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WO2018014093A1 - Procédé de production de fer à partir de minerai de fer contenant du phosphore - Google Patents

Procédé de production de fer à partir de minerai de fer contenant du phosphore Download PDF

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Publication number
WO2018014093A1
WO2018014093A1 PCT/BG2016/000020 BG2016000020W WO2018014093A1 WO 2018014093 A1 WO2018014093 A1 WO 2018014093A1 BG 2016000020 W BG2016000020 W BG 2016000020W WO 2018014093 A1 WO2018014093 A1 WO 2018014093A1
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WIPO (PCT)
Prior art keywords
iron
phosphorus
concentrate
mixture
coal
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Ceased
Application number
PCT/BG2016/000020
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English (en)
Russian (ru)
Inventor
Крассимир ИОНКОВ
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Individual
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Priority to PCT/BG2016/000020 priority Critical patent/WO2018014093A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • 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
    • C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • 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 invention relates to the enrichment of minerals and ferrous metallurgy, and more particularly relates to a method for removing sulfur and phosphorus from iron ore and coal through their simultaneous heat treatment with the addition of alkali, followed by enrichment, acid leaching, direct reduction of iron by a hard reducer and melting of iron in result of eddy currents.
  • the main way to produce cast iron is a blast furnace process.
  • the inefficiency of sulfur and phosphorus removal is reflected in the steel industry, where this process continues through oxygen purging and the addition of powder reagents in molten iron.
  • the inefficient removal of phosphorus from iron ore and sulfur from coal limits the amount of deposits suitable for the extraction of raw materials for the blast furnace process.
  • the alkalinity modulus in the blast furnace is maintained at or slightly more than 1, mainly due to the addition of limestone and dolomite.
  • a method for removing phosphorus from iron ores is proposed, as described in Chinese patent CN 104451124, including crushing, enrichment of high intensity magnetic separation, and the resulting concentrate is mixed with anthracite in a ratio of 1.5: 1 to 1: 1.
  • the following steps are granulation, magnetizing firing at 800-850 ° C, fast cooling, grinding to 90% - 0074 mm, selective flocculation with the addition of potassium oleate, mixing and low-intensity magnetic separation.
  • a concentrate of 65% iron was obtained and phosphorus is reduced to 0.1%.
  • Physical separation methods are effective when phosphorus is present in the form of individual minerals, and also due to a significant difference in their properties from those of iron minerals, they can be removed using magnetic separation, flotation, or using a more complex enrichment scheme, as described in the patent.
  • Water-soluble salts are removed by aqueous leaching and unburned coke is returned by flotation.
  • the magnetic fraction is recovered from a low intensity magnetic separation pulp.
  • Phosphorus from the iron concentrate is leached with sulfuric acid, followed by low-intensity magnetic separation again.
  • An embodiment of the method shows that it is possible to obtain a concentrate with 65% iron and 0.12% phosphorus. Magnetizing firing with NaOH and acid leaching are effective in removing phosphorus, but this process does not include the removal of harmful components of coal.
  • Microwave heating is one of the most promising directions for the direct reduction of iron oxides, because many intermediate processes can be avoided and the absence of countercurrent hot gases allows the use of fine concentrates or ores without the manufacture of pellets. It combines more simplicity in execution, sparing use of a reducer, uniform heat distribution in the mixture volume and low level of carbon dioxide emissions into the atmosphere. Iron and carbon oxides are good receivers of microwave energy, but after metallization, adsorption drops sharply due to the skin effect. Further, the process of supplying heat can be continued through electric arc, induction or other type of heating.
  • the methods described above relate to the removal of sulfur and phosphorus in the processes of enrichment or metallurgy, but their removal in depth, together with waste in practice, is usually achieved in steel production.
  • the objective of the present invention is to develop a method for the production of cast iron with a low content of phosphorus and sulfur from widespread iron ores and coal, as sulfur, phosphorus and gangue are initially removed by enrichment and hydrometallurgy and then subjected to direct reduction of iron and induction from the obtained iron ore concentrate and semi-coke swimming trunks get cast iron, suitable for steel production.
  • Another objective of the present invention is to reduce carbon dioxide emissions and improve the thermal efficiency of the process.
  • the aim of this invention is the effective removal of sulfur and phosphorus from iron ore and coal, in order to increase the number of deposits that may be used for the metallurgical industry.
  • World reserves of phosphorus-containing iron ores are estimated at approximately 370 Mt (megatons), but due to the weak removal of phosphorus, they are considered unusable.
  • Specific conditions for the formation of iron ore deposits and a high degree of hydration determine the inclusion of phosphorus and some rare elements in limonite in the form of a solid solution. When heated to 300 to 350 ° C, goethite separates water and crystallizes into hematite.
  • Sodium hydroxide and hydrochloric acid are obtained in situ by chlor-alkali electrolysis of brine.
  • the semi-coke and iron concentrate obtained in this step are used in the metallurgical industry, in which the mixture is heated using microwave radiation, and the result of direct reduction of iron is melted by the induction of eddy currents. This is done by mixing Iron concentrate with semi-coke and quicklime, then dried, and then served in a tubular microwave oven, where it is heated to a temperature of 1200 - 1250 ° C.
  • the recovery process is simplified by using microwave heating, acting in the full volume of the mixture, semi-coke is used only as a reducing agent, and the absence of countercurrent hot gases also eliminates the problem of the removal of small particles.
  • microwave heating acting in the full volume of the mixture
  • semi-coke is used only as a reducing agent
  • the absence of countercurrent hot gases also eliminates the problem of the removal of small particles.
  • the efficiency of heating and melting of the reduced iron decreases in the induction furnace.
  • a layer of quicklime is laid in the lower part of the furnace, which, after melting the iron, is smelted on the surface of cast iron by cleaning the metal of residual amounts of sulfur, phosphorus, Si0 2 and A1 2 0z.
  • the end product is a cast iron suitable for steelmaking.
  • Figure 1 is a flowchart of a method for producing iron from iron ore containing phosphorus and steam coal in accordance with the present invention.
  • the method includes two main stages, enclosed in rectangles with dashed lines in figure 1:
  • the first stage begins with the mixing of 104 pre-crushed to 90% - 5 mm iron ore containing phosphorus 101 with steam coal 102 having approximately the same particle size, which are fed to a conveyor belt conveyor using metering devices.
  • 25 to 32% NaOH 129 solution is added to it and the mixture is simultaneously dried 106 and homogenized at a temperature of 120-150 0 ⁇ to a moisture content of less than 5%.
  • the optimal ratio between ore 101 and coal 102 is determined by extracting from them iron concentrate 146 and semicoke 147, which are mixed in stage B for direct reduction of iron 206 in a 3: 1 ratio.
  • One example of a suitable ratio of iron ore containing 48-50% Fe, Si0 2 . 10 - 12%, AO3 - 5 - 6% and P 0.6 - 0.8% and coal with an ash content of 15-20%, 1-3% sulfur and volatile substances below 30% is 1: 1.
  • a 15% solution of NaOH 129 is added to this mixture.
  • Sodium hydroxide 129 and hydrochloric acid 128 are obtained in situ by chlor-alkali electrolysis of 127 brine 103 based membrane technology, which is well known in practice. On-site picking reduces costs, eliminates the risk of transporting hazardous chemicals, and does not have to increase the concentration of solutions more than necessary for the process.
  • the dried mixture 107 is subjected to heat treatment at a temperature of 800-1000 ° C in a microwave tube furnace with an emitter operating frequency of 2.45 GHz for a duration of -30-45 minutes. It is equipped with a hopper and feeder in such a way that it operates continuously and with adjustable power. It is possible to heat the furnace to replace traditionally used resistive elements made of SiC, ferhal and others.
  • a microwave tube furnace with an emitter operating frequency of 2.45 GHz for a duration of -30-45 minutes. It is equipped with a hopper and feeder in such a way that it operates continuously and with adjustable power. It is possible to heat the furnace to replace traditionally used resistive elements made of SiC, ferhal and others.
  • hematite recrystallizes to magnetite, coal pyrolysis, and a chemical reaction of NaOH with acidic oxide of rocks, sulfur, and phosphorus.
  • the main product of these reactions is liquid glass, which melts at this temperature, and a significant part of the harmful components dissolve in this liquid
  • the tube furnace is made of a material that reflects microwave radiation, which has thermal and abrasion resistance and maintains an alkaline effect at high temperatures. Microwave heating during heat treatment 108 provides a uniform distribution of heat throughout the volume of mixture 107 and under these conditions, carbon particles 102 in contact with those ores 101 take part of the oxygen from hematite, after which it crystallizes into magnetite having ferrimagnetic properties. First, the reaction occurs with the formation of carbon monoxide, which is also a reducing agent.
  • Pulp 111 is fed to a rod or ball mill, in which grinding is controlled within 40 - 45% - 0.074 mm.
  • the next step is to remove the semi-coke 117 from the pulp 113 through flotation 116.
  • the pulp 113 is conditioned 114 in a vessel with constant stirring with a collector reagent such as diesel fuel or kerosene 200-250 g / t (pre-emulsified) and as a foaming agent Methyl isobutyl carbinol (MIBK) is 8-10 g / t.
  • MIBK Methyl isobutyl carbinol
  • Semi-coke 117 leach 131 with hydrochloric acid 128 at pH 1.5 - 2 for 15-30 minutes at ambient temperature in a reactor with continuous stirring, after which pulp 133 is fed to neutralization 135 with NaOH 129 in a vessel with a stirrer preventing deposition . Neutral pH protects the filters from corrosion. Salt pulp 137 is washed 139 countercurrent washing and thickening. Pulp 141 is sent to filter 145 using a slurry pump, where the semi-coke is dehydrated to obtain a filter cake of semi-coke 147. Chamber product 118 from flotation 116 is fed with low-intensity magnetic separation 119 and the magnetic fraction is coarse iron concentrate 121.
  • magnetite it 121 it is additionally crushed122, and then the concentrate 123 is subjected to the following low-intensity magnetic separation 124.
  • an iron cone is obtained centrate with 63-65% Fe.
  • Physical separation contributes to the removal of most phosphorus and sulfur, and their deep removal is achieved by leaching 130 hydrochloric acid 128.
  • Acid pulp 132 is neutralized 134 with NaOH 129, after which salts of pulp 136 are washed 138 by countercurrent washing.
  • the thickened pulp 140 from this operation 138 is fed to a filtration 144, in which the iron concentrate is dried to a moisture content of about 15% and the cake 146 is transported and stored in a hopper.
  • Waste 120, 125 from low-intensity magnetic separation 119, 124, overflow 142, 143 from countercurrent washes 136, 139 salts and filtrates 148, 149 from filtration 144, 145 are collected and transported 150 to the tailings using slurry pumps or by gravity.
  • stage B iron concentrate 146 is mixed 202 with semi-coke 147 in a weight ratio of 3: 1, and 2-4% quicklime 201 is added to the resulting mixture.
  • the amount of reducing agent is higher than stoichiometric, since with a decrease in carbon, the metallization efficiency deteriorates.
  • dosing devices they (146, 147 and 201) are fed on a conveyor belt, which transports them to the dryer drum.
  • the mixture 203 is dried 204 at a temperature of 120 to 150 ° C, and then the mixture 205 is transported to the furnace hopper for direct reduction of iron 206.
  • the process 206 is performed by a tube furnace equipped with a microwave heater and a screw feeder with an adjustable rotation speed.
  • the dried mixture 205 is heated to a temperature of 1200-1250 ° C, which activates the reduction process 206. It is similar to that already described by heat treatment 108, but at this temperature it is carried out in depth to direct reduction of iron. Volumetric heating in the furnace and in the absence of a stream of hot gases is a significant advantage, which allows them to avoid premature consolidation. Heating can be done using microwave radiation with a frequency of 2.45 GHz, but experimental studies have shown that the process proceeds more efficiently when using microwave radiation, the millimeter range [5]. Magnetite decreases first to wustite, and then to metallic iron. The degree of metallization is usually 90-97%.
  • the purpose of CaO 201 obtained in step 206 is to react with residual amounts of sulfur, phosphorus and acid oxides, and then the resulting compounds can be exported to slag 210 during melting 208.
  • the hot channels and unreacted semi-coke 207 are discharged directly into the induction furnace for melting 208 eddy currents.
  • a layer of flux - quicklime 201 Lined at the bottom of the oven a layer of flux - quicklime 201, which helps to complete the process of removing sulfur and phosphorus from iron.
  • CaO 201 floats to the surface of cast iron 209 in the form of slag cleansing the metal and preventing foaming.
  • the reduction process continues in the induction furnace for the remaining 3 to 10% of unreduced iron, which reduces the ego loss in slag 210.
  • the resulting cast iron 209 can be cast into billets or drained in oxygen furnaces for steel production.
  • the final product of the method according to the invention is cast iron 209 with a low

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Le procédé consiste initialement à éliminer le soufre, le phosphore et les roches stériles du minerai et du charbon par une combustion magnétisante à partir d'un additif alcalin et d'une lixiviation acide. Le mélange de roches broyées, de charbon et de NaOH est chauffé à une température de 800 - 1000 ° С par chauffage par microondes, processus au cours duquel, outre la réduction, on effectue une pyrolyse du charbon et on assiste à une réaction chimique entre l'alcali et les minéraux des roches stériles. Le semi-coke ainsi obtenu est séparé par flottaison, et la magnétite par séparation magnétique de faible intensité. Les deux produits sont lixiviés avec de l'acide chlorhydrique pour éliminer le phosphore et le soufre en profondeur, après quoi les pulpes sont neutralisées jusqu'à atteindre un pH de 6,0 - 7,0. Les sels sont rincés par contre-lavage. Après filtration du concentré de fer et du semi-coke, ceux-ci sont mélangés, on ajoute du CaO, et on soumet le tout à un chauffage par microondes jusqu'à une température de 1200 - 1250 ° С pour effectuer une réduction directe du fer. Les lingots obtenus par la réduction directe du fer sont envoyés dans un four à induction au-dessus d'une couche de chaux vive où ils sont fondus et où les quantités résiduelles de soufre et de phosphore sont éliminées dans les scories. Le produit final consiste en de la fonte convenant à la production d'acier.
PCT/BG2016/000020 2016-07-21 2016-07-21 Procédé de production de fer à partir de minerai de fer contenant du phosphore Ceased WO2018014093A1 (fr)

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PCT/BG2016/000020 WO2018014093A1 (fr) 2016-07-21 2016-07-21 Procédé de production de fer à partir de minerai de fer contenant du phosphore

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PCT/BG2016/000020 WO2018014093A1 (fr) 2016-07-21 2016-07-21 Procédé de production de fer à partir de minerai de fer contenant du phosphore

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108842056A (zh) * 2018-09-07 2018-11-20 安徽工业大学 一种鲕状赤铁矿快速加热还原制备还原铁粉的方法
CN109160744A (zh) * 2018-10-25 2019-01-08 青岛盈坤源国际贸易有限公司 赤泥磁化焙烧综合利用系统及工艺
CN116590022A (zh) * 2023-04-25 2023-08-15 湖北三峡实验室 一种利用磷石膏和硫铁矿生产酸性土壤调理剂的方法
CN117551882A (zh) * 2022-08-03 2024-02-13 攀枝花市先力矿业有限公司 高磷钛精矿的降磷方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KZ15838B (fr) * 2003-04-16 2009-07-15
WO2014009769A1 (fr) * 2012-07-10 2014-01-16 Arcelormittal Investigacion Y Desarrollo, S.L. Procédé de traitement d'un minerai de fer contenant du phosphore, le minerai de fer ayant une gangue
CN103725869A (zh) * 2013-12-24 2014-04-16 师兆忠 硝酸-盐酸联合处理硫铁矿烧渣制取铁精矿工艺

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KZ15838B (fr) * 2003-04-16 2009-07-15
WO2014009769A1 (fr) * 2012-07-10 2014-01-16 Arcelormittal Investigacion Y Desarrollo, S.L. Procédé de traitement d'un minerai de fer contenant du phosphore, le minerai de fer ayant une gangue
CN103725869A (zh) * 2013-12-24 2014-04-16 师兆忠 硝酸-盐酸联合处理硫铁矿烧渣制取铁精矿工艺

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108842056A (zh) * 2018-09-07 2018-11-20 安徽工业大学 一种鲕状赤铁矿快速加热还原制备还原铁粉的方法
CN109160744A (zh) * 2018-10-25 2019-01-08 青岛盈坤源国际贸易有限公司 赤泥磁化焙烧综合利用系统及工艺
CN117551882A (zh) * 2022-08-03 2024-02-13 攀枝花市先力矿业有限公司 高磷钛精矿的降磷方法
CN116590022A (zh) * 2023-04-25 2023-08-15 湖北三峡实验室 一种利用磷石膏和硫铁矿生产酸性土壤调理剂的方法

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