阅读说明：本技术 一种由高磷含钒物料生产五氧化二钒的方法 (A method of vanadic anhydride is produced by high phosphorus vanadium-containing material ) 是由 高明磊 李兰杰 祁健 李九江 郑天新 耿立唐 于 2019-10-17 设计创作，主要内容包括：本发明提供了一种由高磷含钒物料生产五氧化二钒的方法,所述方法包括：将高磷含钒物料与碱液混合后进行溶出反应,液固分离得到第一溶出液和尾渣；将第一溶出液冷却结晶,得到混合晶体和第二溶出液；将混合晶体溶解后与钙化剂混合,反应生成固体沉淀；将固体沉淀制成浆液后与铵化剂混合,加热条件下反应,得到偏钒酸铵溶液和混合固体；将偏钒酸铵溶液冷却结晶后煅烧处理,得到五氧化二钒产品。本发明通过采用碱液高效溶出高磷含钒物料,钒的溶出率达到93％以上,再通过钙化沉淀和铵化转型,实现了钒和磷的高效分离,制得的五氧化二钒产品的纯度达到98.5％以上；所述方法操作简单,条件温和,可实现介质的循环利用,具备工业可操作性。(The present invention provides a kind of methods by high phosphorus vanadium-containing material production vanadic anhydride, which comprises carries out dissolution after mixing high phosphorus vanadium-containing material with lye and reacts, solid-liquor separation obtains the first dissolution fluid and tailings；By the first dissolution fluid crystallisation by cooling, mixed crystal and the second dissolution fluid are obtained；It is mixed after mixed crystal is dissolved with calcification agent, reaction generates solid precipitating；Solid precipitating is made after slurries and is mixed with ammonium agent, is reacted under heating condition, obtains ammonium metavanadate solution and hybrid solid；By calcination processing after ammonium metavanadate solution crystallisation by cooling, vanadic anhydride product is obtained.The present invention dissolves out high phosphorus vanadium-containing material by using alkali liquor efficient, and the dissolution rate of vanadium reaches 93% or more, then is made the transition by calcification precipitating and ammoniumization, realizes efficiently separating for vanadium and phosphorus, the purity of vanadic anhydride product obtained reaches 98.5% or more；The method is easy to operate, and mild condition has industrial operability, it can be achieved that medium recycles.)

1. a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, which is characterized in that the described method comprises the following steps:

(1) it carries out dissolution after mixing high phosphorus vanadium-containing material with lye to react, solid-liquor separation obtains the first dissolution fluid and tailings；

(2) the first dissolution fluid crystallisation by cooling for obtaining step (1), solid-liquor separation obtains mixed crystal and the second dissolution again Liquid；

(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, reaction generates solid precipitating；

(4) the solid precipitating that step (3) obtains is made after slurries and is mixed with ammonium agent, reacted under heating condition, obtain inclined vanadium Acid ammonium solution and hybrid solid；

(5) calcination processing after the ammonium metavanadate solution crystallisation by cooling for obtaining step (4), obtains vanadic anhydride product.

2. the method according to claim 1, wherein phosphorus pentoxide in step (1) the high phosphorus vanadium-containing material Content be 3~45wt%；

Preferably, step (1) described lye includes sodium hydroxide solution and/or potassium hydroxide solution；

Preferably, the concentration of step (1) described lye is 10~80wt%；

Preferably, it is (3~8) that step (1) lye and the liquid of high phosphorus vanadium-containing material, which consolidate mass ratio: 1.

3. method according to claim 1 or 2, which is characterized in that step (1) it is described dissolution reaction temperature be 80~ 260℃；

Preferably, the time of step (1) the dissolution reaction is 0.5~6h；

Preferably, step (1) the dissolution reaction pressure is 0~1.5MPa；

Preferably, when step (1) dissolution is reacted, it is passed through oxidizing gas；

Preferably, the oxidizing gas includes oxygen and/or air.

4. method according to claim 1-3, which is characterized in that the temperature of step (2) described crystallisation by cooling is 10~45 DEG C；

Preferably, step (2) the second dissolution fluid return step (1) is used for the dissolution of high phosphorus vanadium-containing material.

5. method according to claim 1-4, which is characterized in that step (3) the calcification agent include calcium oxide, Any one in calcium hydroxide, calcium chloride or calcium nitrate or at least two combination；

Preferably, it is (1.2~2) that the additional amount of step (3) the calcification agent, which meets calcium vanadium molar ratio: 1.

6. method according to claim 1-5, which is characterized in that the temperature of step (3) described reaction be 80~ 100℃；

Preferably, step (3) the solid precipitating includes calcium vanadate and calcium phosphate；

Preferably, after step (3) described reaction, solid-liquor separation obtains solid precipitating and mother liquor of precipitation of ammonium；

Preferably, the mother liquor of precipitation of ammonium returns to the dissolution for mixed crystal in step (3).

7. method according to claim 1-6, which is characterized in that step (4) the solid precipitating uses water system At slurries；

Preferably, the concentration of the slurries is 20~30g/L；

Preferably, step (4) the ammonium agent includes ammonium carbonate and/or ammonium hydrogen carbonate；

Preferably, it is (1.2~1.6) that the additional amount of step (4) the ammonium agent, which meets ammonium vanadium molar ratio: 1；

Preferably, step (4) heating temperature is not less than 80 DEG C, preferably 80~100 DEG C.

8. method according to claim 1-7, which is characterized in that step (5) ammonium metavanadate solution is cooling It is crystallized to 40 DEG C or less；

Preferably, solid-liquor separation after step (5) described crystallization, gained liquid phase return step (4) are used as solid precipitating and prepare slurries When water phase.

9. method according to claim 1-8, which is characterized in that the temperature of step (5) described calcination processing is 400~550 DEG C；

Preferably, the time of step (5) described calcination processing is 0.5~3h.

10. -9 described in any item methods according to claim 1, which is characterized in that the described method comprises the following steps:

(1) the high phosphorus vanadium-containing material that phosphorus pentoxide content is 3~45wt% is mixed with lye, the concentration of the lye is 10 It is (3~8) that the liquid of~80wt%, the lye and high phosphorus vanadium-containing material, which consolidates mass ratio: 1, then carry out dissolution reaction, reaction temperature Degree is 80~260 DEG C, and the time is 0.5~6h, and reaction pressure is 0~1.5MPa, and solid-liquor separation obtains the first dissolution fluid and tailings；

(2) temperature of the first dissolution fluid crystallisation by cooling for obtaining step (1), crystallisation by cooling is 10~45 DEG C, then not good liquor divides admittedly From mixed crystal and the second dissolution fluid is obtained, the second dissolution fluid return step (1) is used for the dissolution of high phosphorus vanadium-containing material；

(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, the calcification agent includes calcium oxide, hydroxide Any one in calcium, calcium chloride or calcium nitrate or at least two combination, reaction generates solid precipitating, the temperature of reaction is 80~ 100 DEG C, solid-liquor separation obtains solid precipitating and mother liquor of precipitation of ammonium after reaction；

(4) solid that step (3) obtains precipitating is made after slurries and mix with ammonium agent, the ammonium agent include ammonium carbonate with/ Or ammonium hydrogen carbonate, heating condition are reacted to 80 DEG C or more, and ammonium metavanadate solution and hybrid solid are obtained；

(5) ammonium metavanadate solution that step (4) obtains is cooled to 40 DEG C or less to crystallize, then calcination processing, calcining temperature Degree is 400~550 DEG C, and the time is 0.5~3h, obtains vanadic anhydride product.

Technical field

The invention belongs to metallurgical vanadium extraction technical fields, are related to a kind of side by high phosphorus vanadium-containing material production vanadic anhydride Method.

Background technique

Vanadium is applied as a kind of important transition metal element in fields such as steel, aerospace, chemical industry, electronic technology Extensively, as the improvement of downstream application product upgrades, to the purity of vanadium product, more stringent requirements are proposed.The content of phosphorus is to measure One important index of vanadium-containing material, the presence of phosphorus can significantly reduce the toughness of vanadium and vanadium alloy, plasticity, strong influence vanadium The use of product.However often phosphorus content is higher for presently used vanadium-containing material, and in addition to stone containing navajoite, some waste materials containing vanadium, such as During the recyclings such as discarded vanadium containing catalysts, slag containing vanadium smelting, it is also desirable to separate vanadium and phosphorus, five oxygen of high-purity are made Change two vanadium.

Vanadium-containing material is obtained firstly the need of leaching containing vanadium solution, then carries out subsequent removal of impurities, purification, traditional processing method It generally requires and first carries out calcining process, as sodium roasting, calcification baking or empty roasting are leached to obtain clinker, then using process is leached Clinker is to obtain containing vanadium leachate, and since calcining process energy consumption is higher, vanadium will be contained by the way of acidleach or alkali leaching at present by also having Material directly leaches, and then using the removal of impurities of the methods of extraction, chemical precipitation or ion exchange, when wherein phosphorus content is higher, needs Dephosphorization processing first is carried out to leachate, just can be carried out subsequent precipitation technique, and current phosphorus removing method is usually that dephosphorization agent is added, It will cause a large amount of vanadium loss while dephosphorization.

CN 109207740A discloses a kind of extraction vanadium method of vanadium-bearing slag of high calcium and high phosphor, and vanadium-bearing slag of high calcium and high phosphor is roasted to obtain Then clinker uses sulfuric acid leaching, obtain the first leachate and the first residue, and the first leachate accesses bodied ferric sulfate as dephosphorization Agent obtains solution containing vanadium after separation；After first residue leaches again, leachate alkaline reagent dephosphorization again is then used as level-one The mother liquor of leaching, solution containing vanadium carry out precipitation, solid product calcining.Vanadium can be equally taken out of during this method dephosphorization, cause vanadium Loss, and operating procedure is complex, process is numerous, and energy consumption is higher.

CN 105800689A discloses a kind of preparation method of ultrapure vanadic anhydride, is first cleaned in advance, and it is molten will to contain vanadium Phosphorus and silicon in liquid are transferred to solid phase removing, then carry out calcification precipitation, and the impurity such as chromium, manganese, potassium, sodium are stayed and are removed in liquid phase, then The transferred vanadium to solid phase turns molten to liquid phase using ammonium salt, using ammonium type cation exchange system, by the micro of liquid phase remnants Cation replacement is ammonium ion, realizes deep purifying, then calcine to obtain vanadic anhydride through cooling precipitation and deamination.This method is only Suitable for the lower processing containing vanadium solution of phosphorus content, if solution containing vanadium cleans when higher for phosphorus content, it will cause a large amount of of vanadium Loss, and this method is related to the removal of impurities of different kinds of ions, operating procedure is numerous.

In conclusion the processing for high phosphorus vanadium-containing material, also needs Optimal improvements processing method, vanadium and phosphorus can either be realized Efficiently separate, obtain high-purity vanadium product, and can simplify operating procedure, reduce cost.

Summary of the invention

In view of the problems of the existing technology, the purpose of the present invention is to provide one kind produces five oxygen by high phosphorus vanadium-containing material Change the method for two vanadium, the method is turned on the basis of alkali liquor efficient dissolves out high phosphorus vanadium-containing material by calcification separation and ammoniumization Type realizes efficiently separating for vanadium and phosphorus, and the vanadic anhydride product of high-purity is prepared, it is right to greatly reduce phosphorus content height The influence of product quality.

To achieve this purpose, the present invention adopts the following technical scheme:

The present invention provides a kind of methods by high phosphorus vanadium-containing material production vanadic anhydride, and the method includes following steps It is rapid:

(1) it carries out dissolution after mixing high phosphorus vanadium-containing material with lye to react, solid-liquor separation obtains the first dissolution fluid and tail Slag；

(2) the first dissolution fluid crystallisation by cooling for obtaining step (1), solid-liquor separation obtains mixed crystal and second molten again Liquid out；

(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, reaction generates solid precipitating；

(4) the solid precipitating that step (3) obtains is made after slurries and is mixed with ammonium agent, reacted, obtain under heating condition Ammonium metavanadate solution and hybrid solid；

(5) calcination processing after the ammonium metavanadate solution crystallisation by cooling for obtaining step (4), obtains vanadic anhydride product.

In the present invention, high phosphorus vanadium-containing material is dissolved out using lye first, by crystallization so that need it is to be separated at Dividing mainly includes vanadate and phosphate, recycles the difference of the two solubility, passes through calcification precipitating and ammoniumization makes the transition and realizes vanadium With efficiently separating for phosphorus, high purity vanadic anhydride product is further prepared；The method is easy to operate, mild condition, cost compared with Low, separation product can recycle, no waste discharge.

It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.

As currently preferred technical solution, the content of phosphorus pentoxide is 3 in step (1) the high phosphorus vanadium-containing material ~45wt%, such as 3wt%, 6wt%, 10wt%, 15wt%, 20wt%, 25wt% or 30wt%, 40wt% or 45wt% Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.

Preferably, step (1) described lye includes sodium hydroxide solution and/or potassium hydroxide solution.

Preferably, the concentration of step (1) described lye be 10~80wt%, such as 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt% or 80wt% etc., it is not limited to cited numerical value, in the numberical range its His unlisted numerical value is equally applicable.

Preferably, it is (3~8) that step (1) lye and the liquid of high phosphorus vanadium-containing material, which consolidate mass ratio: 1, such as 3:1,4: 1,5:1,6:1,7:1 or 8:1 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same Sample is applicable in.

As currently preferred technical solution, the temperature of step (1) the dissolution reaction is 80~260 DEG C, such as 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 240 DEG C or 260 DEG C etc., it is not limited to cited numerical value, the number It is equally applicable to be worth other unlisted numerical value in range.

Preferably, the time of step (1) the dissolution reaction is 0.5~6h, such as 0.5h, 1h, 2h, 3h, 4h, 5h or 6h Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.

Preferably, step (1) the dissolution reaction pressure be 0~1.5MPa, such as 0,0.2MPa, 0.5MPa, 0.8MPa, 1.0MPa, 1.2MPa or 1.5MPa etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range It is equally applicable.Wherein, heretofore described reaction pressure refers to gauge pressure.

In the present invention, due to the difference of the type of high phosphorus vanadium-containing material, when being dissolved out with lye, the concentration of required lye, Additional amount has difference, and by the selection of dissolution reaction temperature, pressure, improves the dissolution rate of vanadium as far as possible.

Preferably, when step (1) dissolution is reacted, it is passed through oxidizing gas.

Preferably, the oxidizing gas includes oxygen and/or air.

In the present invention, the vanadium in vanadium product and vanadium-containing material is generally pentavalent vanadium, but may also have in vanadium-containing material The presence of Low Valent Vanadium needs to be oxidized in dissolution, therefore is passed through oxidizing gas.

As currently preferred technical solution, the temperature of step (2) described crystallisation by cooling is 10~45 DEG C, such as 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C or 45 DEG C etc., it is not limited to cited numerical value, the numberical range Other interior unlisted numerical value are equally applicable.

Preferably, step (2) the second dissolution fluid return step (1) is used for the dissolution of high phosphorus vanadium-containing material.

In the present invention, in step (2) lolute crystallization rate can reach 70~80%, such as 70%, 72%, 74%, 76%, 78% or 80% etc., and dissolve out the general excessive addition of lye when reacting, then after lolute crystallization, can still it be deposited in the second dissolution fluid In lye and uncrystallized vanadate, phosphate, the dissolution that step (1) is re-used for vanadium-containing material is returned it into, it can also be again It is secondary that uncrystallized vanadium is recycled.

In addition, the tailings that step (1) obtains usually is stained with the ion in dissolution fluid, washed, after washing Tailings liquid can be with the common return step of the second dissolution fluid (1).

As currently preferred technical solution, step (3) the calcification agent includes calcium oxide, calcium hydroxide, calcium chloride Any one in calcium nitrate or at least two combination, the combination is typical but non-limiting example has: calcium oxide and hydrogen-oxygen Change the combination of calcium, the combination of calcium hydroxide and calcium chloride, calcium oxide, calcium hydroxide and combination of calcium nitrate etc..

Preferably, it is (1.2~2) that the additional amount of step (3) the calcification agent, which meets calcium vanadium molar ratio: 1, such as 1.2:1, 1.3:1,1.5:1,1.6:1,1.8:1 or 2:1 etc., it is not limited to cited numerical value, interior other of the numberical range are not arranged The numerical value of act is equally applicable.

As currently preferred technical solution, the temperature of step (3) described reaction is 80~100 DEG C, such as 80 DEG C, 84 DEG C, 88 DEG C, 90 DEG C, 93 DEG C, 96 DEG C or 100 DEG C etc., it is not limited to cited numerical value, other are not arranged in the numberical range The numerical value of act is equally applicable.

Preferably, step (3) the solid precipitating includes calcium vanadate and calcium phosphate.

In the present invention, vanadic acid root and phosphate radical are precipitated by the addition of calcification agent, in the reaction temperature and alkalinity Under the conditions of, vanadic acid root can generally be converted into metavanadic acid root, generate the separation for being convenient for subsequent vanadium and phosphorus after precipitating.

Preferably, after step (3) described reaction, solid-liquor separation obtains solid precipitating and mother liquor of precipitation of ammonium.

Preferably, the mother liquor of precipitation of ammonium returns to the dissolution for mixed crystal in step (3).

As currently preferred technical solution, slurries are made using water in step (4) the solid precipitating.

Preferably, the concentration of the slurries be 20~30g/L, such as 20g/L, 22g/L, 24g/L, 25g/L, 27g/L, 28g/L or 30g/L etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.

Preferably, step (4) the ammonium agent includes ammonium carbonate and/or ammonium hydrogen carbonate.

Preferably, it is (1.2~1.6) that the additional amount of step (4) the ammonium agent, which meets ammonium vanadium molar ratio: 1, such as 1.2: 1,1.3:1,1.4:1,1.5:1 or 1.6:1 etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value it is equally applicable.

In the present invention, calcium vanadate is converted to by using ammonium agent the calcium precipitation of more indissoluble, to obtain metavanadic acid Ammonium, the characteristic changed greatly using ammonium metavanadate solubility with temperature are separated it with calcium precipitations such as calcium phosphate.

Preferably, step (4) heating temperature is not less than 80 DEG C, such as 80 DEG C, 83 DEG C, 85 DEG C, 88 DEG C, 90 DEG C, 93 DEG C, 96 DEG C, 98 DEG C, 100 DEG C or 102 DEG C etc., it is not limited to cited numerical value, other are unlisted in the numberical range Numerical value is equally applicable, and preferably 80~100 DEG C.

In the present invention, the hybrid solid that step (4) obtains mainly includes calcium phosphate and calcium carbonate, can be used after washing Make basic chemical industry raw material.

As currently preferred technical solution, step (5) described ammonium metavanadate solution is cooled to 40 DEG C or less and is tied Crystalline substance, such as 40 DEG C, 36 DEG C, 32 DEG C, 30 DEG C, 27 DEG C, 25 DEG C or 20 DEG C etc., it is not limited to cited numerical value, the numerical value Other unlisted numerical value are equally applicable in range.

Preferably, solid-liquor separation after step (5) described crystallization, gained liquid phase return step (4) are used as solid precipitating preparation Water phase when slurries.

As currently preferred technical solution, the temperature of step (5) described calcination processing is 400~550 DEG C, such as 400 DEG C, 420 DEG C, 450 DEG C, 480 DEG C, 500 DEG C, 520 DEG C or 550 DEG C etc., it is not limited to cited numerical value, the numerical value Other unlisted numerical value are equally applicable in range.

Preferably, the time of step (5) described calcination processing be 0.5~3h, such as 0.5h, 1h, 1.5h, 2h, 2.5h or 3h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.

As currently preferred technical solution, the described method comprises the following steps:

(1) the high phosphorus vanadium-containing material that phosphorus pentoxide content is 3~45wt% is mixed with lye, the concentration of the lye For 10~80wt%, the liquid-solid ratio of the lye and high phosphorus vanadium-containing material is (3~8): 1, then carry out dissolution reaction, reaction temperature Degree is 80~260 DEG C, and the time is 0.5~6h, and reaction pressure is 0~1.5MPa, and solid-liquor separation obtains the first dissolution fluid and tailings；

(2) the first dissolution fluid crystallisation by cooling for obtaining step (1), the temperature of crystallisation by cooling is 10~45 DEG C, then not good liquor Gu isolated mixed crystal and the second dissolution fluid, the second dissolution fluid return step (1) is molten for high phosphorus vanadium-containing material Out；

(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, the calcification agent includes calcium oxide, hydrogen Any one in calcium oxide, calcium chloride or calcium nitrate or at least two combination, reaction generates solid precipitating, and the temperature of reaction is 80~100 DEG C, solid-liquor separation obtains solid precipitating and mother liquor of precipitation of ammonium after reaction；

(4) the solid precipitating that step (3) obtains is made after slurries and is mixed with ammonium agent, the ammonium agent includes ammonium carbonate And/or ammonium hydrogen carbonate, heating condition are reacted to 80 DEG C or more, and ammonium metavanadate solution and hybrid solid are obtained；

(5) ammonium metavanadate solution that step (4) obtains is cooled to 40 DEG C or less to crystallize, then calcination processing, is forged Burning temperature is 400~550 DEG C, and the time is 0.5~3h, obtains vanadic anhydride product.

Compared with prior art, the invention has the following advantages:

(1) present invention dissolves out high phosphorus vanadium-containing material using alkali liquor efficient first, and the dissolution rate of vanadium reaches 93% or more, then leads to Calcification precipitating and ammoniumization transition are crossed, realizes efficiently separating for vanadium and phosphorus, the purity of vanadic anhydride product obtained reaches 98.5% or more；

(2) the method for the invention is easy to operate, it can be achieved that medium recycles, having industry can grasp mild condition The property made.

Detailed description of the invention

Fig. 1 is the technique stream by high phosphorus vanadium-containing material production vanadic anhydride method that the specific embodiment of the invention 1 provides Cheng Tu.

Specific embodiment

In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention Bright but following embodiment is only simple example of the invention, does not represent or limit the scope of the present invention, this hair Bright protection scope is subject to claims.

Specific embodiment of the invention part provides a kind of method by high phosphorus vanadium-containing material production vanadic anhydride, institute State method the following steps are included:

(1) it carries out dissolution after mixing high phosphorus vanadium-containing material with lye to react, solid-liquor separation obtains the first dissolution fluid and tail Slag；

(2) the first dissolution fluid crystallisation by cooling for obtaining step (1), solid-liquor separation obtains mixed crystal and second molten again Liquid out；

(3) it is mixed after dissolving the mixed crystal that step (2) obtains with calcification agent, reaction generates solid precipitating；

(4) the solid precipitating that step (3) obtains is made after slurries and is mixed with ammonium agent, reacted, obtain under heating condition Ammonium metavanadate solution and hybrid solid；

(5) calcination processing after the ammonium metavanadate solution crystallisation by cooling for obtaining step (4), obtains vanadic anhydride product.

The following are typical but non-limiting embodiments of the invention: