阅读说明：本技术 一种高纯金属铬的制造工艺 (Manufacturing process of high-purity metal chromium ) 是由 唐翔 于 2020-07-02 设计创作，主要内容包括：一种高纯金属铬的制造工艺,其特征：采用新工艺,从多种含铬物质中,液相法提取高纯铬物质,得到99.99％高纯铬生产所需高纯原料三氧化二铬及三价铬物质,再通过电解法、还原法、置换法制取99.99％高纯金属铬。本发明制取的产品纯度高,质量好,市场需求大,节能环保,经济效益好,前景广阔。(A manufacturing process of high-purity metal chromium is characterized by comprising the following steps: the new process is adopted to extract high-purity chromium substances from various chromium-containing substances by a liquid phase method to obtain high-purity raw materials of chromium sesquioxide and trivalent chromium substances required by 99.99 percent of high-purity chromium production, and 99.99 percent of high-purity metal chromium is prepared by an electrolysis method, a reduction method and a replacement method. The product prepared by the method has high purity, good quality, large market demand, energy conservation, environmental protection, good economic benefit and wide prospect.)

1. A manufacturing process of high-purity metal chromium is characterized by comprising the following steps:

dissolving one or more of chromium alloy, metal chromium, chromium ore, chromium compound, chromium-containing sludge and chromium-containing waste in acid, adding special substances to remove impurities to obtain high-purity chromium solution, and preparing the high-purity chromium solution into high-purity metal chromium and chromium series products.

(1) Grinding one or more of metal chromium, chromium alloy, chromium ore, chromium compound, chromium-containing sludge and chromium-containing waste into fine powder, adding acid to dissolve, wherein the acid is one or more of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and heating to 20-120 ℃ to completely dissolve chromium into chromium ions.

(2) And filtering the solution to remove impurities to obtain the chromium solution.

(3) Adding one or more of reducing agent, alkali, oxidant, xanthate, hematite, oxalic acid, nitrosophenylhydroxylamine and sodium ferulate into the chromium solution, heating and stirring, reacting completely, removing impurities, and filtering to obtain filtrate Cr³⁺And (3) solution.

(4) Partial Cr prepared in the step (3)³⁺The solution produces different products:

firstly, Cr is mixed³⁺Evaporating, crystallizing and drying the solution to prepare a product trivalent chromium salt, and then preparing inorganic chromium, organic chromium, hexavalent chromium salt and chromic anhydride.

② mixing Cr³⁺Putting the solution into an electrolytic tank for electrolysis, and putting Cr into a cathode³⁺Solution and electrolytic assistant, sulfuric acid and Cr are put into the anode³⁺And electrifying the solution, keeping the optimal current density, the optimal voltage and the optimal ion concentration of the cathode and the anode in the electrolytic tank, preparing chromic anhydride at the anode, and preparing high-purity metal chromium at the cathode.

③ mixing Cr³⁺Putting the solution and auxiliary agent into cathode, putting sulfuric acid and 2-methylnaphthalene into anode, electrifying, maintaining the optimum current density, optimum voltage and optimum ion concentration of cathode and anode in electrolytic bath, obtaining 2-methyl-4-naphthoquinone at anode, adding sulfurous acid and alkali into 2-methyl-4-naphthoquinone, refining to obtain vitamin K₃And preparing high-purity metal chromium from the cathode.

Fourthly, respectively putting the aluminum, the magnesium and the zinc into the Cr³⁺And preparing high-purity metal chromium from the solution.

Fifthly, preparing inorganic chromium, organic chromium, hexavalent chromium salt and chromic anhydride from the chromic hydroxide.

(5) Partial Cr prepared in the step 3³⁺Adding one or more of ammonia water, urea, alkali, carbonate and bicarbonate into the solution to make Cr³⁺Completely precipitating to obtain chromium hydroxide, cleaning and drying the chromium hydroxide to obtain high-purity chromium hydroxide, calcining the chromium hydroxide to obtain chromium sesquioxide, and preparing the chromium sesquioxide into high-purity metal chromium.

Firstly, putting chromium sesquioxide into a high-temperature furnace, adding carbon powder and an auxiliary agent, and carrying out high-temperature reduction to prepare high-purity metal chromium.

② putting chromic oxide into a vacuum furnace, introducing 99.9 percent-99.999 percent hydrogen, and reducing at 900-1600 ℃ to prepare high-purity metallic chromium.

Thirdly, putting the chromium sesquioxide into a high-temperature furnace, and adding high-purity aluminum powder and an auxiliary agent to prepare high-purity metal chromium.

Putting the chromium sesquioxide into a melting electrolysis tank for electrolysis, adding a proper auxiliary agent, and preparing high-purity metal chromium by a cathode.

(6) Introducing hydrogen into the chromium chloride, and heating to 800-1400 ℃ to obtain the high-purity metal chromium.

(7) And calcining the prepared chromium iodide at high temperature to prepare high-purity metal chromium.

(8) Calcining the prepared chromium sulfate at high temperature of 700-1400 ℃ to prepare chromium sesquioxide, putting the chromium sesquioxide into a vacuum furnace, introducing high-purity hydrogen, and reducing at high temperature of 900-1700 ℃ to prepare high-purity metal chromium.

(9) And melting and electrolyzing the prepared chromium chloride and the auxiliary agent to prepare high-purity metal chromium.

Technical Field

The invention relates to a manufacturing process of high-purity metal chromium, belonging to the field of fine chemical engineering and metallurgical manufacturing.

Background

With the rapid development of science and technology, high-purity chromium metal plays an important role in the scientific and technological and economic development of the world, and is widely applied to the fields of aerospace industry, jet aircraft manufacturing, gas turbine manufacturing, high-end weapons, electronic information technology, biomedical industry and the like.

Because the actual content of the high-purity metal chromium reaches 99.99 percent, the temperature resistance of the high-purity metal chromium reaches more than 1980 ℃, the application field of the high-purity metal chromium can be greatly expanded, and the high-purity metal chromium can be widely applied to steel smelting, so that the high-temperature resistance, the strength and the corrosion resistance of steel are improved.

In the original production of metal chromium, chromic oxide is mainly used as a raw material at home and abroad, an aluminothermic method, a carbon reduction method and a fusion electrolysis method are adopted for preparation, few enterprises adopt sodium, aluminum and zinc to reduce chromium chloride to prepare pure chromium, and electrolyze an aqueous solution of chromium chloride, an aqueous solution of chromic acid and an aqueous solution of chromium ammonium alum to prepare chromium.

The original production of chromium trioxide at home and abroad adopts a blast furnace roasting method to firstly produce hexavalent chromate or chromic anhydride, and then produces the chromium trioxide by a reduction method, or reduces the chromium hydroxide produced by hexavalent chromium and then calcines to prepare the chromium trioxide, and the chromium trioxide contains a large amount of impurities.

Industrial chromium chloride, chromium ammonium alum, chromic anhydride, chromic oxide and the like are used as raw materials, wherein the impurity content is high, so that the content of other impurities, heavy metals and the like in the produced metal chromium is also high, and the purity of the chromium is difficult to reach 90%.

Such as: the invention discloses a method for producing high-purity metal chromium by electrolysis, and the patent No. 200710180044.7 discloses that the high-purity metal chromium is prepared by a chromic anhydride electrolysis method, and the actual content of the metal chromium prepared by electrolysis is only 81% because the chromic anhydride contains a large amount of other impurity metals.

Therefore, the actual content of the high-purity metal chromium cannot reach 95% at all by detecting the high-purity metal chromium produced in the United states, Japan, Russia, China and the like internationally by adopting the most advanced scientific method all over the world.

Disclosure of Invention

The invention aims to change the original manufacturing method of high-purity metallic chromium, create new development from the production of raw materials, adopt a new technical process, purify the chromium from various chromium-containing substances into 99.99 percent of trivalent chromium, produce 99.99 percent of high-purity chromium sesquioxide products, and then prepare high-end high-quality high-purity metallic chromium 99.99 percent products, thereby meeting the requirements of various industries on high-end chromium products and benefiting mankind.

In order to achieve the purpose, the invention adopts the following technical scheme.

A manufacturing process of high-purity metal chromium is characterized by comprising the following steps:

1. dissolving one or more of chromium alloy, metal chromium, chromium ore, chromium compound, chromium-containing sludge and chromium-containing waste in acid, adding special substances to remove impurities to obtain high-purity chromium solution, and preparing the high-purity chromium solution into high-purity metal chromium and chromium series products.

(1) Grinding one or more of metal chromium, chromium alloy, chromium ore, chromium compound, chromium-containing sludge and chromium-containing waste into fine powder, adding acid to dissolve, wherein the acid is one or more of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, and heating to 20-120 ℃ to completely dissolve chromium into chromium ions.

(2) And filtering the solution to remove impurities to obtain the chromium solution.

(3) Adding one or more of reducing agent, alkali, oxidant, xanthate, hematite, oxalic acid, nitrosophenylhydroxylamine and sodium ferulate into the chromium solution, heating and stirring, reacting completely, removing impurities, and filtering to obtain filtrate Cr³⁺And (3) solution.

(4) Partial Cr prepared in the step (3)³⁺The solution produces different products:

firstly, Cr is mixed³⁺Evaporating, crystallizing and drying the solution to prepare a product trivalent chromium salt, and then preparing inorganic chromium, organic chromium, hexavalent chromium salt and chromic anhydride.

② mixing Cr³⁺Putting the solution into an electrolytic tank for electrolysis, and putting Cr into a cathode³⁺Solution and electrolytic assistant, sulfuric acid and Cr are put into the anode³⁺And electrifying the solution, keeping the optimal current density, the optimal voltage and the optimal ion concentration of the cathode and the anode in the electrolytic tank, preparing chromic anhydride at the anode, and preparing high-purity metal chromium at the cathode.

③ mixing Cr³⁺The solution and the auxiliary agent are put into a cathode, sulfuric acid and 2I are put into an anodeElectrifying methylnaphthalene, maintaining the optimal current density, voltage and ion concentration of cathode and anode in the electrolytic bath, obtaining 2-methyl-4-naphthoquinone at the anode, adding sulfurous acid and alkali into 2-methyl-4-naphthoquinone, and refining to obtain vitamin K₃And preparing high-purity metal chromium from the cathode.

Fourthly, respectively putting the aluminum, the magnesium and the zinc into the Cr³⁺And preparing high-purity metal chromium from the solution.

Fifthly, preparing inorganic chromium, organic chromium, hexavalent chromium salt and chromic anhydride from the chromic hydroxide.

(5) Partial Cr prepared in the step 3³⁺Adding one or more of ammonia water, urea, alkali, carbonate and bicarbonate into the solution to make Cr³⁺Completely precipitating to obtain chromium hydroxide, cleaning and drying the chromium hydroxide to obtain high-purity chromium hydroxide, calcining the chromium hydroxide to obtain chromium sesquioxide, and preparing the chromium sesquioxide into high-purity metal chromium.

Firstly, putting chromium sesquioxide into a high-temperature furnace, adding carbon powder and an auxiliary agent, and carrying out high-temperature reduction to prepare high-purity metal chromium.

② putting chromic oxide into a vacuum furnace, introducing 99.9 percent-99.999 percent hydrogen, and reducing at 900-1600 ℃ to prepare high-purity metallic chromium.

Thirdly, putting the chromium sesquioxide into a high-temperature furnace, and adding high-purity aluminum powder and an auxiliary agent to prepare high-purity metal chromium.

Putting the chromium sesquioxide into a melting electrolysis tank for electrolysis, adding a proper auxiliary agent, and preparing high-purity metal chromium by a cathode.

(6) Introducing hydrogen into the chromium chloride, and heating to 800-1400 ℃ to obtain the high-purity metal chromium.

(7) And calcining the prepared chromium iodide at high temperature to prepare high-purity metal chromium.

(8) Calcining the prepared chromium sulfate at high temperature of 700-1400 ℃ to prepare chromium sesquioxide, putting the chromium sesquioxide into a vacuum furnace, introducing high-purity hydrogen, and reducing at high temperature of 900-1700 ℃ to prepare high-purity metal chromium.

(9) And melting and electrolyzing the prepared chromium chloride and the auxiliary agent to prepare high-purity metal chromium.

Detailed Description

Because the chromium metal has high melting point, stable property, oxidation resistance and corrosion resistance, the chromium metal is widely applied to the fields of aerospace, weaponry, ships and warships, airplanes, automobiles, electronic information technology, daily necessities, electroplating, biomedicine, cosmetics, steel smelting and the like.

The invention grasps the exact process steps and data through the following specific experiments, and lays a foundation for further expanding the production.

Examples 1,

(1) 50 g of ferrochromium and 50% of chromium are taken and ground into 100 meshes, 100 g of electroplating chromium-containing sludge is ground into powder, sulfuric acid is added to dissolve 300 g of electroplating chromium-containing sludge, and the mixture is heated to 90 ℃ to completely dissolve the chromium into chromium ions.

(2) And filtering the solution to remove impurities to obtain the chromium solution.

(3) Adding 5 g of reducing agent, 4 g of alkali, 3.5 g of oxidant, 5 g of yellow blood salt, 120 g of red blood salt and 50 g of sodium ferbamate into the chromium solution, heating and stirring, completely reacting, removing impurities, and filtering to obtain filtrate which is high-purity Cr³⁺1000 g of the solution.

(4) Taking 600 g of Cr prepared in the step (3)³⁺Putting the solution and auxiliary agent into cathode, putting sulfuric acid and 2-methylnaphthalene into anode, electrifying, maintaining the optimum current density, optimum voltage and optimum ion concentration of cathode and anode in electrolytic bath, obtaining 2-methyl-4-naphthoquinone at anode, adding sulfurous acid and alkali into 2-methyl-4-naphthoquinone, refining to obtain vitamin K₃And the cathode prepares 38 g of high-purity metal chromium with the purity of 99.98 percent.

(5) And (3) adding sodium hydroxide into the remaining 400 g of trivalent chromium solution obtained in the steps (3) and (4) to enable the trivalent chromium to be completely generated into chromium hydroxide, and filtering, washing and drying for multiple times to obtain the high-purity chromium hydroxide.

Firstly, putting chromium hydroxide into a high-temperature furnace to be heated to 1100-1300 ℃ to prepare chromium sesquioxide.

② putting chromic oxide into a reduction furnace, adding carbon powder and a proper amount of auxiliary agent, controlling the temperature at 1200-1650 ℃ for 3-7 hours, and obtaining 21.5 g of high-purity metal chromium with the purity of 99.975 percent.

Example 2

(1) Dissolving 30 g of 90% chromium metal and 80 g of chromium-containing waste in 500 g of hydrochloric acid, adding 6 g of alkali, 70 g of sodium ferbamate and 20 g of nitrosophenylhydroxylamine, adding water, heating and stirring at 95 ℃, completely reacting, and removing impurities to obtain the high-purity chromium solution.

(2) Cr to be produced³⁺Adding ammonia water into the solution to lead Cr to be³⁺Completely precipitating to obtain chromium hydroxide, cleaning and drying the chromium hydroxide to obtain high-purity chromium hydroxide, calcining the chromium hydroxide to obtain chromium sesquioxide,

(3) putting chromic oxide into a vacuum furnace, introducing 99.9-99.999% hydrogen, and reducing at 900-1600 deg.C to obtain high-purity metal chromium 38.75 g with purity of 99.989%.