CN112830694B - Method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid - Google Patents

Method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid Download PDF

Info

Publication number
CN112830694B
CN112830694B CN202110054818.1A CN202110054818A CN112830694B CN 112830694 B CN112830694 B CN 112830694B CN 202110054818 A CN202110054818 A CN 202110054818A CN 112830694 B CN112830694 B CN 112830694B
Authority
CN
China
Prior art keywords
vanadium
titanium dioxide
slag
liquid
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110054818.1A
Other languages
Chinese (zh)
Other versions
CN112830694A (en
Inventor
高俊
肖大才
胥杰翰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panzhihua Hengtong Titanium Co ltd
Original Assignee
Panzhihua Hengtong Titanium Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Panzhihua Hengtong Titanium Co ltd filed Critical Panzhihua Hengtong Titanium Co ltd
Priority to CN202110054818.1A priority Critical patent/CN112830694B/en
Publication of CN112830694A publication Critical patent/CN112830694A/en
Application granted granted Critical
Publication of CN112830694B publication Critical patent/CN112830694B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C04B22/143—Calcium-sulfate
    • C04B22/146—Calcium-sulfate other waste Ca-sulfate
    • 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
    • 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
    • C22B7/007—Wet processes by acid 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
    • 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
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/20—Retarders
    • C04B2103/22—Set retarders
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

The invention discloses a method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid, which comprises the following steps: 1) crushing and grinding vanadium-containing slag, and mixing and stirring the vanadium-containing slag and dilute acid to form a premixed solution; the dilute acid is from acid-containing wastewater generated in each titanium dioxide preparation process by flue spraying in the sulfuric acid method for preparing the titanium dioxide; 2) mixing and stirring the premixed solution and waste acid for reaction to form slurry, and performing solid-liquid separation after the reaction is finished to obtain solid which is acidic high-sulfur offwhite gypsum slag; the liquid is vanadium-containing solution; the waste acid is from waste sulfuric acid which is remained and is difficult to recycle after acidolysis in the sulfuric acid method titanium dioxide industry; 3) adding iron powder into the obtained vanadium-containing solution, stirring and reducing, adding liquid alkali until the pH of the reaction solution is 3.8-4.5, precipitating to obtain qualified slurry, and carrying out solid-liquid separation to obtain a vanadium-containing filter cake. The method provided by the invention can effectively treat vanadium-containing slag and titanium dioxide waste acid, realize comprehensive recycling of the vanadium-containing slag and the titanium dioxide waste acid, can reduce treatment cost, and is used for industrial scale treatment.

Description

Method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid
Technical Field
The invention relates to the technical field of waste recycling treatment, in particular to a method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid.
Background
In the existing technology for preparing titanium dioxide by a sulfuric acid method, a large amount of solid waste red gypsum is produced due to treatment of waste acid. For example, in the region climbing flowers where titanium dioxide is concentrated by a sulfuric acid method, tens of thousands of tons of red gypsum need to be buried every month, and the local solid waste treatment capacity reaches the red line.
The gypsum slag is an essential auxiliary material in cement production, wherein SO2The components are used for balancing the sulfur-alkali ratio in clinker calcination, so that the calcination operation and the service life of refractory materials are improved, and therefore, the gypsum slag with high sulfur content can be used as: 1. raw materials, producing sulphoaluminate system cement, gypsum slag cement, gypsum bauxite expansive cement and the like; 2. mineralizer, reduce the calcining temperature, save coal; 3. the cement coagulation regulator has a retarding effect, so that the cement coagulation time meets the requirements of national standards and users; 4. asThe sulfate excitant excites the activity of industrial waste residues such as fly ash, slag and the like and improves the strength of fly ash cement and slag cement; 5. a proper amount of gypsum can improve the cement properties such as strength, shrinkage and corrosion resistance. Therefore, gypsum slag, especially gypsum slag with high sulfur content, is in great demand in cement plants.
The production raw materials of the vanadium market mainly have three main sources, 1, vanadium slag blown from steel making in large-scale steel plants such as Panzhi steel and Chengde steel has high characteristic content, high market share, highly controlled defect resources and high cost of purchased raw materials. 2. The vanadium-containing coal gangue and the vanadium soil are from vanadium-containing coal gangue and vanadium soil, the characteristic resources are huge, but the content of vanadium pentoxide is low, the content of vanadium pentoxide is below 1.7%, the production cost is high, and the environmental pollution is large. 3. Part of the high-calcium vanadium-containing higher vanadium slag in the vanadium extraction slag of the steel mill. Therefore, how to extract vanadium from the high-calcium vanadium-containing higher vanadium slag is a research focus for many years.
In the prior art, the method of ball-making roasting, acid leaching and resin adsorption or extraction is adopted for extracting vanadium, so that the problems of high production cost, high production energy consumption and environmental pollution are caused, and once the vanadium price in the market slides down, the continuous production is difficult. The reason is that no enterprises apply the technology to extract vanadium from the high-calcium vanadium-containing slag pickle liquor at present.
Disclosure of Invention
In view of the above, the present invention aims to provide a method which is suitable for industrialization, can effectively reduce production cost, and can realize comprehensive utilization of vanadium-containing slag and titanium dioxide waste acid.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid comprises the following steps:
1) crushing and grinding vanadium-containing slag, and mixing and stirring the vanadium-containing slag and dilute acid to form a premixed solution; the dilute acid is acid-containing wastewater generated in each titanium dioxide preparation process by flue spraying in the titanium dioxide preparation method by using sulfuric acid, wherein the content of sulfuric acid is 1-5%;
2) mixing and stirring the premixed liquid and waste acid for reaction to form slurry, and performing solid-liquid separation after the reaction is finished to obtain solid which is acidic high-sulfur offwhite gypsum slag; the liquid is vanadium-containing solution; the waste acid is waste sulfuric acid which is remained and difficult to recycle after acidolysis in the sulfuric acid method titanium dioxide industry, wherein the content of the sulfuric acid is 10-30%;
3) adding iron powder into the vanadium-containing solution obtained in the step 2), stirring and reducing, adding liquid alkali until the pH of the reaction liquid is 3.8-4.5, precipitating to obtain qualified slurry, and carrying out solid-liquid separation to obtain a vanadium-containing filter cake.
Preferably, in the step 1), the vanadium-containing slag is crushed and ground to a particle size of 120 meshes or more than 80%, and bright iron is screened out at the same time.
Preferably, in the step 1), after the vanadium-containing slag is crushed and ground, the vanadium-containing slag is mixed and stirred with dilute acid, and the concrete steps are as follows: according to the solid-liquid ratio of 1: 2-5, firstly adding dilute acid, and under the stirring condition of 150-300 r/min, adding the crushed and ground vanadium-containing furnace slag at a constant speed to form a premixed solution, wherein the pH value of the premixed solution is 2.5-3.5, and the temperature is 40-50 ℃.
Preferably, in the step 2), the reaction time is 30-60 min, the reaction temperature is 40-50 ℃, and the pH value of the slurry is 1.6-1.8.
Preferably, the step 2) further comprises naturally settling the vanadium-containing solution, cooling to normal temperature, and then filtering.
Preferably, in the step 3), iron powder is added according to the mass ratio of the vanadium-containing slag of 2.5-3.5%, and the reduction time is 30-60 min.
Preferably, in the step 3), the stirring speed is 50-300 r/min; the liquid alkali is NaOH solution; after solid-liquid separation, the content of vanadium pentoxide in the clear liquid is lower than 0.05 g/L.
Preferably, in the step 3), a flocculating agent is added into the obtained qualified slurry for treatment, the flocculation time is longer than 60min, and the volume ratio of the adding amount of the flocculating agent to the qualified slurry is 1: 20.
preferably, the method further comprises the step 4): mixing the vanadium-containing filter cake obtained in the step 3) with pulping liquid according to a solid-to-liquid ratio of 1: 3, mixing, pulping and washing, wherein the pulping liquid is formed by adding the dilute acid into water and adjusting the pH to 3.8-4.5, and the pulping and washing time is 30-60 min; solid-liquid separation to obtain the low-calcium high-content vanadium raw material.
The invention has the beneficial effects that:
(1) avoids the adoption of ball-making roasting, resin adsorption or extraction to extract vanadium, can effectively reduce the production and treatment cost, and is suitable for industrial production.
(2) Is beneficial to environmental protection and reduces the damage of ecological pollution. In the process of preparing titanium dioxide by using a sulfuric acid method, a large amount of solid waste red gypsum is produced due to the treatment of waste acid. For example, in the region climbing flowers where titanium dioxide is concentrated by a sulfuric acid method, tens of thousands of tons of red gypsum need to be buried every month, and the local solid waste treatment capacity reaches the red line.
(3) Realizing the comprehensive utilization of resources. A. The waste acid and dilute acid in the process of preparing titanium dioxide by the sulfuric acid method are changed into production auxiliary materials from hazardous wastes which must be treated. B. The vanadium-containing slag becomes a raw material for neutralizing waste acid by the invention from the building material which can only be used for paving, and is used as a raw material for producing gypsum slag and a raw material for producing low-calcium high-content vanadium products.
(4) Has high economic benefit. The invention A and the sulfuric acid method for preparing titanium dioxide greatly reduce the wastewater treatment cost. The treatment cost of 23 percent of the sulfuric acid content of 1 prescription for treating the waste acid is about 500 yuan, and the treatment cost is reduced to 50 yuan/ton after the invention is used. B. At present, taking Panzhihua as an example, the treatment cost of red gypsum generated by titanium dioxide wastewater treatment is 60 yuan per ton. The high-sulfur gypsum slag produced by the method can be sold to cement plants, and the purchase price of part of the cement plants reaches about 200 yuan/ton at present. C. Producing the raw material with low calcium and high content of vanadium. According to the invention, the low-calcium high-content vanadium raw material with the vanadium pentoxide content of 5-50% can be obtained, and the low-calcium vanadium raw material with the vanadium pentoxide content of 1.5% in the current market, taking Pan steel as an example, is sold at a price of more than 600 yuan/ton.
Drawings
FIG. 1 is a flow chart of the operation of the present invention.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms than those specifically described herein, and it will be apparent to those skilled in the art that many more modifications are possible without departing from the spirit and scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the embodiment, the raw materials are selected as follows:
the vanadium-containing slag comprises the following main components in percentage by weight as shown in the following table 1:
table 1: the components and contents of the vanadium-containing slag
V2O5 MgO Al2O3 CaO Fe2O3 TiO2 SiO2
1.9 3.9 2.6 40 34 0.1 10
MnO SO3 Cr2O3 Na2O P2O5
1.8 0.1 / 0.3 /
Waste acid: the sulfuric acid content of the waste sulfuric acid which is difficult to recycle and is left after acidolysis in the sulfuric acid method titanium dioxide industry is 23 percent.
Diluted acid: acid-containing wastewater generated in each titanium dioxide preparation process by flue spraying in the sulfuric acid method for preparing the titanium dioxide has 3 percent of sulfuric acid content.
Liquid caustic soda: the NaOH content is 50 percent.
Example 1
A method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid comprises the following steps:
(1) crushing and grinding the vanadium-containing slag, sieving the crushed vanadium-containing slag with a 120-mesh sieve, and magnetically selecting 6% of bright iron. Weighing 20kg of slag powder for later use; injecting 60L of dilute acid into a reaction tank, gradually adding 20kg of slag powder under the condition of stirring at the rotating speed of 300r/min, and finishing the adding after about 5 minutes to obtain a premixed solution, wherein the temperature is 42 ℃, and the pH value is 3.3;
(2) slowly adding waste acid into the premixed solution to adjust the pH value to about 1.8, reacting for 45min at the reaction temperature of 50 ℃, and consuming 47L of waste acid; after the reaction is finished, performing solid-liquid separation by using a negative pressure centrifuge to obtain 29.6kg of ton of acidic high-sulfur offwhite gypsum slag and 100L of vanadium-containing solution; gypsum slag SO3Greater than 35%, moisture 22%, V2O5The content is 0.20 percent, the dry basis weight is 23.2KG, the vanadium leaching rate is obtained by conversion, the vanadium leaching rate is 87.79 percent, (the moisture content of the high-sulfur gypsum slag is lower than 25 percent and the moisture content is settled in the current cement industry, so the high-sulfur gypsum slag can be directly used in the cement industry), V is in 100L vanadium-containing solution2O5The concentration was 3.34g/L and the pH was 1.8. Naturally precipitating for 4 hours, cooling to normal temperature, filtering again, and injecting into a precipitation reaction tank;
(3) adjusting the stirring speed of the settling tank to 50r/min, adding 600g of iron powder for reduction, and reacting for 45min to adjust the solution in the settling tank to be blue; and slowly injecting liquid caustic soda, adjusting the pH value to 3.5, stopping adding the liquid caustic soda, consuming 1.5L of the liquid caustic soda, stirring for 20 minutes, slowly increasing the pH value of the slurry to 3.9, and starting sampling. V in the clear liquid of the precipitate2O5The content is 0.03g/L, qualified slurry is obtained, solid-liquid separation is carried out, a vanadium-containing filter cake is obtained after the separation time is 60 minutes, and the precipitation recovery rate is 99.1 percent;
(4) pulping the vanadium-containing filter cake again, adding an acidic solution with the pH value of 3.8 (prepared by adding a small amount of dilute acid into tap water) according to the solid-to-liquid ratio of 1/3; stirring at a rotation speed of 200 rpm for washing for 20 minutes; and (4) performing plate and frame filter pressing, and then blowing by compressed air to obtain the low-calcium high-content vanadium raw material. Weighing and testing after drying, wherein the weight is 1031.25g, and the vanadium pentoxide content is 32%; the total recovery rate of vanadium is 86.84%.
The components and contents of the gypsum slag and the low-calcium high-content vanadium raw material prepared in this example are shown in tables 2 and 3 below.
Table 2: the components and contents of the gypsum slag
V2O5 MgO Al2O3 CaO Fe2O3 TiO2
0.2 1.0 2.2 35 24 /
MnO SO3 Cr2O3 Na2O P2O5 SiO2
0.6 36 / 0.1 / 0.7
Table 3: the components and contents of the low-calcium high-content vanadium raw material
V2O5 MgO Al2O3 CaO Fe2O3 TiO2
32 1.2 10.5 0.3 18 /
MnO SO3 Cr2O3 Na2O P2O5 SiO2
0.1 18 / 1.6 / 15
As can be seen from the above tables 1 and 2, the main components of the gypsum slag can completely replace the natural gypsum in the application of the cement industry, and the low-calcium high-content vanadium raw material completely meets the direct use standard in the vanadium industry.
Example 2
A method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid comprises the following steps:
(1) crushing and grinding the vanadium-containing slag, sieving the vanadium-containing slag by a 120-mesh sieve, and magnetically selecting bright iron to obtain slag powder; according to the liquid-solid ratio of 1: 4, adding 20kg of slag powder into 80L of dilute acid, stirring and mixing at the rotating speed of 200r/min to obtain a premixed solution, wherein the temperature is 45 ℃, and the pH value is 2.8;
(2) slowly adding waste acid into the premixed solution to adjust the pH value to about 1.7, wherein the reaction time is 50min, and the reaction temperature is 52 ℃; after the reaction is finished, carrying out solid-liquid separation by using a negative pressure centrifuge to obtain 31.58kg of hydrous acidic high-sulfur offwhite gypsum slag and 118L of vanadium-containing solution; SO in gypsum slag340%, moisture 23%, V2O5The content is 0.22 percent, the dry basis weight is 24kg, and the vanadium leaching rate is 86.11 percent by conversion. 118L of vanadium-containing solution, V2O5The concentration was 2.77g/L and the pH was 1.7. Naturally precipitating for 4 hours, cooling to normal temperature, filtering again, and injecting into a precipitation reaction tank;
(3) adjusting the stirring speed of a precipitation tank to 50r/min, adding iron powder according to the proportion of 3% of the slag powder by mass, stirring and reducing for 60min, and then, enabling the reaction liquid to be blue; then, the liquid caustic soda was slowly injected, the pH value was adjusted to 3.7, the addition of the liquid caustic soda (1.8L of the liquid caustic soda was consumed) was stopped, the mixture was stirred for another 20 minutes, the pH of the slurry was slowly increased to 4.0, and sampling was started. V in the supernatant2O5The content is 0.02g/L, qualified slurry is obtained, a flocculating agent is added into the qualified slurry for treatment, the flocculation time is 90min, and the flocculating agent is prepared by adding water into more than 1000 ten thousand units of high-molecular low-charge amphoteric organic flocculating agent according to the proportion of 1/1000; the volume ratio of the addition amount of the flocculating agent in the qualified slurry to the qualified slurry is 1:20; after flocculation is finished, performing solid-liquid separation (2 flat pressing a filter plate frame), wherein a vanadium-containing filter cake is obtained after the separation time is 25 minutes, and the recovery rate of precipitation is 99.38%;
(4) pulping the vanadium-containing filter cake again, and adding an acidic solution with the pH value of 4 (prepared by adding a small amount of dilute acid into tap water) according to the solid-to-liquid ratio of 1/3; washing at a stirring speed of 200 revolutions per minute for 20 minutes; adding a flocculating agent into the washed slurry for treatment, wherein the flocculating time is 90min, and the flocculating agent is prepared by adding water into more than 1000 ten thousand units of high-molecular low-charge amphoteric organic flocculating agents according to the proportion of 1/1000; the volume ratio of the addition amount of the flocculating agent in the qualified slurry to the qualified slurry is 1: 20. 2, carrying out filter pressing on the raw materials by a flat plate frame (the filter pressing time is 25 minutes), and then drying the raw materials by air compression to obtain the low-calcium high-content vanadium raw materials. 1121.4g of dried powder is weighed, wherein the content of vanadium pentoxide is 29 percent, and CaO is 0.4; the total recovery rate of vanadium is 85.58%.
Example 3
A method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid comprises the following steps:
(1) crushing and grinding the vanadium-containing slag, sieving the vanadium-containing slag by a 120-mesh sieve, and magnetically selecting bright iron to obtain slag powder; according to the liquid-solid ratio of 1: 2.5, adding 20kg of slag powder into 50L of dilute acid, stirring and mixing at the rotating speed of 300r/min to obtain a premixed solution, wherein the temperature is 50 ℃, and the pH value is 3.5;
(2) slowly adding waste acid into the premixed solution to adjust the pH value to 1.6, reacting for 60min at the reaction temperature of 55 ℃, and consuming 58L of waste acid; after the reaction is finished, carrying out solid-liquid separation by using a negative pressure centrifuge to obtain 32.47KG aqueous acidic high-sulfur offwhite gypsum slag and vanadium-containing solution; SO in gypsum residue343%, moisture 23%, V2O5The content is 0.36 percent, the dry basis is 25KG, and the vanadium leaching rate is 76.32 percent by conversion. V in vanadium-containing solution2O5The concentration was 3.33g/L and the pH was 1.6. Naturally precipitating for 4 hours, cooling to normal temperature, filtering again, and injecting into a precipitation reaction tank;
(3) adjusting the stirring speed of a settling tank to 250r/min, adding iron powder according to the proportion of 3% of the slag powder by mass, stirring and reducing for 40min, wherein the reaction liquid is blue; slowly injecting liquid alkali, and adjustingThe addition of caustic soda liquid (2L of caustic soda liquid was consumed) was stopped when the pH increased to 3.8, and stirring was continued for another 20 minutes, and the slurry pH slowly increased to 4.2, and sampling was started. V in the clear liquid of the precipitate2O5The content is 0.02g/L, qualified slurry is obtained, solid-liquid separation is carried out, a vanadium-containing filter cake is obtained, and the separation time is 70 minutes (2 flat plate frame filter presses), the precipitation recovery rate is 99.28 percent;
(4) pulping the vanadium-containing filter cake again, adding an acidic solution with the pH value of 3.8 (prepared by adding a small amount of dilute acid into tap water) according to the solid-to-liquid ratio of 1/3; stirring at a rotation speed of 200 rpm for washing for 20 minutes; and (5) performing plate and frame filter pressing (for 60 minutes), and then drying by air compression to obtain the low-calcium high-content vanadium raw material. 1028.3g of dried powder is weighed, wherein the content of vanadium pentoxide is 28 percent, and CaO is 0.4; the total recovery rate of vanadium is 75.77%.
Comparative example 1
A method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid comprises the following steps:
(1) crushing and grinding the vanadium-containing slag, sieving the vanadium-containing slag by a 120-mesh sieve, magnetically selecting bright iron, and weighing 20kg of slag powder for later use;
(2) adding the slag powder solid-liquid ratio 1/3 into tap water and stirring. Adding waste acid and adjusting the reaction liquid to about 1.8, reacting for 50min at 72 ℃, and consuming 71L of waste acid; after the reaction is finished, carrying out solid-liquid separation by using a negative pressure centrifuge to obtain 33.33KG acidic high-sulfur offwhite gypsum slag and 116L vanadium-containing solution; SO in gypsum residue341%, moisture 25%, V2O5The content is 0.68 percent, the dry basis weight is 25KG, and the vanadium leaching rate is 55.26 percent. In vanadium-containing solution, V2O5The concentration was 1.81g/L and the pH was 1.8. Naturally precipitating for 4 hours, cooling to normal temperature, filtering again, and injecting into a precipitation reaction tank;
(3) adjusting the stirring speed of the settling tank to 50r/min, adding 600g of iron powder for reduction, and reacting for 45min to ensure that the solution in the settling tank is adjusted to be bright blue; and slowly injecting liquid caustic soda, adjusting the pH value to 3.5, stopping adding the liquid caustic soda, consuming 2L of the liquid caustic soda, stirring for 20 minutes, slowly increasing the pH value of the slurry to 4.00, and starting sampling. V in the clear liquid of the precipitate2O5The content is 0.05g/L, qualified slurry is obtained, and solid-liquid separation is carried out (2 flat plate frame)Filter press), the separation time is 75 minutes, a filter cake containing vanadium is obtained, and the recovery rate of the precipitate is 97.23%;
(4) pulping the vanadium-containing filter cake again, adding an acidic solution with the pH value of 3.8 (prepared by adding a small amount of dilute acid into tap water) according to the solid-to-liquid ratio of 1/3; stirring at a rotation speed of 200 rpm for washing for 20 minutes; and (3) performing plate-and-frame filter pressing for 70 minutes (2 flat plate-and-frame filter presses), and then drying by air compression to obtain the low-calcium high-content vanadium raw material. Weighing and testing after drying, wherein the weight is 699.1g, and the vanadium pentoxide content is 29.2%; the total recovery rate of vanadium is 53.72 percent.
The components and contents of the gypsum slag and the low-calcium high-vanadium raw material prepared in this example are shown in tables 4 and 5 below.
Table 4: the components and contents of the gypsum slag
V2O5 MgO Al2O3 CaO Fe2O3 TiO2
0.68 1.6 2.8 32 19 /
MnO SO3 Cr2O3 Na2O P2O5 SiO2
0.6 41 / 0.2 / 0.7
Table 5: the components and contents in the low-calcium high-content vanadium raw material
V2O5 MgO Al2O3 CaO Fe2O3 TiO2
29.2 0.2 7.4 0.3 22 /
MnO SO3 Cr2O3 Na2O P2O5 SiO2
0.1 13 / 0.6 / 23
Comparative example 2
A method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid comprises the following steps:
(1) crushing and grinding the vanadium-containing slag, sieving the crushed vanadium-containing slag with a 120-mesh sieve, and magnetically selecting 6% of bright iron. Weighing 20kg of slag powder for later use; injecting 60L of dilute acid into a reaction tank, gradually adding 20kg of slag powder under the condition of stirring at the rotating speed of 300r/min, and finishing the adding after about 5 minutes to obtain a premixed solution, wherein the temperature is 43 ℃, and the pH value is 3.3;
(2) slowly adding waste acid into the premixed solution to adjust the pH value to about 1.8, reacting for 45min at the reaction temperature of 58 ℃, and consuming 47L of waste acid; after the reaction is finished, carrying out solid-liquid separation by using a negative pressure centrifuge to obtain 29.9KG (dry basis 23KG) of hydrous acidic high-sulfur offwhite gypsum slag and 101L of vanadium-containing solution; SO in gypsum residue337% water, 23% V2O5The content is 0.21 percent, the dry basis weight is 23KG, and the vanadium leaching rate is 87.37 percent by conversion. In the vanadium-containing solution, the vanadium-containing solution is added,V2O5the concentration was 3.29g/L and the pH was 1.8. Naturally precipitating for 4 hours, cooling to normal temperature, filtering again, and injecting into a precipitation reaction tank;
(3) and adjusting the stirring speed of the settling tank to 100r/min, slowly injecting liquid caustic soda, adjusting the pH value to 3.5, stopping adding the liquid caustic soda, consuming 3.2L of the liquid caustic soda, stirring for 20 minutes again, slowly increasing the pH value of the slurry to 3.9, and starting sampling. V in the clear liquid of the precipitate2O5The content is 0.03g/L, qualified slurry is obtained, solid-liquid separation is carried out, a vanadium-containing filter cake is obtained, and the recovery rate of precipitation is 99.09%;
(4) pulping the vanadium-containing filter cake again, and adding an acidic solution with the pH value of 3.8 (prepared by adding a small amount of dilute acid into tap water) according to the solid-to-liquid ratio of 1/3; stirring at a rotation speed of 200 rpm for washing for 20 minutes; and (4) performing plate and frame filter pressing, and then blowing by compressed air to obtain the low-calcium high-content vanadium raw material. Weighing and testing after drying, wherein the weight is 2383.8g, and the vanadium pentoxide content is 13.8%; the total recovery rate of vanadium is 86.57%.
The components and contents of the gypsum slag and the low-calcium high-vanadium raw material prepared in this example are shown in tables 6 and 7 below.
Table 6: the components and contents of the gypsum slag
V2O5 MgO Al2O3 CaO Fe2O3 TiO2
0.21 2.2 1.8 38 16 /
MnO SO3 Cr2O3 Na2O P2O5 SiO2
0.2 36 / / / 1.2
Table 7: the components and contents of the low-calcium high-content vanadium raw material
V2O5 MgO Al2O3 CaO Fe2O3 TiO2
13.8 0.2 7.2 0.3 48.0 /
MnO SO3 Cr2O3 Na2O P2O5 SiO2
0.1 13 / / / 13.0
Comparative example 3
A method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid comprises the following steps:
(1) crushing and grinding the vanadium-containing slag, sieving the crushed vanadium-containing slag with a 120-mesh sieve, and magnetically selecting 6% of bright iron. Weighing 20kg of slag powder for later use;
(2) injecting 40L of clear water into a reaction barrel, then injecting 60L of waste acid, stirring at the rotating speed of 300r/min, slowly adding 20kg of slag powder, reacting at the initial reaction pH of 0.4 and at the reaction temperature of 85 ℃ for 60min, and then reacting at the initial reaction pH of 1.9. After the reaction is finishedAfter the completion, carrying out solid-liquid separation by using a negative pressure centrifuge to obtain 28.5KG (dry basis 22KG) of hydrous acidic high-sulfur offwhite gypsum slag and 93L of vanadium-containing solution; SO in gypsum residue332%, moisture 22.8%, V2O5The content is 0.98 percent, the dry basis weight is 22KG, and the vanadium leaching rate is 43.26 percent by conversion. In vanadium-containing solution, V2O5The concentration was 1.77g/L and the pH was 1.9. Naturally precipitating for 4 hours, cooling to normal temperature, filtering again, and injecting into a precipitation reaction tank;
(3) adjusting the stirring speed of the settling tank to 100r/min, slowly injecting liquid caustic soda, adjusting the pH value to 3.5, stopping adding the liquid caustic soda, consuming 3.1L of the liquid caustic soda, stirring for another 20 minutes, slowly increasing the pH value of the slurry to 3.9, and starting sampling. V in the supernatant2O5The content is 0.05g/L, qualified slurry is obtained, solid-liquid separation is carried out, a vanadium-containing filter cake is obtained, and the precipitation recovery rate is 97.18%;
(4) pulping the vanadium-containing filter cake again, adding an acidic solution with the pH value of 3.8 (prepared by adding a small amount of dilute acid into tap water) according to the solid-to-liquid ratio of 1/3; stirring at a rotation speed of 200 rpm for washing for 20 minutes; and (4) performing plate and frame filter pressing, and then blowing by compressed air to obtain the low-calcium high-content vanadium raw material. Weighing and testing after drying, wherein the weight is 2212.6g, and the vanadium pentoxide content is 7.22%; the total recovery rate of vanadium is 42.04%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (6)

1. A method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid is characterized by comprising the following steps:
1) crushing and grinding vanadium-containing slag, and mixing and stirring the vanadium-containing slag with dilute acid to form a premixed solution; the dilute acid is acid-containing wastewater generated in each titanium dioxide preparation process by flue spraying in the titanium dioxide preparation method by using sulfuric acid, wherein the content of sulfuric acid is 1-5%;
specifically, according to the solid-liquid ratio of the reaction of 1: 2-5, firstly adding dilute acid, and under the stirring condition of 150-300 r/min, adding the crushed and ground vanadium-containing furnace slag at a constant speed to form a premixed liquid, wherein the pH value of the premixed liquid is 2.5-3.5, and the temperature is 40-50 ℃;
2) mixing and stirring the premixed liquid and waste acid for reaction to form slurry, wherein the reaction time is 30-60 min, the reaction temperature is 40-50 ℃, and after the reaction is finished, carrying out solid-liquid separation to obtain solid which is acidic high-sulfur off-white gypsum slag; the liquid is vanadium-containing solution; the waste acid is waste sulfuric acid which is remained and difficult to recycle after acidolysis in the sulfuric acid method titanium dioxide industry, wherein the content of the sulfuric acid is 10-30%;
3) adding iron powder into the vanadium-containing solution obtained in the step 2), stirring and reducing, adding liquid alkali until the pH of the reaction liquid is 3.8-4.5, precipitating to obtain qualified slurry, and carrying out solid-liquid separation to obtain a vanadium-containing filter cake;
and in the step 3), a flocculating agent is added into the obtained qualified slurry for treatment, wherein the flocculating agent is prepared by adding water into a macromolecular low-charge amphoteric organic flocculating agent with the unit of more than 1000 ten thousand according to the proportion of 1/1000, the flocculation time is more than 60min, and the volume ratio of the adding amount of the flocculating agent to the qualified slurry is 1: 20;
further comprising step 4): mixing the vanadium-containing filter cake obtained in the step 3) with pulping liquid according to a solid-to-liquid ratio of 1: 3, mixing, pulping and washing, wherein the pulping liquid is formed by adding the dilute acid into water and adjusting the pH to 3.8-4.5, and the pulping and washing time is 30-60 min; solid-liquid separation to obtain the low-calcium high-content vanadium raw material.
2. The method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid as claimed in claim 1, wherein in step 1), the vanadium-containing slag is crushed and ground to a particle size of 120 meshes or more and 80%, and bright iron is screened out.
3. The method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid according to claim 1, wherein in the step 2), the pH value of the slurry is 1.6-1.8.
4. The method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid according to claim 1, wherein the step 2) further comprises naturally settling the vanadium-containing solution, cooling to normal temperature, and filtering.
5. The method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid as claimed in claim 1, wherein in step 3), iron powder is added according to the mass ratio of the vanadium-containing slag of 2.5-3.5%, and the reduction time is 30-60 min.
6. The method for comprehensively treating vanadium-containing slag and titanium dioxide waste acid according to claim 1, wherein in the step 3), the stirring speed is 50-300 r/min; the liquid alkali is NaOH solution; after solid-liquid separation, the content of vanadium pentoxide in the clear liquid is lower than 0.05 g/L.
CN202110054818.1A 2021-01-15 2021-01-15 Method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid Active CN112830694B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110054818.1A CN112830694B (en) 2021-01-15 2021-01-15 Method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110054818.1A CN112830694B (en) 2021-01-15 2021-01-15 Method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid

Publications (2)

Publication Number Publication Date
CN112830694A CN112830694A (en) 2021-05-25
CN112830694B true CN112830694B (en) 2022-07-19

Family

ID=75928424

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110054818.1A Active CN112830694B (en) 2021-01-15 2021-01-15 Method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid

Country Status (1)

Country Link
CN (1) CN112830694B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101397150A (en) * 2007-09-25 2009-04-01 攀钢集团攀枝花钢铁研究院 Method for extracting vanadium pentoxide from vanadium-containing rotary furnace steel slag
CN102011010A (en) * 2009-09-07 2011-04-13 杨秋良 Method for totally extracting vanadium, gallium and scandium by using titanium dioxide hydrolysis waste acid to leach steel slag containing vanadium
CN102745742B (en) * 2012-07-18 2014-04-09 云南昆欧科技有限责任公司 Method for producing titanium-rich material by processing vanadium-titanium-containing blast furnace slag with titanium white waste acid
CN103922423B (en) * 2014-03-31 2015-08-26 攀钢集团攀枝花钢铁研究院有限公司 A kind of method utilizing titanium white waste acid to improve v slag grade
CN104178632B (en) * 2014-08-12 2016-06-22 东北大学 A kind of method of titanium white waste acid comprehensive utilization
CN106884089A (en) * 2015-12-15 2017-06-23 北京矿冶研究总院 Method for recovering vanadium from non-blast furnace titanium slag
CN108467945A (en) * 2018-04-09 2018-08-31 攀枝花市红杉钒制品有限公司 A kind of processing method of slag, titanium white waste acid
CN109825711A (en) * 2019-03-14 2019-05-31 何耀 A kind of titanium dioxide waste acid by sulfuric acid process resource utilization method

Also Published As

Publication number Publication date
CN112830694A (en) 2021-05-25

Similar Documents

Publication Publication Date Title
CN103103361B (en) Method for preparing rare earth oxide from rare earth polishing powder waste
CN109516484B (en) Method for producing alumina by sintering carbide slurry fly ash and coal gangue
CN103288116B (en) Method for preparing high-purity calcium hydroxide from carbide slag
CN102515280B (en) Method for separation of aluminum and iron from acid leaching solution of coal gangue with high iron content
CN101125656A (en) Method for firstly extracting silicon and secondly extracting aluminum from fly ash
CN102311136A (en) Method for producing low iron aluminum sulfate by utilization of coal gangue
CN101381100A (en) Method for recovering zirconia, mullite and rare-earth from foundry molding sand waste
CN110172538B (en) Efficient red mud resource utilization system and process
CN113248095A (en) Ferric salt sludge treatment process and treatment system
CN100577331C (en) Process for producing steel scoria unburned brick
CN108726550A (en) A method of preparing active calcium oxide using carbide slag
CN104477982B (en) A kind of high titanium gangue is prepared the method for titanium dioxide
CN112830694B (en) Method for comprehensively treating vanadium-containing furnace slag and titanium dioxide waste acid
CN111994937B (en) Method for recycling calcium fluoride from fluorine-containing sludge
CN101543830A (en) Comprehensive utilization method for recycling manganese oxide slag
CN114314778A (en) Method for producing water purifying agent and white carbon black by roasting-free and reinforced acid leaching coal gangue
CN115572084B (en) Multi-steel slag synergistic all-solid-waste cementing material and preparation method thereof
CN102198956A (en) New process for producing aluminum and silicon chemical products by low-grade bauxite or kaolin raw material based on alkaline method
CN107188436A (en) A kind of green cement and preparation method thereof
CN110817919A (en) Preparation method of calcium oxide balls regenerated from carbide slag
CN105316479A (en) Red mud vanadium extracting and ore-blending sintering method
CN102180492B (en) Method for producing alumina from fly ash
CN113025827B (en) Method for recovering vanadium from vanadium-containing waste
CN113636583A (en) Preparation method of calcium oxide regenerated from carbide slag
CN115365274A (en) Method for improving steel slag grinding efficiency and iron resource recovery rate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant