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)3)3→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.