WO2022227185A1 - 一种侧顶复合吹熔融还原高铁赤泥的综合利用方法 - Google Patents

一种侧顶复合吹熔融还原高铁赤泥的综合利用方法 Download PDF

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WO2022227185A1
WO2022227185A1 PCT/CN2021/096803 CN2021096803W WO2022227185A1 WO 2022227185 A1 WO2022227185 A1 WO 2022227185A1 CN 2021096803 W CN2021096803 W CN 2021096803W WO 2022227185 A1 WO2022227185 A1 WO 2022227185A1
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reduction
red mud
iron
gas
iron red
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PCT/CN2021/096803
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English (en)
French (fr)
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张廷安
豆志河
吕国志
郭军华
刘燕
张子木
赫冀成
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东北大学
东大有色固废技术研究院(辽宁)有限公司
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Publication of WO2022227185A1 publication Critical patent/WO2022227185A1/zh

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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
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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 comprehensive utilization of Bayer process red mud, in particular to a method for comprehensive utilization of high-speed iron red mud by side-roof composite blowing and melting reduction.
  • the present invention proposes a method for obtaining low-residue high-quality pig iron products by adopting side-roof composite blowing and melting reduction of high-speed iron red mud.
  • the reducing agent is a mixture of one or more of pulverized coal, coke or waste cathode carbon block in any proportion, and the molar ratio of the carbon in the reducing agent to the iron oxide in the high iron red mud is (1.5 ⁇ 6 ): 1;
  • Described slag making agent is calcium source, is one or more in limestone, slaked lime or calcium carbide slag mixed with arbitrary proportions, in calcium source, in calcium oxide and high iron red mud, silicon oxide and aluminum oxide The ratio of the sum of the mass is (0.8 ⁇ 1.5):1; the amount of fluorite added is 8% ⁇ 15% of the calcium oxide.
  • the mixed raw materials are added to the molten pool of the reduction furnace to carry out the reduction reaction.
  • the reduction reaction temperature is 1450-1700° C., and the reaction time is 20-140 min.
  • the mixture is injected into the molten pool of the reduction furnace by side blowing lance.
  • the sodium oxide in the high-speed iron red mud is volatilized at high temperature during the reduction process and enters into the reduction flue gas for enrichment and recovery.
  • a mixed gas of reducing gas and oxygen is sprayed on the side, wherein the reducing gas is one or more mixed gases of hydrogen, carbon monoxide or natural gas mixed in any proportion, and the mixing ratio of reducing gas and oxygen is CO.
  • the molar ratio of , H 2 or (CO+H 2 ) to O 2 is (0.2 ⁇ 1.8):1, or the molar ratio of CH 4 to O 2 in natural gas is (1 ⁇ 2):1.
  • Oxygen-enriched air and gas are injected at the top of the reduction process.
  • Low-sulfur and low-phosphorus pig iron and reduced slag are obtained by compound blowing smelting reduction on the side roof, and the hot reduced slag is used to prepare rock wool products or direct water quenching to prepare cement after quenching and tempering, centrifugation and wire drawing. clinker.
  • the low sulfur and low phosphorus specifically meet the requirements of sulfur ⁇ 0.05%, phosphorus ⁇ 0.05%, and lower than L03 high-quality steel-making pig iron sulfur (less than or equal to 0.07%) and phosphorus ( ⁇ 0.1%) content.
  • the method of the present invention can realize the continuous reduction of high-iron red mud, and directly obtain low-residue and high-quality pig iron products; the reduction rate of iron in the high-iron red mud by the method of the present invention reaches more than 95%, and the sodium oxide recovered in the form of flue gas is recovered at the same time. rate of more than 70%.
  • the CO produced by smelting reduction is fully burned, and the molten pool is heated to ensure the heat balance in the furnace to fully utilize the energy and reduce the comprehensive energy consumption.
  • the reduced slag can be used to prepare products such as rock wool or water quenched as cement raw materials, realizing the high-value utilization of multi-components in high-speed iron red mud.
  • Fig. 1 is the side top composite blowing molten pool reduction furnace adopted by the method of the present invention; wherein 1- raw material feeding port, 2- vortex zone, 3, 4, 5, 6, 7- top blowing spray gun, 8- tail gas discharge port, 9- - Slag outlet, 10- tap hole, 11, 12, 13, 14, 15 - side blowing gun.
  • FIG. 1 The structure of the side-roof composite blowing molten pool reduction furnace adopted in Examples 1 to 3 of the present invention is shown in FIG. 1 .
  • the main components of the high iron red mud used in the embodiment of the present invention are: Fe 2 O 3 41.63%, Al 2 O 3 17.25%, SiO 2 10.20%, TiO 2 8.50%, Na 2 O 6.50%, CaO 1.61% and other substances.
  • the main components of the reducing agent pulverized coal used are: fixed carbon 69.17%, ash 11.13%, and volatile matter 19.42%.
  • the main components of the reducing agent coke used are: fixed carbon 84.5%, ash 12.1%, and volatile matter 2.3%.
  • the main components of the used reducing agent cathode carbon block are: fixed carbon 52.1%, ash content 37.2%, volatile matter 9.1%.
  • the effective CaO content in the lime used is 80%, and the rest are SiO 2 and other substances.
  • the content of CaF 2 in the used fluorite is 86%, and the remaining components are Al 2 O 3 , SiO 2 and other substances.
  • the production content of the present invention is not limited to the use of such raw materials.
  • the reducing agent can also be replaced by pulverized coal, and the amount of fluorite can be reduced; the lime can also be replaced by calcium carbonate or calcium carbide smelting waste residue.
  • a comprehensive utilization method of side roof composite blowing melting reduction high-speed iron red mud comprising the following steps:
  • the mixture is added to the vortex area of the reduction furnace from the vortex feeding port, and it is rolled into the molten pool under the action of the molten pool vortex to carry out the reduction reaction.
  • the reduction reaction temperature was 1650°C, and the reduction reaction time was 20 min.
  • the mixed gas of CO and O 2 is introduced from the side of the reduction furnace, and the molar ratio of CO to O 2 is 0.2:1.
  • oxygen-enriched air and gas are blown into the top to ensure that the CO released by the reduction is fully burned to ensure that the furnace is fully burned. Internal heat balance.
  • a comprehensive utilization method of side roof composite blowing melting reduction high-speed iron red mud comprising the following steps:
  • the mixture is added to the vortex area of the reduction furnace from the vortex feeding port, and it is rolled into the molten pool under the action of the molten pool vortex to carry out the reduction reaction.
  • the reduction reaction temperature was 1450°C, and the reduction reaction time was 140 min.
  • the mixed gas of CO and O 2 is introduced from the side of the reduction furnace, and the molar ratio of CO to O 2 is 1.8:1.
  • oxygen-enriched air and gas are blown into the top to ensure that the CO released by the reduction is fully burned to ensure that the furnace is fully burned. Internal heat balance.
  • a comprehensive utilization method of side roof composite blowing melting reduction high-speed iron red mud comprising the following steps:
  • the mixture is added to the vortex area of the reduction furnace from the vortex feeding port, and it is rolled into the molten pool under the action of the molten pool vortex to carry out the reduction reaction.
  • the reduction reaction temperature was 1500°C
  • the reduction reaction time was 60 min.
  • the mixed gas of CO and O 2 is introduced from the side of the reduction furnace, and the molar ratio of CO and O 2 is 1:1.
  • oxygen-enriched air and gas are blown into the top to ensure that the CO released by the reduction is fully burned to ensure that the furnace is fully burned. Internal heat balance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Iron (AREA)

Abstract

一种侧顶复合吹熔融还原高铁赤泥的综合利用方法，主要包括以下步骤：将高铁赤泥与还原剂、造渣剂、萤石混合；将混合后的原料加入到还原炉熔池内，进行还原反应，还原过程中侧部喷吹还原气体和氧气的混合气体，顶部喷吹富氧空气和燃气；经侧顶复合吹熔融还原得到低硫低磷生铁和还原渣，热态还原渣经调质、离心、拉丝工序后用于制备岩棉产品或直接水淬制备水泥熟料。利用本发明的侧顶复合吹熔融还原，可实现高铁赤泥连续还原，直接获得低残留高品质生铁产品，铁的还原率能达到95%以上，同时以烟气形式回收的氧化钠的收率达到70%以上。

Description

一种侧顶复合吹熔融还原高铁赤泥的综合利用方法 技术领域
本发明属于拜耳法赤泥综合利用领域，具体涉及一种侧顶复合吹熔融还原的高铁赤泥的综合利用方法。
 背景技术
随着我国钢铁工业和铝工业的快速发展，铁、铝矿资源日趋紧张，我国正以不足世界3%的铝土矿储量生产着世界50%以上的氧化铝和40%以上的电解铝。我国的铁矿资源和铝土矿对外依存以超过60%。致使我国钢铁工业和铝工业的生成成本大幅增加。同时，我国大量的低品质铁、铝土矿资源却没有得到有效的综合利用，闲置的高铁铝土矿资源在15亿t以上，此外，全球的赤泥库存估计超过27亿t，且正在以1.2亿t的速度在增长。因此，高铁赤泥的综合利用技术对我国铁、铝资源的安全供给具有重要的战略意义。
现有的高铁赤泥的综合利用方法虽然可以实现赤泥中铁/铝等多组分的利用，但多存在不能直接获得生铁产品，或者还原生铁过程需要铁浴等辅助手段以及无法实现赤泥大规模消纳等问题。
 技术解决方案
本发明针对现有高铁拜耳法赤泥利用技术存在的不足，提出一种采用侧顶复合吹熔融还原高铁赤泥，获得低残留高品质生铁产品的方法。
本发明的技术方案按以下步骤进行：
（1）将高铁赤泥（三水铝石矿和一水铝石矿产生的赤泥）为原料，与还原剂、造渣剂、萤石混合。其中，所述还原剂为粉煤、焦炭或废阴极碳块中的一种或几种以任意比例混合的混合物，还原剂中的碳与高铁赤泥中氧化铁的摩尔比为(1.5~6):1；所述造渣剂即为钙源，是石灰石、熟石灰或电石渣中的一种或几种以任意比例混合的混合物，钙源中氧化钙与高铁赤泥中氧化硅和氧化铝质量之和的比为(0.8~1.5):1；萤石添加量为氧化钙量的8%~15%。
（2）将混合后的原料加入到还原炉熔池内，进行还原反应。所述还原反应温度为1450~1700℃，反应时间为20~140min。混合料的加入方式有以下两种：由涡流加料口将混合料加入到还原炉涡流区内，在熔池涡流作用下将其卷入熔池内部；或者采用富氧空气和还原气作为载气将混合料由侧吹喷枪喷吹加入到还原炉熔池。
还原过程主要反应如下：
3H 2+Fe 2O 3=3H 2O+2Fe
3C+Fe 2O 3=3CO+2Fe
3CO+Fe 2O 3=3CO 2+2Fe
CH 4+Fe 2O 3=CO 2+2H 2O+2Fe
高铁赤泥中的氧化钠在还原过程中高温挥发进入到还原烟气中富集进行回收。
还原过程中侧部喷吹还原气体和氧气的混合气体，其中还原气体为氢气、一氧化碳或天然气中的一种或几种以任意比例混合的混合气体，还原气体与氧气的混合比例为其中的CO、H 2或（CO+H 2）与O 2摩尔比为(0.2~1.8):1，或者天然气中CH 4与O 2的摩尔比为(1~2):1。还原过程顶部喷吹富氧空气和燃气。
（3）经侧顶复合吹熔融还原得到低硫低磷生铁和还原渣（即熔融渣），热态还原渣经调质、离心、拉丝工序后用于制备岩棉产品或直接水淬制备水泥熟料。所述的低硫低磷具体为，满足硫<0.05%，磷<0.05%，低于L03优质炼钢生铁硫（小于等于0.07%）、磷(<0.1%)含量的要求。
 有益效果
本发明的特点和有益效果：
（1）本发明方法能实现高铁赤泥连续还原，直接获得低残留高品质生铁产品；采用本发明方法高铁赤泥中铁的还原率达到95%以上，同时以烟气形式回收的氧化钠的收率达到70%以上。将熔融还原产生的CO充分燃烧，对熔池进行提温加热，保证炉内热平衡实现能量的充分利用，降低了综合能耗。
（2）采用涡流熔融还原，可实现反应物料快速卷吸加入，强化物料的弥散，加速还原效率。
（3）还原渣经调质可用于制备岩棉等产品或水淬作为水泥原料，实现了高铁赤泥中多组分的高值化利用。
 附图说明
图1为本发明方法采用的侧顶复合吹熔池还原炉；其中1-原料加入口，2-涡流区，3,4,5,6,7-顶吹喷枪，8-尾气排放口，9-出渣口，10-出铁口，11,12,13,14,15-侧吹喷枪。
 本发明的实施方式
本发明实施例1~3的采用的侧顶复合吹熔池还原炉结构如图1所示。
本发明实施例所采用的高铁赤泥主要成分为：Fe 2O 341.63%，Al 2O 317.25%，SiO 210.20%，TiO 28.50%，Na 2O6.50%，CaO1.61%及其它物质。
所采用的还原剂粉煤的主要成分为：固定碳69.17%，灰分11.13%，挥发分19.42%。
所采用的还原剂焦炭的主要成分为：固定碳84.5%，灰分12.1%，挥发分2.3%。
所采用的还原剂阴极炭块的主要成分为：固定碳52.1%，灰分37.2%，挥发分9.1%。
所采用的石灰中有效CaO含量为80%，其余成分为SiO 2及其它物质。
所采用的萤石中CaF 2含量为86%，其余成分为Al 2O 3、SiO 2及其它物质。
本发明所述的生产内容不局限于采用该类原料，如还原剂还可以采用煤粉代替，并降低萤石用量；石灰也可以采用碳酸钙或电石冶炼废渣替代。
实施例1
一种侧顶复合吹熔融还原高铁赤泥的综合利用方法，包括以下步骤：
（1）将高铁赤泥与还原剂、石灰石、萤石混合，其中还原剂为粉煤，还原剂中的碳与高铁赤泥中氧化铁的摩尔比为1.5:1；添加的石灰石中氧化钙与高铁赤泥中氧化硅和氧化铝质量之和的比为1.5:1；萤石添加量为钙源中氧化钙量的8%。
（2）将混合料由涡流加料口加入到还原炉涡流区内，在熔池涡流作用下将其卷入熔池内部，进行还原反应。还原反应温度为1650℃，还原反应时间为20min。还原过程中CO与O 2的混合气体从还原炉侧部通入，CO与O 2摩尔比为0.2:1，同时顶部吹入富氧空气和燃气，保证还原释放的CO得到充分燃烧以保证炉内热平衡。
（3）经侧顶复合吹熔融还原得到低硫低磷生铁和熔融渣，热态还原渣经调质、离心、拉丝工序后用于制备岩棉产品。本实施例中，高铁赤泥中的铁的还原率为96.5%，同时以烟气形式回收的氧化钠的收率为85%。
实施例2
一种侧顶复合吹熔融还原高铁赤泥的综合利用方法，包括以下步骤：
（1）将高铁赤泥与还原剂、石灰石、萤石混合，其中还原剂为废阴极碳块，还原剂中的碳与高铁赤泥中氧化铁的摩尔比为6.5:1；添加的石灰石中氧化钙与高铁赤泥中氧化硅和氧化铝质量之和的比为0.8:1；萤石添加量为氧化钙量的15%。
（2）将混合料由涡流加料口加入到还原炉涡流区内，在熔池涡流作用下将其卷入熔池内部，进行还原反应。还原反应温度为1450℃，还原反应时间为140min。还原过程中CO与O 2的混合气体从还原炉侧部通入，CO与O 2摩尔比为1.8:1，同时顶部吹入富氧空气和燃气，保证还原释放的CO得到充分燃烧以保证炉内热平衡。
（3）经侧顶复合吹熔融还原得到低硫低磷生铁和熔融渣，热态还原渣经调质、离心、拉丝工序后用于制备岩棉产品。本实施例中，高铁赤泥中的铁的还原率为95.0%，同时以烟气形式回收的氧化钠的收率为71%。
实施例3
一种侧顶复合吹熔融还原高铁赤泥的综合利用方法，包括以下步骤：
（1）将高铁赤泥与还原剂、石灰石、萤石混合，其中还原剂为废阴极碳块，还原剂中的碳与高铁赤泥中氧化铁的摩尔比为4:1；添加的石灰石中氧化钙与高铁赤泥中氧化硅和氧化铝质量之和的比为1:1；萤石添加量为氧化钙量的10%。
（2）将混合料由涡流加料口加入到还原炉涡流区内，在熔池涡流作用下将其卷入熔池内部，进行还原反应。还原反应温度为1500℃，还原反应时间为60min。还原过程中CO与O 2的混合气体从还原炉侧部通入，CO与O 2摩尔比为1:1，同时顶部吹入富氧空气和燃气，保证还原释放的CO得到充分燃烧以保证炉内热平衡。
（3）经侧顶复合吹熔融还原得到低硫低磷生铁和熔融渣，热态还原渣经调质、离心、拉丝工序后用于制备岩棉产品。本实施例中，高铁赤泥中的铁的还原率为95.8%，同时以烟气形式回收的氧化钠的收率为78%。

Claims (4)

  1. 一种侧顶复合吹熔融还原高铁赤泥的综合利用方法，其特征在于，包括以下步骤：
    （1）将高铁赤泥与还原剂、造渣剂、萤石混合；所述还原剂中的碳与高铁赤泥中氧化铁的摩尔比为(1.5~6):1；所述造渣剂中氧化钙与高铁赤泥中氧化硅和氧化铝质量之和的比为(0.8~1.5):1；萤石添加量为氧化钙量的8%~15%；
    （2）将混合后的原料加入到还原炉熔池内，进行还原反应；所述还原反应温度为1450~1700℃，反应时间为20~140min；
    还原过程中侧部喷吹还原气体和氧气的混合气体，顶部喷吹富氧空气和燃气；其中，还原气体为氢气、一氧化碳或天然气中的一种或几种以任意比例混合的混合气体，还原气体与氧气的混合比例为其中的CO、H 2或（CO+H 2）与O 2摩尔比为(0.2~1.8):1，或天然气中CH 4与O 2的摩尔比为(1~2):1；
    （3）经侧顶复合吹熔融还原得到低硫低磷生铁和还原渣，热态还原渣经调质、离心、拉丝工序后用于制备岩棉产品或直接水淬制备水泥熟料。
  2. 根据权利要求1所述的一种侧顶复合吹熔融还原高铁赤泥的综合利用方法，其特征在于，所述步骤（1）中，所述还原剂为粉煤、焦炭或废阴极碳块中的一种或几种以任意比例混合的混合物；所述造渣剂即为钙源，是石灰石、熟石灰或电石渣中的一种或几种以任意比例混合的混合物。
  3. 根据权利要求1所述的一种侧顶复合吹熔融还原高铁赤泥的综合利用方法，其特征在于，所述步骤（2）中，混合料的加入方式有以下两种：由涡流加料口将混合料加入到还原炉涡流区内，在熔池涡流作用下将其卷入熔池内部；或者采用富氧空气和还原气体作为载气将混合料由侧吹喷枪喷吹加入到还原炉熔池。
  4. 根据权利要求1所述的一种侧顶复合吹熔融还原高铁赤泥的综合利用方法，其特征在于，高铁赤泥中铁的还原率达到95%以上，同时以烟气形式回收的氧化钠的收率达到70%以上。
PCT/CN2021/096803 2021-04-28 2021-05-28 一种侧顶复合吹熔融还原高铁赤泥的综合利用方法 WO2022227185A1 (zh)

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