CN101531355A - Method for preparing high purity ferric phosphate using ferrous sulfate as by-product of white titanium pigment - Google Patents
Method for preparing high purity ferric phosphate using ferrous sulfate as by-product of white titanium pigment Download PDFInfo
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Abstract
The invention relates to a preparation method of pure ferric phosphate, characterized in that: iron vitriol, phosphorus source as by-product of white titanium pigment are used as reactant and purificant and oxidant are added into the reactant and the reaction temperature is controlled at 25-100 DEG C and the reaction time is 0.5-10 hours, thus white ferric phosphate powder (FePO[4]2-4H[2]O) with 2-4 crystal water is obtained. The technological process has features of simple process, low production cost, high product purity, increased added value of ferrous sulfate as by-product of white titanium pigment and the product can be used as ceramic metal glaze-color glaze material and raw material for producing lithium iron phosphate as lithium ionization cell anode material.
Description
Technical field:
The present invention relates to the production method of tertiary iron phosphate, particularly prepare the method for high-purity phosphoric acid iron, belong to field of inorganic materials by the titanium dioxide ferrous sulfate by-product.
Background technology:
In the technology that adopts Titanium White Production By Sulfuric Acid Process, 1 ton of titanium dioxide of every production just produces about 3.5～4 tons of by product green vitriols (iron vitriol, molecular formula FeSO
47H
2O).Sulfuric acid process is mainly adopted in the production of China's titanium white powder at present, the a large amount of by product green vitriol of annual generation, these by product parts are used for fodder additives, water purification agent, farming fertilizer, a part is used to produce iron oxide pigment (as iron oxide red, iron oxide yellow, barba hispanica, iron oxide black) etc., can't be utilized effectively but still have greatly.In the open source literature that relevant titanium dioxide ferrous sulfate by-product is recycled, Pan Guolong has reported method (Liaoning chemical industry, 1993 the 4th phases: 28-30) of utilizing titanium white by product product ferrous sulfate to prepare bodied ferric sulfate; Chinese patent (publication number CN1415665), Chinese patent (publication number CN101172663), Chinese patent (publication number CN1491997) provide the method for producing ferric oxide red colorant with the useless ferrous sulfate by-product of titanium white respectively, and Chinese patent (publication number CN1766005) and Chinese patent (publication number CN101077945) provide byproduct ferrous sulfate of titanium dioxide to prepare the method for high purity iron oxide yellow and red iron oxide or black iron oxide pigment respectively; Chinese patent (publication number CN1336327), Chinese patent (publication number CN1830815), Chinese patent (publication number CN1374254) provide respectively with the titanium white by product ferrous sulfate and have produced high-purity magnetic iron oxide or the soft magnetism method with high purity ferric oxide or high purity ferric oxide; Chinese patent (publication number CN1944274) provides a kind of method for preparing the controlled iron mica of particle diameter and colour-change with the titanium white by product iron vitriol; Chinese patent (publication number CN1994868) provides a kind of method of producing sulfuric acid and iron ore concentrate with the titanium white by product iron vitriol; Chinese patent (publication number CN1439463) provides titanium white waste acid and titanium white by product product ferrous sulfate to handle the method for incineration residue; Chinese patent (publication number CN1974410) provides a kind of method of producing the ferric lithium phosphate precursor ferric oxide from the titanium white ferrous sulfate as side product.
Tertiary iron phosphate is a kind of broad-spectrum industrial chemicals, can be used as the thickening material of food and mends chalybeate, can also be used for catalyzer, the ceramic metal glaze colour glaze of pigment, organic synthesis.In recent years, tertiary iron phosphate has important use and is worth again as the raw material of producing lithium ion battery anode material lithium iron phosphate.In the preparation method of Chinese patent CN 1581537, CN 1753216, CN 1958440, CN 1958441,1884053, CN101172594, CN101190785, CN1821062, CN1834004, the disclosed LiFePO 4 material of CN1635648, all mention with tertiary iron phosphate as main synthesis material.The industrialized preparing process of tertiary iron phosphate is at high temperature to be reacted by molysite and phosphoric acid salt to form, and molysite wherein mainly is iron(ic) chloride, iron nitrate, ferric sulfate etc.It is ferric oxide or iron protoxide or Z 250 that Chinese patent (publication number CN101172595) provides a kind of preparation method of ferric phosphate, its source of iron.Chinese patent (publication number CN101244813) discloses the preparation method of a kind of alkali formula ammonium ferric phosphate and preparation method, preparation method of ferric phosphate and LiFePO 4, and tertiary iron phosphate wherein is that alkali formula ammonium ferric phosphate makes through 550 ℃～700 ℃ calcinations.Chinese patent (publication number CN1635648) discloses a kind of preparation method of high-density spherical ferric lithium phosphate as anode material of lithium-ion battery, its method is earlier with the trivalent iron salt aqueous solution, the phosphorus source aqueous solution, alkali aqueous solution reaction synthesizing spherical or class ball shape ferric phosphate presoma, again with tertiary iron phosphate presoma and lithium salts prepared in reaction spherical LiFePO 4.Chinese patent (publication number CN101327918) discloses a kind of preparation method of Orthophosphoric acid Ferrum, and its source of iron is ferrous sulfate or iron protochloride.Chinese patent (publication number CN1974410) provides a kind of method of producing the ferric lithium phosphate precursor ferric oxide from the titanium white ferrous sulfate as side product, it is raw material that the by-product ferrous sulfate during in the production process of titanium pigment is adopted in this invention, by purification and impurity removal, add the beneficial element that some can improve lithium ion battery anode material lithium iron phosphate, post precipitation is with dry under the throw out vacuum, and roasting obtains the presoma product ferric oxide of lithium ion battery anode material lithium iron phosphate.
In above-described document and the patent, have only Chinese patent (publication number CN1974410) that the raw material of byproduct ferrous sulfate of titanium dioxide as lithium ion battery anode material lithium iron phosphate production is used, but its preparation is the ferric lithium phosphate precursor ferric oxide.So far for this reason, do not see pertinent literature and the patent for preparing high-purity phosphoric acid iron with byproduct ferrous sulfate of titanium dioxide.
Summary of the invention:
The object of the present invention is to provide a kind of method of utilizing byproduct ferrous sulfate of titanium dioxide to prepare high-purity phosphoric acid iron, this method technical process is simple, production cost is low, product purity is high, has improved the added value of byproduct ferrous sulfate of titanium dioxide simultaneously.
The preparation method of high-purity phosphoric acid iron of the present invention is to be reactant with titanium white by product thing iron vitriol and phosphorus source, and adds an amount of scavenging agent and oxygenant that wherein the starting point concentration scope in phosphorus source is 0.05～1molL
-1, Fe in P and the iron vitriol in the phosphorus source
2+The mass ratio of material be 1.0～1.5:1.0, reaction system pH=1～5.Temperature of reaction is controlled at 25～100 ℃, and in 0.5～10 hour reaction times, products obtained therefrom is the white ferric phosphate powder body (FePO that contains 2～4 crystal water
42～4H
2O).
Described phosphorus source is phosphoric acid, phosphoric acid salt, acid phosphate or poly-phosphate, comprises Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, Secondary ammonium phosphate, primary ammonium phosphate, potassium primary phosphate, dipotassium hydrogen phosphate or sodium acid pyrophosphate Na
2H
2P
2O
7Deng, also can use the mixture between them, the mixture of potassium primary phosphate and primary ammonium phosphate for example, the mixture of Sodium phosphate dibasic and SODIUM PHOSPHATE, MONOBASIC etc.
Described scavenging agent is sodium sulphite (Na
2S), sodium polysulphide or chelate liquid resin etc., for example Xing Tiantai development in science and technology company limited in the Tianjin-supply heavy metal scavenging agent .ZX-2060.Add-on is 1～3% of a titanium white by product thing iron vitriol massfraction.
Described oxygenant is hydrogen peroxide or sodium chlorate, and the add-on of hydrogen peroxide or sodium chlorate is 10-30% of an iron vitriol quality, also can aerating oxygen, or air or oxygen ozoniferous or ozone-containing air, the mode of ventilation is a bubbling style.
The preparation technology of described ferric phosphate powder body is as follows:
1. the water-soluble after-filtration of titanium white by product iron vitriol is removed water-fast impurity such as sandstone, add decontaminant solutions then and remove other heavy metal ion, obtain pure copperas solution.
The aqueous solution in 2. pure copperas solution and phosphorus source, with acid or alkali regulator solution pH=1～5, under agitation in solution, add oxygenant, or be put into aerating oxygen in the bubble tower, or air or oxygen ozoniferous or ozone-containing air, temperature of reaction is controlled at 25～100 ℃, 0.5～10 hour reaction times.Gained high-purity phosphoric acid iron product purity is greater than 99%, and Fe content is greater than 29%.
Chemical reaction process of the present invention is as follows:
Advantage of the present invention is:
1, titanium white by product iron vitriol molecular formula is FeSO
47H
2O, the blue-greenish colour monoclinic system crystal is corrosive, oxidation in damp atmosphere easily, caking.Be mainly used in fields such as pigment, dyestuff, Treatment of Industrial Water and chemical reagent, fodder additives, trace element fertilizer.Produce iron vitriol at present mainly by scrap iron and gas washing in SA production; Steel Plant's pickling also produces the ferrous sulfate byproduct; Enterprise in Titanium White Production By Sulfuric Acid Process, since need be with the titanium iron ore sulfuric acid reaction, so produce many ferrous sulfate byproducts, these byproducts generally exist with the form of iron vitriol, one ton of titanium dioxide of general every production just has 3 tons of left and right sides iron vitriol byproduct outputs.China is 700,000 tons with the annual output of Titanium White Production By Sulfuric Acid Process at present, thereby seven water sulfurous acid iron of 2,100,000 tons of also corresponding outputs.As water purification agent, fertilizer and the fodder additives, the byproduct ferrous sulfate of most titanium powder plants is abandoned as waste, not only wastes sulphur and iron resources, goes back serious environment pollution except that a small amount of.Along with the development of titanium dioxide industry, production-scale continuous expansion, it is extremely urgent to solve titanium white by product product Comprehensive Utilization of Ferrous Sulfate problem.Up to the present, domestic also do not have a complete full scale plant that can effectively fully utilize the titanium white by product ferrous sulfate.The present invention produces tertiary iron phosphate with the titanium white by product iron vitriol, not only solved environmental pollution, produced again and had agricultural, used in electronic industry product high added value, marketable, the raw material that can be used as ceramic metal glaze colour glaze and production lithium ion battery anode material lithium iron phosphate, belong to the processing of cleaning mineral, modern green chemical industry new technology, have very high economic benefit and social benefit.
2, technical process is simple, production cost is low, product purity is high, has improved the added value of byproduct ferrous sulfate of titanium dioxide simultaneously.
Embodiment
Describe the present invention in detail by following examples:
1. embodiment 1 is dissolved in 1kg water with 139g titanium white by product iron vitriol and (is equivalent to the about 0.5molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 2.78g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 60g strong phosphoric acid, after stirring, with ammoniacal liquor regulator solution pH=2, under agitation drip 60g 30% hydrogen peroxide in solution, reacted 6 hours down at 25 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.42%, purity 99.5%.
1. embodiment 2 is dissolved in 1kg water with 278g titanium white by product iron vitriol and (is equivalent to the about 1molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 5.56g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 120g strong phosphoric acid, after stirring, use sodium hydrate regulator solution pH=1.8, under agitation aerating oxygen in solution reacted 10 hours down at 40 ℃, and reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.43%, purity 99.5%.
1. embodiment 3 is dissolved in 1kg water with 834g titanium white by product iron vitriol and (is equivalent to the about 3molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 8.34g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 350g strong phosphoric acid, after stirring, with potassium hydroxide aqueous solution regulator solution pH=2.5, under agitation bubbling air in solution reacted 10 hours down at 70 ℃, and reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.38%, purity 99.5%.
1. embodiment 4 is dissolved in 1kg water with 139g titanium white by product iron vitriol and (is equivalent to the about 0.5molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 2.78g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 82.5g sodium phosphate, after stirring, with aqueous nitric acid regulator solution pH=2, under agitation feed ozone-containing air in solution, reacted 8 hours down at 70 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.35%, purity 99.5%.
1. embodiment 5 is dissolved in 1kg water with 55.6g titanium white by product iron vitriol and (is equivalent to ferrous sulfate concentration 0.2molL
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 0.556g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 35g Sodium phosphate dibasic, after stirring, with aqueous sulfuric acid regulator solution pH=1.8, under agitation feed oxygen ozoniferous in solution, reacted 6 hours down at 70 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.37%, purity 99.5%.
1. embodiment 6 is dissolved in 1kg water with 27.8g titanium white by product iron vitriol and (is equivalent to ferrous sulfate concentration 0.1molL
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 0.278g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 18.2g SODIUM PHOSPHATE, MONOBASIC, after stirring, with aqueous sulfuric acid regulator solution pH=2, under agitation drip 12g 30% hydrogen peroxide in solution, reacted 2 hours down at 75 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.42%, purity 99.5%.
1. embodiment 7 is dissolved in 1kg water with 55.6g titanium white by product iron vitriol and (is equivalent to the about 0.2molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 1g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 110g tripoly phosphate sodium STPP, after stirring, with aqueous nitric acid regulator solution pH=1.5, under agitation drip 25g 30% hydrogen peroxide in solution, reacted 1 hour down at 90 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.51%, purity 99.5%.
1. embodiment 8 is dissolved in 1kg water with 55.6g titanium white by product iron vitriol and (is equivalent to the about 0.2molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 1g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 183.5g Sodium hexametaphosphate 99, after stirring, with aqueous nitric acid regulator solution pH=1.8, under agitation drip 25g 30% hydrogen peroxide in solution, reacted 0.5 hour down at 100 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.47%, purity 99.5%.
1. embodiment 9 is dissolved in 1kg water with 139g titanium white by product iron vitriol and (is equivalent to the about 0.5molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 2.78g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 70g Secondary ammonium phosphate, after stirring, with nitric acid regulator solution pH=2.5, under agitation drip 60g 30% hydrogen peroxide in solution, reacted 3 hours down at 70 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.36%, purity 99.4%.
1. embodiment 10 is dissolved in 1kg water with 139g titanium white by product iron vitriol and (is equivalent to the about 0.5molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 2.78g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 75g primary ammonium phosphate, after stirring, with ammoniacal liquor regulator solution pH=4, under agitation drip the 60g sodium chlorate in solution, reacted 3 hours down at 75 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.34%, purity 99.1%.
1. embodiment 11 is dissolved in 1kg water with 278g titanium white by product iron vitriol and (is equivalent to the about 1molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 8.34g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 180g dipotassium hydrogen phosphate, after stirring, with nitric acid regulator solution pH=3, under agitation drip the 120g sodium chlorate in solution, reacted 3 hours down at 75 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.23%, purity 99.1%.
1. embodiment 12 is dissolved in 1kg water with 139g titanium white by product iron vitriol and (is equivalent to the about 0.5molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 2.78g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add the 75g potassium primary phosphate, after stirring, with potassium hydroxide regulator solution pH=5, under agitation drip the 60g sodium chlorate in solution, reacted 3 hours down at 70 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.28%, purity 99.1%.
1. embodiment 13 is dissolved in 1kg water with 139g titanium white by product iron vitriol and (is equivalent to the about 0.5molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 2.78g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. the mixture (each 35 gram of potassium primary phosphate and primary ammonium phosphate) that in pure copperas solution, adds 70g potassium primary phosphate and primary ammonium phosphate, after stirring, with nitric acid regulator solution pH=2.5, under agitation drip the 60g30% hydrogen peroxide in solution, reacted 3 hours down at 70 ℃, reaction finishes, filter, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.36%, purity 99.4%.
1. embodiment 14 is dissolved in 1kg water with 55.6g titanium white by product iron vitriol and (is equivalent to the about 0.2molL of ferrous sulfate concentration
-1), remove by filter water-insoluble solid impurity such as sandstone, in filtrate, add 1g powdery sodium sulphite then while stirring, treat to occur in the solution to continue to stir 10 minutes after the black precipitate, remove by filter black precipitate, obtain pure copperas solution.2. in pure copperas solution, add 50g tripoly phosphate sodium STPP and 60g Sodium hexametaphosphate 99, after stirring, with aqueous nitric acid regulator solution pH=1.5, blistering reaction tower aerating oxygen reaction 5 hours, 50 ℃ of temperature of reaction are filtered then, wash filter cake with water 3 times, filter cake 105 ℃ of oven dry down, is obtained white ferric phosphate powder body.Products obtained therefrom Fe content 29.51%, purity 99.5%.
Claims (7)
1, a kind of preparation method of high-purity phosphoric acid iron is characterized in that: with titanium white by product thing iron vitriol and phosphorus source is reactant, and wherein the starting point concentration in phosphorus source is 0.05～1molL
-1, Fe in P and the iron vitriol in the phosphorus source
2+The mass ratio of material be 1.0～1.5:1.0, reaction system pH=1～5, and add an amount of scavenging agent and oxygenant, 25～100 ℃ of temperature of reaction, 0.5～10 hour reaction times.
2, the preparation method of high-purity phosphoric acid iron according to claim 1 is characterized in that: described phosphorus source is phosphoric acid, phosphoric acid salt, acid phosphate or poly-phosphate.
3, the preparation method of high-purity phosphoric acid iron according to claim 1 is characterized in that: described scavenging agent is sodium sulphite, sodium polysulphide or chelate liquid resin, and add-on is 1～3% of a titanium white by product thing iron vitriol massfraction.
4, the preparation method of high-purity phosphoric acid iron according to claim 1 is characterized in that: described oxygenant is hydrogen peroxide or sodium chlorate, and the add-on of hydrogen peroxide or sodium chlorate is 10-30% of an iron vitriol quality.
5, the preparation method of high-purity phosphoric acid iron according to claim 1 is characterized in that: described oxygenant is oxygen, air, oxygen ozoniferous or ozone-containing air.
6, a kind of preparation method of ferric phosphate powder body as claimed in claim 1, concrete processing step is as follows:
1. the water-soluble after-filtration of titanium white by product iron vitriol is removed water-fast impurity such as sandstone, add scavenging agent then and remove other heavy metal ion, obtain pure copperas solution;
The aqueous solution in 2. pure copperas solution and phosphorus source, with acid or alkali regulator solution pH=1～5, under agitation in solution, add oxygenant, or aerating oxygen, air, oxygen ozoniferous or ozone-containing air, temperature of reaction is controlled at 25～100 ℃, 0.5～10 hour reaction times.
7, a kind of preparation method's products obtained therefrom of ferric phosphate powder body as claimed in claim 1 is characterized in that: product is the white ferric phosphate powder body that contains 2～4 crystal water.
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