WO2011029269A1 - 利用冶金焙烧和高炉对铬渣进行无害化处理的方法 - Google Patents
利用冶金焙烧和高炉对铬渣进行无害化处理的方法 Download PDFInfo
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- WO2011029269A1 WO2011029269A1 PCT/CN2010/001358 CN2010001358W WO2011029269A1 WO 2011029269 A1 WO2011029269 A1 WO 2011029269A1 CN 2010001358 W CN2010001358 W CN 2010001358W WO 2011029269 A1 WO2011029269 A1 WO 2011029269A1
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- core
- sintering
- chromium
- chromium slag
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Classifications
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
- C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/008—Composition or distribution of the charge
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/02—Making special pig-iron, e.g. by applying additives, e.g. oxides of other metals
-
- 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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2200/00—Recycling of non-gaseous waste material
-
- 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
Definitions
- the present invention relates to the field of environmentally friendly treatment of metallurgical ironmaking and chromium slag. Background technique
- the melting method is a process in which a toxic substance is detoxified by hexavalent chromium by adding an auxiliary agent at a high temperature.
- the incineration treatment technology of chromium slag mainly includes carbon reduction method, sinter method, dry reduction method and cyclone furnace sintering method.
- the sinter method is one step after the blast furnace method, so it is the most thorough method for detoxification.
- this method is an existing method in the metallurgical enterprise, the method that is carried out in the normal production process, it is also the most economical method.
- the valuable elements in the chromium slag can be fully utilized, such as the transfer of the value of chromium, iron, calcium and magnesium to the production of sintering and iron making.
- dolomite containing CaO and MgO In the blast furnace ironmaking, in order to discharge the impurities Si0 2 and A1 2 0 3 in the iron ore and coke from the blast furnace in molten form, dolomite containing CaO and MgO must be added as a flux, and the melting point with Si0 2 and A1 2 0 is formed. Lower eutectic to achieve liquid discharge.
- the content of CaO and MgO in the chromium slag is equivalent to the content of both in the dolomite.
- the solid chrome slag can be used as a flux for sintering iron.
- the sinter method of the incineration treatment of chromium slag is to reduce the hexavalent chromium in the sintered high-temperature reducing chromium slag to trivalent chromium (half-way reduction- or high-price detoxification reduction), and in the blast furnace ironmaking
- the trivalent chromium is reduced to a single mass (full reduction - or low-cost reduction) to achieve the harmless treatment of the chromium residue.
- the technology mainly consists of two processes:
- chromium slag is used as an alkaline flux and a chromium-containing raw material, and is mixed with iron-containing raw materials and fuel (coal) such as iron ore powder, and sintered to form a sinter containing bismuth;
- the second is to use the sinter as the main raw material, and smelt it in a blast furnace to produce chrome-containing pig iron (2.5-4%) or pig iron for steelmaking.
- the chromium slag used in the production of self-fluxing sinter is sintered with chromium slag as an alkaline flux instead of conventionally used lime mixed with iron-containing raw materials and fuel, and is sintered at the same time as manufacturing.
- the strong reducing atmosphere makes the residual hexavalent chromium of the chromium residue and the reducing agent C and CO fully act, and is converted into trivalent chromium (in the form of Cr 2 0 3 ) by half-reduction, thereby achieving the purpose of reduction and detoxification.
- the hexavalent chromium in the chromium slag is reduced to trivalent chromium by C, CO, etc. during the sintering process, and the reduction rate can reach over 96%.
- the hexavalent chromium reduction rate is above 99.5%
- the remaining trivalent chromium enters the blast furnace slag in the form of Cr 2 0 3
- the liquid blast furnace slag is subjected to water quenching and cold granulation treatment. It can be used as a raw material for cement production.
- the conventional sintering process is required to ensure sintering under an oxidizing atmosphere to ensure the quality index of the sinter (good strength, good reductibility; low FeO content). Therefore, the sintering process for producing self-fluxing sintered ore from chromium slag already used in China has the following disadvantages:
- this method needs to change the sintering process conditions to achieve the treatment of chromium slag, which is unrealistic in the metallurgical industry of large-scale production. It can be seen that the pretreatment and thorough treatment of chromium slag by using the sintering machine and blast furnace of metallurgical enterprises is an effective safe and economical method. However, the hexavalent chromium, a toxic substance in the chromium slag, must be effectively and thoroughly treated under high temperature and reducing atmosphere.
- the blast furnace is a high-temperature reducing atmosphere, and the sintering is a high-temperature oxidizing atmosphere.
- the dust removal ash in metallurgical iron-containing scrap is a waste that can be reused.
- the dust removal load has many adverse effects on the sintering process.
- blast furnace gravity dust removal ash because the carbon content is relatively low, and it is quite unstable, it cannot be included in the sintering fuel use plan, and it cannot be used, resulting in waste. Therefore, it is difficult to use the dust ash ball in the metallurgical iron-containing scrap.
- bentonite or humic acid as a binder is not ideal. Unless it is used in over-metering, it will reduce the iron content of raw materials. This is an indisputable reality in the metallurgical industry.
- the object of the present invention is to provide a new method for harmless treatment of chromium slag by metallurgical roasting and blast furnace in view of the deficiencies of the prior art, without changing the oxidizing atmosphere of metallurgical sintering.
- the conventional process of metallurgical sintering and blast furnace is changed to achieve detoxification treatment of chromium slag.
- a method for treating chromium slag using metallurgical roasting and blast furnace production processes comprising the following steps -
- the core is made of the raw material of the sintered ore or the dust and ash in the metallurgical iron-containing waste, and the composite ball of the sinter or the metallurgical iron-containing waste is used as the spherical shell.
- the dust-removing ash in the iron-containing waste is a composite ball of a spherical shell, and enters the pelletizing furnace to form a pellet.
- the detoxification of the chromium residue is realized by using a small atmosphere of a small spherical core in a reducing atmosphere. deal with;
- the sintered ore or pellet is fed to the blast furnace and used as a blast furnace raw material for ironmaking. Thoroughly detoxify the chromium residue.
- the weight percentages of the chromium slag and the pulverized coal and/or the coke powder which are made of the core are respectively determined by the total amount of the core material of the core. 38-88% and 10-60%, when the gravity dust is used as the reducing agent, the weight percentage of both the chromium residue and the gravity dust is 3-5-90% and 8-93%, respectively, and the weight percentage of the binder Both are 1-2%; the diameter of the core is 2-9 faces;
- the amount of the core is 5%-100% of the amount of the dust in the sinter raw material or the pellet raw material or the metallurgical iron-containing waste, and the weight percentage of the adhesive is 1-2. %.
- the composite pellets produced have a diameter of 3-16 mm.
- the core can also replace the dolomite in the flux used in the production of sinter by 1-100%.
- the binder is selected from bentonite and humic acid.
- the present invention particularly provides a binder comprising syrup, which comprises industrial syrup, civil syrup, such as: high fructose syrup, fructose pulp, starch syrup, and the like. As long as the national syrup standard is met.
- humic acid, ferrous oxide, or further borax may be further added to the syrup to form a binder, and the weight ratio thereof is 70-80% of syrup, 10-20% of humic acid, and 5-10 of ferrous oxide. %, borax 5-10%, which can improve the hydrophilicity and activity of the dust-removing ash in the metallurgical iron-containing waste.
- the adhesive is poured into water, and after heating to 50 ⁇ - 160 Torr in a closed pressure vessel, the raw material is sprayed and mixed, so that Can solve this problem well.
- the steps (1) and (2) for the preparation of the core and the composite pellet are as follows: 1 is to mix the chromium residue, the coal powder and/or the coke powder or the gravity dust, the adhesive and the adhesive. , enter the granulator, independently make the core production outside the sintering line; then enter the nucleus with the sinter raw material or the dust ash and binder in the metallurgical iron-containing scrap into the sintering mixer or into the pellet The granulator of the production line forms a composite pellet, which is then sintered by a sintering machine or a pelletizing furnace to form a sintered ore or pellet, and finally enters the blast furnace;
- the chromium slag, pulverized coal and/or coke powder or gravity dust ash, and the binder are mixed and mixed, and then sent to the sintering feed bin, and the chromium slag feed bin in the sintering batching chamber.
- the granulator is installed at the discharge port to directly form the core, and then the core is put into a mixer, a second mixer, or directly into the ball.
- Into the second mixer mixed with the sinter raw materials or the dust and ash in the metallurgical iron-containing scrap to form a composite pellet;
- the chromium slag, pulverized coal and/or coke powder or gravity dust ash, and the binder are mixed and mixed, and then sent to the sintering feed bin, and the chromium slag feed bin in the sintering batching chamber.
- the discharge port is equipped with a mist spray pipe to directly form the core, and then enter a mixer, a second mixer, or directly into the second mixer, and the dust or ash in the raw material of the sinter or the metallurgical iron-containing waste.
- the binders are mixed together to form a composite pellet.
- the chromium slag raw material is crushed and dried before use, and the water content requirement is 3-7.5%, and the particle size requirement is -200 mesh up to 70% or more. Since the treatment of chromium slag cannot be directly processed in the sintering production line of the oxidizing atmosphere, the original production process of the sintering production line should not be changed for the treatment of the chromium slag. Therefore, the present invention uses the method of secondary spheronization to form the chromium slag required for processing.
- the mechanism for detoxification of chromium residue by the method of the present invention is as follows:
- the hexavalent chromium in the chromium residue is mainly in the form of sodium chromate and calcium chromate, so sodium chromate is taken as an example.
- sodium chromate is taken as an example.
- the reduction reaction of Na 2 Cr0 4 is:
- C, CO, Si and Fe can reduce Cr0 3 to Cr 2 0 3 , and C and Si can further reduce Cr 2 0 3 to CrO and metallic chromium.
- Sinter ore is an artificial rich ore produced by high-temperature sintering, which is one of the main iron-containing raw materials for blast furnace iron making.
- sintering that is, a variety of powdery iron-containing raw materials, with an appropriate amount of alkaline flux and fuel (coke powder, anthracite powder), mixed and placed on the sintering equipment for combustion, a series of materials in the high temperature process
- alkaline flux and fuel coke powder, anthracite powder
- the physicochemical reaction produces a part of the fusible substance in the mixture and softens and melts to form a certain amount of liquid phase, wets and sticks the surrounding unmelted solid particles, solidifies after cooling, and bonds the original bulk material into a block shape.
- the chromium slag in order to satisfy the reducing atmosphere requirement for the chromium slag treatment without changing the oxidizing atmosphere of the sintering machine, the chromium slag is made into a core together with a reducing agent such as pulverized coal or coke powder, together with the sintering raw material.
- the second ball is formed by sintering the raw material wrapped around the core to form a spherical shell.
- the core of the reducing agent is at a higher temperature, and the reducing agent pulverized coal or coke powder is inside the spherical shell.
- a small environment with a reducing atmosphere is formed (the nucleus forms a reducing atmosphere, and the oxidizing atmosphere at the periphery of the spherical shell), so that the chromium can be smoothly reduced, and the reduction rate can reach 96% or more.
- the conventional sinter is entered into the blast furnace, and after smelting in the blast furnace, the hexavalent chromium reduction rate can reach 99.5% or more from the sinter to the blast furnace slag.
- the invention can also comprehensively utilize metallurgical iron-containing waste (dust-removing ash):
- the dust-removing ash in the metallurgical iron-containing waste is in the flue gas collected by the steel enterprise in the production process (including sintering, iron making, steel making) dust removal.
- a kind of iron-containing dust, the total amount of dust removal ash in the three links accounts for 10-12% of the steel output.
- Sintering dust ash Among them, organic head dust ash, tail dust ash, ring cold dust ash, finished dust ash and pellet dust ash, these dust ash do not contain carbon, can only be made when the ball is double 2.
- Iron dust removal ash Among them, gravity dust ash, washing dust ash, these dust ash have high carbon content, can be used as a reducing agent for the core of the second ball, but the washing dust ash contains zinc. Higher, zinc can not be used as a reducing agent for the core of the second ball before being sorted; 3.
- Steel dust removal ash one of the dust removal ash, the secondary dust removal ash, the wet dust removal sludge, these dust removal Ash does not contain carbon, and can only be used for ball shells when it is double-rounded.
- the project improves the iron grade, quality and output of the sinter, saving a lot of energy.
- the invention treats the dust-removing ash using metallurgical iron-containing waste material and uses it as a reducing agent, and improves the hydrophilicity and activity by using a special binder, so that it can effectively form a ball and achieve all effective for dust removal ash.
- Use improve the sintering gas permeability, improve the iron content, quality and yield of the sintered ore, and also interpret the chromium residue. Compared with the original processing method, it has the following advantages:
- the sintering gas permeability is improved.
- the invention processes the metallurgical iron-containing scrap (dust-removing ash) secondary ball metallurgy pellet, has good ore-forming performance, can fully fuse with the mixture, and has no deposition, thereby improving the gas permeability of the sintering, and the quality of the sintered ore is greatly improved. The effect is good.
- the invention adopts the technique of secondary spheronization.
- the reducing atmosphere is automatically generated inside the core, and the iron can be reduced to remove the oxygen to improve the grade of the sinter iron.
- the increase in iron grade is generally around 13%.
- the coke ratio is lowered, thereby increasing the metallization rate of the metallic iron and the grade of the sinter.
- the full utilization page of the dust improves the metal recovery rate, saves resources and reduces costs.
- the present invention utilizes it as a reducing agent to improve the iron grade, quality and quality of the sinter. Production, saving a lot of energy and reducing carbon dioxide emissions.
- the amount of gravity dust ash is about 2% of iron production, and its carbon content is about 40%. According to the output of 1 million tons of iron, there is 20,000 tons of gravity dust ash and 9251 kilograms of standard coal.
- the invention adopts secondary ball formation, uses metallurgical iron-containing scrap (dust removal ash) to treat chromium slag, breaks through the environmental protection technology problem of chromium slag treatment, and is a new social benefit, environmental benefit and economic benefit.
- Technology with simple process, strong maneuverability, thorough detoxification, no secondary pollution, small investment, high level of resource recycling, effective management and environmental benefits Out, social benefits and other advantages.
- it can also reduce a large amount of carbon dioxide. Taking 120,000 tons of chromium slag per year as an example, it can reduce carbon dioxide emissions by 131,700 tons per year.
- the method of the invention directly utilizes the metallurgical sintering and the conventional production process of the blast furnace, and can effectively treat the chromium slag without changing the oxidizing atmosphere of the whole sintering, which is economical and environmentally friendly, and is easy to implement.
- the ball-making raw material of the present invention can all adopt metallurgical iron-containing scrap, and the problem of bonding of the ball is well solved. Therefore, the technology of the present invention exhibits remarkable advantages in resource utilization, energy saving and environmental protection.
- Treatment of chromium slag Next to the chromium slag dumping site of the chromium salt production plant, build a chromium slag ball production line; crush and dry the chromium slag (water content less than 4%, ball milled to -200 mesh up to 30-70%) Calculated by taking a total of 10 tons of core material, taking 7.8 tons of chromium slag, 2 tons of pulverized coal (-200 mesh), using syrup 70%, humic acid 20% and ferrous oxide 10% by weight.
- the adhesive is 0.2 tons, the adhesive is dissolved in water, heated to 120 ⁇ in a closed pressure vessel, and then injected into the raw material, mixed into the disc granulator by a mixer, and the diameter is 2-5 legs.
- the core of the ball, the semi-finished product after the vibrating screen, the special transporter that enters the seal is sent to the batching room of the sintering plant, the chromium slag ball core is placed in the sealed silo, and enters the sintering production line, and the whole process does not go down; the above 10 tons of chromium residue
- the core of the sphere that is, the dolomite in the same amount of flux is replaced by a chromium slag core
- the dolomite in the flux is reduced by 7.8 tons according to the original weight, because the core is replaced by the chromium residue core.
- a spherical shell is formed outside the core of the chromium slag core to form a composite pellet having a diameter of 5-10 mm, and then sintered into a sintering machine to carry out the slag Reduction pretreatment; After high temperature sintering above 120CTC, the sintered ore is discharged, cooled, crushed, sieved, and finished into the next process - blast furnace ironmaking, and the chromium residue is completely detoxified.
- the above sintering production process refers to the conventional production process of sinter, and the equipment and process conditions do not need to be changed.
- the chromium slag core of the above manner is independently produced outside the sintering line.
- the chromium slag core can also be made together in the sintering line by mixing the chromium slag, pulverized coal and/or coke powder or gravity dust ash and binder, and then feeding it into the sintering feed.
- warehouse in the slag feed bin outlet of the sintering batching chamber, add a mist spray pipe and / or granulator, directly form the core, then enter a mixer, two mixers, or directly into the two mixing
- the machine forms a spherical shell from the raw material of the sintered ore to form a composite pellet.
- the above-mentioned reducing agent used in the production of the chromium slag core may be gravity dedusting ash.
- the core material of the core is 50% chromium slag, 48% of iron blast furnace gravity dust removal ash, and the binder is 2% (made by 70% syrup, 20% humic acid and 10% ferrous oxide). 1 kg, made of a core diameter of 5 mm.
- the spherical shell material adopts 97% of sintered dust ash, 55% of iron grade; 3% of binder (using syrup); a spherical shell is formed outside the core, the weight of the spherical shell is 2 kg, and the diameter of the spherical shell is 8 mm; The total weight is 3 kg.
- the binder is heated to 50 ° C, and then atomized and sprayed onto the raw material for mixing.
- the calcination test is carried out in the test furnace; the test atmosphere is an oxidizing atmosphere; the liquefied gas is used as the fuel, and the green ball is placed in the furnace for firing; (the whole process simulates the sintering machine thermal system)
- the product is taken out for each test;
- the chrome is 1. 5%; the total chromium of the sinter is 0. 45; the hexavalent chromium is 0. 0002% (less than the national emission standard 5mg / k g is 0. 0005%).
- Detoxification pretreatment Purpose is carried out in the test furnace; the test atmosphere is an oxidizing atmosphere; the liquefied gas is used as the fuel, and the green ball is placed in the furnace for firing; (the whole process simulates the sintering machine thermal system)
- the product is taken out for each test;
- the chrome is 1. 5%; the total chromium of the sinter is 0. 45; the hexavalent chromium is 0. 0002% (less than
- the falling strength of the raw balls reached 8 times/average each; the compressive strength reached 10N/average each; and all other indicators reached the national standard.
- the core material of the core is 78.5% of chromium residue and 20% of coal powder; the binder is made of (70% by weight of syrup, 20% of humic acid and 10% by weight of ferrous oxide) 1.5%, and the weight of the core is 1 kg. Made into a core (diameter 5 earned);
- the spherical shell material uses 98% iron ore powder and 55% iron content; the binder is humic acid (2%); the spherical shell is formed outside the core, the weight of the spherical shell is 2 kg, and the diameter of the secondary sphere is 10 mm. The total weight of the ball is 3 kg.
- the smelting test is carried out in a test furnace; the test atmosphere is an oxidizing atmosphere; the liquefied gas is used as a fuel, and the raw material is placed in a furnace for calcination; 0001% (less than the national emission standard 5mg / kg or 0. 0005%).
- the total chromium content of the sinter is 0. 3; To achieve the purpose of detoxification pretreatment.
- the falling strength of the raw balls reached 8 times/average each; the compressive strength reached 10N/average each; and all other indicators reached the national standard.
- the core material of the sphere is made of chromium slag 18.5%, gravity dust ash 80% (gravity dust ash contains 35% of coke powder); binder 1.5% (80% syrup, 15% humic acid and 5% ferrous oxide) The weight ratio is obtained); the weight of the core is 1 kg; the core is made (diameter 5 mm);
- the shell material is made of iron ore powder (98%); the iron grade is 63%; the (carbon-free) binder is bentonite (2%); the spherical shell is formed outside the core; the shell weight is 1 kg; Ball diameter 8 mm; total weight 2 kg; roasting test in a self-made test furnace; test atmosphere is oxidizing atmosphere; liquefied gas is used as fuel, raw ball is placed in the furnace for roasting;
- the total collateral of the sulphide is 1.5%; the total chromium of the sinter is 0. 45; the hexavalent chromium is 0. 0002% (less than the national emission standard 5mg/kg or 0. 0005°/ .).
- Example 5 Preparation of raw materials: Drying chromium slag (water content less than 4%), crushing (ball milling to -200 mesh up to 70%); drying gravity dust ash (water less than 4%), crushing (ball milling to - 200 mesh reaches more than 70%); the total amount of nuclear material is 80 tons, and 40 tons of chromium slag, 38.4 tons of gravity dust ash, 80% syrup, 10% humic acid and 10% ferrous oxide. 1.6 tons. The total amount of spherical shell raw materials is calculated according to 120 tons.
- the steelmaking sludge ie, steelmaking wet dust removal ash
- TFe 55%) syrup is 75%
- humic acid is 10%
- ferrous oxide is 10%
- the binder made of 5% by weight of borax is 2.4 tons.
- the two silos are filled with iron gravity gravity dust ash and chrome crucible, and the feed speed is controlled by a disc feeder, and the uniform speed is distributed on the belt conveyor.
- the belt conveyor feeds the raw material into the grinding machine (or powerful mixer), then grinds it (or stirs), then sends it to the disc pelletizer through a belt conveyor, and uses a water-soluble binder to heat it in a closed pressure vessel. 160 V, and then sprayed into the raw material to form a core.
- the core After the core is formed, it passes through the belt conveyor and the vibrating screen and then enters the next process (the spherical shell becomes a ball); the fine material under the vibrating screen is returned to the grinding machine for grinding.
- the two silos are filled with the dried steel sludge and core, and the feed speed is controlled by a disc feeder, and the uniform speed is clothed on the belt conveyor.
- the belt conveyor feeds the raw materials into the disc pelletizer for pelletizing; using a water-soluble binder, heating in a closed pressure vessel to 160 ° C, and then spraying the binder into the disc pelletizer to make it Spherical shell. After the spherical shell is formed, it passes through the belt conveyor and the vibrating screen and then enters the next process (baking); the fine material under the vibrating screen is returned to the ball core production line for grinding in the grinding machine.
- Pellet roasting process After the second ball is formed by a disc pelletizer, and then passed through the vibrating sieve, the raw ball after the scraping is sent to the distributing machine by the belt conveyor, and the uniform cloth is applied to the drying bed at the top of the shaft furnace. Heated by hot air at 570 °C. The raw ball is gradually dried and preheated on the drying bed, slowly descending, gradually heating up, and takes about 1 hour; the calcination zone in the hot section of the wind wall is heated to 1150 ° C, which takes about 1.5 hours. It gradually enters the cooling zone and is slowly discharged after being air-cooled twice. The temperature at the time of tapping is about 20 CTC, and the whole process takes about 6 hours.
- the ball After the tapping, the ball is slowly transported away on the chain belt machine and further cooled. It is sent to the vibrating screen. After the crushing of the scraped material, the ball can enter the finished product yard, or directly enter the next process - blast furnace Iron making. 00015% (less than the national emission standard 5mg / the total chromium in the raw material chromium slag is 5. 3%; hexavalent chromium is 1. 3%; Kg is 0. 0005%). The purpose of detoxification pretreatment is achieved. The next step is to enter the blast furnace for complete reduction treatment, and the slag is used very well. The falling strength of the raw balls reached 10 times / average each; the compressive strength reached 10N / average each; and all other indicators reached the national standard.
- Example 6 Preparation of raw materials: Drying chromium slag (water content less than 4%), crushing (ball milling to -200 mesh up to 30%); drying gravity dust ash (water less than 4%), crushing (ball milling to - 200 mesh up to 30% or more); the total amount of nuclear material is 100 tons, taking 70 tons of chromium slag, 29 tons of pulverized coal, 80% syrup, 10% humic acid and 10% ferrous oxide. Tons of adhesive. The total amount of raw material of the spherical shell is calculated as 200 tons, and 3 tons of binder is prepared by taking 197 tons of pellet dust (TFe 55%), 80% of syrup, 10% of humic acid and 10% of ferrous oxide.
- Secondary ball formation (1) Ball core ball formation process
- the two silos are filled with pulverized coal, chromium slag, and the feed rate is controlled by a disc feeder, and the uniform speed is distributed on the belt conveyor.
- the belt conveyor feeds the raw material into the grinding machine (or powerful mixer), then grinds it (or stirs), then sends it to the disc pelletizer through a belt conveyor, dissolves the binder with water, and heats it in a closed pressure vessel. At 160 ° C, the raw material was sprayed in a spray to form a core.
- the core After the core is formed, it passes through the belt conveyor and the vibrating screen and then enters the next process (the spherical shell becomes a ball); The fine material under the sieve is returned to the grinding machine for grinding.
- the two silos are filled with the pellet dust and the core, and the feed speed is controlled by the disc feeder, and the cloth is evenly distributed on the belt conveyor.
- the belt conveyor feeds the raw material into the disc pelletizer to make the ball; the water is dissolved in the adhesive, heated to 160 ° C in a closed pressure vessel, and then sprayed, and the binder is sprayed into the disc pelletizer to make Good spherical shell. After the spherical shell is formed, it passes through the belt conveyor and the vibrating screen and then enters the next process (baking); the fine material under the vibrating screen is returned to the ball core production line for grinding in the grinding machine.
- Pellet roasting process After the second ball is formed by a disc pelletizer, and then passed through the vibrating sieve, the raw ball after the scraping is sent to the distributing machine by the belt conveyor, and the uniform cloth is applied to the drying bed at the top of the shaft furnace. Heated by hot air at 570 °C.
- the raw ball is gradually dried and preheated on the drying bed, slowly descending, gradually heating up, and takes about 1 hour; the calcination zone in the soaking section of the wind wall is heated to 115 CTC, which takes about 1.5 hours, gradually After entering the cooling zone, it is slowly discharged after being air-cooled twice.
- the temperature at the time of tapping is about 20 CTC, and the whole process takes about 6 hours.
- the ball After the tapping, the ball is slowly transported away on the chain belt machine and further cooled. It is sent to the vibrating screen. After the crushing of the scraped material, the ball can enter the finished product yard, or directly enter the next process - blast furnace Iron making. 00018% (less than the national emission standard 5mg / the total chromium in the raw material chromium slag is 5. 05%; hexavalent chromium is 1. 6%; the total chromium of the sinter is 0. 3; hexavalent chromium is 0. 00018% (less than the national emission standard 5mg / Kg is 0. 0005%). The purpose of detoxification pretreatment is achieved. The next step is to enter the blast furnace for complete reduction treatment, and the chromium residue is well utilized. The falling strength of the raw balls reached 8 times/average each; the compressive strength reached 10N/average; and all other indicators reached the national standard.
- Tons In the binder and fuel, enter a mixer, two mixers, two times of water and secondary mixing, (or directly into the two mixers), forming a spherical shell outside the core of the chromium slag, forming a diameter of 5 - 10 mm composite pellets, then sintered into a sintering machine, and subjected to reduction pretreatment of chromium slag; after sintering at a high temperature of 1200 ° C or higher, the sinter is discharged, cooled, crushed, sieved, and finished into the next process - Ironmaking in blast furnace, complete detoxification of chromium residue .
- the above sintering production process refers to the conventional production process of sinter, and the equipment and process conditions do not need to be changed. It is only necessary to replace the amount of dolomite in some or all of the flux with a chromium slag core, that is, adjust the amount of flux. can.
- the total chromium in the raw material chromium slag is 4.9%; the hexavalent chromium is 1. 3%; the total chromium of the sinter is 0. 31; the hexavalent chromium is 0. 00011% (less than the national emission standard 5mg / Kg is 0. 0005%). Achieve the purpose of detoxification pretreatment.
- the next step is to enter the blast furnace for complete reduction treatment, and the chromium residue is well utilized.
- the falling strength of the raw balls reached 8 times/average each; the compressive strength reached 10N/average, and all other indicators reached the national standard.
- Treatment of chromium slag in the chromium slag ball production line; crushing and drying the chromium slag (water content less than 4%, ball milling to -200 mesh up to 50%), taking 158 tons of total nuclear material Chromium slag, 400 tons of iron gravity dust ash, adhesive 20 tons (70% syrup, 20% humic acid and 10% ferrous oxide weight ratio); Machine, make a 2-5 mm diameter core, the semi-finished product after the vibrating screen, enter the sealed special transport vehicle and send it to the batching room of the sintering plant, put the chromium residue core into the sealed silo, and enter the sintering production line.
- the above sintering production process refers to the conventional production process of sinter, and the equipment and process conditions do not need to be changed. It is only necessary to replace the amount of dolomite in some or all of the flux with a chromium slag core, that is, adjust the amount of flux. can.
- the total chromium content of the slag is 1. 8%; the total sinter of the sinter is 0. 28; the hexavalent chromium is 0. 00014% (less than the national emission standard 5mg / Kg is 0. 0005%).
- the purpose of detoxification pretreatment is achieved.
- the next step is to enter the blast furnace for thorough reduction, and the chromium residue is used very well.
- Example 9 Preparation of raw materials: drying the slag (water content less than 4%), crushing (ball milling to -200 mesh up to 40%); drying the gravity dust ash (water less than 4%), crushing (ball milling to - 200 mesh reaches more than 60%); the total amount of nuclear material is 500 tons, taking 300 tons of chromium residue, 190 tons of gravity dust, and 10 tons of adhesive using syrup.
- the total amount of raw materials of the spherical shell is calculated according to 1000 tons, and 980 tons (TFe 55%) of dust removal ash is used for one time, and 80°/ syrup is used. 20% by weight of humic acid 10% and ferrous oxide 10% by weight.
- the two silos are filled with gravity dust ash and chromium slag, and the feed speed is controlled by a disc feeder, and the uniform speed is clothed on the belt conveyor.
- the belt conveyor feeds the raw material into the grinding machine (or powerful mixer), then grinds it (or stirs), then sends it to the disc pelletizer through a belt conveyor, dissolves the binder with water, and heats it in a closed pressure vessel. To At 150 ° C, the raw material was sprayed in a spray to form a core.
- the core After the core is formed, it passes through the belt conveyor and the vibrating screen and then enters the next process (the spherical shell becomes a ball); the fine material under the vibrating screen is returned to the grinding machine for grinding.
- the two silos are filled with steel dust and nucleus, and the feed rate is controlled by a disc feeder.
- the uniform speed is distributed on the belt conveyor.
- the belt conveyor feeds the raw material into a disc pelletizer for pelletizing; the water is dissolved in the binder, heated to 150 ° C in a high pressure sealed container, and then sprayed, and the binder is sprayed into the disc pelletizer. Make a good shell. After the spherical shell is formed, it passes through the belt conveyor and the vibrating screen and then enters the next process (baking); the fine material under the vibrating screen is returned to the ball core production line for grinding in the grinding machine.
- Pellet roasting process after the second ball is formed by the disc pelletizer, and then the raw ball after the vibrating sieve is scraped, the belt is sent to the distributing machine by the belt conveyor, and the uniform cloth is applied to the drying bed at the top of the shaft furnace. Heated by hot air at 570 °C.
- the raw ball is gradually dried and preheated on the drying bed, slowly descending, gradually heating up, and takes about 1 hour; the calcination zone in the hot section of the wind wall is heated to 1150 ° C, which takes about 1.5 hours. It gradually enters the cooling zone and is slowly discharged after being air-cooled twice.
- the temperature at the time of tapping is about 200 °C, and the whole process takes about 6 hours.
- the ball After the tapping, the ball is slowly transported away on the chain belt machine and further cooled. It is sent to the vibrating screen. After the crushing of the scraped material, the ball can enter the finished product yard, or directly enter the next process - blast furnace Iron making. 00019% (less than the national emission standard 5mg / the total chromium in the raw material chromium slag is 5. 36%; hexavalent chromium is 1. 9%; the total chromium of the sinter is 0. 34; hexavalent chromium is 0. 00019% (less than the national emission standard 5mg / Kg is 0. 0005%). To achieve the purpose of detoxification pretreatment.
- Example 10 Preparation of raw materials: Drying of chromium residue (less than 4% moisture), crushing (ball milling to -200 mesh up to 60%) Above); Gravity dust ash drying (moisture less than 4%), crushing (ball milling to -200 mesh up to 60% or more); total nuclear material of the ball is calculated according to 1000 tons, taking 760 tons of chromium slag, 220 pulverized coal ton, A binder of 20 tons was prepared using a weight percentage of syrup 80%, humic acid 10%, and ferrous oxide 10%. The total amount of spherical shell raw materials is calculated according to 2000 tons, taking 1950 tons of iron ore fines (TFe 63%) and using bentonite 50 tons.
- the two silos are filled with pulverized coal, chromium slag, and the feed rate is controlled by a disc feeder, and the uniform speed is distributed on the belt conveyor.
- the belt conveyor feeds the raw material into the grinding machine (or powerful mixer), then grinds it (or stirs), then sends it to the disc pelletizer through a belt conveyor, and uses a water-soluble binder to heat it in a closed pressure vessel.
- the material was sprayed at 160 ° C and sprayed to form a core.
- the core After the core is formed, it passes through the belt conveyor and the vibrating screen and then enters the next process (the spherical shell becomes a ball); the fine material under the vibrating screen is returned to the grinding machine for grinding.
- the two silos are filled with steel dust and nucleus, and the feed rate is controlled by a disc feeder.
- the uniform speed is distributed on the belt conveyor.
- the belt conveyor feeds the raw materials into the disc pelletizer to make the ball; the tap water is used to make the spherical shell. After the spherical shell is formed, it passes through the belt conveyor and the vibrating screen and then enters the next process (baking); the fine material under the vibrating screen is returned to the ball core production line for grinding in the grinding machine.
- Pellet roasting process after the second ball is formed by the disc pelletizer, and then the raw ball after the vibrating sieve is scraped, the belt is sent to the distributing machine by the belt conveyor, and the uniform cloth is applied to the drying bed at the top of the shaft furnace. Heated by hot air at 570 °C.
- the raw ball is gradually dried and preheated on the drying bed, slowly descending, gradually heating up, and takes about 1 hour; the calcination zone in the hot section of the wind wall is heated to 1150 ° C, which takes about 1.5 hours. It gradually enters the cooling zone and is slowly discharged after being air-cooled twice.
- the temperature at the time of tapping is about 200 °C, and the whole process takes about 6 hours.
- the ball after the release is slowly transported away on the chain machine and further cooled, it is sent to vibrate Screening, sifting the ball into the finished product yard, or directly into the next process - blast furnace ironmaking.
- 00017% (less than the national emission standard 5mg / the total chromium in the raw material chromium slag is 5. 15%; hexavalent chromium is 2. 1%; the total chromium of the sinter is 0. 3; hexavalent chromium is 0. 00017% (less than the national emission standard 5mg / Kg is 0. 0005%).
- the next step is to enter the blast furnace for thorough reduction treatment, and the chromium residue is well utilized.
Description
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CN200910253865.8 | 2009-12-01 | ||
CN201010273143.1A CN101942571B (zh) | 2010-09-06 | 2010-09-06 | 铬渣与冶金废料无害化处理及再生利用的方法 |
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Cited By (11)
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CN103232068A (zh) * | 2012-05-19 | 2013-08-07 | 唐翔 | 循环再利用处理铬渣及废水工艺 |
CN103725875A (zh) * | 2013-12-30 | 2014-04-16 | 吴雪健 | 一种高性能的球团矿 |
CN104498707A (zh) * | 2013-12-30 | 2015-04-08 | 吴雪健 | 一种生球团的制造方法 |
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CN109468456A (zh) * | 2018-12-28 | 2019-03-15 | 安徽工业大学 | 一种冶金固废回收有价组分的包覆方法 |
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