WO2019029615A1 - Method for cleanly producing vanadium trioxide by vanadium-containing solution - Google Patents

Method for cleanly producing vanadium trioxide by vanadium-containing solution Download PDF

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WO2019029615A1
WO2019029615A1 PCT/CN2018/099613 CN2018099613W WO2019029615A1 WO 2019029615 A1 WO2019029615 A1 WO 2019029615A1 CN 2018099613 W CN2018099613 W CN 2018099613W WO 2019029615 A1 WO2019029615 A1 WO 2019029615A1
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vanadium
containing solution
solution
reaction
sodium
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PCT/CN2018/099613
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French (fr)
Chinese (zh)
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白瑞国
常福增
李兰杰
陈华
黄山珊
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河钢股份有限公司承德分公司
承德钢铁集团有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • the invention relates to the field of vanadium chemical industry, in particular to a method for clean production of vanadium pentoxide from a vanadium-containing solution.
  • Vanadium oxide is mainly used in the production of alloys, ceramic printing and dyeing colorants, all vanadium redox flow battery electrolytes, sulfuric acid and petrochemical catalysts such as metallurgy, electronics, dyes, energy, chemical and other industries.
  • Vanadium oxide mainly vanadium pentoxide (V 2 O 5), vanadium trioxide (V 2 O 3) and vanadium (VO 2) and the like dioxide, oxides of different preparation process vary.
  • Vanadium pentoxide is an ideal raw material for the production of vanadium-nitrogen alloys and vanadium-iron alloys.
  • the general method for producing vanadium pentoxide is based on ammonium metavanadate, ammonium polyvanadate, vanadium pentoxide, etc., using natural gas and gas.
  • the reducing gas such as hydrogen is reduced at 800-1000 ° C to obtain a vanadium pentoxide product having a grade of 64% or more.
  • the method has a long production process, high production cost, and is difficult to handle in the preparation of raw materials.
  • CN103922404B discloses a method for preparing vanadium pentoxide by using vanadium pentoxide by uniformly mixing a ratio of vanadium pentoxide and carbon powder to a ratio of 2:1; and pressing the mixed raw materials into a block and then feeding the material.
  • the block is covered with carbon powder; the formed block is fired at 950 ° C - 1050 ° C for 3-5 h to obtain vanadium pentoxide.
  • the reduction temperature of the invention is above 900 ° C, and the energy consumption is high, which is not conducive to promotion.
  • CN103695954B discloses a method for preparing vanadium pentoxide by direct electrolysis of vanadate, using vanadate as raw material, using alkali metal or alkaline earth metal chloride as molten salt, and heating to 150 ° C under nitrogen or argon atmosphere- 250 ° C, constant temperature 12h-24h to remove the water in the molten salt, and then heated to 500 ° C -1000 ° C, electrolysis, cell voltage 2.5-5.0V, electrolysis time 3h-12h, the product in the lower part of the cathode to obtain vanadium pentoxide products .
  • electrolytic preparation there is also a problem of excessive energy consumption.
  • CN106006736A discloses a method for preparing vanadium pentoxide from a vanadium-containing solution by using hydrogen, using a vanadium-containing solution having a hydrogen and vanadium concentration of more than 6 g/L and a hydrogen ion concentration of 10 -4 -10 -14 in a high temperature and high pressure reaction device.
  • the reaction is carried out at 50-300 ° C and a partial pressure of hydrogen of 1 MPa or more for 1 hour or more to obtain a vanadium pentoxide product.
  • the method has the disadvantages of harsh reaction conditions and incomplete reduction reaction, and at the same time, a large amount of low-concentration sodium hydroxide solution is produced by-product, which is difficult to recycle, and must be treated by other methods.
  • the present invention provides a method for cleanly producing vanadium pentoxide from a vanadium-containing solution, which utilizes H 2 to reduce the vanadium-containing solution after acidification by sulfuric acid, thereby solving the vanadium hydrogen reduction process.
  • the problem of difficulty in the reduction reaction caused by the formation of sodium hydroxide is that the reduction rate of vanadate is ⁇ 99.3%, and the purity of vanadium pentoxide product is more than 99%.
  • the process flow is shortened, the production cost is reduced, the recycling of water resources is realized, and the generation of acidic ammonia nitrogen wastewater in the vanadium precipitation process is avoided.
  • the present invention provides a method for the clean production of vanadium pentoxide from a vanadium containing solution, the method comprising the steps of:
  • vanadate will produce hydroxide ions during the hydrogen reduction process, which will gradually increase the alkalinity of the solution, resulting in a weakening trend of hydrogen reduction of vanadate, a difficulty in reduction, and a complete reduction reaction. carry out.
  • the invention firstly acidifies the vanadium-containing solution by using sulfuric acid, and then passes the H 2 gas to carry out the reduction reaction, and the acidized solution has sufficient hydrogen ions to consume the hydroxide ions generated during the reduction process, thereby prompting the reaction to proceed, greatly improving the reaction.
  • the reactivity of vanadate solves the technical problem that it is difficult to carry out the reduction reaction by generating sodium hydroxide during the hydrogenation of vanadate hydrogen.
  • the reaction temperature and the partial pressure of hydrogen are effectively reduced, which is beneficial to reducing the temperature and pressure load of the device and reducing the energy consumption of the reaction.
  • the vanadium-containing solution is acidified using sulfuric acid according to a molar ratio of sodium ion in the vanadium-containing solution to sulfate in the sulfuric acid of 30:(10-16), and the molar ratio may be 30:10, 30:10.5, 30: 11, 30:11.5, 30:12, 30:12.5, 30:13, 30:13.5, 30:14, 30:14.5, 30:15, 30:15.5 or 30:16, and the specific point between the above values Values, limited by length and for the sake of brevity, the present invention is no longer exhaustive.
  • the above molar ratio is the key to the present invention.
  • a sufficient amount of hydrogen ions are present in the reaction system to promote the reaction in the forward direction; when the amount of sulfuric acid added is too small, the late reaction system.
  • the pH value is too high, the hydrogen ion content is insufficient, the reaction rate and the reaction degree are weakened, and the reduction reaction is difficult to be thorough; when the amount of sulfuric acid added is too large, waste of the acid solution is caused, and the production cost is increased.
  • the vanadium-containing solution of the step (1) is a vanadium-containing alkaline solution obtained by sodium roasting, wet leaching of a vanadium-containing mineral or other routes.
  • the vanadium-containing solution contains any one of sodium orthovanadate, sodium metavanadate or sodium metavanadate.
  • the concentration of vanadium in the vanadium-containing solution in the step (1) is 20-45 g/L, and may be, for example, 20 g/L, 23 g/L, 25 g/L, 28 g/L, 30 g/L, 33 g/L. 35g/L, 38g/L, 40g/L, 42g/L or 45g/L, and the specific point values between the above values, which are limited in scope and for the sake of brevity, the present invention is not exhaustively enumerated.
  • the concentration of sodium in the vanadium-containing solution in the step (1) is 9-75 g/L, and may be, for example, 9 g/L, 15 g/L, 20 g/L, 25 g/L, 30 g/L, 35 g/L. , 40g / L, 45g / L, 50g / L, 55g / L, 60g / L, 65g / L, 70g / L or 75g / L, and the specific value between the above values, limited space and for concise It is contemplated that the invention is not exhaustively enumerated.
  • the concentration of silicon in the vanadium-containing solution is ⁇ 50 mg/L
  • the concentration of phosphorus is ⁇ 15 mg/L
  • the concentration of chromium is ⁇ 30 mg/L.
  • the temperature of the reaction in the step (2) is 80-180 ° C, for example, 80 ° C, 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 °C or 180 ° C, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention is no longer exhaustive.
  • the partial pressure of H 2 during the reaction in the step (2) is 0.5 to 2.0 MPa, and may be, for example, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa. , 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa or 2.0 MPa, and the specific point values between the above values, limited by space and for the sake of brevity, the present invention is no longer exhaustive .
  • the reaction time of the step (2) is 0.5-3 h, for example, 0.5 h, 0.8 h, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, 2.3 h, 2.5 h, 2.8 h or 3 h,
  • the specific point values between the above values which are limited in scope and for the sake of brevity, the present invention is no longer exhaustive.
  • the stirring in the step (2) is carried out at a rate of 200-600 r/min, and the stirring is advantageous for accelerating the progress of the reaction.
  • the stirring speed may be 200 r/min, 250 r/min, 300 r/min, 350 r. /min, 400r/min, 450r/min, 500r/min, 550r/min or 600r/min, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention is no longer exhaustive.
  • the vanadium pentoxide solid obtained in the step (2) is dried under a protective atmosphere to obtain a vanadium pentoxide product.
  • the protective atmosphere is any one or a combination of at least two of nitrogen, argon or helium, and may be, for example, any one of nitrogen, argon or helium, typical but not limited.
  • the combination is: nitrogen and argon; nitrogen and helium; argon and helium; nitrogen, argon and helium.
  • the drying temperature is 105-350 ° C, for example 105 ° C, 125 ° C, 150 ° C, 175 ° C, 200 ° C, 235 ° C, 250 ° C, 275 ° C, 300 ° C, 325 ° C or 350 ° C
  • the specific point values between the above values which are limited in length and for the sake of brevity, the present invention is no longer exhaustive.
  • the separation liquid obtained in the step (2) is adjusted in pH and then cooled and crystallized to obtain a sodium sulfate crystal and a crystal solution.
  • the specific operation is: adjusting the pH of the separation liquid to 6.5-7.5, and rapidly cooling the separation liquid after adjusting the pH to 0-10 ° C in a cooling crystallizer for cooling crystallization.
  • the pH of the separation liquid after the pH adjustment is 6.5-7.5, which may be, for example, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4 or 7.5, and the specific value between the above values Point values, limited to length and for the sake of brevity, the present invention is no longer exhaustive.
  • the invention returns the obtained crystallization liquid to the vanadium-containing solution preparation step for recycling; preferably, it is recycled to the step of returning to the vanadium-containing mineral by wet vanadium extraction to prepare a vanadate solution.
  • the solid-liquid separation according to the present invention is carried out by means known in the art, and may be, for example, filtration, suction filtration, centrifugation, sedimentation, etc., but is not limited thereto, and the separation process should be convenient for the operation.
  • the method for cleaning the vanadium pentoxide from the vanadium-containing solution comprises the following steps:
  • the present invention has at least the following beneficial effects:
  • the present invention firstly uses sulfuric acid to acidify a vanadium-containing solution, and then passes H 2 gas to carry out a reduction reaction, thereby greatly increasing the reactivity of vanadate, and solving the reduction of sodium hydroxide formed during the reduction of vanadate hydrogen.
  • the technical problem of difficult reaction At the same time, the reaction temperature and the partial pressure of hydrogen are effectively reduced, which is beneficial to reduce the temperature and pressure load of the equipment.
  • the invention directly prepares a high-quality vanadium pentoxide product by using a vanadium-containing solution, and eliminates a series of process steps of preparing a vanadium-containing solution by ammonium salt precipitation vanadium, and then reducing the temperature, thereby shortening the process flow.
  • the invention avoids the generation of acidic ammonia nitrogen wastewater in the vanadium precipitation process, and has the advantages of short process flow, low production cost and environmental friendliness.
  • the present invention can achieve high-efficiency reduction of vanadate, and its reduction rate is ⁇ 99.3%, and at the same time, a vanadium pentoxide product having a purity greater than 99% is obtained.
  • the method of the invention obtains pure sodium sulfate crystal by cooling and crystallization, and the solution after de-sodium can be returned to the vanadium-containing mineral by steam extraction to prepare vanadate solution, thereby realizing the recycling of water resources. Achieve zero discharge of wastewater.
  • 1 is a process flow diagram provided by an embodiment of the present invention.
  • the process of one embodiment of the present invention may be: adding sulfuric acid to a vanadium-containing solution obtained by vanadium extraction by wet method; and introducing H 2 into the acidified solution for heating and pressurizing reaction.
  • a vanadium pentoxide slurry is obtained, and solid-liquid separation is performed to obtain a vanadium pentoxide solid and a separation liquid; the vanadium pentoxide solid is dried under a protective atmosphere to obtain a vanadium pentoxide product; and the pH of the separation liquid is adjusted,
  • cooling and crystallization are carried out to obtain a sodium sulfate crystal and a crystallization liquid, and the obtained crystallization liquid is returned to the step of preparing a vanadium-containing solution by wet extraction of vanadium.
  • the reduction rate of vanadate in this example was 99.6%, and the purity of vanadium trioxide was more than 99%.
  • the partial pressure of H 2 is 1.5 MPa, and reacting in a high temperature and high pressure reactor for 2.5 hours at 150 ° C and a stirring speed of 500 r / min. After the reaction is completed, the separation and separation of the vanadium trioxide solid and the separation liquid are obtained by filtration;
  • the pH of the separation liquid obtained in the adjustment step (2) is 7.2, and then rapidly cooled to 0 ° C in a cooling crystallizer for crystallization, and the sodium sulfate crystal and the crystallization solution are separated by filtration, and the obtained crystallization liquid is returned to sodium metavanadate.
  • the solution preparation process is recycled.
  • the reduction rate of vanadate in this example was 99.4%, and the purity of vanadium trioxide was more than 99%.
  • the pH of the separation liquid obtained in the adjustment step (2) is 7.1, and then rapidly cooled to 5 ° C in a cooling crystallizer for crystallization, which is separated by filtration to obtain sodium sulfate crystals and a crystal solution, and the obtained crystal solution is returned to sodium metavanadate.
  • the solution preparation process is recycled.
  • the reduction rate of vanadate in this example was 99.3%, and the purity of vanadium trioxide was more than 99%.
  • H 2 is introduced into the acidified solution in the step (1), and the partial pressure of H 2 is 2 MPa, and the reaction is carried out in a high-temperature high-pressure reactor at 170 ° C and a stirring speed of 600 r / min for 1.5 hours. After the reaction is completed, the separation and filtration are carried out to obtain a vanadium pentoxide solid and a separation liquid;
  • the pH of the separation liquid obtained in the adjustment step (2) is 6.5, and then rapidly cooled to 0 ° C in a cooling crystallizer for crystallization, and the sodium sulfate crystal and the crystallization solution are separated by filtration, and the obtained crystal solution is returned to sodium metavanadate.
  • the solution preparation process is recycled.
  • the reduction rate of vanadate in this example was 99.5%, and the purity of vanadium trioxide was more than 99%.
  • the reduction rate of vanadate in this example was 99.4%, and the purity of vanadium trioxide was more than 99%.
  • H 2 and H 2 have a partial pressure of 1.5 MPa at 120 ° C and a stirring speed of 500 r/min.
  • the reaction was carried out for 2 hours in a high temperature and high pressure reactor, and after completion of the reaction, the vanadium pentoxide solid and the separation liquid were separated by filtration. (ie, directly reducing the vanadium-containing solution with hydrogen gas as compared with Example 1)
  • the reduction rate of vanadate in the comparative example was 91.6%, and the purity of vanadium trioxide was more than 99%.
  • Example 1 The other portions were identical to those of Example 1 except that the molar ratio of sodium ion to sulfate ion in the step (1) was changed to 10:1 as compared with Example 1. (ie insufficient amount of sulfuric acid added)

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Abstract

A method for cleanly producing vanadium trioxide by a vanadium-containing solution, comprising: adding sulfuric acid to the vanadium-containing solution, wherein the molar ratio of sodium ions to sulfate radicals in the vanadium-containing solution is 30 to (10-16); and introducing H2 into the acidified solution to carry out heating and pressurizing reaction, and then carrying out solid-liquid separation after the reaction is complete to obtain vanadium trioxide solids and a separating solution. According to the method, the H2 is used for reducing the vanadium-containing solution which is acidified by the sulfuric acid, so that the reactivity of vanadate is greatly improved, and the problem wherein it is difficult to carry out a reduction reaction due to the fact that sodium hydroxide is generated in a hydrogen reduction process of vanadate is solved. The reduction rate of the vanadate is greater than or equal to 99.3%, and the purity of a vanadium trioxide product is greater than 99%. The vanadium trioxide product is directly prepared by utilizing the vanadium-containing solution, the processing process is shortened and the production cost is reduced; the cyclic utilization of water resources is implemented; meanwhile, the production of acidic ammonia nitrogen wastewater in a vanadium precipitation process is avoided, so that the method is suitable for industrial popularization.

Description

一种由含钒溶液清洁生产三氧化二钒的方法Method for cleanly producing vanadium pentoxide from vanadium containing solution 技术领域Technical field
本发明涉及钒化工领域，具体涉及一种由含钒溶液清洁生产三氧化二钒的方法。The invention relates to the field of vanadium chemical industry, in particular to a method for clean production of vanadium pentoxide from a vanadium-containing solution.
背景技术Background technique
钒氧化物主要用于生产合金、陶瓷印染的着色剂、全钒液流电池电解液、硫酸和石油化工的催化剂等冶金、电子、染料、能源、化工等行业。钒氧化物主要有五氧化二钒(V 2O 5)、三氧化二钒(V 2O 3)和二氧化钒(VO 2)等，不同的氧化物的制备工艺各不相同。 Vanadium oxide is mainly used in the production of alloys, ceramic printing and dyeing colorants, all vanadium redox flow battery electrolytes, sulfuric acid and petrochemical catalysts such as metallurgy, electronics, dyes, energy, chemical and other industries. Vanadium oxide mainly vanadium pentoxide (V 2 O 5), vanadium trioxide (V 2 O 3) and vanadium (VO 2) and the like dioxide, oxides of different preparation process vary.
三氧化二钒是生产钒氮合金和钒铁合金的理想原料，目前，生产三氧化二钒的普遍方法是以偏钒酸铵、多钒酸铵、五氧化二钒等为原料，用天然气、煤气、氢气等还原性气体在800-1000℃下还原，获得品位64％以上的三氧化二钒产品，该方法的生产流程长，生产成本高，原料制备存在氨氮废水难以处理等问题。Vanadium pentoxide is an ideal raw material for the production of vanadium-nitrogen alloys and vanadium-iron alloys. Currently, the general method for producing vanadium pentoxide is based on ammonium metavanadate, ammonium polyvanadate, vanadium pentoxide, etc., using natural gas and gas. The reducing gas such as hydrogen is reduced at 800-1000 ° C to obtain a vanadium pentoxide product having a grade of 64% or more. The method has a long production process, high production cost, and is difficult to handle in the preparation of raw materials.
CN103922404B公开了一种五氧化二钒制备三氧化二钒的方法，通过将五氧化二钒和碳粉按摩尔比2∶1的比例混合均匀；将混合后的原料压制成料块，再在料块上覆盖碳粉；将成型的料块在950℃-1050℃烧制3-5h得三氧化二钒。该发明还原温度在900℃以上，能耗较高，不利于推广。CN103922404B discloses a method for preparing vanadium pentoxide by using vanadium pentoxide by uniformly mixing a ratio of vanadium pentoxide and carbon powder to a ratio of 2:1; and pressing the mixed raw materials into a block and then feeding the material. The block is covered with carbon powder; the formed block is fired at 950 ° C - 1050 ° C for 3-5 h to obtain vanadium pentoxide. The reduction temperature of the invention is above 900 ° C, and the energy consumption is high, which is not conducive to promotion.
CN103695954B公开了一种由钒酸盐直接电解制备三氧化二钒的方法，以钒酸盐为原料，以碱金属或碱土金属氯化物为熔盐，在氮气或氩气气氛下升温至150℃-250℃，恒温12h-24h除去熔盐中的水分，然后升温至500℃-1000℃，进行电解，槽电压2.5-5.0V，电解时间为3h-12h，在阴极下部获得产物三氧化二钒 产品。然而电解制备的过程中同样存在能耗过高的问题。CN103695954B discloses a method for preparing vanadium pentoxide by direct electrolysis of vanadate, using vanadate as raw material, using alkali metal or alkaline earth metal chloride as molten salt, and heating to 150 ° C under nitrogen or argon atmosphere- 250 ° C, constant temperature 12h-24h to remove the water in the molten salt, and then heated to 500 ° C -1000 ° C, electrolysis, cell voltage 2.5-5.0V, electrolysis time 3h-12h, the product in the lower part of the cathode to obtain vanadium pentoxide products . However, in the process of electrolytic preparation, there is also a problem of excessive energy consumption.
CN106006736A公开了一种利用氢气从含钒溶液中制备三氧化二钒的方法，采用氢气与钒浓度大于6g/L、氢离子浓度为10 -4-10 -14的含钒溶液在高温高压反应装置中于50-300℃、氢气分压1MPa以上反应1小时以上，获得三氧化二钒产品。该方法存在着反应条件苛刻、还原反应不完全的缺点，同时副产大量低浓度的氢氧化钠溶液，难以循环利用，必须采用其他方法处理。 CN106006736A discloses a method for preparing vanadium pentoxide from a vanadium-containing solution by using hydrogen, using a vanadium-containing solution having a hydrogen and vanadium concentration of more than 6 g/L and a hydrogen ion concentration of 10 -4 -10 -14 in a high temperature and high pressure reaction device. The reaction is carried out at 50-300 ° C and a partial pressure of hydrogen of 1 MPa or more for 1 hour or more to obtain a vanadium pentoxide product. The method has the disadvantages of harsh reaction conditions and incomplete reduction reaction, and at the same time, a large amount of low-concentration sodium hydroxide solution is produced by-product, which is difficult to recycle, and must be treated by other methods.
综上可知，本行业亟待开发一种生产流程短，能耗低，无氨氮废水产生且还原反应能够高效进行的制备三氧化二钒新方法。In summary, the industry urgently needs to develop a new method for preparing vanadium pentoxide with short production process, low energy consumption, no ammonia nitrogen wastewater generation and efficient reduction.
发明内容Summary of the invention
鉴于现有技术中存在的问题，本发明提供了一种由含钒溶液清洁生产三氧化二钒的方法，利用H 2对硫酸酸化后的含钒溶液进行还原，解决了钒酸盐氢气还原过程中生成氢氧化钠而造成还原反应难以进行的问题，钒酸盐的还原率≥99.3％，三氧化二钒产品的纯度大于99％。同时缩短了工艺流程，降低了生产成本，实现了水资源的循环利用，避免了沉钒过程酸性氨氮废水的产生。 In view of the problems existing in the prior art, the present invention provides a method for cleanly producing vanadium pentoxide from a vanadium-containing solution, which utilizes H 2 to reduce the vanadium-containing solution after acidification by sulfuric acid, thereby solving the vanadium hydrogen reduction process. The problem of difficulty in the reduction reaction caused by the formation of sodium hydroxide is that the reduction rate of vanadate is ≥99.3%, and the purity of vanadium pentoxide product is more than 99%. At the same time, the process flow is shortened, the production cost is reduced, the recycling of water resources is realized, and the generation of acidic ammonia nitrogen wastewater in the vanadium precipitation process is avoided.
为达此目的，本发明采用以下技术方案：To this end, the present invention employs the following technical solutions:
本发明提供一种由含钒溶液清洁生产三氧化二钒的方法，所述方法包括以下步骤：The present invention provides a method for the clean production of vanadium pentoxide from a vanadium containing solution, the method comprising the steps of:
(1)向含钒溶液中加入硫酸；所述含钒溶液中含有钠离子，所述含钒溶液中钠离子与硫酸中硫酸根的摩尔比为30∶(10-16)；(1) adding sulfuric acid to the vanadium-containing solution; the vanadium-containing solution contains sodium ions, the molar ratio of sodium ions to sulfate in the vanadium-containing solution is 30: (10-16);
(2)向步骤(1)酸化后的溶液中通入H 2进行加热加压反应，反应完成后固液分离，得到三氧化二钒固体和分离液。 (2) The H 2 is introduced into the acidified solution in the step (1) to carry out a heat and pressure reaction, and after the completion of the reaction, solid-liquid separation is carried out to obtain a vanadium trioxide solid and a separation liquid.
典型钒酸盐的氢还原反应式为：The hydrogen reduction reaction of a typical vanadate is:
2H XVO 4 (3-X) -+2H 2(g)＝V 2O 3+(6-2X)OH -+(2X-1)H 2O(其中X为0-2) 2H X VO 4 (3-X ) - +2H 2 (g)=V 2 O 3 +(6-2X)OH - +(2X-1)H 2 O (where X is 0-2)
由反应式可以看出，钒酸盐在氢气还原过程中会产生氢氧根离子，使溶液的碱性逐渐增强，造成氢气还原钒酸盐的趋势变弱，还原难度逐渐增加，还原反应不能彻底完成。It can be seen from the reaction formula that vanadate will produce hydroxide ions during the hydrogen reduction process, which will gradually increase the alkalinity of the solution, resulting in a weakening trend of hydrogen reduction of vanadate, a difficulty in reduction, and a complete reduction reaction. carry out.
本发明先使用硫酸将含钒溶液酸化，然后通入H 2气体进行还原反应，酸化后的溶液存在足够的氢离子消耗还原过程中产生的氢氧根离子，促使反应正向进行，大大提高了钒酸盐的反应活性，解决了钒酸盐氢气还原过程中生成氢氧化钠而造成还原反应难以进行的技术难题。同时有效降低了反应温度和氢气分压，有利于减轻设备的温度和压力负荷，降低了反应能耗。 The invention firstly acidifies the vanadium-containing solution by using sulfuric acid, and then passes the H 2 gas to carry out the reduction reaction, and the acidized solution has sufficient hydrogen ions to consume the hydroxide ions generated during the reduction process, thereby prompting the reaction to proceed, greatly improving the reaction. The reactivity of vanadate solves the technical problem that it is difficult to carry out the reduction reaction by generating sodium hydroxide during the hydrogenation of vanadate hydrogen. At the same time, the reaction temperature and the partial pressure of hydrogen are effectively reduced, which is beneficial to reducing the temperature and pressure load of the device and reducing the energy consumption of the reaction.
本发明按照含钒溶液中钠离子与硫酸中硫酸根为30∶(10-16)的摩尔比使用硫酸对含钒溶液进行酸化，所述摩尔比可以为30∶10、30∶10.5、30∶11、30∶11.5、30∶12、30∶12.5、30∶13、30∶13.5、30∶14、30∶14.5、30∶15、30∶15.5或30∶16，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。According to the present invention, the vanadium-containing solution is acidified using sulfuric acid according to a molar ratio of sodium ion in the vanadium-containing solution to sulfate in the sulfuric acid of 30:(10-16), and the molar ratio may be 30:10, 30:10.5, 30: 11, 30:11.5, 30:12, 30:12.5, 30:13, 30:13.5, 30:14, 30:14.5, 30:15, 30:15.5 or 30:16, and the specific point between the above values Values, limited by length and for the sake of brevity, the present invention is no longer exhaustive.
上述摩尔比是本发明的关键，按照上述摩尔比使用硫酸对含钒溶液进行酸化后，反应体系中存在足够量的氢离子促使反应向正向进行；当加入的硫酸量过少时，反应后期体系PH值过高，氢离子含量不足将使反应速率及反应程度变弱，还原反应难以彻底；当加入的硫酸量过多时，造成对酸液的浪费，增加生产成本。The above molar ratio is the key to the present invention. After the vanadium-containing solution is acidified according to the above molar ratio using sulfuric acid, a sufficient amount of hydrogen ions are present in the reaction system to promote the reaction in the forward direction; when the amount of sulfuric acid added is too small, the late reaction system When the pH value is too high, the hydrogen ion content is insufficient, the reaction rate and the reaction degree are weakened, and the reduction reaction is difficult to be thorough; when the amount of sulfuric acid added is too large, waste of the acid solution is caused, and the production cost is increased.
根据本发明，步骤(1)所述含钒溶液为含钒矿物经钠化焙烧、湿法浸出的溶液或其他途径获得的含钒碱性溶液。According to the present invention, the vanadium-containing solution of the step (1) is a vanadium-containing alkaline solution obtained by sodium roasting, wet leaching of a vanadium-containing mineral or other routes.
根据本发明，所述含钒溶液中含有正钒酸钠、焦钒酸钠或偏钒酸钠中的任意一种。According to the invention, the vanadium-containing solution contains any one of sodium orthovanadate, sodium metavanadate or sodium metavanadate.
根据本发明，步骤(1)所述含钒溶液中钒的浓度为20-45g/L，例如可以是20g/L、23g/L、25g/L、28g/L、30g/L、33g/L、35g/L、38g/L、40g/L、42g/L或 45g/L，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。According to the present invention, the concentration of vanadium in the vanadium-containing solution in the step (1) is 20-45 g/L, and may be, for example, 20 g/L, 23 g/L, 25 g/L, 28 g/L, 30 g/L, 33 g/L. 35g/L, 38g/L, 40g/L, 42g/L or 45g/L, and the specific point values between the above values, which are limited in scope and for the sake of brevity, the present invention is not exhaustively enumerated.
根据本发明，步骤(1)所述含钒溶液中钠的浓度为9-75g/L，例如可以是9g/L、15g/L、20g/L、25g/L、30g/L、35g/L、40g/L、45g/L、50g/L、55g/L、60g/L、65g/L、70g/L或75g/L，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。According to the present invention, the concentration of sodium in the vanadium-containing solution in the step (1) is 9-75 g/L, and may be, for example, 9 g/L, 15 g/L, 20 g/L, 25 g/L, 30 g/L, 35 g/L. , 40g / L, 45g / L, 50g / L, 55g / L, 60g / L, 65g / L, 70g / L or 75g / L, and the specific value between the above values, limited space and for concise It is contemplated that the invention is not exhaustively enumerated.
根据本发明，所述含钒溶液中硅的浓度≤50mg/L，磷的浓度≤15mg/L，铬的浓度≤30mg/L。According to the invention, the concentration of silicon in the vanadium-containing solution is ≤50 mg/L, the concentration of phosphorus is ≤15 mg/L, and the concentration of chromium is ≤30 mg/L.
根据本发明，步骤(2)所述反应的温度为80-180℃，例如可以是80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃或180℃，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。According to the present invention, the temperature of the reaction in the step (2) is 80-180 ° C, for example, 80 ° C, 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 °C or 180 ° C, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention is no longer exhaustive.
根据本发明，步骤(2)所述反应过程中H 2的分压为0.5-2.0MPa，例如可以是0.5MPa、0.6MPa、0.7MPa、0.8MPa、0.9MPa、1.0MPa、1.1MPa、1.2MPa、1.3MPa、1.4MPa、1.5MPa、1.6MPa、1.7MPa、1.8MPa、1.9MPa或2.0MPa，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。 According to the present invention, the partial pressure of H 2 during the reaction in the step (2) is 0.5 to 2.0 MPa, and may be, for example, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa. , 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa or 2.0 MPa, and the specific point values between the above values, limited by space and for the sake of brevity, the present invention is no longer exhaustive .
根据本发明，步骤(2)所述反应的时间0.5-3h，例如可以是0.5h、0.8h、1h、1.2h、1.5h、1.8h、2h、2.3h、2.5h、2.8h或3h，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。According to the present invention, the reaction time of the step (2) is 0.5-3 h, for example, 0.5 h, 0.8 h, 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, 2.3 h, 2.5 h, 2.8 h or 3 h, And the specific point values between the above values, which are limited in scope and for the sake of brevity, the present invention is no longer exhaustive.
根据本发明，步骤(2)所述反应过程中以200-600r/min的速度进行搅拌，搅拌有利于加快反应进程，所述搅拌速度可以为200r/min、250r/min、300r/min、350r/min、400r/min、450r/min、500r/min、550r/min或600r/min，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。According to the present invention, the stirring in the step (2) is carried out at a rate of 200-600 r/min, and the stirring is advantageous for accelerating the progress of the reaction. The stirring speed may be 200 r/min, 250 r/min, 300 r/min, 350 r. /min, 400r/min, 450r/min, 500r/min, 550r/min or 600r/min, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention is no longer exhaustive.
本发明将步骤(2)得到的三氧化二钒固体在保护气氛下进行干燥，得到三氧化二钒产品。In the present invention, the vanadium pentoxide solid obtained in the step (2) is dried under a protective atmosphere to obtain a vanadium pentoxide product.
根据本发明，所述保护性气氛为氮气、氩气或氦气中的任意一种或至少两种的组合，例如可以是氮气、氩气或氦气中的任意一种，典型但非限定性的组合为：氮气和氩气；氮气和氦气；氩气和氦气；氮气、氩气和氦气。According to the present invention, the protective atmosphere is any one or a combination of at least two of nitrogen, argon or helium, and may be, for example, any one of nitrogen, argon or helium, typical but not limited. The combination is: nitrogen and argon; nitrogen and helium; argon and helium; nitrogen, argon and helium.
根据本发明，所述干燥的温度为105-350℃，例如可以是105℃、125℃、150℃、175℃、200℃、235℃、250℃、275℃、300℃、325℃或350℃，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。According to the invention, the drying temperature is 105-350 ° C, for example 105 ° C, 125 ° C, 150 ° C, 175 ° C, 200 ° C, 235 ° C, 250 ° C, 275 ° C, 300 ° C, 325 ° C or 350 ° C And the specific point values between the above values, which are limited in length and for the sake of brevity, the present invention is no longer exhaustive.
本发明对步骤(2)得到的分离液调节pH后进行冷却结晶，得到硫酸钠晶体和结晶液。具体操作为：将分离液的pH调节为6.5-7.5，将调节pH后的分离液在降温结晶器中急速冷却到0-10℃进行冷却结晶。In the present invention, the separation liquid obtained in the step (2) is adjusted in pH and then cooled and crystallized to obtain a sodium sulfate crystal and a crystal solution. The specific operation is: adjusting the pH of the separation liquid to 6.5-7.5, and rapidly cooling the separation liquid after adjusting the pH to 0-10 ° C in a cooling crystallizer for cooling crystallization.
根据本发明，所述调节pH后分离液的pH为6.5-7.5，例如可以是6.5、6.6、6.7、6.8、6.9、7.0、7.1、7.2、7.3、7.4或7.5，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举。According to the present invention, the pH of the separation liquid after the pH adjustment is 6.5-7.5, which may be, for example, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4 or 7.5, and the specific value between the above values Point values, limited to length and for the sake of brevity, the present invention is no longer exhaustive.
本发明将得到的结晶液返回至含钒溶液制备工序循环使用；优选为返回至含钒矿物湿法提钒制备钒酸盐溶液工序循环使用。The invention returns the obtained crystallization liquid to the vanadium-containing solution preparation step for recycling; preferably, it is recycled to the step of returning to the vanadium-containing mineral by wet vanadium extraction to prepare a vanadate solution.
本发明所述固液分离选用本领域公知的手段进行，例如可以是过滤、抽滤、离心分离以及沉降等，但非仅限于此，分离过程应以便于操作为宜。The solid-liquid separation according to the present invention is carried out by means known in the art, and may be, for example, filtration, suction filtration, centrifugation, sedimentation, etc., but is not limited thereto, and the separation process should be convenient for the operation.
作为优选的技术方案，所述由含钒溶液清洁生产三氧化二钒的方法包括以下步骤：As a preferred technical solution, the method for cleaning the vanadium pentoxide from the vanadium-containing solution comprises the following steps:
(1)向含钒溶液中加入硫酸；所述含钒溶液中含有钠离子，所述含钒溶液中钠离子与硫酸中硫酸根的摩尔比为30∶(10-16)；(1) adding sulfuric acid to the vanadium-containing solution; the vanadium-containing solution contains sodium ions, the molar ratio of sodium ions to sulfate in the vanadium-containing solution is 30: (10-16);
(2)向步骤(1)酸化后的溶液中通入H 2进行加热加压反应，反应完成后 固液分离，得到三氧化二钒固体和分离液； (2) to the step (1) solution after acidification H 2 into a pressurized reactor is heated, after the completion of the reaction solid-liquid separation to obtain solid vanadium trioxide and a separated liquid;
(3)将步骤(2)得到的三氧化二钒固体在保护气氛下进行干燥，得到三氧化二钒产品；(3) drying the vanadium pentoxide solid obtained in the step (2) under a protective atmosphere to obtain a vanadium pentoxide product;
(4)对步骤(2)得到的分离液调节pH后进行冷却结晶，得到硫酸钠晶体和结晶液，将所得结晶液返回至含钒溶液制备工序循环使用。(4) The pH of the separation liquid obtained in the step (2) is adjusted to be cooled and crystallized to obtain a sodium sulfate crystal and a crystal solution, and the obtained crystal liquid is returned to the vanadium-containing solution preparation step for recycling.
与现有技术方案相比，本发明至少具有以下有益效果：Compared with the prior art solutions, the present invention has at least the following beneficial effects:
(1)本发明先使用硫酸将含钒溶液酸化，然后通入H 2气体进行还原反应，大大提高了钒酸盐的反应活性，解决了钒酸盐氢气还原过程中生成氢氧化钠而造成还原反应难以进行的技术难题。同时有效降低了反应温度和氢气分压，有利于减轻设备的温度和压力负荷。 (1) The present invention firstly uses sulfuric acid to acidify a vanadium-containing solution, and then passes H 2 gas to carry out a reduction reaction, thereby greatly increasing the reactivity of vanadate, and solving the reduction of sodium hydroxide formed during the reduction of vanadate hydrogen. The technical problem of difficult reaction. At the same time, the reaction temperature and the partial pressure of hydrogen are effectively reduced, which is beneficial to reduce the temperature and pressure load of the equipment.
(2)本发明利用含钒溶液直接制备得到了高品质的三氧化二钒产品，省掉了含钒溶液经铵盐沉钒制备中间产品，再高温还原等一系列工序过程，缩短了工艺流程，避免了沉钒过程酸性氨氮废水的产生，具有工艺流程短、生产成本低、环境友好等优点。(2) The invention directly prepares a high-quality vanadium pentoxide product by using a vanadium-containing solution, and eliminates a series of process steps of preparing a vanadium-containing solution by ammonium salt precipitation vanadium, and then reducing the temperature, thereby shortening the process flow. The invention avoids the generation of acidic ammonia nitrogen wastewater in the vanadium precipitation process, and has the advantages of short process flow, low production cost and environmental friendliness.
(3)本发明能够实现对钒酸盐的高效还原，其还原率≥99.3％，同时得到纯度大于99％的三氧化二钒产品。(3) The present invention can achieve high-efficiency reduction of vanadate, and its reduction rate is ≥99.3%, and at the same time, a vanadium pentoxide product having a purity greater than 99% is obtained.
(4)本发明方法通过冷却结晶的方式获得了纯净的硫酸钠晶体，脱钠后的溶液可以返回含钒矿物湿法提钒制备钒酸盐溶液工序循环使用，实现了水资源的循环利用，达到废水零排放的目的。(4) The method of the invention obtains pure sodium sulfate crystal by cooling and crystallization, and the solution after de-sodium can be returned to the vanadium-containing mineral by steam extraction to prepare vanadate solution, thereby realizing the recycling of water resources. Achieve zero discharge of wastewater.
附图说明DRAWINGS
图1是本发明一种具体实施方式提供的工艺流程图。1 is a process flow diagram provided by an embodiment of the present invention.
下面对本发明进一步详细说明。但下述的实例仅仅是本发明的简易例子，并不代表或限制本发明的权利保护范围，本发明的保护范围以权利要求书为准。The invention is further described in detail below. However, the following examples are merely illustrative of the invention and are not intended to limit the scope of the invention, and the scope of the invention is defined by the appended claims.
具体实施方式Detailed ways
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.
如图1所示，本发明一种具体实施方式的工艺流程可以为：向湿法提钒得到的含钒溶液中加入硫酸；向酸化后的溶液中通入H 2进行加热加压反应，反应完成后得到三氧化二钒浆料，固液分离，得到三氧化二钒固体和分离液；将三氧化二钒固体在保护气氛下进行干燥，得到三氧化二钒产品；调节分离液的pH，然后进行冷却结晶，得到硫酸钠晶体和结晶液，将所得结晶液返回至湿法提钒制备含钒溶液工序循环使用。 As shown in FIG. 1 , the process of one embodiment of the present invention may be: adding sulfuric acid to a vanadium-containing solution obtained by vanadium extraction by wet method; and introducing H 2 into the acidified solution for heating and pressurizing reaction. After completion, a vanadium pentoxide slurry is obtained, and solid-liquid separation is performed to obtain a vanadium pentoxide solid and a separation liquid; the vanadium pentoxide solid is dried under a protective atmosphere to obtain a vanadium pentoxide product; and the pH of the separation liquid is adjusted, Then, cooling and crystallization are carried out to obtain a sodium sulfate crystal and a crystallization liquid, and the obtained crystallization liquid is returned to the step of preparing a vanadium-containing solution by wet extraction of vanadium.
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：In order to better explain the present invention, it is convenient to understand the technical solution of the present invention, and a typical but non-limiting embodiment of the present invention is as follows:
实施例1Example 1
(1)以钒浓度为45g/L，钠浓度为23g/L的偏钒酸钠溶液为原料，按照钠离子与硫酸根离子为2∶1的摩尔比向偏钒酸钠溶液中加入硫酸；(1) using sodium vanadate solution having a vanadium concentration of 45 g/L and a sodium concentration of 23 g/L as a raw material, and adding sulfuric acid to the sodium metavanadate solution according to a molar ratio of sodium ion to sulfate ion of 2:1;
(2)向步骤(1)酸化后的溶液中通入H 2，H 2的分压为1.5MPa，在120℃、搅拌速度为500r/min的条件下，于高温高压反应器中反应2小时，反应完成后过滤分离得到三氧化二钒固体和分离液； (2) introducing H 2 to the acidified solution in the step (1), and the partial pressure of H 2 is 1.5 MPa, and reacting in a high-temperature high-pressure reactor for 2 hours at 120 ° C and a stirring speed of 500 r/min. After the reaction is completed, the separation and separation of the vanadium trioxide solid and the separation liquid are obtained by filtration;
(3)将步骤(2)得到的三氧化二钒固体于105℃、氮气气氛下进行干燥，得到三氧化二钒产品；(3) drying the vanadium pentoxide solid obtained in the step (2) at 105 ° C under a nitrogen atmosphere to obtain a vanadium pentoxide product;
(4)调节步骤(2)得到的分离液的pH为7，然后在降温结晶器中急速冷却到10℃进行结晶，过滤分离得到硫酸钠晶体和结晶液，将所得结晶液返回偏钒酸钠溶液制备工序循环使用。(4) The pH of the separation liquid obtained in the adjustment step (2) is 7, and then rapidly cooled to 10 ° C in a cooling crystallizer for crystallization, and separated by filtration to obtain sodium sulfate crystals and a crystal solution, and the obtained crystal solution is returned to sodium metavanadate. The solution preparation process is recycled.
经过检测，本实施例中钒酸盐的还原率为99.6％，三氧化二钒的纯度大于99％。After testing, the reduction rate of vanadate in this example was 99.6%, and the purity of vanadium trioxide was more than 99%.
实施例2Example 2
(1)以钒浓度为28g/L，钠浓度为20g/L的偏钒酸钠溶液为原料，按照钠离子与硫酸根离子为30∶13的摩尔比向偏钒酸钠溶液中加入硫酸；(1) using sodium vanadate solution having a vanadium concentration of 28 g/L and a sodium concentration of 20 g/L as a raw material, and adding sulfuric acid to the sodium metavanadate solution according to a molar ratio of sodium ion to sulfate ion of 30:13;
(2)向步骤(1)酸化后的溶液中通入H 2，H 2的分压为1.5MPa，在150℃、搅拌速度为500r/min的条件下，于高温高压反应器中反应2.5小时，反应完成后过滤分离得到三氧化二钒固体和分离液； (2) introducing H 2 to the acidified solution in the step (1), the partial pressure of H 2 is 1.5 MPa, and reacting in a high temperature and high pressure reactor for 2.5 hours at 150 ° C and a stirring speed of 500 r / min. After the reaction is completed, the separation and separation of the vanadium trioxide solid and the separation liquid are obtained by filtration;
(3)将步骤(2)得到的三氧化二钒固体于220℃、氮气气氛下进行干燥，得到三氧化二钒产品；(3) drying the vanadium pentoxide solid obtained in the step (2) at 220 ° C under a nitrogen atmosphere to obtain a vanadium pentoxide product;
(4)调节步骤(2)得到的分离液的pH为7.2，然后在降温结晶器中急速冷却到0℃进行结晶，过滤分离得到硫酸钠晶体和结晶液，将所得结晶液返回偏钒酸钠溶液制备工序循环使用。(4) The pH of the separation liquid obtained in the adjustment step (2) is 7.2, and then rapidly cooled to 0 ° C in a cooling crystallizer for crystallization, and the sodium sulfate crystal and the crystallization solution are separated by filtration, and the obtained crystallization liquid is returned to sodium metavanadate. The solution preparation process is recycled.
经过检测，本实施例中钒酸盐的还原率为99.4％，三氧化二钒的纯度大于99％。After testing, the reduction rate of vanadate in this example was 99.4%, and the purity of vanadium trioxide was more than 99%.
实施例3Example 3
(1)以钒浓度为20g/L，钠浓度为10g/L的偏钒酸钠溶液为原料，按照钠离子与硫酸根离子为5∶2的摩尔比向偏钒酸钠溶液中加入硫酸；(1) using sodium vanadate solution having a vanadium concentration of 20 g/L and a sodium concentration of 10 g/L as a raw material, and adding sulfuric acid to the sodium metavanadate solution according to a molar ratio of sodium ion to sulfate ion of 5:2;
(2)向步骤(1)酸化后的溶液中通入H 2，H 2的分压为1MPa，在180℃、搅拌速度为600r/min的条件下，于高温高压反应器中反应3小时，反应完成后过滤分离得到三氧化二钒固体和分离液； (2) introducing a H 2 to the acidified solution in the step (1), and the partial pressure of H 2 is 1 MPa, and reacting in a high-temperature high-pressure reactor for 3 hours at 180 ° C and a stirring speed of 600 r/min. After the reaction is completed, the separation and filtration are carried out to obtain a vanadium pentoxide solid and a separation liquid;
(3)将步骤(2)得到的三氧化二钒固体于270℃、氩气气氛下进行干燥，得到三氧化二钒产品；(3) drying the vanadium pentoxide solid obtained in the step (2) at 270 ° C under an argon atmosphere to obtain a vanadium pentoxide product;
(4)调节步骤(2)得到的分离液的pH为7.1，然后在降温结晶器中急速冷却到5℃进行结晶，过滤分离得到硫酸钠晶体和结晶液，将所得结晶液返回偏 钒酸钠溶液制备工序循环使用。(4) The pH of the separation liquid obtained in the adjustment step (2) is 7.1, and then rapidly cooled to 5 ° C in a cooling crystallizer for crystallization, which is separated by filtration to obtain sodium sulfate crystals and a crystal solution, and the obtained crystal solution is returned to sodium metavanadate. The solution preparation process is recycled.
经过检测，本实施例中钒酸盐的还原率为99.3％，三氧化二钒的纯度大于99％。After testing, the reduction rate of vanadate in this example was 99.3%, and the purity of vanadium trioxide was more than 99%.
实施例4Example 4
(1)以钒浓度为45g/L，钠浓度为67g/L的焦钒酸钠溶液为原料，按照钠离子与硫酸根离子为3∶1的摩尔比向焦钒酸钠溶液中加入硫酸；(1) using a sodium vanadium divanate solution having a vanadium concentration of 45 g/L and a sodium concentration of 67 g/L as a raw material, and adding sulfuric acid to the sodium pyro vanadate solution according to a molar ratio of sodium ion to sulfate ion of 3:1;
(2)向步骤(1)酸化后的溶液中通入H 2，H 2的分压为2MPa，在170℃、搅拌速度为600r/min的条件下，于高温高压反应器中反应1.5小时，反应完成后过滤分离得到三氧化二钒固体和分离液； (2) H 2 is introduced into the acidified solution in the step (1), and the partial pressure of H 2 is 2 MPa, and the reaction is carried out in a high-temperature high-pressure reactor at 170 ° C and a stirring speed of 600 r / min for 1.5 hours. After the reaction is completed, the separation and filtration are carried out to obtain a vanadium pentoxide solid and a separation liquid;
(3)将步骤(2)得到的三氧化二钒固体于130℃、氩气气氛下进行干燥，得到三氧化二钒产品；(3) drying the vanadium pentoxide solid obtained in the step (2) at 130 ° C in an argon atmosphere to obtain a vanadium pentoxide product;
(4)调节步骤(2)得到的分离液的pH为6.5，然后在降温结晶器中急速冷却到0℃进行结晶，过滤分离得到硫酸钠晶体和结晶液，将所得结晶液返回偏钒酸钠溶液制备工序循环使用。(4) The pH of the separation liquid obtained in the adjustment step (2) is 6.5, and then rapidly cooled to 0 ° C in a cooling crystallizer for crystallization, and the sodium sulfate crystal and the crystallization solution are separated by filtration, and the obtained crystal solution is returned to sodium metavanadate. The solution preparation process is recycled.
经过检测，本实施例中钒酸盐的还原率为99.5％，三氧化二钒的纯度大于99％。After testing, the reduction rate of vanadate in this example was 99.5%, and the purity of vanadium trioxide was more than 99%.
实施例5Example 5
(1)以钒浓度为20g/L，钠浓度为31g/L的正钒酸钠溶液为原料，按照钠离子与硫酸根离子为30∶11的摩尔比向正钒酸钠溶液中加入硫酸；(1) using a sodium vanadate solution having a vanadium concentration of 20 g/L and a sodium concentration of 31 g/L as a raw material, and adding sulfuric acid to the sodium orthovanadate solution according to a molar ratio of sodium ion to sulfate ion of 30:11;
(2)向步骤(1)酸化后的溶液中通入H 2，H 2的分压为0.5MPa，在180℃、搅拌速度为600r/min的条件下，于高温高压反应器中反应3小时，反应完成后过滤分离得到三氧化二钒固体和分离液； (2) introducing H 2 to the acidified solution in the step (1), and the partial pressure of H 2 is 0.5 MPa, and reacting in a high-temperature high-pressure reactor for 3 hours at 180 ° C and a stirring speed of 600 r/min. After the reaction is completed, the separation and separation of the vanadium trioxide solid and the separation liquid are obtained by filtration;
(3)将步骤(2)得到的三氧化二钒固体于230℃、氮气气氛下进行干燥， 得到三氧化二钒产品；(3) drying the vanadium pentoxide solid obtained in the step (2) at 230 ° C under a nitrogen atmosphere to obtain a vanadium pentoxide product;
(4)调节步骤(2)得到的分离液的pH为6.8，然后在降温结晶器中急速冷却到0℃进行结晶，过滤分离得到硫酸钠晶体和结晶液，将所得结晶液返回偏钒酸钠溶液制备工序循环使用。(4) The pH of the separation liquid obtained in the adjustment step (2) is 6.8, and then rapidly cooled to 0 ° C in a cooling crystallizer for crystallization, and the sodium sulfate crystal and the crystallization solution are separated by filtration, and the obtained crystallization liquid is returned to sodium metavanadate. The solution preparation process is recycled.
经过检测，本实施例中钒酸盐的还原率为99.4％，三氧化二钒的纯度大于99％。After testing, the reduction rate of vanadate in this example was 99.4%, and the purity of vanadium trioxide was more than 99%.
对比例1Comparative example 1
向钒浓度为45g/L，钠浓度为23g/L的偏钒酸钠溶液中通入H 2，H 2的分压为1.5MPa，在120℃、搅拌速度为500r/min的条件下，于高温高压反应器中反应2小时，反应完成后过滤分离得到三氧化二钒固体和分离液。(即与实施例1相比用氢气直接对含钒溶液进行还原) To a sodium metavanadate solution having a vanadium concentration of 45 g/L and a sodium concentration of 23 g/L, H 2 and H 2 have a partial pressure of 1.5 MPa at 120 ° C and a stirring speed of 500 r/min. The reaction was carried out for 2 hours in a high temperature and high pressure reactor, and after completion of the reaction, the vanadium pentoxide solid and the separation liquid were separated by filtration. (ie, directly reducing the vanadium-containing solution with hydrogen gas as compared with Example 1)
经过检测，本对比例中钒酸盐的还原率为91.6％，三氧化二钒的纯度大于99％。After testing, the reduction rate of vanadate in the comparative example was 91.6%, and the purity of vanadium trioxide was more than 99%.
对比例2Comparative example 2
与实施例1相比，除了将步骤(1)中钠离子与硫酸根离子为的摩尔比替换为10∶1外，其他部分与实施例1完全相同。(即硫酸的加入量不足)The other portions were identical to those of Example 1 except that the molar ratio of sodium ion to sulfate ion in the step (1) was changed to 10:1 as compared with Example 1. (ie insufficient amount of sulfuric acid added)
经过检测，本对比例中钒酸盐的还原率为93.2％，三氧化二钒的纯度大于99％。After testing, the reduction rate of vanadate in this comparative example was 93.2%, and the purity of vanadium trioxide was more than 99%.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重 复，本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention has various possibilities. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (11)

  1. 一种由含钒溶液清洁生产三氧化二钒的方法，其特征在于，所述方法包括以下步骤：A method for the clean production of vanadium pentoxide from a vanadium-containing solution, characterized in that the method comprises the steps of:
    (1)向含钒溶液中加入硫酸；所述含钒溶液中含有钠离子，所述含钒溶液中钠离子与硫酸中硫酸根的摩尔比为30∶(10-16)；(1) adding sulfuric acid to the vanadium-containing solution; the vanadium-containing solution contains sodium ions, the molar ratio of sodium ions to sulfate in the vanadium-containing solution is 30: (10-16);
    (2)向步骤(1)酸化后的溶液中通入H 2进行加热加压反应，反应完成后固液分离，得到三氧化二钒固体和分离液。 (2) The H 2 is introduced into the acidified solution in the step (1) to carry out a heat and pressure reaction, and after the completion of the reaction, solid-liquid separation is carried out to obtain a vanadium trioxide solid and a separation liquid.
  2. 如权利要求1所述的方法，其特征在于，步骤(1)所述含钒溶液为含钒矿物经钠化焙烧、湿法浸出的溶液或其他途径获得的含钒碱性溶液。The method according to claim 1, wherein the vanadium-containing solution in the step (1) is a vanadium-containing alkaline solution obtained by sodium roasting, wet leaching of a vanadium-containing mineral or other route.
  3. 如权利要求1所述的方法，其特征在于，所述含钒溶液中含有正钒酸钠、焦钒酸钠或偏钒酸钠中的任意一种。The method according to claim 1, wherein said vanadium-containing solution contains any one of sodium orthovanadate, sodium metavanadate or sodium metavanadate.
  4. 如权利要求1所述的方法，其特征在于，步骤(1)所述含钒溶液中钒的浓度为20-45g/L，钠的浓度为9-75g/L；The method according to claim 1, wherein the vanadium-containing solution in step (1) has a concentration of vanadium of 20-45 g/L and a sodium concentration of 9-75 g/L;
    优选地，所述含钒溶液中硅的浓度≤50mg/L，磷的浓度≤15mg/L，铬的浓度≤30mg/L。Preferably, the concentration of silicon in the vanadium-containing solution is ≤50 mg/L, the concentration of phosphorus is ≤15 mg/L, and the concentration of chromium is ≤30 mg/L.
  5. 如权利要求1所述的方法，其特征在于，步骤(2)所述反应的温度为80-180℃；The method according to claim 1, wherein the temperature of the reaction in the step (2) is 80-180 ° C;
    优选地，步骤(2)所述反应过程中H 2的分压为0.5-2.0MPa； Preferably, the partial pressure of H 2 during the reaction in the step (2) is 0.5-2.0 MPa;
    优选地，步骤(2)所述反应的时间0.5-3h；Preferably, the reaction time of step (2) is 0.5-3 h;
    优选地，步骤(2)所述反应过程中以200-600r/min的速度进行搅拌。Preferably, the stirring is carried out at a rate of 200-600 r/min during the reaction in the step (2).
  6. 如权利要求1所述的方法，其特征在于，将步骤(2)得到的三氧化二钒固体在保护气氛下进行干燥，得到三氧化二钒产品。The method according to claim 1, wherein the vanadium pentoxide solid obtained in the step (2) is dried under a protective atmosphere to obtain a vanadium pentoxide product.
  7. 如权利要求6所述的方法，其特征在于，所述保护气氛为氮气、氦气或氩气中的任意一种或至少两种的组合；The method of claim 6 wherein said protective atmosphere is any one or a combination of at least two of nitrogen, helium or argon;
    优选地，所述干燥的温度为105-350℃。Preferably, the drying temperature is from 105 to 350 °C.
  8. 如权利要求1所述的方法，其特征在于，对步骤(2)得到的分离液调节pH后进行冷却结晶，得到硫酸钠晶体和结晶液。The method according to claim 1, wherein the separation liquid obtained in the step (2) is adjusted in pH and then cooled and crystallized to obtain a sodium sulfate crystal and a crystal solution.
  9. 如权利要求8所述的方法，其特征在于，将分离液的pH调节为6.5-7.5；The method according to claim 8, wherein the pH of the separation liquid is adjusted to 6.5-7.5;
    优选地，将调节pH后的分离液在降温结晶器中急速冷却到0-10℃进行冷却结晶。Preferably, the pH-adjusted separation liquid is rapidly cooled to 0-10 ° C in a cooling crystallizer for cooling crystallization.
  10. 如权利要求8所述的方法，其特征在于，将得到的结晶液返回至含钒溶液制备工序循环使用；The method according to claim 8, wherein the obtained crystallization liquid is returned to the vanadium-containing solution preparation step for recycling;
    优选地，将得到的结晶液返回至含钒矿物湿法提钒制备钒酸盐溶液工序循环使用。Preferably, the obtained crystallization liquid is returned to the vanadium-containing mineral by wet extraction of vanadium to prepare a vanadate solution.
  11. 如权利要求1-10任一项所述的方法，其特征在于，所述方法包括以下步骤：The method of any of claims 1 to 10, wherein the method comprises the steps of:
    (1)向含钒溶液中加入硫酸；所述含钒溶液中含有钠离子，所述含钒溶液中钠离子与硫酸中硫酸根的摩尔比为30∶(10-16)；(1) adding sulfuric acid to the vanadium-containing solution; the vanadium-containing solution contains sodium ions, the molar ratio of sodium ions to sulfate in the vanadium-containing solution is 30: (10-16);
    (2)向步骤(1)酸化后的溶液中通入H 2进行加热加压反应，反应完成后固液分离，得到三氧化二钒固体和分离液； (2) to the step (1) solution after acidification H 2 into a pressurized reactor is heated, after the completion of the reaction solid-liquid separation to obtain solid vanadium trioxide and a separated liquid;
    (3)将步骤(2)得到的三氧化二钒固体在保护气氛下进行干燥，得到三氧化二钒产品；(3) drying the vanadium pentoxide solid obtained in the step (2) under a protective atmosphere to obtain a vanadium pentoxide product;
    (4)对步骤(2)得到的分离液调节pH后进行冷却结晶，得到硫酸钠晶体和结晶液，将所得结晶液返回至含钒溶液制备工序循环使用。(4) The pH of the separation liquid obtained in the step (2) is adjusted to be cooled and crystallized to obtain a sodium sulfate crystal and a crystal solution, and the obtained crystal liquid is returned to the vanadium-containing solution preparation step for recycling.
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