high requirements on reaction equipment, generates high temperature during reaction, is difficult to control and is difficult to be used practically.
Wet oxidation (also known as hypochlorite oxidation): the principle of the method is that sodium hypochlorite and ferric nitrate are added into a strong alkaline solution, ferric iron is oxidized into ferrous ferrate ions by the sodium hypochlorite to generate sodium ferrate, chlorine gas needs to be introduced in the preparation process, and a reaction container is easy to corrode; the generated ferrate is easily decomposed into iron oxides with different valence states under the catalytic action of metals such as Mn and the like, so that the yield of the ferrate is reduced.
Electrolytic oxidation method: the method is characterized in that an iron substance anode is used for generating sodium ferrate through anode-iron electrode reaction in an electrolyte of high-concentration NaOH, KOH is added to generate potassium ferrate precipitate, and solid-liquid separation, organic washing and vacuum drying are carried out to generate solid potassium ferrate. Compared with other two methods, the electrolytic oxidation method has the advantages of low raw material consumption and convenient operation. But has high requirements on the materials of the electrolytic cell and other accessories, and the anode electrode is easy to passivate, so that the reaction yield is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention providesThe green preparation method of potassium ferrate can effectively avoid chlorine (Cl)2) And hypochlorite (ClO)-) The use of the method can avoid the decomposition of the potassium ferrate at high temperature.
A green preparation method of potassium ferrate comprises the following steps:
(1) preparing intermediate sodium ferrite: dissolving ferric nitrate nonahydrate in a sodium hydroxide deionized water solution to form a premix, respectively preheating the premix and 3-6mol/L of sodium hydroxide solution, then mixing, introducing preheated compressed air, stirring, reacting at the temperature of 220-300 ℃ for 1-4 hours, cooling, separating and settling to obtain a liquid which is a sodium ferrite solution;
(2) preparing sodium ferrate by an electrolytic oxidation method: putting the sodium ferrite solution obtained in the step (1) into an electrolytic bath, and carrying out electrolytic reaction to obtain a sodium ferrate solution;
(3) preparing potassium ferrate: and (3) under the condition of ice-water bath, adding a KOH saturated solution into the sodium ferrate solution obtained in the step (2), separating out a purple black solid, filtering and drying to obtain the potassium ferrate.
Preferably, in the premix, the ratio of iron nitrate nonahydrate: deionized water: the mass ratio of the sodium hydroxide is (4-4.5) to (10-30) to (8-10).
Preferably, the mass ratio of the premix to the 3-6mol/L sodium hydroxide solution is (2.5-3.6): 1.
preferably, the preheating is all preheated to 50-70 ℃.
Preferably, in the electrolytic reaction, the electrolytic materials of the cathode and the anode are inert electrodes.
Preferably, the inert electrode is graphite, carbon rod or nickel sheet.
Preferably, in the electrolytic reaction, the current is 300mA-540mA, and the current density is 50-90A/cm2And the electrolytic reaction time is 3-4 hours.
Preferably, in step (3), the molar amounts of sodium ferrate and KOH are equal.
In the step (3), the drying is vacuum drying at 60-70 ℃ to constant weight.
The ice-water bath is a water bath reaction carried out under an ice-water mixture.
The chemical principle and the reaction equation related by the invention are as follows:
step 1: NaOH + Fe (NO)33→NaFeO2+NaNO3+H2O
Step 2: FeO2 -+OH-→FeO4 2-+H2O+e-
And step 3: na (Na)2FeO4+KOH→K2FeO4+NaOH
The invention has the advantages that:
the invention effectively avoids chlorine (Cl) when the wet oxidation method is used for preparing the potassium ferrate in the prior art by preparing the intermediate sodium ferrite2) And hypochlorite (ClO)-) The use of the method avoids the decomposition of the potassium ferrate at high temperature, and is a green preparation method.
Drawings
FIG. 1 is an infrared spectrum.
Detailed Description
Example 1
A green preparation method of potassium ferrate comprises the following steps:
(1) preparing intermediate sodium ferrite: preparing 16g of sodium hydroxide and 40g of deionized water to obtain a sodium hydroxide solution, adding 8g of ferric nitrate nonahydrate to form 64g of premix, respectively preheating 25g of the premix and 3mol/L of the sodium hydroxide solution to 70 ℃, mixing, introducing compressed air preheated to 70 ℃, reacting for 1.5 hours at 220 ℃, cooling, separating and settling to obtain a liquid sodium ferrite solution;
(2) preparing sodium ferrate by an electrolytic oxidation method: putting the sodium ferrite solution obtained in the step (1) into an electrolytic bath for electrolytic reaction, wherein the electrolytic materials of a cathode and an anode are graphite electrodes, the current is 400mA, and the current density is 60A/cm2Electrolyzing for 3 hours to obtain a sodium ferrate solution;
(3) preparing potassium ferrate: adding a KOH saturated solution into the sodium ferrate solution obtained in the step (2) under the condition of ice-water bath, wherein the mole numbers of the sodium ferrate and the KOH are equal, separating out a purple black solid, filtering, and drying in vacuum at 60 ℃ to constant weight to obtain potassium ferrate;
4.7g of potassium ferrate was obtained with a yield of 75%.
Example 2
A green preparation method of potassium ferrate comprises the following steps:
(1) preparing intermediate sodium ferrite: preparing 16g of sodium hydroxide and 40g of deionized water to obtain a sodium hydroxide solution, adding 9 g of ferric nitrate nonahydrate to form 65 g of premix, respectively preheating 25g of the premix and 6mol/L of the sodium hydroxide solution to 50 ℃, mixing, introducing compressed air preheated to 50 ℃, reacting for 4 hours at 220 ℃, cooling, separating and settling to obtain a liquid sodium ferrite solution;
(2) preparing sodium ferrate by an electrolytic oxidation method: putting the sodium ferrite solution obtained in the step (1) into an electrolytic bath for electrolytic reaction, wherein the electrolytic materials of a cathode and an anode are graphite electrodes, the current is 540mA, and the current density is 50A/cm2Electrolyzing for 4 hours to obtain a sodium ferrate solution;
(3) preparing potassium ferrate: adding a KOH saturated solution into the sodium ferrate solution obtained in the step (2) under the condition of ice-water bath, wherein the mole numbers of the sodium ferrate and the KOH are equal, separating out a purple black solid, filtering, and drying in vacuum at 60 ℃ to constant weight to obtain potassium ferrate;
5.7g of potassium ferrate were obtained in a yield of 78%.
Example 3
A green preparation method of potassium ferrate comprises the following steps:
(1) preparing intermediate sodium ferrite: preparing 20g of sodium hydroxide and 60g of deionized water to obtain a sodium hydroxide solution, adding 8g of ferric nitrate nonahydrate to form 88 g of premix, respectively preheating 25g of the premix and 4mol/L of the sodium hydroxide solution to 60 ℃, mixing, introducing compressed air preheated to 60 ℃, reacting for 1 hour at 300 ℃, cooling, separating and settling to obtain a liquid sodium ferrite solution;
(2) preparing sodium ferrate by an electrolytic oxidation method: mixing the ferrite of step (1)The sodium solution is placed in an electrolytic bath for electrolytic reaction, the electrolytic materials of the cathode and the anode are graphite electrodes, the current is 300mA, and the current density is 90A/cm2Electrolyzing for 3 hours to obtain a sodium ferrate solution;
(3) preparing potassium ferrate: adding a KOH saturated solution into the sodium ferrate solution obtained in the step (2) under the condition of ice-water bath, wherein the mole numbers of the sodium ferrate and the KOH are equal, separating out a purple black solid, filtering, and drying in vacuum at 70 ℃ to constant weight to obtain potassium ferrate;
5.0g of potassium ferrate was obtained with a yield of 80%.
Example 4
A green preparation method of potassium ferrate comprises the following steps:
(1) preparing intermediate sodium ferrite: preparing 20g of sodium hydroxide and 40g of deionized water to obtain a sodium hydroxide solution, adding 9 g of ferric nitrate nonahydrate to form 69 g of premix, respectively preheating 25g of the premix and 5mol/L of the sodium hydroxide solution to 70 ℃, mixing, introducing compressed air preheated to 70 ℃, reacting for 2 hours at 250 ℃, cooling, separating and settling to obtain a liquid sodium ferrite solution;
(2) preparing sodium ferrate by an electrolytic oxidation method: putting the sodium ferrite solution obtained in the step (1) into an electrolytic bath for electrolytic reaction, wherein the electrolytic materials of a cathode and an anode are graphite electrodes, the current is 400mA, and the current density is 80A/cm2Electrolyzing for 3 hours to obtain a sodium ferrate solution;
(3) preparing potassium ferrate: adding a KOH saturated solution into the sodium ferrate solution obtained in the step (2) under the condition of ice-water bath, wherein the mole numbers of the sodium ferrate and the KOH are equal, separating out a purple black solid, filtering, and drying in vacuum at 70 ℃ to constant weight to obtain potassium ferrate;
5.7g of potassium ferrate were obtained in a yield of 78%.
Performance detection
The purple black material obtained in example 1 was subjected to infrared spectroscopic examination, and the results are shown in FIG. 1.
It can be seen that the distance is 801cm-1Has a strong absorption peak, which is the ferrateThe characteristic absorption peak of the root can be obtained, and the obtained substance is potassium ferrate.

Claims (9)

1. A green preparation method of potassium ferrate is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing intermediate sodium ferrite: dissolving ferric nitrate nonahydrate in a sodium hydroxide deionized water solution to form a premix, respectively preheating the premix and 3-6mol/L of sodium hydroxide solution, then mixing, introducing preheated compressed air, stirring, reacting at the temperature of 220-300 ℃ for 1-4 hours, cooling, separating and settling to obtain a liquid which is a sodium ferrite solution;
(2) preparing sodium ferrate by an electrolytic oxidation method: putting the sodium ferrite solution obtained in the step (1) into an electrolytic bath, and carrying out electrolytic reaction to obtain a sodium ferrate solution;
(3) preparing potassium ferrate: and (3) under the condition of ice-water bath, adding a KOH saturated solution into the sodium ferrate solution obtained in the step (2), separating out a purple black solid, filtering and drying to obtain the potassium ferrate.
2. The green process for the preparation of potassium ferrate according to claim 1, wherein: in the premix, iron nitrate nonahydrate: deionized water: the mass ratio of the sodium hydroxide is (4-4.5) to (10-30) to (8-10).
3. The green process for the preparation of potassium ferrate according to claim 2, wherein: the mass ratio of the premix to 3-6mol/L sodium hydroxide solution is (2.5-3.6): 1.
4. the green process for the preparation of potassium ferrate according to claim 1, wherein: preheating to 50-70 ℃.
5. The green process for the preparation of potassium ferrate according to claim 3, wherein: in the electrolytic reaction, the electrolytic materials of the cathode and the anode are inert electrodes.
6. The green process for the preparation of potassium ferrate according to claim 5, wherein: the inert electrode is graphite, a carbon rod or a nickel sheet.
7. The green process for the preparation of potassium ferrate according to claim 5, wherein: in the electrolytic reaction, the current is 300mA-540mA, and the current density is 50-90A/cm2And the electrolytic reaction time is 3-4 hours.
8. The green process for the preparation of potassium ferrate according to claim 1, wherein: in the step (3), the mole numbers of the sodium ferrate and the KOH are equal.
9. The green process for the preparation of potassium ferrate according to claim 1, wherein: in the step (3), the drying is vacuum drying at 60-70 ℃ to constant weight.
CN202111001648.7A 2021-08-30 2021-08-30 Green preparation method of potassium ferrate Pending CN113697860A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1760133A (en) * 2004-10-14 2006-04-19 北京化工大学 Method for directly synthesizing potassium ferrate by doping hypochlorite
CN1865509A (en) * 2006-04-07 2006-11-22 福建师范大学 Novel dipolar membrane and use thereof in electrolysis preparation of ferrate
CN101318707A (en) * 2008-07-01 2008-12-10 上海大学 A kind of preparation method of stable composite potassium ferrate solution
US20110076223A1 (en) * 2009-09-28 2011-03-31 Florida Institute Of Technology Apparatus and Method For Producing Liquid Ferrate
CN103193275A (en) * 2013-04-22 2013-07-10 重庆民丰化工有限责任公司 Method for preparing potassium ferrate
CN105692668A (en) * 2016-03-21 2016-06-22 南阳东方应用化工研究所 Method for preparing high-molecule-ratio cryolite from coal gangue and fly ash
US20210023546A1 (en) * 2019-07-24 2021-01-28 Toyota Motor Engineering & Manufacturing North America, Inc. MICROWAVE SYNTHESIS OF IRON OXIDE CATALYSTS FOR COLD START NOx REMOVAL

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1760133A (en) * 2004-10-14 2006-04-19 北京化工大学 Method for directly synthesizing potassium ferrate by doping hypochlorite
CN1865509A (en) * 2006-04-07 2006-11-22 福建师范大学 Novel dipolar membrane and use thereof in electrolysis preparation of ferrate
CN101318707A (en) * 2008-07-01 2008-12-10 上海大学 A kind of preparation method of stable composite potassium ferrate solution
US20110076223A1 (en) * 2009-09-28 2011-03-31 Florida Institute Of Technology Apparatus and Method For Producing Liquid Ferrate
CN103193275A (en) * 2013-04-22 2013-07-10 重庆民丰化工有限责任公司 Method for preparing potassium ferrate
CN105692668A (en) * 2016-03-21 2016-06-22 南阳东方应用化工研究所 Method for preparing high-molecule-ratio cryolite from coal gangue and fly ash
US20210023546A1 (en) * 2019-07-24 2021-01-28 Toyota Motor Engineering & Manufacturing North America, Inc. MICROWAVE SYNTHESIS OF IRON OXIDE CATALYSTS FOR COLD START NOx REMOVAL

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