CN115882021A - Preparation method of vanadium electrolyte of 3.5-valent sulfate acid system - Google Patents
Preparation method of vanadium electrolyte of 3.5-valent sulfate acid system Download PDFInfo
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Abstract
The invention provides a preparation method of a 3.5-valent sulfate acid system vanadium electrolyte, which comprises the following steps: respectively taking a sulfate acid solution of vanadium ions with valence of 4 and a sulfuric acid solution of vanadium ions with valence of (4+x) as negative and positive electrode electrolytes for electrolysis to respectively obtain a vanadium electrolyte solution of a sulfate acid system with valence of 3.5 and a sulfuric acid solution of vanadium ions with valence of (4+y) at the negative and positive electrodes; reducing the sulfuric acid solution of (4+y) valence vanadium ions to prepare a sulfuric acid solution of (4+x) valence vanadium ions; the sulfuric acid solution of (4+x) valence vanadium ions can be used as the positive electrolyte of the all-vanadium redox flow battery and the sulfate acid solution of 4 valence vanadium ions of the negative electrode for charging electrolysis, and the sulfate acid system vanadium electrolyte of 3.5 valence is obtained at the negative electrode. The preparation method of the 3.5-valent sulfate acid system vanadium electrolyte provided by the invention has the advantages of rapid electrolysis, rapid reduction, safety, reliability, economy, high efficiency and recyclability.
Description
Technical Field
The invention relates to the technical field of all-vanadium redox flow batteries, in particular to a preparation method of a 3.5-valent sulfate acid system vanadium electrolyte.
Background
The all-vanadium redox flow battery is the first choice of a large-capacity long-time energy storage battery, and vanadium electrolyte is respectively circulated to flow through a positive electrode and a negative electrode to carry out electrochemical reaction, so that mutual conversion of electric energy and chemical energy is realized.
Patent application CN201310542929.2 discloses a preparation method of 3.5-valent vanadium electrolyte, which adopts an electrolysis device, uses half volume of 4-valent vanadium solution as positive electrode electrolyte, uses one volume of 4-valent vanadium solution as negative electrode electrolyte, controls electrolysis electric quantity under the action of current given by a power supply, reduces vanadium of the negative electrode electrolyte from 4-valent to 3.5-valent, and oxidizes vanadium of the positive electrode electrolyte from 4-valent to 5-valent. And after the electrolysis is finished, discharging the 3.5-valent vanadium solution of the negative electrode, adding 4-valent vanadium with the same volume, adding a reducing agent into the positive electrode to reduce the 5-valent vanadium to 4-valent vanadium, and repeating the previous electrolysis.
However, this method has the following serious drawbacks: first, the method requires that the concentrations of vanadium at valence 4 of a half volume of a solution of vanadium at valence 4 as the positive electrolyte and a half volume of a solution of vanadium at valence 4 as the negative electrolyte of the electrolyzer must be completely equal to make it possible to reduce the vanadium at valence 4 to valence 3.5 of the negative electrolyte when the vanadium at the positive electrolyte is oxidized from valence 4 to valence 5. Secondly, electrolysis needs to oxidize all the vanadium in the positive electrolyte from 4 to 5 (otherwise, the vanadium valence of the negative electrolyte is higher than 3.5), which can be completed in a very long time, and therefore, the electrolysis is not practical, because the concentration of the vanadium in the positive electrolyte is lower and tends to zero along with the progress of the electrolysis reaction, the electrolysis reaction rate is slower and tends to zero, the electrolysis current is smaller and tends to zero, and theoretically, the vanadium in the positive electrolyte can be oxidized from 4 to 5 in an infinite time. In addition, a reducing agent is required to be added into the positive electrolyte to completely reduce the vanadium with the valence of 5 to 4 (otherwise, the vanadium valence of the negative electrolyte in the next electrolysis is reduced to less than 3.5), if the reducing agent is added according to the stoichiometric ratio of completely reducing the vanadium with the valence of 5 to 4, the situation that the vanadium with the valence of 5 is completely reduced to 4 is also possible to completely reduce the vanadium with the valence of 5, and the practicability is poor, because the concentration of the vanadium with the valence of 5 and the concentration of the reducing agent in the positive electrolyte are lower and tend to zero, the reduction reaction rate also tends to be lower and tend to zero, and theoretically, an infinite time is required to completely reduce the vanadium with the valence of 5 to 4 in the positive electrolyte.
If the incompletely reduced positive electrolyte is directly used for next electrolysis, the unreacted reducing agent (such as hydrazine hydrate, oxalic acid and the like) in the positive electrolyte and the newly generated vanadium (5) in valence state can generate oxidation-reduction reaction, and a large amount of N is generated in the positive electrolyte 2 、CO 2 When bubbles exist, the anode electrolyte magnetic circulating pump is frequently broken, idles and even burns the pump, and the smooth proceeding of the electrolytic reaction is seriously influenced.
If the reducing agent is excessively added, although the vanadium in the positive electrode electrolyte can be completely reduced from 5-valent to 4-valent within a short time, the residual reducing agent (such as hydrazine hydrate, oxalic acid and the like) in the positive electrode electrolyte can also generate oxidation reduction reaction with newly generated 5-valent vanadium in the next electrolytic process, and a large amount of N is generated in the positive electrode electrolyte 2 、CO 2 When bubbles occur, the magnetic force circulating pump of the positive electrolyte is frequently broken, idled and even burnt, the smooth proceeding of the electrolytic reaction is seriously influenced, and due to the accumulation effect, the residual reducing agent in the positive electrolyte is more than once, and the generated N 2 、CO 2 The amount of the bubbles is larger than that of the bubbles at one time, and the situations of liquid break, idling, even pump burning and the like of the magnetic circulating pump of the anode electrolyte are more frequent and serious than that of the bubbles at one time, so that the method is completely ineffective finally.
Therefore, a preparation method of 3.5-valent sulphate acid system vanadium electrolyte with rapid electrolysis, rapid reduction, safety, reliability, economy and high efficiency is needed at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a 3.5-valent sulphate acid system vanadium electrolyte which has the advantages of quick electrolysis, quick reduction, safety, reliability, economy, high efficiency and capability of being carried out circularly.
In order to solve the technical problem, the invention provides a preparation method of a 3.5-valent sulfate acid system vanadium electrolyte, which is characterized by comprising the following steps:
respectively taking a sulfate acid solution of vanadium ions with valence of 4 and a sulfuric acid solution of vanadium ions with valence of 4 as electrolytes of a negative electrode and a positive electrode for charging electrolysis to obtain a sulfate acid system vanadium electrolyte with valence of 3.5 at the negative electrode and obtain a sulfuric acid solution of vanadium ions with valence of (4+z) at the positive electrode;
adding oxalic acid into the sulfuric acid solution of (4+z) valence vanadium ions to react to obtain the sulfuric acid solution of (4+x) valence vanadium ions, wherein 1 >;
respectively taking a sulfate acid solution of vanadium ions with valence of 4 and a sulfuric acid solution of vanadium ions with valence of (4+x) as negative and positive electrolytes for charging electrolysis to obtain a sulfate acid system vanadium electrolyte with valence of 3.5 at the negative electrode and a sulfuric acid solution of vanadium ions with valence of (4+y) at the positive electrode;
adding oxalic acid into the sulfuric acid solution of (4+y) valence vanadium ions to react to obtain the sulfuric acid solution of (4+x) valence vanadium ions, wherein 1>y >;
and (4+x) taking the sulfuric acid solution of the vanadium ions with valence of (5363) as the positive electrolyte and the sulfate acid solution of the vanadium ions with valence of (4) as the negative electrode for charging electrolysis to obtain the vanadium electrolyte with valence of (3.5) in a sulfate acid system at the negative electrode.
Furthermore, x is more than or equal to 0.1, and y is more than or equal to 0.9.
Further, the sulfate acid solution of the vanadium ions with valence 4 is prepared by adding hydrochloric acid into the sulfuric acid solution of the vanadium ions with valence 4.
Further, the volume, the concentration of the vanadium ions with 4 valences, the concentration of the S element and the concentration of the Cl element of the sulfuric acid solution containing the vanadium ions with 4 valences after hydrochloric acid is added are respectively equal to the volume, the total vanadium concentration, the concentration of the S element and the concentration of the Cl element of the vanadium electrolyte of a sulfate acid system with 3.5 valences obtained at the negative electrode.
Further, the sulfuric acid solution of the 4-valent vanadium ions is prepared by reducing vanadium pentoxide by using an oxalic acid sulfate solution.
Further, the charging electrolysis is performed in an all-vanadium flow battery.
According to the preparation method of the 3.5-valent sulfate acid system vanadium electrolyte provided by the invention, the vanadium valence state of the anode electrolyte is between 4 and 5, the sulfate acid solution of 4-valent vanadium ions and the sulfuric acid solution of (4+x) -valent vanadium ions are respectively used as the cathode electrolyte and the anode electrolyte of the all-vanadium redox flow battery for charging electrolysis, the sulfate acid solution of 3.5-valent vanadium ions, namely the 3.5-valent sulfate acid system vanadium electrolyte, is obtained at the cathode, the sulfuric acid solution of (4+y) -valent vanadium ions is obtained at the anode, oxalic acid is added into the obtained sulfuric acid solution of (4+y) -valent vanadium ions according to the stoichiometric ratio for reduction, and the sulfuric acid solution of (4+x) -valent vanadium ions is obtained again, wherein 1 y > x 0. The steps are repeated in such a circulating way, and the new 3.5-valent sulfate acid system vanadium electrolyte can be prepared at the negative electrode.
In addition, the preparation method of the 3.5-valent sulfate acid system vanadium electrolyte provided by the invention is simple and convenient, and does not require that the concentrations of the 4-valent vanadium which are respectively used as the positive electrode electrolyte and the negative electrode electrolyte of the all-vanadium redox flow battery are equal to each other, and the volume of the electrolyte is not required to be different by one time. In addition, during charging and electrolysis of the all-vanadium redox flow battery, only vanadium in the positive electrode electrolyte needs to be oxidized from (4+x) valence to (4+y) valence, wherein 1 >x 0, namely, only part of vanadium with valence 4 needs to be oxidized to valence 5, and all vanadium with valence 4 does not need to be oxidized to valence 5, so that the electrolysis reaction rate is high, and the electrolysis step time is greatly shortened. Meanwhile, the invention only needs to quantitatively add oxalic acid into the sulfuric acid solution of (4+y) valence vanadium ions obtained by the anode after charging and electrolysis of the all-vanadium redox flow battery according to the stoichiometric ratio to reduce and obtain the sulfuric acid solution of (4+x) valence vanadium ions again, wherein 1> < x >0, namely, only needs to reduce part of 5 valence vanadium to 4 valence without reducing all of 5 valence vanadium to 4 valence, so the reduction reaction rate is high, and the reduction step time is greatly shortened.
More importantly, in the reduction step of the positive electrolyte after the all-vanadium redox flow battery is charged and electrolyzed, the 5-valent vanadium is always kept excessive relative to the oxalic acid reducing agent, so that the reduction reaction rate is high, the reduction step time is short, and the reduced positive electrolyte does not have residual oxalic acid reducing agent, thereby fundamentally avoiding the situations of liquid break, idling, even pump burning and the like of a magnetic circulating pump of the positive electrolyte during the next charging and electrolysis and ensuring the smooth operation of the subsequent electrolysis step.
Therefore, the preparation method of the 3.5-valent sulfate acid system vanadium electrolyte provided by the invention overcomes the defect that the electrolytes of the positive and negative electrodes adopt 4-valent vanadium in the current preparation method of 3.5-valent vanadium electrolyte, and has the characteristics of quick electrolysis, quick reduction, safety, reliability, economy, high efficiency, recyclability and the like.
Drawings
Fig. 1 is a flow chart of a method for preparing a 3.5-valent sulfated acid system vanadium electrolyte provided by an embodiment of the invention.
Detailed Description
Referring to fig. 1, the preparation method of the 3.5-valent sulfated acid system vanadium electrolyte provided by the embodiment of the invention comprises the following steps:
step 1) taking a sulfate acid solution of vanadium ions with valence of 4 and a sulfuric acid solution of vanadium ions with valence of 4 as a negative electrode electrolyte and a positive electrode electrolyte of the all-vanadium redox flow battery respectively for charging electrolysis to obtain a sulfate acid system vanadium electrolyte with valence of 3.5 at the negative electrode and obtain a sulfuric acid solution of vanadium ions with valence of (4+z) at the positive electrode.
Wherein, the sulfate acid solution of the vanadium ions with the valence of 4 is prepared by adding the sulfuric acid solution of the vanadium ions with the valence of 4 into hydrochloric acid.
And the volume, the concentration of the vanadium ions with valence 4, the concentration of the S element and the concentration of the Cl element of the sulfuric acid solution with vanadium ions with valence 4 after hydrochloric acid is added are respectively equal to the volume, the total vanadium concentration, the concentration of the S element and the concentration of the Cl element of the vanadium electrolyte of a sulfate acid system with valence 3.5 obtained at the negative electrode.
Wherein, the sulfuric acid solution of the 4-valent vanadium ions is prepared by reducing vanadium pentoxide by using an oxalic acid sulfate solution, and the generated reaction completely reacts according to the following reaction equation:
0.5V 2 O 5 +2H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O =VO(HSO 4 ) 2 +CO 2 ↑+2.5H 2 O
and respectively determining the molar weight of vanadium pentoxide and the molar weight of sulfuric acid according to the molar weight of total vanadium (namely the sum of the molar weights of vanadium in 3-valence and vanadium in 4-valence) in the prepared 3.5-valence sulphate acid system vanadium electrolyte and the molar weight of an S element, and determining the required molar weight of oxalic acid according to a reaction equation and the molar weight of vanadium pentoxide. After the reaction is completed, pure water is added to dilute the solution to the volume and the concentration of the sulfuric acid solution of the required vanadium ions with valence 4.
And step 2) adding oxalic acid into the sulfuric acid solution of (4+z) valence vanadium ions for reduction to prepare the sulfuric acid solution of (4+x) valence vanadium ions, wherein 1> z x >0.
Wherein, in the process of adding oxalic acid into the sulfuric acid solution of (4+z) valence vanadium ions to reduce the sulfuric acid solution of (4+x) valence vanadium ions, the following reaction equation of reducing 5 valence vanadium into 4 valence vanadium by oxalic acid is used for reaction, and the adding amount of oxalic acid is set:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
reduction of (z-x). Times.1 mol of VO 2 HSO 4
(z-x). Times.1 mol of VO (HSO) was produced 4 ) 2
0.5 (z-x). Times.1 mol of H is added 2 C 2 O 4 ·2H 2 O
And 3) respectively taking the sulfate acid solution of the vanadium ions with the valence of 4 and the sulfuric acid solution of the vanadium ions with the valence of (4+x) as a negative electrode electrolyte and a positive electrode electrolyte of the all-vanadium redox flow battery for charging electrolysis to obtain a sulfate acid system vanadium electrolyte with the valence of 3.5 at the negative electrode and obtain a sulfuric acid solution of the vanadium ions with the valence of (4+y) at the positive electrode.
And 4) adding oxalic acid into the sulfuric acid solution of (4+y) valence vanadium ions for reduction to prepare the sulfuric acid solution of (4+x) valence vanadium ions, wherein 1> < x >0.
Wherein, in the process of adding oxalic acid into the sulfuric acid solution of (4+y) valence vanadium ions to reduce and prepare the sulfuric acid solution of (4+x) valence vanadium ions, the reaction is carried out according to the following reaction equation of reducing 5 valence vanadium into 4 valence vanadium by oxalic acid and the adding amount of oxalic acid is set:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
reduction of (y-x). Times.1 mol of VO 2 HSO 4
(y-x). Times.1 mol of VO (HSO) is produced 4 ) 2
0.5 (y-x). Times.1 mol of H is added 2 C 2 O 4 ·2H 2 O
And 5) the sulfuric acid solution of the vanadium ions with the valence of (4+x) can be used as the positive electrolyte of the all-vanadium redox flow battery and the sulfate acid solution of the vanadium ions with the valence of 4 of the negative electrode for charging electrolysis, and the vanadium electrolyte with the valence of 3.5 in the sulfate acid system can be obtained at the negative electrode.
Wherein x is more than or equal to 0.1, and y is more than or equal to 0.9.
The charging electrolysis is carried out in an all vanadium redox flow battery comprising a galvanic pile, a pipeline, positive and negative vanadium electrolyte containers and the like, and the 3.5-valent sulphate acid system vanadium electrolyte is prepared by charging electrolysis by filling corresponding vanadium electrolyte into the positive and negative vanadium electrolyte containers of the all vanadium redox flow battery.
When 3.5-valent sulfate acid system vanadium electrolyte is prepared by charging electrolysis, the charging current and the electrolytic voltage are respectively regulated according to the electrode area of the single battery in series connection in the all-vanadium redox flow battery pile and the number of the single batteries in series connection. The electrolysis time is determined by the charging current, the volume and concentration of the negative electrode vanadium electrolyte. The charging voltage limiting of the electric pile can be used as the electrolytic voltage to carry out constant voltage charging, so that the charging current is maximum, the electrolytic time is shortest, and the electrolytic efficiency can be improved. Of course, the constant-current charging can be performed first, and then the constant-voltage charging can be performed, so that the electrolysis time is longer.
After the sulfuric acid solution of vanadium ions with valence of the positive electrode (4+x) is charged and electrolyzed, because part of the vanadium ions with valence of 4 lose electrons to become vanadium ions with valence of 5, the average valence of the vanadium ions is increased to (4+y), vanadium ions with valence of (4+y) are reduced by adding oxalic acid in a quantitative manner and are returned to (4+x), so that the vanadium ions can be matched with the newly prepared sulfate acid solution (serving as negative electrode solution) of vanadium ions with valence of 4 to carry out a new round of charging electrolysis, vanadium electrolyte of a sulfate acid system with valence of 3.5 is obtained at the negative electrode, the valence of vanadium ions in the electrolyte of the positive electrode is increased to (4+y) and can be reduced again to (4+x) by adding oxalic acid in a quantitative manner, and the circulation is repeated, and new vanadium electrolyte of the sulfate acid system with valence of 3.5 can be continuously prepared at the negative electrode.
At present, oxalic acid is added into the charged and electrolyzed positive electrolyte manually. Part of 5-valent vanadium ions are reduced to 4-valent vanadium ions by oxalic acid to release CO 2 The ionic reaction of the gas, although fast, still takes several hours to complete the reaction, and stirring accelerates the completion of the reaction.
After each charge electrolysis, the container for containing the positive electrode (4+y) valence vanadium electrolyte is pulled out from the all-vanadium redox flow battery, then oxalic acid is added into the container to reduce the electrolyzed positive electrode electrolyte, and another positive electrode (4+x) valence vanadium electrolyte container which is completely reduced in advance is replaced, and a new round of charge electrolysis is started, so that the production efficiency can be greatly improved.
If oxalic acid is added into the positive electrolyte for reduction during charging electrolysis, CO continuously generated in the positive electrolyte 2 The bubbles will frequently cause the liquid break, idle running and even pump burning of the magnetic circulating pump of the anode electrolyte, and the smooth proceeding of the electrolytic reaction is seriously influenced.
The preparation method of the 3.5-valent sulfated acid system vanadium electrolyte provided by the invention is specifically described by the following embodiments.
Example 1
2M 0.5(VCl 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) Preparation of 3.5-valent sulfate acid vanadium electrolyte (M represents mol/L, the same applies below)
Step 1: 500L 3.2M VO (HSO) in two portions 4 ) 2 Preparation of 4-valent vanadium electrolyte
0.5V 2 O 5 +2H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O =VO(HSO 4 ) 2 +CO 2 ↑+2.5H 2 O
V 2 O 5 The mass of (A): 2 × 500 × 3.2 × 0.5 × 182 = 291.2 (kg)
H 2 SO 4 The mass of (A): 2 × 500 × 3.2 × 2 × 98.1 = 628 (kg)
H 2 C 2 O 4 ·2H 2 Mass of O: 2 × 500 × 3.2 × 0.5 × 126 = 201.6 (kg)
600L of pure water was added to the reaction tank, and 628kg of H was slowly added thereto with stirring 2 SO 4 And 201.6kg of H 2 C 2 O 4 ·2H 2 And O, stirring uniformly. 291.2kg of V was added slowly with stirring 2 O 5 The reaction is carried out until no bubbles are generated. Filtering the solution, dividing into two 1000L packaging barrels, adding pure water to 500L, and adjusting to obtain 500L 3.2M VO (HSO) 4 ) 2 Vanadium (IV) 4And (3) an electrolyte.
Step 2:800L2M VO (HSO) 4 ) 2 Preparation of +2HCl 4-valent vanadium electrolyte
A portion of 500L 3.2MVO (HSO) obtained in step 1 4 ) 2 Adding 116.7kg HCl into 4-valent vanadium electrolyte, and adding pure water to adjust to 800L to obtain 800L2M VO (HSO) 4 ) 2 +2HCl vanadium 4 electrolyte.
Mass of HCl: 800 × 2 × 2 × 36.46 = 116.7 (kg).
And step 3:500L2M VO (HSO) 4 ) 2 +H 2 SO 4 Preparation of 4-valent vanadium electrolyte
Another 500L 3.2MVO (HSO) fraction from step 1 4 ) 2 500L multiplied by 2M/3.2M =312.5L is taken out from the 4-valent vanadium electrolyte, and 98.1kg of H is added 2 SO 4 Adding pure water to 500L to obtain 500L2M VO (HSO) 4 ) 2 +H 2 SO 4 A vanadium (V) electrolyte of valence 4.
H 2 SO 4 The mass of (A): 500 × 2 × 1 × 98.1 = 98.1 (kg)
And 4, step 4: first portion 800L2M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) Preparation of vanadium electrolyte of 3.5-valent sulfate acid system
800L2M VO (HSO) prepared in step 2 4 ) 2 Using +2HCl 4-valent vanadium electrolyte as the cathode electrolyte of a 37-piece 5kW all-vanadium redox flow battery, and mixing the 500L2M VO (HSO) prepared in the step 3 4 ) 2 +H 2 SO 4 Using a 4-valent vanadium electrolyte as a positive electrode electrolyte, charging at constant voltage of 60V by 579.5Ah:
SOC － = 37×579.5/(800×2×26.8) = 50%
SOC + = 37×579.5/(500×2×26.8) = 80%
negative electrode: VO (HSO) 4 ) 2 +3HCl+H + +e = VCl 3 +2H 2 SO 4 +H 2 O
And (3) positive electrode: VO (HSO) 4 ) 2 +H 2 O－H + －e = VO 2 HSO 4 +H 2 SO 4 。
The negative electrode is obtained as the first 800L2M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) The positive electrode of the 3.5-valent sulfate acid system vanadium electrolyte is 500L2M 0.8VO 2 HSO 4 +0.2VO(HSO 4 ) 2 +1.8H 2 SO 4 A 4.8-valent vanadium electrolyte.
And 5:500L 2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Preparation of 4.1-valent vanadium electrolyte
500L2M 0.8VO prepared in step 4 2 HSO 4 +0.2VO(HSO 4 ) 2 +1.8H 2 SO 4 44.1kg H is added into 4.8 valence vanadium electrolyte 2 C 2 O 4 ·2H 2 O, stirring for about 2 hours till no bubbles are generated, and obtaining 500L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1-valent vanadium electrolyte:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
H 2 C 2 O 4 ·2H 2 mass of O: 0.7 × 500 × 2 × 0.5 × 126 = 44.1 (kg)
Step 6:800L 2M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) Preparation of vanadium electrolyte of 3.5-valent sulfate acid system
Repeating the steps 1 and 2, and adding new 800L2M VO (HSO) 4 ) 2 +2HCl 4-valent vanadium electrolyte as negative electrolyte of 37-piece 5kW all-vanadium redox flow battery prepared from 500L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Using a 4.1-valent vanadium electrolyte as a positive electrode electrolyte, charging at constant voltage of 60V by 579.5Ah:
SOC － = 37×579.5/(800×2×26.8) = 50%
SOC + = 10% + 37×579.5/(500×2×26.8) = 90%
negative electrode: VO (HSO) 4 ) 2 +3HCl+H + +e = VCl 3 +2H 2 SO 4 +H 2 O
And (3) positive electrode: VO (HSO) 4 ) 2 +H 2 O－H + －e = VO 2 HSO 4 +H 2 SO 4
2M 0.5 (VCl) was obtained as a negative electrode 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) The vanadium electrolyte of 3.5-valent sulfate acid system and the positive pole are 500L2M 0.9VO 2 HSO 4 +0.1VO(HSO 4 ) 2 +1.9H 2 SO 4 A 4.9 valent vanadium electrolyte.
And 7:500L 2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Preparation of 4.1-valent vanadium electrolyte
VO at 500L2M 0.9 2 HSO 4 +0.1VO(HSO 4 ) 2 +1.9H 2 SO 4 50.4kg of H is added into the 4.9-valent vanadium electrolyte 2 C 2 O 4 ·2H 2 O, stirring for about 2 hours until no bubbles are generated, and obtaining 500L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1-valent vanadium electrolyte:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
H 2 C 2 O 4 ·2H 2 mass of O: 0.8 × 500 × 2 × 0.5 × 126 = 50.4 (kg)
And step 8: repeating the steps 6 and 7
The method is circulated, and the new vanadium electrolyte of the 3.5-valent sulfate acid system can be continuously prepared at the negative electrode.
Example 2
2.5M 0.5(VCl 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Preparation of vanadium electrolyte of 3.5-valent sulfate acid system
Step 1: two 500L 4M VO (HSO) 4 ) 2 Preparation of 4-valent vanadium electrolyte
0.5V 2 O 5 +2H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O =VO(HSO 4 ) 2 +CO 2 ↑+2.5H 2 O
V 2 O 5 The mass of (A): 2 × 500 × 4 × 0.5 × 182 = 364 (kg)
H 2 SO 4 The mass of (A): 2 × 500 × 4 × 2 × 98.1 = 785 (kg)
H 2 C 2 O 4 ·2H 2 Mass of O: 2 × 500 × 4 × 0.5 × 126 = 252 (kg).
500L of pure water was added to the reaction vessel, and 785kg of H was slowly added thereto with stirring 2 SO 4 And 252kg of H 2 C 2 O 4 ·2H 2 And O, stirring uniformly. 364kg of V were slowly added with stirring 2 O 5 The reaction is carried out until no bubbles are generated. Filtering the solution, uniformly distributing the solution into two 1000L packaging barrels, respectively adding pure water to regulate the volume to 500L to obtain two 500L 4M VO (HSO) portions 4 ) 2 A vanadium (V) electrolyte of valence 4.
And 2, step: 800L2.5M VO (HSO) 4 ) 2 +1.5HCl 4-valent vanadium electrolyte preparation
One part of 500L 4MVO (HSO) prepared in step 1 4 ) 2 Adding 109.4kg HCl into 4-valent vanadium electrolyte, adding pure water to adjust to 800L to obtain 800L2.5M VO (HSO) 4 ) 2 +1.5hcl vanadium 4 electrolyte.
Mass of HCl: 800 × 2.5 × 1.5 × 36.46 = 109.4 (kg)
And 3, step 3:625L2M VO (HSO) 4 ) 2 +H 2 SO 4 Preparation of 4-valent vanadium electrolyte
Another 500L 4MVO (HSO) prepared from step 1 4 ) 2 625L multiplied by 2M/4M =312.5L is taken out of the 4-valent vanadium electrolyte, and 122.6kg of H is added 2 SO 4 Adding pure water to 625L to obtain 625L2M VO (HSO) 4 ) 2 +H 2 SO 4 A vanadium (V) electrolyte of valence 4.
H 2 SO 4 The mass of (A): 625 × 2 × 1 × 98.1 = 122.6 (kg)
And 4, step 4: first portion 800L2.5M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Preparation of vanadium electrolyte of 3.5-valent sulfate acid system
800L2.5M VO (HSO) prepared in step 2 4 ) 2 +1.5HCl 4-valent vanadium electrolyte is used as the negative electrolyte of a 37-piece 5kW all-vanadium redox flow battery, and the 625L2M VO (HSO) prepared in the step 3 is used 4 ) 2 +H 2 SO 4 Using a 4-valent vanadium electrolyte as a positive electrode electrolyte, charging at constant voltage of 60V by 724.4Ah:
SOC － = 37×724.4/(800×2.5×26.8) = 50%
SOC + = 37×724.4/(625×2×26.8) = 80%
negative electrode: VO (HSO) 4 ) 2 +3HCl+H + +e = VCl 3 +2H 2 SO 4 +H 2 O
And (3) positive electrode: VO (HSO) 4 ) 2 +H 2 O－H + －e = VO 2 HSO 4 +H 2 SO 4
The first portion 800L2.5M 0.5 (VCl) is obtained at the negative electrode 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Vanadium electrolyte of 3.5-valent sulfate acid system and 625L2M 0.8VO obtained by positive electrode 2 HSO 4 +0.2VO(HSO 4 ) 2 +1.8H 2 SO 4 A 4.8-valent vanadium electrolyte.
And 5:625L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Preparation of 4.1-valent vanadium electrolyte
625L2M 0.8VO produced in step 4 2 HSO 4 +0.2VO(HSO 4 ) 2 +1.8H 2 SO 4 55.13kg of H is added into 4.8-valent vanadium electrolyte 2 C 2 O 4 ·2H 2 O, stirring for about 2 hours till no bubbles are generated, and obtaining 625L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1-valent vanadium electrolyte:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
H 2 C 2 O 4 ·2H 2 mass of O: 0.7 × 625 × 2 × 0.5 × 126 = 55.13 (kg)
Step 6:800L 2.5M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Preparation of vanadium electrolyte of 3.5-valent sulfate acid system
Repeating the steps 1 and 2, and mixing the prepared 800L2.5M VO (HSO) 4 ) 2 + 1.5HCl4-valent vanadium electrolyte was used as a negative electrode electrolyte of a 37-piece 5kW all-vanadium redox flow battery, and 625L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Using a 4.1-valent vanadium electrolyte as a positive electrode electrolyte, charging at constant voltage of 60V by 724.4Ah:
SOC － = 37×724.4/(800×2.5×26.8) =50%
SOC + = 10% + 37×724.4/(625×2×26.8) = 90%
negative electrode: VO (HSO) 4 ) 2 +3HCl+H + +e = VCl 3 +2H 2 SO 4 +H 2 O
And (3) positive electrode: VO (HSO) 4 ) 2 +H 2 O－H + －e = VO 2 HSO 4 +H 2 SO 4
Negative electrode thus obtained 800L2.5M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Vanadium electrolyte of 3.5-valent sulfate acid system and 625L2M 0.9VO obtained by positive electrode 2 HSO 4 +0.1VO(HSO 4 ) 2 +1.9H 2 SO 4 A vanadium electrolyte with valence of 4.9.
And 7:625L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Preparation of 4.1-valent vanadium electrolyte
In 625L2M 0.9VO 2 HSO 4 +0.1VO(HSO 4 ) 2 +1.9H 2 SO 4 63kg of H is added into 4.9-valent vanadium electrolyte 2 C 2 O 4 ·2H 2 O, stirring for about 2 hours until no bubbles are generated, and obtaining 625L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1-valent vanadium electrolyte:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
H 2 C 2 O 4 ·2H 2 mass of O: 0.8 × 625 × 2 × 0.5 × 126 = 63 (kg)
And 8: repeating the steps 6 and 7
The method is circulated, and the new vanadium electrolyte of the 3.5-valent sulfate acid system can be continuously prepared at the negative electrode.
According to the preparation method of the 3.5-valent sulphate acid system vanadium electrolyte provided by the invention, the vanadium valence state of the anode electrolyte is between 4 and 5, the serious defect of the preparation method of the 3.5-valent vanadium electrolyte of which the anode electrolyte and the cathode electrolyte are 4-valent vanadium in a common electrolytic device is completely overcome, and the preparation method has the outstanding advantages of quick electrolysis, quick reduction, simplicity, reliability, capability of being carried out circularly and the like, and can be effectively used for the efficient and low-cost preparation of the 3.5-valent sulphate acid system vanadium electrolyte.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (6)
1. A preparation method of a 3.5-valent sulfate acid system vanadium electrolyte is characterized by comprising the following steps:
respectively taking a sulfate acid solution of vanadium ions with valence of 4 and a sulfuric acid solution of vanadium ions with valence of 4 as electrolytes of a negative electrode and a positive electrode for charging electrolysis to obtain a sulfate acid system vanadium electrolyte with valence of 3.5 at the negative electrode and obtain a sulfuric acid solution of vanadium ions with valence of (4+z) at the positive electrode;
adding oxalic acid into the sulfuric acid solution of (4+z) valence vanadium ions for reaction to obtain a sulfuric acid solution of (4+x) valence vanadium ions, wherein 1> x >0;
respectively taking a sulfate acid solution of vanadium ions with valence of 4 and a sulfuric acid solution of vanadium ions with valence of (4+x) as negative and positive electrolytes for charging electrolysis to obtain a sulfate acid system vanadium electrolyte with valence of 3.5 at the negative electrode and a sulfuric acid solution of vanadium ions with valence of (4+y) at the positive electrode;
adding oxalic acid into the sulfuric acid solution of (4+y) valence vanadium ions to react to obtain the sulfuric acid solution of (4+x) valence vanadium ions, wherein 1>y >;
and (4+x) taking the sulfuric acid solution of the vanadium ions with valence of (5363) as the positive electrolyte and the sulfate acid solution of the vanadium ions with valence of (4) as the negative electrode for charging electrolysis to obtain the vanadium electrolyte with valence of (3.5) in a sulfate acid system at the negative electrode.
2. The method for preparing the 3.5-valent sulfated acid-system vanadium electrolyte according to claim 1, wherein: x is more than or equal to 0.1, and y is more than or equal to 0.9.
3. The method for preparing 3.5-valent sulfated acid system vanadium electrolyte as claimed in claim 1, wherein: the sulfate acid solution of the vanadium ions with the valence of 4 is prepared by adding hydrochloric acid into a sulfuric acid solution of the vanadium ions with the valence of 4.
4. The method for preparing 3.5-valent sulfated acid system vanadium electrolyte as claimed in claim 3, wherein: the volume, the concentration of the vanadium ions with 4 valence, the concentration of the S element and the concentration of the Cl element of the sulfuric acid solution with 4 valence vanadium ions added with hydrochloric acid are respectively equal to the volume, the total vanadium concentration, the concentration of the S element and the concentration of the Cl element of the vanadium electrolyte of a sulfate acid system with 3.5 valence obtained at the negative electrode.
5. The method for preparing 3.5-valent sulfated acid system vanadium electrolyte as claimed in claim 1, wherein: the sulfuric acid solution of the 4-valent vanadium ions is prepared by reducing vanadium pentoxide with an oxalic acid sulfate solution.
6. The method for preparing the 3.5-valent sulfated acid-system vanadium electrolyte according to claim 1, wherein: the charging electrolysis is carried out in an all-vanadium flow battery.
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