WO2021244616A1 - 基于气基能源的两步法高磷含铁资源铁磷高效分离的方法 - Google Patents

基于气基能源的两步法高磷含铁资源铁磷高效分离的方法 Download PDF

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WO2021244616A1
WO2021244616A1 PCT/CN2021/098176 CN2021098176W WO2021244616A1 WO 2021244616 A1 WO2021244616 A1 WO 2021244616A1 CN 2021098176 W CN2021098176 W CN 2021098176W WO 2021244616 A1 WO2021244616 A1 WO 2021244616A1
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iron
phosphorus
gas
agglomerates
melting
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PCT/CN2021/098176
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English (en)
French (fr)
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王静松
王广
薛庆国
郭占成
左海滨
佘雪峰
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北京科技大学
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B11/00—Making pig-iron other than in blast furnaces
    • 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
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • 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
    • C22B1/16—Sintering; Agglomerating
    • 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
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • 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
    • 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
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
    • 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

Definitions

  • the invention belongs to the field of ironmaking and comprehensive utilization of resources, and relates to a method for separating iron and phosphorus from high-phosphorus iron-containing resources and preparing high-quality steel-making pig iron (or semi-steel), and is used for the development and utilization of high-phosphorus iron-containing resources.
  • the physical beneficiation method mainly uses the difference in the physical properties of iron minerals and gangue impurities to achieve the enrichment of iron and the removal of phosphorus to a certain extent.
  • Commonly used methods include reverse flotation, high gradient magnetic separation, and gravity separation.
  • the physical separation method is relatively simple, because the mineral intercalation in oolitic hematite is extremely fine, and often coexists with or wraps with oolitic chlorite and phosphorus-containing minerals, there is a general presence of concentrates by conventional physical separation methods. Problems such as low iron grade, low iron recovery rate, and poor phosphorus removal effect.
  • Phosphorus reduction by leaching is mainly divided into two methods: chemical leaching and microbial leaching.
  • the chemical leaching method uses acidic media such as sulfuric acid, nitric acid or hydrochloric acid to leaching iron ore to selectively dissolve the phosphate minerals in the ore, thereby achieving the purpose of reducing phosphorus.
  • the chemical leaching method can effectively realize the separation of iron and phosphorus.
  • this method consumes more acid and has a higher cost, which easily leads to the dissolution of iron-containing minerals in the ore and forms iron loss; although the microbial method has low cost and environmental pollution It has many advantages, but the production cycle is longer.
  • oolitic high-phosphorus hematite the minerals are packed and densely embedded in layers, and the monomer is difficult to dissociate.
  • the hematite is gradually reduced to metallic iron, and iron particles and gangues aggregate and grow separately. It changes the original combination state of iron-containing minerals and gangue minerals, and the efficient separation of iron and phosphorus can be achieved through the subsequent grinding-separation process.
  • a certain dephosphorization agent needs to be added during the reduction process.
  • the direct reduction-magnetic separation method to treat oolitic hematite is superior to the above-mentioned methods in terms of product iron grade, recovery rate and dephosphorization effect.
  • residues in the product There are some phosphorus, high production cost, large consumption of dephosphorization agent, etc.
  • the final CO-reduced ore sample is melted and separated to obtain a
  • the iron sample containing 0.27% phosphorus and the ore sample reduced by H 2 are melted and separated to obtain an iron sample containing 0.33% phosphorus.
  • this process is more reasonable than coal-based reduction smelting, but the process of reducing ore smelting is the key to the control of phosphorus in iron. Due to the relatively long smelting cycle of electric furnaces, the slag-gold reaction is relatively sufficient, and part of the phosphorus in the slag is reduced, which is difficult Obtain molten iron or semi-steel with lower phosphorus content.
  • Commonly used pretreatment equipment includes molten iron ladle (or torpedo tanker) and dedicated dephosphorization converter.
  • Commonly used dephosphorization slag systems are soda-based and lime-based. Soda can significantly reduce the phosphorus content and can obtain molten iron with a phosphorus content of less than 0.1%.
  • the converter dephosphorization hot metal has less temperature drop, no pre-desiliconization, no powder spraying, simple and reliable process equipment, low slag amount, and the obtained dephosphorization slag contains high phosphorus, which has good fertilizer efficiency on crops, but the process cannot simultaneously desulfurize.
  • the hot metal pretreatment dephosphorization process can only treat low-phosphorus hot metal with a phosphorus content of about 0.10%.
  • the double slag method should be used. The process is technically difficult. High, high production cost.
  • the purpose of the present invention is to find a gas-based energy-based comprehensive utilization method of high-phosphorus iron-containing resources that is technically feasible, economically reasonable and suitable for industrialization, and opens up a process for the clean comprehensive utilization of low-grade high-phosphorus-containing iron resources and gas-based energy.
  • the invention uses natural gas as the reductant (after reforming) and the heating fuel during the reduction-melting process. Compared with the process using coal as the reductant and energy, low-phosphorus pig iron (or semi-steel) can be produced cleanly and gas pollution is reduced.
  • the reduction of phosphorus minerals in iron-containing resources can be significantly inhibited, and the phosphorus in pig iron (or semi-steel) can be reduced in principle.
  • the present invention controls the reduction process of metal iron gas phase carburization and internal solid carburizing agent, so as to further achieve iron-phosphorus separation through high temperature and rapid slag iron melting
  • the present invention realizes the rapid smelting of metallized charge through a smelting furnace using natural gas as energy, thereby further completing iron-phosphorus separation and metal product extraction
  • the liquid metal and molten slag water quenching process is an important measure to ensure that the slag-gold contact reaction time is reduced and the phosphorus content in the pig iron (or semi-steel) is reduced.
  • a gas-based energy-based two-step high-phosphorus iron-containing resource iron and phosphorus efficient separation method wherein the method includes:
  • Step 1 Add high-phosphorus iron resources, carburizing agent, flux, and binder according to a predetermined ratio and mix them, add an appropriate amount of water to moisten, mix again and press to form a mass with a certain compressive strength;
  • Step 2 After the agglomerates are dried, they are loaded into a shaft furnace for gas-based reduction.
  • the reducing gas comes from the reforming of natural gas and the tail gas of the reduction furnace to produce metalized agglomerates;
  • Step 3 Discharge the metalized agglomerates, directly heat them into the melting furnace, use natural gas as fuel for rapid melting, and produce solid granular pig iron and glass slag after water quenching and magnetic separation.
  • step 1 the compressive strength of the agglomerates is greater than 200N/piece.
  • step 2 the reducing gas composition is H 2 /CO>1.0.
  • the total iron content of the high-phosphorus iron-containing resource is between 30% and 70%, the phosphorus content is between 0.1% and 1.5%, and the particle size is less than 1 mm.
  • the gas-based smelting furnace uses natural gas burners to quickly heat the metallized agglomerates to achieve rapid slag and iron smelting.
  • the molten pig iron or semi-steel and molten slag are quickly discharged into the pool for processing. Water quenching.
  • step 3 the melting temperature is 1450-1600°C, and the melting time is less than 10 min.
  • the carburizing agent is anthracite coal or coke powder, in which the fixed carbon is about 80%, the ash content is below 15%, and the particle size is less than 1 mm.
  • the flux is limestone and technical grade sodium carbonate, and the particle size is less than 1 mm.
  • the agglomerate alkalinity is controlled at 1.0-1.6, the internal carburizing agent is 0-2% of the weight of the iron-containing material, and the sodium carbonate ratio is 0-3% of the weight of the iron-containing material;
  • the end-point reduction degree of the metalized agglomerate is 85-95%, and the end-point gas-phase carburizing amount of the metalized agglomerate is controlled at 2 to 3%.
  • the obtained solid granular pig iron (or semi-steel) has a phosphorus content of 0.05% to 0.1%, which meets steelmaking requirements.
  • the raw material of the invention has strong adaptability, simple operation, strong controllability, fast reaction speed, high production efficiency, high dephosphorization efficiency, and easy realization of automation.
  • natural gas is used as a reducing agent and slag iron melting process energy source, and pollutant discharge Less and environmentally friendly.
  • the adopted pre-reduction process namely gas-based shaft furnace direct reduction technology, is a cutting-edge technology in the field of ironmaking and has a good development trend at home and abroad.
  • FIG 1 shows the principle flow of the process of the present invention.
  • a and/or B can mean: A alone exists, A and B exist at the same time, and B exists alone.
  • the present invention takes gas-based reduction shaft furnace and gas-based melting furnace as main equipment, and auxiliary equipment includes feeding system, silo, electronic belt scale, mixer, pelletizer, dryer, discharge machine, belt conveying equipment And airtight high temperature chain plate feeder.
  • auxiliary equipment includes feeding system, silo, electronic belt scale, mixer, pelletizer, dryer, discharge machine, belt conveying equipment And airtight high temperature chain plate feeder.
  • the raw material conditions are:
  • the total iron content of high-phosphorus iron resources is between 30% and 70%, the content of P is between 0.1% and 1.5%, and the particle size is less than 1mm above 100%.
  • the carburizing agent is anthracite coal or coke powder, in which the fixed carbon is about 80%, the ash content is below 15%, and the particle size is above 100% and less than 1mm.
  • the flux is limestone and industrial-grade sodium carbonate, with a particle size of more than 100% and less than 1mm.
  • the main production process is:
  • the reducing gas comes from natural gas reforming to produce metalized agglomerates
  • a high-phosphorus iron resource with a P content of 0.8% and a TFe grade of 55% a coal powder with a weight of 2% of the high-phosphorus iron resource and a high-phosphorus iron resource by weight 3 % Sodium carbonate, 2% by weight of high-phosphorus iron-containing resources, as well as limestone powder that can adjust the binary alkalinity of the slag system to 1.5, are conveyed to the mixer through a belt for mixing, and the water content of the mixture is adjusted to 7%.
  • the mixed material is conveyed through a belt to a roller ball press to form agglomerates, the pressure is 15MPa, and the size is 40 ⁇ 30 ⁇ 20mm pillow shape.
  • the agglomerates are loaded into the shaft furnace, and are gradually reduced by the hot reducing gas.
  • the reducing gas comes from natural gas reforming.
  • the gas temperature is 1000°C
  • the reduction time is 2h
  • the end point reduction degree of the metalized agglomerate is 90%
  • the metalized agglomerates are discharged and directly heated into the gas-based melting furnace.
  • the melting furnace uses natural gas as fuel for rapid melting.
  • the melting temperature is 1500°C.
  • the molten pig iron and molten slag are quickly discharged into the pool for processing. Water quenching, crushing and magnetic separation of the water quenched iron and slag to obtain solid granular pig iron and water quenched glass slag.
  • Solid granular pig iron can be used as a charge for steelmaking, and glass slag can be used as a raw material for the production of cement.
  • the composition of pig iron obtained by melting is shown in Table 1.
  • Binder and limestone powder that can adjust the binary alkalinity of the slag system to 1.2 are conveyed to the mixer through a belt for mixing, and the moisture of the mixed material is adjusted to 7%.
  • the mixed material is conveyed through a belt to a roller ball press to form agglomerates, the pressure is 15MPa, and the size is 40 ⁇ 30 ⁇ 20mm pillow shape. After being dried, the agglomerates are loaded into a shaft furnace, and are gradually reduced by hot reducing gas.
  • the reducing gas comes from natural gas reforming.
  • the gas temperature is 950°C
  • the reduction time is 4h
  • the end point reduction degree of the metalized agglomerate is 95%
  • the metallized agglomerates are discharged and directly charged into the melting furnace.
  • the melting furnace uses natural gas as fuel for rapid melting.
  • the melting temperature is 1550°C.
  • the liquid semi-steel and molten slag are quickly discharged into the pool for water
  • the water-quenched semi-steel and slag are crushed and magnetically separated to obtain solid granular semi-steel and water-quenched glass slag.
  • Solid granular semi-steel can be used as a charge for steelmaking, and glass slag can be used as a raw material for cement production.
  • the composition of the semi-steel obtained by melting is shown in Table 2.
  • the invention discloses a two-step high-phosphorus iron-containing resource iron-phosphorus efficient separation method based on gas-based energy, and belongs to the field of ironmaking and comprehensive utilization of resources. It relates to a method for separating iron and phosphorus from high-phosphorus-containing iron resources and preparing high-quality steel-making pig iron (or semi-steel), which is used for the development and utilization of high-phosphorus-containing iron resources. It is characterized by using high-phosphorus iron resources, carburizing agent, flux, and binder as raw materials, through batching, mixing, agglomeration, gas-based shaft furnace reduction, gas furnace rapid melting, and water quenching separation.
  • High-quality solid granular pig iron (or semi-steel) with a phosphorus content of 0.05% to 0.1% can be used as a raw material for steelmaking, and the gangue is condensed into slag and then water-quenched into a glass state, which can be used as a raw material for the production of cement.
  • the process uses natural gas as the energy source and gets rid of the dependence on coal, thereby reducing pollution and carbon emissions caused by coal. At the same time, it can make full use of high-phosphorus iron resources, reduce waste generation, and achieve cleaner production. This method has simple process, high efficiency and thorough separation of iron and phosphorus.
  • the solid granular pig iron (or semi-steel) obtained by the separation can meet the needs of steelmaking production in the iron and steel industry. It has good social and economic benefits, and is especially suitable for oil and gas resources, high phosphorus Promotion in areas with rich iron resources and high environmental requirements.

Abstract

本发明公开了一种基于气基能源的两步法高磷含铁资源铁磷高效分离的方法，属于炼铁和资源综合利用领域。该方法包括：将高磷含铁资源、渗碳剂、熔剂、粘结剂按预定配比添加并混匀，加适量水分润湿，再次混匀后压制成具有一定抗压强度的团块；团块经烘干后，装入竖炉进行气基还原，还原气体来自于天然气与还原炉尾气重整，制得金属化团块；将金属化团块排出，直接热装入熔分炉，以天然气为燃料进行快速熔分，经水淬和磁选，生产出固态粒状生铁和玻璃渣。本发明原料适应性强、操作简单、可控性强、反应速度快、生产效率高、脱磷效率高、易于实现自动化。

Description

基于气基能源的两步法高磷含铁资源铁磷高效分离的方法 技术领域
本发明属于炼铁和资源综合利用领域，涉及高磷含铁资源中铁磷分离和制备高品质炼钢生铁(或半钢)的方法，用于高磷含铁资源的开发利用。
背景技术
现代钢铁工业的发展已经历较长的历史时期，世界范围内，随着高品位铁矿资源的消耗，铁矿石呈劣化趋势，矿石中硅、铝、磷、烧损含量不断增加。国内外高磷铁矿资源储量巨大，其综合利用问题一直是矿业和冶金学科领域的重点研究方向之一。磷会损害钢的脆性，在低温时尤为明显(俗称“冷脆”)，必须将其降到合理水平。一般情况，铁矿石中的磷含量要小于0.2％，炼钢生铁中的磷含量要小于0.1％。高磷铁矿的合理利用核心在于如何经济有效地实现铁磷分离并提高铁品位，从而获得满足高炉炼铁要求的矿石或满足炼钢要求的洁净铁源。针对上述问题，国内外很多研究学者进行了诸多方面的探索，总体来说有两种思路：一是在矿石入炉前进行预处理脱磷，如选矿、湿法浸出、直接还原-分选等方法，获得合格的铁精矿用于炼铁生产；二是在冶炼中采用针对性处理脱除磷，如铁水预脱磷。
物理选矿法主要是借助铁矿物和脉石杂质物理性质的差异，在一定程度上实现铁元素的富集和磷元素的脱除，常用的有反浮选、高梯度磁选、重选等。虽然物理分选方法工艺相对简单，但由于鲕状赤铁矿中的矿物嵌布粒度极为细微，且经常与鲕绿泥石和含磷矿物共生或相互包裹，采用常规物理选矿法普遍存在精矿铁品位低、铁回收率低、磷脱除效果差等问题。
浸出法降磷主要分为化学浸矿法和微生物浸矿法两种方法。化学浸矿法是用硫酸、硝酸或盐酸等酸性介质对铁矿石进行浸矿，选择性地使矿石中的磷矿物溶解，从而达到降磷的目的。化学浸出法可以有效地实现铁和磷元素的分离，然而该方法耗酸较多、成本较高，容易导致矿石中含铁矿物的溶解而形成铁损；微生物法虽然有成本低、环境污染小诸多优势，但是生产周期较长。
鲕状高磷赤铁矿中，矿物层层包裹、嵌布致密，单体解离困难，但是经过直接还原焙烧后，赤铁矿被逐步还原为金属铁，铁颗粒和脉石分别聚集、长大，改变了含铁矿物和脉石矿物的原始结合状态，通过后续的磨矿-分选工艺便可实现铁-磷的高效分离。为了获得高的铁精矿品位、铁回收率和磷脱除率，还原过程中需要添加一定的脱磷剂。直接还原-磁选法处理鲕状赤铁矿在产品铁品位、回收率和脱磷效果方面都优于上述各种方法，但若投入工业应用还存在一系列技术 经济问题，如产品中仍残留有部分磷、生产成本高、脱磷剂消耗量大等。
有研究考察了高磷铁矿含碳球团还原熔分对脱磷的影响，基于铁矿含碳球团还原熔分特点和磷、铁矿物选择性还原特性，产品为与高炉生铁性质类似的珠铁，铁中的磷含量受渣系碱度、熔剂(碳酸钠、萤石等)，提高碱度有助于降低珠铁中磷含量，但是该工艺严重依赖于煤炭资源，然而使用煤炭会导致尾气中SOx、NOx排放增加，污染大气环境。同时，由于没有成熟的还原熔分设备，该工艺很难实现工业化生产。也有研究采用气体还原-电炉熔分的技术处理高磷铁矿实现铁-磷分离，磷矿物在固态还原阶段不能被还原，在熔分阶段通过渣铁熔分脱除磷和脉石，从而获得高品质生铁。研究表明，采用气基直接还原处理高磷矿，在800℃下分别用CO和H 2还原矿粉2h，然后再1600℃下加入CaO进行熔融分离30min，最终CO还原矿样经熔化分离得到含磷0.27％的铁样，H 2还原矿样经熔化分离得到含磷0.33％的铁样。该工艺原理上较煤基还原熔分更合理，但是还原矿熔分过程是铁中磷控制的关键，由于电炉冶炼周期相对较长，渣-金反应较为充分，部分渣中磷被还原，难以获得磷含量较低的铁水或半钢。
当铁水中磷含量较高时必须通过铁水预处理将其脱除。常用的预处理设备有铁水包(或鱼雷罐车)和专用的脱磷转炉。常用的脱磷渣系有苏打系和石灰系，苏打可以显著降低磷含量，可以得到含磷低于0.1％的铁水。转炉脱磷铁水温降少，无须预先脱硅，无须喷粉、工艺设备简单可靠，渣量少，得到的脱磷渣含磷高，对农作物有很好的肥效，但是过程中不能同步脱硫，生产效率降低，且设备投资高；铁水包和鱼雷罐中脱磷设备投资相对较低，可以同时脱磷和脱硫，对炼钢生产不会造成不利影响，但是有渣量大、温降多、废渣污染环境且不能做肥料等不足。而且实际生产中铁水预处理脱磷工艺只能处理磷含量0.10％左右的低磷铁水，对高磷铁水的脱磷存在一定困难，对于中高磷含量的铁水要采用双渣法，过程对技术难度高，生产成本高。
虽然世界范围内在铁矿石降磷各个方面取得了很大的进展，但总的来说还存在着很多问题，主要是难以同时满足脱磷率高、金属回收率高、精矿产品含铁品位高的要求；不同工艺的原料适应性、投资成本、技术复杂度、生产效率等也限制了其工业化应用。特别是对于油气资源、高磷含铁资源丰富且环境要求高的地区，更没有合适且成熟的高磷含铁资源利用技术。
发明内容
本发明的目的在于找到一种技术上可行、经济上合理且适于工业化的基于气基能源的高磷含铁资源综合利用方法，打通低品位高磷含铁资源气基能源清洁综合利用的流程，从而充分利用现有低品位铁矿资源，满足钢铁工业可持续发展的 要求。本发明以天然气为还原剂(重整后)和还原-熔分过程加热燃料，与以煤炭作还原剂和能源的工艺相比，可清洁制得低磷生铁(或半钢)，减少气体污染物和碳排放；与高磷铁矿煤基还原相比，由于本发明还原温度低，可明显抑制含铁资源中磷矿物的还原，从原理上可以降低生铁(或半钢)中的磷含量；与现有的高磷铁矿气基还原相比，本发明通过控制还原过程金属铁气相渗碳和内配固体渗碳剂，从而为进一步通过高温快速渣铁熔分实现铁-磷分离提供重要基础；不同于现有的基于电能的高磷铁矿熔分利用工艺，本发明通过以天然气为能源的熔分炉实现金属化炉料快速熔分从而进一步完成铁-磷分离和金属产品提质，能耗更低；液态金属和熔渣水淬工序是保证减少渣金接触反应时间进而减少生铁(或半钢)中磷含量的重要措施，也是金属化炉料熔分过程能够快速通畅进行的重要保证。综合分析本发明全流程的优点可知，本发明相比于现有的高磷含铁资源的利用技术，更易于实现工业化，更低碳，更环保，特别适合于在油气资源、高磷含铁资源丰富且环境要求高的地区推广应用。
根据本发明技术方案，提供一种基于气基能源的两步法高磷含铁资源铁磷高效分离的方法，其中，所述方法包括：
步骤1：将高磷含铁资源、渗碳剂、熔剂、粘结剂按预定配比添加并混匀，加适量水分润湿，再次混匀后压制成具有一定抗压强度的团块；
步骤2：团块经烘干后，装入竖炉进行气基还原，还原气体来自于天然气与还原炉尾气重整，制得金属化团块；
步骤3：将金属化团块排出，直接热装入熔分炉，以天然气为燃料进行快速熔分，经水淬和磁选，生产出固态粒状生铁和玻璃渣。
进一步的，步骤1中，所述团块的抗压强度大于200N/个。
进一步的，步骤2中，所述还原气体组成为H 2/CO>1.0。
进一步的，步骤1中，高磷含铁资源的全铁含量在30～70％之间，磷含量在0.1～1.5％，粒度小于1mm。
进一步的，步骤3中，气基熔分炉采用天燃气烧嘴对金属化团块进行快速加热，实现渣铁快速熔分，熔分后的液态生铁或半钢和熔渣迅速排入水池进行水淬。
进一步的，步骤3中，熔分温度为1450～1600℃，熔分时间小于10min。
进一步的，渗碳剂为无烟煤或焦粉，其中的固定碳在80％左右，灰分在15％以下，粒度小于1mm。
进一步的，熔剂为石灰石和工业级碳酸钠，粒度小于1mm。
进一步的，团块碱度控制在1.0～1.6，内配渗碳剂为含铁物料重量的0～2％，碳酸钠配比为含铁物料重量的0～3％；
进一步的，金属化团块的终点还原度85～95％，金属化团块终点气相渗碳量 控制在2～3％。
进一步的，所得固态粒状生铁(或半钢)磷含量为0.05％～0.1％，满足炼钢要求。
本发明技术方案的有益效果：
本发明原料适应性强、操作简单、可控性强、反应速度快、生产效率高、脱磷效率高、易于实现自动化，此外，以天然气为还原剂和渣铁熔分过程能源，污染物排放少，环境友好。所采用的预还原工艺即气基竖炉直接还原技术是炼铁领域的前沿技术，在国内外均有较好的发展趋势。
附图说明
图1为本发明工艺的原则流程。
具体实施方式
这里将详细地对示例性实施例进行说明，其示例表示在附图中。下面的描述涉及附图时，除非另有表示，不同附图中的相同数字表示相同或相似的要素。以下示例性实施例中所描述的实施方式并不代表与本公开相一致的所有实施方式。相反，它们仅是与如所附权利要求书中所详述的、本公开的一些方面相一致的装置和方法的例子。
本公开的说明书和权利要求书中的术语“第一”、“第二”等是用于区别类似的对象而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本公开的实施例例如能够以除了在这里图示或描述的那些以外的顺序实施。
此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
多个，包括两个或者两个以上。
和/或，应当理解，对于本公开中使用的术语“和/或”，其仅仅是一种描述关联对象的关联关系，表示可以存在三种关系。例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。
本发明以气基还原竖炉和气基熔分炉为主要设备，辅助设备包括上料系统、料仓、电子皮带秤、混料机、造球机、烘干机、出料机、皮带输送设备和气密高温链板式给矿机。具体的生产过程是：
原料条件为：
高磷含铁资源的全铁含量在30～70％之间，P含量在0.1～1.5％，粒度100％以上小于1mm。
渗碳剂为无烟煤或焦粉，其中的固定碳在80％左右，灰分在15％以下，粒度达到100％以上小于1mm。
熔剂为石灰石和工业级碳酸钠，粒度达到100％以上小于1mm。
主要生产工艺流程为：
(1)将高磷含铁资源、渗碳剂、熔剂、粘结剂按预定配比添加，加适量水分润湿，再次混匀后压制成具有较高抗压强度的团块；
(2)团块经烘干后，装入竖炉进行气基还原，还原气体来自于天然气重整，制得金属化团块；
(3)将金属化团块排出，直接热装入燃气炉，进行快速熔分，经水淬和磁选，生产出可作为炼钢原料的固态粒状生铁(或半钢)和可作为水泥原料的玻璃渣。
实施例1
按照图1所示的工艺流程，将某P含量为0.8％、TFe品位为55％的高磷含铁资源、重量为高磷含铁资源2％的煤粉、重量为高磷含铁资源3％的碳酸钠、重量为高磷含铁资源2％的粘结剂以及可将渣系二元碱度调节至1.5的石灰石粉经过皮带输送至混料机混匀，并调节混匀料水分至7％。将混合好的混匀料经皮带输送至对辊压球机制成团块，压力为15MPa，尺寸为40×30×20mm的枕状。团块经干燥后装入竖炉，被热还原气逐步还原，还原气体来自于天然气重整，气体温度为1000℃，还原时间为2h，金属化团块终点还原度90％，终点渗碳量2.0％。将金属化团块排出，直接热装入气基熔分炉，熔分炉以天然气为燃料，进行快速熔分，熔分温度1500℃，熔分后的液态生铁和熔渣迅速排入水池进行水淬，将水淬铁和渣进行破碎和磁选分离，得到固态粒状生铁和水淬玻璃渣。固态粒状生铁可以用作炼钢炉料，玻璃渣可以用作生产水泥的原料。熔分所得生铁的成分如表1所示。
表1 生铁主要成分
Figure PCTCN2021098176-appb-000001
实施例2
按照图1所示的工艺流程，将某P含量为0.3％、TFe品位为65％的高磷含铁资源、重量为高磷含铁资源2％的碳酸钠、重量为高磷含铁资源2％的粘结剂 以及可将渣系二元碱度调节至1.2的石灰石粉经过皮带输送至混料机混匀，并调节混匀料水分至7％。将混合好的混匀料经皮带输送至对辊压球机制成团块，压力为15MPa，尺寸为40×30×20mm的枕状。团块经干燥后装入竖炉，被热还原气逐步还原，还原气体来自于天然气重整，气体温度为950℃，还原时间为4h，金属化团块终点还原度95％，终点渗碳量4.0％。将金属化团块排出，直接热装入熔分炉，熔分炉以天然气为燃料，进行快速熔分，熔分温度1550℃，熔分后的液态半钢和熔渣迅速排入水池进行水淬，将水淬半钢和渣进行破碎和磁选分离，得到固态粒状半钢和水淬玻璃渣。固态粒状半钢可以用作炼钢炉料，玻璃渣可以用作生产水泥的原料。熔分所得半钢的成分如表2所示。
表2 生铁主要成分
Figure PCTCN2021098176-appb-000002
本发明公开了一种基于气基能源的两步法高磷含铁资源铁磷高效分离的方法，属于炼铁和资源综合利用领域。涉及高磷含铁资源中铁磷分离和制备高品质炼钢生铁(或半钢)的方法，用于高磷含铁资源的开发利用。其特征在于利用高磷含铁资源、渗碳剂、熔剂、粘结剂为原料，经过配料、混匀、造块、气基竖炉还原、燃气炉快速熔分、水淬分离等工序制得磷含量在0.05％～0.1％的高品质固态粒状生铁(或半钢)。生产出的固态粒状生铁(或半钢)可以作为炼钢的原料，脉石凝聚成渣经水淬后成玻璃态，可以用作生产水泥的原料。该工艺以天然气做能源，摆脱了对煤炭的依赖，从而可以减少煤炭造成的污染和碳排放，同时可以充分利用高磷含铁资源，减少废弃物产生，实现清洁生产。此方法工艺简单、效率高、铁磷分离彻底，分离所得固态粒状生铁(或半钢)可以满足钢铁工业炼钢生产的需求，具有较好的社会和经济效益，特别适合在油气资源、高磷含铁资源丰富且环境要求高的地区推广。
上面结合附图对本发明的实施例进行了描述，但是本发明并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本发明的启示下，在不脱离本发明宗旨和权利要求所保护的范围情况下，还可做出很多形式，这些均属于本发明的保护之内。

Claims (10)

  1. 一种基于气基能源的两步法高磷含铁资源铁磷高效分离的方法，其特征在于，所述方法包括：
    步骤1：将高磷含铁资源、渗碳剂、熔剂、粘结剂按预定配比添加并混匀，加适量水分润湿，再次混匀后压制成具有一定抗压强度的团块；
    步骤2：团块经烘干后，装入竖炉进行气基还原，还原气体来自于天然气与还原炉尾气重整，制得金属化团块；
    步骤3：将金属化团块排出，直接热装入熔分炉，以天然气为燃料进行快速熔分，经水淬和磁选，生产出固态粒状生铁和玻璃渣。
  2. 根据权利要求1所述的方法，其特征在于，步骤1中，所述团块的抗压强度大于200N/个。
  3. 根据权利要求1所述的方法，其特征在于，步骤2中，所述还原气体组成为H 2/CO>1.0。
  4. 根据权利要求1所述的方法，其特征在于，步骤1中，高磷含铁资源的全铁含量在30～70％之间，磷含量在0.1～1.5％，粒度小于1mm。
  5. 根据权利要求1所述的方法，其特征在于，步骤3中，气基熔分炉采用天燃气烧嘴对金属化团块进行快速加热，实现渣铁快速熔分，熔分后的液态生铁或半钢和熔渣迅速排入水池进行水淬；熔分温度为1450～1600℃，熔分时间小于10min。
  6. 根据权利要求1所述的方法，其特征在于，步骤1中，渗碳剂为无烟煤或焦粉，其中的固定碳在80％左右，灰分在15％以下，粒度小于1mm。
  7. 根据权利要求1所述的方法，其特征在于，步骤1中，熔剂为石灰石和工业级碳酸钠，粒度小于1mm。
  8. 根据权利要求1所述的方法，其特征在于，步骤1中，团块碱度控制在1.0～1.6，内配渗碳剂为含铁物料重量的0～2％，碳酸钠配比为含铁物料重量的0～3％；
  9. 根据权利要求1所述的方法，其特征在于，步骤2中，金属化团块的终点还原度85～95％，金属化团块终点气相渗碳量控制在2～3％。
  10. 根据权利要求1所述的方法，其特征在于，所得固态粒状生铁磷含量为0.05％～0.1％，满足炼钢要求。
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