CN111575490B - Method for extracting vanadium and chromium from chromium mud - Google Patents

Method for extracting vanadium and chromium from chromium mud Download PDF

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CN111575490B
CN111575490B CN202010554736.9A CN202010554736A CN111575490B CN 111575490 B CN111575490 B CN 111575490B CN 202010554736 A CN202010554736 A CN 202010554736A CN 111575490 B CN111575490 B CN 111575490B
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chromium
vanadium
oxidation reaction
tailings
pressure oxidation
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CN111575490A (en
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刘彪
杜浩
王少娜
吕页清
王新东
李兰杰
耿立唐
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Institute of Process Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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

Abstract

The invention relates to a method for extracting vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution; wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device. According to the invention, the performance of forming bubbles in the aeration device is enhanced by introducing the stabilizer in the reaction, and the introduction of the stabilizer can obviously reduce the sodium content in the tailings, so that the high-efficiency recovery of vanadium and chromium in the chromium mud is realized.

Description

Method for extracting vanadium and chromium from chromium mud
Technical Field
The invention relates to the field of chromium mud recovery, in particular to a method for extracting vanadium and chromium from chromium mud.
Background
At present, vanadium titano-magnetite is a main raw material for extracting vanadium in China, and is a kind of associated ore containing iron, vanadium, chromium and other equivalent elements. At present, the production process flow of a metallurgical enterprise mainly smelting vanadium titano-magnetite generally comprises the following steps: the process flow comprises the steps of blast furnace vanadium-containing molten iron, vanadium extraction in a converter (obtaining vanadium slag which is sent to a vanadium chemical plant to produce vanadium products), semisteel steelmaking, molten steel refining, continuous casting and steel rolling. In the process of extracting vanadium by using chromium sludge, a certain amount of chromium-containing solid waste is generated because chromium and partial vanadium cannot be extracted, and the chromium-containing solid waste is called chromium sludge. Because of containing a highly toxic substance chromium, the chromium mud is a solid dangerous waste which is extremely difficult to treat and has serious environmental pollution. At present, the treatment of the chromium sludge in China mainly aims at resource research.
In order to realize the reutilization of chromium sludge, CN103131852A provides a utilization method of sludge containing chromium and vanadium, which comprises the steps of converting the sludge into sludge balls containing vanadium and chromium through the processes of baking, processing and the like, returning to the refining process of a steel-making LF furnace, and carrying out microalloying on V, Cr elements in the sludge balls to realize the harmless treatment of the sludge containing vanadium and chromium. However, the vanadium-chromium-containing sludge contains more impurity elements, and the return of the sludge to steel making can cause impurity accumulation in a refining process, increase the energy consumption in the steel making process and influence the quality of steel. CN108588427A proposes a resource utilization method of chromium sludge precipitated by vanadium extraction wastewater treatment, which is mainly to roast, wash and filter the chromium sludge, prepare the obtained solid into chromium oxide particles, and use the particles as raw materials for producing chromium-containing steel. However, the process needs high-temperature roasting, so that the energy consumption in the treatment process is greatly increased, the purity of the chromium oxide particles produced by the method is not high, and the quality of the produced steel is low.
The extraction of the vanadium, chromium and other equivalent elements in the chromium mud also has important economic value and environmental protection benefit. The sodium roasting process is a mainstream process for extracting vanadium from vanadium-containing solid waste, and the basic principle of the sodium roasting process is Na2CO3As an additive, converting low-valence vanadium into water-soluble sodium salt of pentavalent vanadium by high-temperature sodium roasting (750-850 ℃), directly soaking a sodium roasting product in water to obtain a vanadium-containing leaching solution, adding ammonium salt to prepare ammonium polyvanadate precipitate, and obtaining an oxide product of vanadium by reduction roasting. The recovery rate of vanadium in the sodium roasting process is low, the recovery rate of vanadium in single roasting is about 70%, and the recovery rate of vanadium after multiple roasting is only 80%; the roasting temperature is high (750-; harmful HCl and Cl are generated in the roasting process2And the like, and pollute the environment.
Although the additives and the temperature schedule of the sodium treatment roasting process are improved differently, the CN1884597A, the CN86108218A and the like have the same basic principle, and the problems of the traditional process such as overhigh roasting temperature and the like cannot be avoided. CN101161831A proposes a method for calcified roasting, which, compared with the sodium roasting process, does not need to go through the process of gradually raising the temperature from low temperature to high temperature during calcified roasting, but directly roasting at high temperature, so that the temperature of the roasting furnace is easier to control, the roasting time is shortened, and the productivity of the equipment is also improved. But the roasting temperature of the calcification roasting is still very high (600 ℃ and 950 ℃).
In order to improve the resource utilization rate and reduce the reaction energy consumption, the wet vanadium extraction is gradually developed into a clean and energy-saving new method. CN107201445A proposes a process for leaching vanadium and chromium elements from vanadium and chromium containing mud by two steps, using sodium hydroxide solution as leaching solution and hydrogen peroxide as oxidant. Firstly, carrying out alkaline leaching treatment on the chromium mud by using a sodium hydroxide solution to extract vanadium, carrying out solid-liquid separation, then carrying out oxidation treatment on leaching tailings by using hydrogen peroxide, and then further carrying out alkaline leaching to extract chromium. However, the process is complex, the leaching process needs nitrogen protection, the consumption of hydrogen peroxide is high, and the process cost is high. And the process still stays in a microminiature experimental stage at present, and experimental verification is still needed to verify whether the process can be applied to large-scale industrial treatment. CN108998676A provides a new method for recovering vanadium, iron and chromium elements from vanadium-containing chromium mud, which comprises the steps of deeply leaching the iron, vanadium and chromium elements from the vanadium-containing chromium mud by using a sulfuric acid solution, removing iron and vanadium from the sulfuric acid solution containing the vanadium, iron and chromium elements under the conditions of high temperature and high pressure, and separating the vanadium and iron elements from an iron-removing and vanadium-removing product by using an alkaline leaching method, thereby realizing the effective separation of the iron, vanadium and chromium elements. However, the consumption of sulfuric acid and alkali liquor in the process is large, the process cost is high, and the purity of the produced chromium sulfate and iron oxide red is not high, so that the chromium sulfate and iron oxide red need to be further purified and refined.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a vanadium extraction method for extracting vanadium and chromium from chromium sludge, which realizes the high-efficiency separation and recovery of vanadium and chromium in chromium sludge through the introduction of a stabilizer and an aeration device.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for extracting vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device.
According to the invention, the performance of forming bubbles in the aeration device is enhanced by introducing the stabilizer in the reaction, and the introduction of the stabilizer can obviously reduce the sodium content in the tailings, so that the high-efficiency recovery of vanadium and chromium in the chromium mud is realized.
As a preferable technical scheme of the invention, the chromium sludge is the chromium sludge generated in the treatment process of the vanadium precipitation liquid wastewater in the vanadium chemical industry.
In a preferred embodiment of the present invention, the stabilizer is calcium oxide.
Preferably, the amount of the stabilizer added is 3 to 5% by mass of the chromium sludge, and may be, for example, 3%, 3.5%, 4%, 4.5%, or 5%, but is not limited to the recited values, and other values not recited in the range are also applicable.
As a preferred technical scheme of the invention, the alkali liquor comprises sodium hydroxide solution.
Preferably, the concentration of the alkali solution is 30-40% by mass, for example, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the mass ratio of the lye to the chromium sludge is (3-5):1, for example 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, but not limited to the values listed, and other values not listed in this range are equally applicable.
As a preferred embodiment of the present invention, the oxidizing medium comprises 1 or a combination of at least 2 of oxygen, air, oxygen-enriched air, or ozone.
The combination may be a combination of oxygen and air, a combination of air and oxygen-enriched air, or a combination of oxygen and ozone, etc., but is not limited to the listed combinations, and other combinations not listed in this range are also applicable.
In a preferred embodiment of the present invention, the oxidizing medium is preheated to 80 to 120 ℃ before use, and may be, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, but is not limited to the recited values, and other values not recited in the range are also applicable.
In a preferred embodiment of the present invention, the partial pressure of the oxidizing medium in the pressure oxidation reaction is 0.5 to 0.8MPa, and may be, for example, 0.5MPa, 0.55MPa, 0.6MPa, 0.65MPa, 0.7MPa, 0.75MPa or 0.8MPa, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the temperature of the pressure oxidation reaction is 155 ℃ to 180 ℃, and may be, for example, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, or 180 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the pressure oxidation reaction time is 2 to 5 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable technical scheme of the invention, the tailings are subjected to three-stage countercurrent washing.
Preferably, the amount of washing water used in the washing is 2 to 4 times, for example, 2 times, 2.2 times, 2.4 times, 2.6 times, 2.8 times, 3 times, 3.2 times, 3.4 times, 3.6 times, 3.8 times, or 4 times, based on the dry mass of the tailings, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the washed post-wash liquor is used for vanadium chromium extraction.
Preferably, the impeller diameter in the aeration device is 20-25cm, for example 20cm, 21cm, 22cm, 23cm, 24cm or 25cm, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the rotation speed of the motor in the aeration device is 1200-3000r/min, such as 1200r/min, 1300r/min, 1400r/min, 1500r/min, 1600r/min, 1700r/min, 1800r/min, 1900r/min, 2000r/min, 2100r/min, 2200r/min, 2300r/min, 2400r/min, 2500r/min, 2600r/min, 2700r/min, 2800r/min, 2900r/min or 3000r/min, but not limited to the values listed, and other values not listed in this range are also applicable.
As a preferred technical solution of the present invention, the method comprises: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 3-5% of the mass of the chromium mud; the alkali liquor comprises sodium hydroxide solution; the mass concentration of the alkali liquor is 30-40%; the mass ratio of the alkali liquor to the chromium mud is (3-5) to 1; the oxidizing medium comprises 1 or a combination of at least 2 of oxygen, air, oxygen-enriched air, or ozone; the oxidizing medium is preheated to 80-120 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.5-0.8 MPa; the temperature of the pressure oxidation reaction is 155-180 ℃; the time of the pressure oxidation reaction is 2-5 h; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 2-4 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 20-25 cm; the rotating speed of the motor in the aeration device is 1200-3000 r/min.
According to the invention, the aeration impeller is arranged above the downward-pressing mechanical stirring blade, and formed micro bubbles are further scattered after passing through the stirring paddle, so that the contact chance of oxidizing gas and chromium mud particles can be further improved, and the oxidation leaching efficiency of chromium mud is improved. Further, the recovery of vanadium and chromium in the chromium sludge can be obviously improved through the strengthening effect of the stabilizing agent on bubbles.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the performance of forming bubbles in the aeration device is enhanced by introducing the stabilizer in the reaction, and the introduction of the stabilizer can obviously reduce the sodium content in the tailings, so that the high-efficiency recovery of vanadium and chromium in the chromium mud is realized.
(2) According to the invention, the aeration impeller is arranged above the downward-pressing mechanical stirring blade, and formed micro bubbles are further scattered after passing through the stirring paddle, so that the contact chance of oxidizing gas and chromium mud particles can be further improved, and the oxidation leaching efficiency of chromium mud is improved. Further, the recovery of vanadium and chromium in the chromium sludge can be obviously improved through the strengthening effect of the stabilizing agent on bubbles.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
In the embodiment, the chromium mud comprises the following components: cr (chromium) component2O3 25％，V2O5 20％，Fe2O3 37％，SiO2 5％Na2O 8％，CaO 5％。
The embodiment provides a method for recovering vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 3% of the mass of the chromium mud; the alkali liquor is sodium hydroxide solution; the mass concentration of the alkali liquor is 30 percent; the mass ratio of the alkali liquor to the chromium mud is 3: 1; the oxidizing medium is air; preheating the oxidizing medium to 80 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.5 MPa; the temperature of the pressure oxidation reaction is 155 ℃; the time of the pressure oxidation reaction is 2 hours; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 2 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 20 cm; the rotating speed of a motor in the aeration device is 3000 r/min.
By detecting the components of the leached tailings, the conversion rate of vanadium in the chromium mud is 97%, the conversion rate of chromium is 90%, and the sodium content in the tailings is 1%.
Example 2
In the embodiment, the chromium mud comprises the following components: cr (chromium) component2O3 27％，V2O5 20％，Fe2O3 35％，SiO2 6％Na2O 7％，CaO 5％。
The embodiment provides a method for recovering vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 5% of the mass of the chromium mud; the alkali liquor is sodium hydroxide solution; the mass concentration of the alkali liquor is 40%; the mass ratio of the alkali liquor to the chromium mud is 5: 1; the oxidizing medium is air; preheating the oxidizing medium to 120 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.8 MPa; the temperature of the pressure oxidation reaction is 180 ℃; the time of the pressure oxidation reaction is 5 hours; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 4 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 25 cm; the rotating speed of a motor in the aeration device is 1200 r/min.
Through component detection of leached tailings, the conversion rate of vanadium in the chromium mud is 98%, the conversion rate of chromium is 93%, and the sodium content in the tailings is 2%.
Example 3
The chromium mud in the embodiment comprises the following components: cr (chromium) component2O3 30％，V2O5 21％，Fe2O3 32％，SiO2 6％Na2O 6％，CaO 5％。
The embodiment provides a method for recovering vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 3.5 percent of the mass of the chromium mud; the alkali liquor is sodium hydroxide solution; the mass concentration of the alkali liquor is 35 percent; the mass ratio of the alkali liquor to the chromium mud is 4: 1; the oxidizing medium comprises air; preheating the oxidizing medium to 90 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.6 MPa; the temperature of the pressure oxidation reaction is 165 ℃; the time of the pressure oxidation reaction is 3 hours; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 3 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 22 cm; the rotating speed of a motor in the aeration device is 2000 r/min.
By detecting the components of the leached tailings, the conversion rate of vanadium in the chromium mud is 99%, the conversion rate of chromium is 94%, and the sodium content in the tailings is 1.3%.
Example 4
The chromium mud in the embodiment comprises the following components: cr (chromium) component2O3 24％，V2O5 21％，Fe2O3 38％，SiO2 5％Na2O 7％，CaO 5％。
The embodiment provides a method for recovering vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 3.8 percent of the mass of the chromium mud; the alkali liquor is sodium hydroxide solution; the mass concentration of the alkali liquor is 33%; the mass ratio of the alkali liquor to the chromium mud is 5: 1; the oxidizing medium pack is air; preheating the oxidizing medium to 100 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.7 MPa; the temperature of the pressure oxidation reaction is 160 ℃; the time of the pressure oxidation reaction is 2.5 h; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 2.7 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 24 cm; the rotating speed of a motor in the aeration device is 2100 r/min.
By detecting the components of the leached tailings, the conversion rate of vanadium in the chromium mud is 96%, the conversion rate of chromium is 91%, and the sodium content in the tailings is 1.7%.
Example 5
The chromium mud in the embodiment comprises the following components: cr (chromium) component2O3 22％，V2O5 22％，Fe2O3 38％，SiO2 6％Na2O 6％，CaO 6％。
The embodiment provides a method for recovering vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 4% of the mass of the chromium mud; the alkali liquor is sodium hydroxide solution; the mass concentration of the alkali liquor is 38%; the mass ratio of the alkali liquor to the chromium mud is 4.5: 1; the oxidizing medium is oxygen; preheating the oxidizing medium to 110 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.5 MPa; the temperature of the pressure oxidation reaction is 175 ℃; the time of the pressure oxidation reaction is 2 hours; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 2 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 22 cm; the rotating speed of a motor in the aeration device is 2200 r/min.
Through component detection of leached tailings, the conversion rate of vanadium in the chromium mud is 98%, the conversion rate of chromium is 93%, and the sodium content in the tailings is 1.5%.
Example 6
The chromium mud in the embodiment comprises the following components: cr (chromium) component2O3 25％，V2O5 22％，Fe2O3 35％，SiO2 5％Na2O 7％，CaO 6％。
The embodiment provides a method for recovering vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 4.2 percent of the mass of the chromium mud; the alkali liquor is sodium hydroxide solution; the mass concentration of the alkali liquor is 37%; the mass ratio of the alkali liquor to the chromium mud is 4: 1; the oxidizing medium bag is oxygen-enriched air; the oxidizing medium is preheated to 85 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.6 MPa; the temperature of the pressure oxidation reaction is 170 ℃; the time of the pressure oxidation reaction is 3 hours; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 2.5 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 24 cm; the rotating speed of a motor in the aeration device is 2500 r/min.
By detecting the components of the leached tailings, the conversion rate of vanadium in the chromium mud is 97%, the conversion rate of chromium is 92%, and the sodium content in the tailings is 1.1%.
Example 7
The chromium mud in the embodiment comprises the following components: cr (chromium) component2O3 24％，V2O5 21％，Fe2O3 37％，SiO2 6％Na2O 7％，CaO 5％。
The embodiment provides a method for recovering vanadium and chromium from chromium sludge, which comprises the following steps: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 4.5 percent of the mass of the chromium mud; the alkali liquor is sodium hydroxide solution; the mass concentration of the alkali liquor is 39%; the mass ratio of the alkali liquor to the chromium mud is 5: 1; the oxidizing medium is ozone; preheating the oxidizing medium to 100 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.5 MPa; the temperature of the pressure oxidation reaction is 175 ℃; the time of the pressure oxidation reaction is 4 hours; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 4 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 25 cm; the rotating speed of a motor in the aeration device is 2800 r/min.
By detecting the components of the leached tailings, the conversion rate of vanadium in the chromium mud is 98%, the conversion rate of chromium is 94%, and the sodium content in the tailings is 1.3%.
Comparative example 1
The difference from the example 4 is only that the oxidation medium is introduced without using an aerator, air is blown in by using a vent pipe with the inner diameter of 3cm, and the conversion rate of vanadium in the chromium mud is 75.4 percent and the conversion rate of chromium is 30.5 percent by detecting the vanadium and chromium content in the tailings after leaching, wherein the sodium content in the tailings is basically unchanged compared with the example 4. It can be seen that the air introduced by the common air blowing method has oxidation inferior to that of the microbubbles generated by the aeration method, and the conversion rate of vanadium and chromium is obviously reduced.
Comparative example 2
The difference from example 4 is that the aeration impeller is arranged below the stirring paddle, and the vanadium content in the tailings after leaching is detected to obtain that the conversion rate of vanadium in the chromium mud is 78.4%, and the conversion rate of chromium is 66.3%, and the sodium content in the tailings is basically unchanged compared with example 4.
Comparative example 3
The difference from the example 4 is that the rotating speed of the motor in the aeration device is 800r/min, and the conversion rate of vanadium in the chromium mud is 85.4 percent by detecting the leached tailings components, and the conversion rate of chromium is 69.3 percent, and the sodium content in the tailings is basically unchanged compared with the example 4. It can be seen that the rotating speed of the aeration impeller has a remarkable influence on the aeration effect, and the reduction of the rotating speed is not beneficial to the oxidation leaching of vanadium and chromium.
Comparative example 4
The difference from the example 4 is only that the rotating speed of the motor in the aeration device is 4000r/min, the conversion rate of vanadium in the chromium mud is 84 percent and the conversion rate of chromium is 77 percent by detecting the components of the leached tailings, and the sodium content in the tailings is basically unchanged compared with the example 4. It can be seen that the rotating speed of the aeration impeller has a significant influence on the aeration effect, and the rotating speed is too high to be beneficial to the oxidation leaching of vanadium and chromium.
Comparative example 5
The difference from the example 4 is only that the impeller diameter in the aeration device is 15 cm; by detecting the components of the leached tailings, the conversion rate of vanadium in the chromium mud is 75.6 percent, the conversion rate of chromium is 58.3 percent, and the content of sodium in the tailings is basically unchanged compared with that in example 4. It can be seen that the diameter of the aeration impeller has a significant effect on the aeration effect, and the conversion rate of vanadium and chromium is significantly reduced when the diameter of the impeller is too small.
Comparative example 6
Only differs from example 4 in that the impeller diameter in the aeration device was 30 cm; by detecting the components of the leached tailings, the conversion rate of vanadium in the chromium mud is 80.6%, the conversion rate of chromium is 68.3%, and the sodium content in the tailings is basically unchanged compared with that in example 4. It can be seen that the diameter of the aeration impeller has a significant effect on the aeration effect, and the conversion rate of vanadium and chromium is significantly reduced when the diameter of the impeller is too large.
Comparative example 7
The only difference from example 4 is that without the addition of the stabilizer, by examining the tailings composition after leaching, the conversion of vanadium in the chromium sludge was 88%, the conversion of chromium was 80%, and the sodium content in the tailings was 10%.
Comparative example 8
The difference from example 4 is only that the addition amount of the stabilizer is 10%, and by detecting the tailings components after leaching, the conversion rate of vanadium in the chromium mud is 81%, the conversion rate of chromium is 72%, and the sodium content in the tailings is basically unchanged compared with example 4.
Comparative example 9
The difference from example 4 is only that the stabilizer is replaced by silicon dioxide, and by detecting the tailings components after leaching, the conversion rate of vanadium in the chromium mud is 72 percent, the conversion rate of chromium is 69 percent, and the sodium content in the tailings is basically unchanged compared with example 4.
From the results of the above examples and comparative examples, it can be seen that the present invention enhances the performance of forming bubbles in the aeration apparatus by introducing the stabilizer during the reaction, and at the same time, the introduction of the stabilizer can significantly reduce the sodium content in the tailings, thereby achieving the efficient recovery of vanadium and chromium from the chromium sludge. The aeration impeller is arranged above the downward-pressing mechanical stirring blade, formed micro bubbles are further scattered after passing through the stirring paddle, the contact chance of oxidizing gas and chromium mud particles can be further improved, and the oxidation leaching efficiency of chromium mud is improved. Further, the recovery of vanadium and chromium in the chromium sludge can be obviously improved through the strengthening effect of the stabilizing agent on bubbles.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (16)

1. A method for extracting vanadium and chromium from chromium sludge, comprising: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution; the stabilizer is calcium oxide; the addition amount of the stabilizer is 3-5% of the mass of the chromium mud;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; and an aeration impeller in the aeration device is arranged above the downward-pressing type mechanical stirring blade.
2. The method according to claim 1, wherein the chromium sludge is chromium sludge produced in a vanadium precipitation liquid wastewater treatment process in the vanadium chemical industry.
3. The method of claim 1, wherein the lye comprises a sodium hydroxide solution.
4. The method of claim 1, wherein the lye has a mass concentration of 30 to 40%.
5. The method of claim 1, wherein the mass ratio of the lye to the chromium sludge is (3-5): 1.
6. The method of claim 1, wherein the oxidizing medium comprises 1 or a combination of at least 2 of oxygen, air, oxygen-enriched air, or ozone.
7. The method of claim 1, wherein the oxidizing medium is preheated to 80-120 ℃ prior to use.
8. The process according to claim 1, wherein the partial pressure of the oxidizing medium in the pressure oxidation reaction is in the range of 0.5 to 0.8 MPa.
9. The method as claimed in claim 1, wherein the temperature of the pressure oxidation reaction is 155-180 ℃.
10. The process according to claim 1, wherein the pressure oxidation reaction is carried out for a period of 2 to 5 hours.
11. The method of claim 1, wherein the tailings are subjected to a three-stage counter current wash.
12. The method of claim 11, wherein the amount of wash water used in the three stages of counter current washing is 2 to 4 times the dry basis weight of the tailings.
13. The method of claim 11, wherein the post-wash liquor of the three-stage counter-current wash is used for vanadium chromium extraction.
14. The method of claim 1, wherein the impeller in the aeration device has a diameter of 20-25 cm.
15. The method as claimed in claim 1, wherein the rotation speed of the motor in the aeration device is 1200-3000 r/min.
16. The method of claim 1, wherein the method comprises: mixing the chromium mud, a stabilizer and alkali liquor, and then sequentially carrying out pressure oxidation reaction and solid-liquid separation to obtain tailings and a vanadium-containing solution;
wherein the oxidizing medium in the pressure oxidation reaction is provided by an aeration device; the chromium mud is generated in the treatment process of vanadium-precipitated liquid wastewater in the vanadium chemical industry; the stabilizer is calcium oxide; the addition amount of the stabilizer is 3-5% of the mass of the chromium mud; the alkali liquor comprises sodium hydroxide solution; the mass concentration of the alkali liquor is 30-40%; the mass ratio of the alkali liquor to the chromium mud is (3-5) to 1; the oxidizing medium comprises 1 or a combination of at least 2 of oxygen, air, oxygen-enriched air, or ozone; the oxidizing medium is preheated to 80-120 ℃ before use; the partial pressure of an oxidation medium in the pressure oxidation reaction is 0.5-0.8 MPa; the temperature of the pressure oxidation reaction is 155-180 ℃; the time of the pressure oxidation reaction is 2-5 h; carrying out three-stage countercurrent washing on the tailings; the amount of washing water in the washing is 2-4 times of the dry basis weight of the tailings; the washed washing liquid is used for extracting vanadium and chromium; the diameter of an impeller in the aeration device is 20-25 cm; the rotating speed of the motor in the aeration device is 1200-3000 r/min.
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