Method for producing battery-grade ferrous oxalate by using ferrous sulfate as titanium pigment byproduct

A technology of ferrous sulfate and ferrous oxalate, applied in the preparation of carboxylate, organic chemistry and other directions, can solve the problems of insufficient utilization of resources, complex process, complicated process, etc., and achieve stable product quality, good product quality, and process technology. Simple process effect

Inactive Publication Date: 2009-11-18
CENT SOUTH UNIV
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Problems solved by technology

Chinese patent 00113589.9 discloses a method for producing high-purity magnetic iron oxide by using ferrous sulfate as a by-product of titanium dioxide. First, freeze and crystallize to remove some impurities, and then dissolve and then use iron sulfate sheet hydrolysis to further remove impurities. The recovery rate of iron is only 50%. Left and right, this method includes two steps of impurity removal process, the process is complicated, the loss rate of iron is very high, and the resources are not fully utilized
Chinese patent 200610018642.X discloses a method for preparing high-purity ferric oxide for soft magnetism with titanium dioxide by-product ferrous sulfate. In order to separate manganese, magnesium and iron, the method first purifies and removes green vitriol, and then uses two steps Neutralization and oxidation, complex process
In addition, the precipitate obtained by this method needs to be roasted at 300-800°C for 3-12 hours to obtain the precursor of lithium iron phosphate, ferric oxide, which requires high energy consumption.
Chinese patent application 200610136902.3 discloses a method for producing lithium iron phosphate precursor iron phosphate from titanium dioxide waste ferrous sulfate. This method also has the problem of duplication of the two processes of removing impurities and adding beneficial metal ions
So far, there is no report on the production of battery-grade ferrous oxalate by using ferrous sulfate, a by-product of titanium dioxide.

Method used

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  • Method for producing battery-grade ferrous oxalate by using ferrous sulfate as titanium pigment byproduct
  • Method for producing battery-grade ferrous oxalate by using ferrous sulfate as titanium pigment byproduct
  • Method for producing battery-grade ferrous oxalate by using ferrous sulfate as titanium pigment byproduct

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Experimental program
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Embodiment 1

[0029] Dissolve 500g of waste paraferrous sulfate in 3L of deionized water, filter, and add 0.1mol sodium dodecylbenzenesulfonate, 0.2mol n-propanol and oxalic acid in an equimolar amount to Fe in the filtrate successively under vigorous stirring, and use Ammonia water and sulfuric acid adjust the pH of the system to 1.0, stop stirring after reacting at 40°C for 30 minutes, age at room temperature for 12 hours, then filter and wash with 30% BaCl 2 The solution detects that there is no sulfate ion, and the precipitate is dried at 80°C to obtain the precursor of lithium iron phosphate, the positive electrode material of lithium ion battery-metal element-doped ferrous oxalate, wherein Fe:Mg:Mn (molar ratio)=100: 0.4:0.2.

Embodiment 2

[0031]Dissolve 500 g of waste ferrous sulfate in 3 L of deionized water, filter, and add 0.05 mol of citric acid, 0.05 mol of tetraethyl glycol, 0.02 mol of triethanolamine and an equimolar amount of Fe to the filtrate successively under vigorous stirring. For ammonium oxalate, use sodium hydroxide and sulfuric acid to adjust the pH of the system to 3.0, react at 60°C for 2 hours, then stop stirring, without aging, directly filter and wash with 30% BaCl 2 The solution detects that there is no sulfate ion, and the precipitate is dried at 80° C. to obtain the precursor of the positive electrode material lithium iron phosphate for lithium-ion batteries-the ferrous oxalate doped with metal elements, wherein Fe: Mg: Al: Ca (molar ratio) = 100:0.2:0.05:0.08.

Embodiment 3

[0033] Dissolve 500g of waste ferrous sulfate in 3L of deionized water, filter, and add 0.05mol hydroxypropyl cellulose, 0.05mol sodium dodecylbenzenesulfonate, and Fe equimolar amounts to the filtrate successively under vigorous stirring. Sodium oxalate and 0.1mol humic acid, use ammonia water and oxalic acid to adjust the pH of the system to 5.0, stop stirring after reacting at 20°C for 5 minutes, age at room temperature for 24 hours, then filter and wash with 30% BaCl 2 The solution detects that there is no sulfate ion, and the precipitate is dried at 80° C. to obtain the precursor of the positive electrode material lithium iron phosphate for lithium-ion batteries-the ferrous oxalate doped with metal elements, wherein Fe: Mg: Al: Ti (molar ratio) = 100:1.2:0.03:0.2.

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Abstract

The invention discloses a method for producing battery-grade ferrous oxalate by using ferrous sulfate as a titanium pigment byproduct. The waste and byproduct ferrous sulfate is dissolved in deionized water; the mixture is filtered; a complexing agent, a surfactant and a precipitation agent are added according to a certain order into the filtrate when violent stirring is carried out; then, aqueous solution of alkaline or acid is used for controlling the pH of the system to be 0.1-5.0, the stirring is not stopped until reaction is carried out at temperature of 20-80 DEG C for 5 min-4 h, aging is carried out for 0-24 h; the obtained sediment is filtered, washed and dried so as to obtain the battery-grade ferrous oxalate, wherein the iron recovery rate can be as high as 99.9 percent. By adjusting the addition order and the addition amount of the additives as well as the pH value of the system, the method causes the types and the amount of metallic elements in the ferrous oxalate to be controllable. The method has the advantages of adequate raw materials, simple process flow, good and stable product quality, low cost and the like, is particularly suitable for providing high-quality iron sources for large production of lithium iron phosphate which is used as the cathode material for a lithium ion battery, and simultaneously also provides a new way for recycling waste residue of ferrous sulfate.

Description

technical field [0001] The invention relates to a method for preparing battery-grade ferrous oxalate, in particular to a method for producing battery-grade ferrous oxalate by using ferrous sulfate as a by-product of titanium dioxide. technical background [0002] Titanium dioxide is a high-quality white pigment. With the development of the world economy and the progress of human science and technology, the application fields of titanium dioxide are becoming wider and wider, and the market demand is also increasing. At present, my country mainly adopts the sulfuric acid method to produce titanium dioxide, and this method produces about 3.5-4 tons of ferrous sulfate (commonly known as green vitriol) for every ton of titanium dioxide produced by this method. Because this ferrous sulfate contains a large amount of impurities such as Mg, Mn, Al, Ca, Ti, it is difficult to directly utilize it. If it is stacked for a long time, it will cause serious pollution to the environment and...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C55/07C07C51/41
Inventor 李新海伍凌王志兴李灵均王小娟方杰李金辉郭华军彭文杰
Owner CENT SOUTH UNIV
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