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WO2020087593A1 - 自熔性复合球团的制备方法 - Google Patents

自熔性复合球团的制备方法 Download PDF

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Publication number
WO2020087593A1
WO2020087593A1 PCT/CN2018/116833 CN2018116833W WO2020087593A1 WO 2020087593 A1 WO2020087593 A1 WO 2020087593A1 CN 2018116833 W CN2018116833 W CN 2018116833W WO 2020087593 A1 WO2020087593 A1 WO 2020087593A1
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Prior art keywords
parts
composite
self
pellets
preparation
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English (en)
French (fr)
Inventor
佘雪峰
钟海
王静松
薛庆国
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • 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
    • C22B1/2413—Binding; Briquetting ; Granulating enduration of pellets

Definitions

  • the invention belongs to the technical field of iron and steel metallurgy, and in particular relates to a preparation method of self-fusion composite pellets.
  • the existing composite flux pellets process by preparing the pellets into double-layer structure pellets, such as a self-fluxing composite metallized pellets disclosed in patent CN104745809A and its production process, it includes a core,
  • the outer shell is composed of iron ore concentrate, limestone, coal powder, and cement in a ratio of 330: 300 to 350: 80 to 120: 6 to 9;
  • the outer shell is made of iron concentrate and bentonite in a mass ratio of 1320: 22 to 25
  • the proportion of the core is 20-25mm, and the thickness of the shell is 5-10mm.
  • Another example is a production method of solvent-based composite carbon-containing pellets for blast furnace disclosed in patent CN104975173A.
  • the raw material composition of mixture A is 65-80% iron concentrate, 1-2% binder, and 10-20% carbonaceous material. .
  • the mixture A is added with water and mixed to make a self-fusible pellet core with a particle size of 5-7 mm.
  • the raw material composition of Mixture B is 75-85% iron concentrate, 1-2% binder, and 5-15% carbonaceous material.
  • Mixing material B is added to the tempering material A to make pellets to produce green pellets containing carbon pellets; after roasting the green pellets, finished flux composite carbon pellets are prepared.
  • the metallurgical properties and microstructure of the above-mentioned composite pellet mineral products are superior to conventional flux pellets.
  • the green ball has poor spheroidization and poor toughness, and the larger amount of binder affects the taste of the finished pellets, and the physical properties of the composite pellets are still not The physical properties of acid pellets are good, and the metallurgical properties of pellets are not good.
  • the technical problem to be solved by the present invention is to provide a method for preparing self-fusible composite pellets.
  • the self-fusible composite pellets prepared by this method solve the problem of high energy consumption and low productivity in the production process of traditional pellets Technical problems, improve the metallurgical properties of pellets.
  • the preparation method of the self-fusible composite pellet provided by the present invention includes the following steps:
  • the raw material composition of Mixture A includes 15 to 25 parts by mass of coke, 8 to 20 parts of fat coal and 50 to 100 parts of quicklime, mixed evenly;
  • the mixed particles A wrapped with the film are mixed with concentrate, magnesite powder and composite binder to make a remix; wherein, according to the mass fraction, the mixed particles A are 80-200 parts, concentrate iron ore 100-300 parts, magnesite powder 20-50 parts, composite binder 20-80 parts, and adjust the amount of mixed particles A and magnesite powder to make the pellet ternary base Degree (CaO 2 + MgO) / SiO 2 is 0.6-1.2;
  • the self-fusible composite pellets of the present invention fully mix and wrap coke, fat coal and quicklime into fine particles through the mixture A. Without the hindrance of the binder, the carbonaceous material can be fully contacted with limestone.
  • the limestone is at a high temperature
  • the lower decomposition produces CO 2 , which improves the coal gasification reaction speed. At high temperature, its CO diffuses outward to the remix and contacts with it, diffuses toward the iron concentrate, and fully contacts to increase the iron concentrate ’s lower temperature. Under the reduction efficiency, improve the kinetic conditions of the reaction.
  • Mixture A made of coke and fat coal makes it have higher porosity and cohesive force, which is conducive to the reduction reaction and molding of the fine particles; further through the film, including the mixing of the mixed particles A, reducing or not
  • the toughness of the mixed particles A can still be plastically toughened to ensure the thermal strength requirements for the furnace.
  • the film layer of the present invention guarantees that the mixed particle A has a certain compressive deformation resistance without adding a binder, and on the other hand, the applicant found that the bonding of the composite binder based on the above remixed particles And the ratio of the added mixed particles A and other remixes are limited. When the finished pellets are impacted in the blast furnace, even if the mixed particles A breaks, it will not cause the whole pellets to break.
  • mixture A further includes 1-10 parts by mass of bentonite or cement.
  • the film material further includes 1 to 10 parts by mass of ethyl cellulose, 1 to 10 parts of gelatin, 1 to 10 parts of coke, and 1 to 8 parts of sodium humate.
  • ethyl cellulose, gelatin and sodium humate makes the film have a certain adhesion, better adhere to the surface of the mixed particles A, and has good deformation toughness, improve the drop strength and compressive strength of the pellets ;
  • coke makes the film layer have a certain porosity, and further improve the reduction kinetic conditions.
  • the thickness of the film encapsulating the mixed particles A is 0.5-3 mm.
  • the remixed composite binder includes 10-50 parts by mass of bentonite, 5-20 parts of phenol resin, 5-20 parts of liquid paraffin, and 3-12 parts of sticky wood powder .
  • the composite binder further includes 8-25 parts by mass of asphalt and 3-20 parts of polyethyleneimine.
  • the composite binder is composed of 35 to 44 parts by mass of bentonite, 8 to 12 parts of phenol resin, 8 to 12 parts of liquid paraffin, 7 to 10 parts of sticky wood powder, 12 ⁇ 20 parts of asphalt and 8-12 parts of polyethyleneimine compound.
  • the preparation method of the composite binder is:
  • the composite binder formed by the joint action of various binders such as bentonite, sticky wood powder, phenolic resin, etc., bentonite and sticky wood powder have a strong affinity bonding function, while sticky wood powder and High-molecular polymer polyethyleneimine is used together with good compatibility.
  • the adhesion of polyethyleneimine matrix to sticky wood powder can promote the dispersion of wood powder, prevent particle agglomeration, improve the strength of pellet products, and make raw balls During the impact, the pellets slide with each other, so that the plastic deformation does not break, and the falling strength of the green ball is improved.
  • the use of sticky wood powder can also improve the hydrophilicity of the remix, promote the rapid formation of pellets, and increase pellet production.
  • the compounding of polyethyleneimine with various adhesives further improves the elasticity and toughness of the adhesive, significantly improves the performance of the composite adhesive, and ensures the requirements for the raw pellets to enter the furnace and the thermal strength requirements during the production process.
  • the temperature during the high-temperature consolidation in step (7) is 1100-1250 ° C, and the time is 35-50 minutes.
  • the size of the composite pellet made in the step (6) is 30-45 mm.
  • the self-fusible composite pellets prepared by the method of the present invention have the advantages of both carbon-containing pellets and flux pellets, and improve the high-temperature metallurgical properties of pellets.
  • the pellets have very little binder addition, good adhesion, and high iron grade of pellets; at the same time, they also have excellent compressive strength.
  • the cold state of the self-fusible composite pellets prepared by the preparation method of the present invention The compressive strength increases.
  • the experiment proves that the self-fusible composite pellets prepared according to the preparation method of the present invention have a cold compressive strength higher than 2440N / piece and a falling strength greater than 8 times / piece, which fully meets the requirements of the blast furnace ironmaking charge.
  • its high-temperature compressive strength is significantly higher than the pellets produced by the existing technology, which can achieve efficient smelting.
  • the self-fusible composite pellet film material according to the present invention is composed of 1 part by mass of ethyl cellulose, 1 part of gelatin, 1 part of coke and 1 part of sodium humate, and evenly added appropriate amount of water. Made into thin film solvent.
  • Raw materials 10 parts bentonite, 5 parts phenolic resin, 5 parts liquid paraffin, 3 parts sticky wood powder;
  • Raw materials 40 parts bentonite, 10 parts phenolic resin, 10 parts liquid paraffin, 8 parts sticky wood powder;
  • the preparation method is the same as that described in Example 4.
  • Raw materials 25 parts of bentonite, 11 parts of phenolic resin, 10 parts of liquid paraffin, 5 parts of sticky wood powder, 8 parts of asphalt, and 3 parts of polyethyleneimine;
  • Raw materials 20 parts bentonite, 9 parts phenolic resin, 11 parts liquid paraffin, 6 parts sticky wood powder, 25 parts asphalt, and 20 parts polyethyleneimine
  • the preparation method is the same as described in Example 6.
  • Raw materials 35 parts of bentonite, 8 parts of phenolic resin, 8 parts of liquid paraffin, 7 parts of sticky wood powder, 12 parts of asphalt, and 8 parts of polyethyleneimine.
  • the preparation method is the same as described in Example 6.
  • Raw materials 44 parts of bentonite, 12 parts of phenolic resin, 12 parts of liquid paraffin, 10 parts of sticky wood powder, 20 parts of asphalt, and 12 parts of polyethyleneimine.
  • the preparation method is the same as described in Example 6.
  • Raw materials 40 parts of bentonite, 10 parts of phenolic resin, 10 parts of liquid paraffin, 8 parts of sticky wood powder, 16 parts of asphalt and 10 parts of polyethyleneimine;
  • the preparation method is the same as described in Example 6.
  • a method for preparing self-fusible composite pellets includes the following steps:
  • the raw material composition of Mixture A includes 15 parts by mass of coke, 8 parts of fat coal, and 50 parts of quicklime, mixed evenly;
  • the mixed particles A wrapped with the film are mixed with concentrate iron ore, magnesite powder and the composite binder prepared in Example 4 to make a remix; where, calculated according to the mass parts, the The mixed particle A is 80 parts, the concentrate iron ore is 100 parts, the magnesite powder is 20 parts, the composite binder is 20 parts, and the dosage of the mixed particle A and the magnesite powder is adjusted to make the pellet ternary alkalinity (CaO 2 + MgO) / SiO 2 is 0.6-1.2;
  • the dried composite pellets undergo high-temperature consolidation in a reduction kiln, where the temperature is 1100-1250 ° C and the time is 35-50 minutes to obtain high-temperature reduced self-fusible composite pellets.
  • the preparation method of self-fusible composite pellets includes the following steps:
  • the raw material composition of Mixture A includes 25 parts by mass of coke, 20 parts of fat coal, and 100 parts of quicklime, mixed evenly;
  • the mixed particles A wrapped with the film are mixed with concentrate iron ore, magnesite powder and the composite binder prepared in Example 5 to make a remix; wherein, calculated according to the mass parts, The mixed particle A is 200 parts, the concentrate iron ore is 300 parts, the magnesite powder is 50 parts, the composite binder is 80 parts, and the dosage of the mixed particle A and the magnesite powder is adjusted to make the pellet ternary alkalinity (CaO 2 + MgO) / SiO 2 is 0.6-1.2;
  • the dried composite pellets undergo high-temperature consolidation in a reduction kiln to obtain high-temperature reduced self-fusible composite pellets, of which the temperature is 1100-1250 ° C and the time is 35-50min.
  • the preparation method of self-fusible composite pellets includes the following steps:
  • the raw material composition of Mixture A includes 25 parts by mass of coke, 20 parts of fat coal, and 100 parts of quicklime, mixed evenly;
  • the mixed particles A wrapped with the film are mixed with concentrate iron ore, magnesite powder and the composite binder prepared in Example 10 to make a remix; wherein, calculated according to the mass parts, The mixed particle A is 200 parts, the concentrate iron ore is 300 parts, the magnesite powder is 50 parts, the composite binder is 80 parts, and the dosage of the mixed particle A and the magnesite powder is adjusted to make the pellet ternary alkalinity (CaO 2 + MgO) / SiO 2 is 0.6-1.2;
  • the dried composite pellets undergo high-temperature consolidation in a reduction kiln to obtain high-temperature-reduced self-fusible composite pellets; of which the temperature is 1100-1250 ° C and the time is 35-50min.
  • the preparation method of self-fusible composite pellets includes the following steps:
  • the raw material composition of Mixture A includes 25 parts by mass of coke, 20 parts of fat coal, 100 parts of quicklime and 1 part of bentonite, mixed evenly;
  • the mixed particles A wrapped with the film are mixed with concentrate iron ore, magnesite powder and the composite binder prepared in Example 10 to make a remix; wherein, calculated according to the mass parts, The mixed particle A is 200 parts, the concentrate iron ore is 300 parts, the magnesite powder is 50 parts, the composite binder is 80 parts, and the dosage of the mixed particle A and the magnesite powder is adjusted to make the pellet ternary alkalinity (CaO 2 + MgO) / SiO 2 is 0.6-1.2;
  • the dried composite pellets undergo high-temperature consolidation in a reduction kiln to obtain high-temperature-reduced self-fusible composite pellets; of which the temperature is 1100-1250 ° C and the time is 35-50min.
  • the preparation method of self-fusible composite pellets includes the following steps:
  • the raw material composition of Mixture A includes 22 parts by mass of coke, 12 parts of fat coal, 75 parts of quicklime, and 10 parts of cement, mixed evenly;
  • the mixed particles A wrapped with the film are mixed with concentrate iron ore, magnesite powder and the composite binder prepared in Example 7 to make a remix; wherein, calculated according to the mass parts, The mixed particle A is 150 parts, the concentrate is 250 parts, the magnesite powder is 35 parts, the composite binder is 60 parts, and the dosage of the mixed particle A and the magnesite powder is adjusted to make the pellet ternary alkalinity (CaO 2 + MgO) / SiO 2 is 0.6-1.2;
  • the dried composite pellets undergo high-temperature consolidation in a reduction kiln to obtain high-temperature reduced self-fusible composite pellets, of which the temperature is 1100-1250 ° C and the time is 35-50min.
  • a method for preparing self-fusible composite pellets includes the following steps:
  • the raw material composition of Mixture A includes 15 parts by mass of coke, 8 parts of fat coal, and 50 parts of quicklime, mixed evenly;
  • Mix A is mixed with concentrate iron ore, magnesite powder and the composite binder prepared in Example 4 to make a remix; wherein, according to mass parts, the mixed particle A 80 parts, concentrate iron ore 100 parts, magnesite powder 20 parts, composite binder 20 parts, and adjust the amount of mixed particles A and magnesite powder to make the ternary alkalinity of the pellets (CaO 2 + MgO) / SiO 2 is 0.6-1.2;
  • the dried composite pellets undergo high-temperature consolidation in a reduction kiln, where the temperature is 1100-1250 ° C and the time is 35-50 minutes to obtain high-temperature reduced self-fusible composite pellets.
  • a method for preparing self-fusible composite pellets includes the following steps:

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Abstract

自熔性复合球团的制备方法，包括下述步骤：(1)焦炭、肥煤和生石灰混合均匀制备混合料A；(2)将混合料A加水混匀制成颗粒状的混粒A；(3)将薄膜原料混合适量的水搅拌至液态状；(4)采用喷洒方式将薄膜料粘附于混粒A表面，静置干燥；(5)制备再混料：包裹薄膜后的混粒A与精铁矿、镁石粉和复合粘结剂混合均匀，制成再混料；调整混粒A和镁石粉的用量使球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；(6)制备球团：将再混料置于造粒机上进行圆盘或圆筒造球，静置干燥，制成复合球团；(7)干燥后的复合球团在还原窑内经过高温固结，得到高温还原的自熔性复合球团。制得的自熔性复合球团提高了球团矿的冶金性能。

Description

自熔性复合球团的制备方法 技术领域
本发明属于钢铁冶金技术领域，具体涉及一种自熔性复合球团的制备方法。
背景技术
作为高炉炼铁的原料，世界上工业化的球团矿有酸性氧化性球团、熔剂性球团和自熔性球团三种。普通酸性球团矿一般存在软熔性能差的问题，即开始软化温度低，软化区间宽和高温还原性能差等缺点，且冶金性能低于高碱度烧结矿，在大高炉上这种球团矿的配比也不可能太高。而传统的自熔性球团矿单独用作高炉原料，其一般含铁62％左右，含有CaO、MgO、SiO 2、Al 2O 3等，用同样的细铁精矿生产的自熔性球团与酸性球团矿相比较，前者含铁量交底、含硫较高；但是自熔性球团矿的气孔率较高，一般在25％左右，因而其强度较低。
针对上述问题，现有复合熔剂性球团的工艺，通过将球团制备为双层结构球团，如专利CN104745809A公开的一种自熔性复合金属化球团及其生产工艺，它包括内核、外壳，内核由铁精矿、石灰石、煤炭粉、水泥按330：300～350：80～120：6～9的比例混合而成，外壳由铁精矿与膨润土按质量比为1320：22～25的比例混合而成，内核的粒度为20～25mm，外壳的厚度为5～10mm。又如专利CN104975173A公开的一种高炉用溶剂型复合含碳球团的生产方法，混合料A原料组成为铁精矿65-80％，粘接剂1-2％，含碳材 料10-20％。将混合料A加水混匀后制成粒度为5～7mm的自熔性球团核。混合料B原料组成为铁精矿75-85％，粘接剂1～2％，含碳材料5-15％。缓和料A中添加混合料B造球，制得含碳球团生球；对生球焙烧后制得成品熔剂性复合含碳球团。上述复合球团矿产品的冶金性能、微观结构等均优于常规熔剂性球团。但上述方法的在使用小量粘结剂时，生球成球性差、韧性差，而粘结剂用量较大，则影响球团矿成品的品味，并且该复合球团矿的物理性能仍没有酸性球团矿的物理性能好，球团矿的冶金性能不佳。
发明内容
本发明要解决的技术问题在于，提供的一种自熔性复合球团的制备方法，该方法制得的自熔性复合球团，解决了传统球团在生产过程中能耗高、产能低的技术问题，提高了球团矿的冶金性能。
为实现上述发明目的，本发明提供的自熔性复合球团的制备方法，包括下述步骤：
(1)制备混合料A：混合料A的原料组成包括质量份数为15～25份的焦炭、8～20份的肥煤和50～100份的生石灰，混合均匀；
(2)混合料A造粒：将混合料A加水混匀，随后用造粒机制成颗粒状的混粒A，其中，所述混粒A的颗粒大小为5-15mm；
(3)制备薄膜料：将薄膜原料混合适量的水搅拌至液态状；
(4)混粒A裹膜：将混粒A置于滚圆机上，采用喷洒方式将薄膜料粘附于混粒A表面，静置干燥；
(5)制备再混料：包裹薄膜后的混粒A与精铁矿、镁石粉和复合粘结剂混合均匀，制成再混料；其中，按照质量份数计算，所述混粒A为80～200 份、精铁矿为100～300份、镁石粉为20～50份，复合粘结剂为20～80份，同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；
(6)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团；
(7)干燥后的复合球团在还原窑内经过高温固结，得到高温还原的自熔性复合球团。
本发明的自熔性复合球团通过混合料A将焦炭、肥煤和生石灰充分混合裹成细颗粒，在没有粘结剂阻碍的状态下，可使含碳材料与石灰石充分接触，石灰石在高温下分解产生CO 2，提高了煤炭的碳气化反应速度，在高温下其CO向外扩散至再混料并与其接触，朝向铁精矿扩散，充分接触，提高铁精矿的在较低温度下的还原效率，改善反应的动力学条件。采用焦炭和肥煤制成的混合料A使其具有较高的气孔率和粘结力，利于该细颗粒状的还原反应和成型；进一步通过薄膜包括对混粒A进行包裹，在减少或不使用粘结剂的情况下，仍可对混粒A塑性提韧，保证其入炉的热强度要求。本发明薄膜层保障了所述混粒A在不添加粘结剂的情况下具有一定的抗压形变性能，而另一方面，申请人发现，基于上述再混粒的复合粘结剂的粘结性以及添加的混粒A和其他再混料的比例限制，当成品球团矿在高炉受到冲击时，即便混粒A破裂，也不会导致整体球团发生破碎。
进一步的，所述混合料A还包括质量份数为1～10份的膨润土或水泥。
进一步的，所述薄膜料还包括质量份数为1～10份的乙基纤维素、1～10份的明胶、1～10份的焦炭和1～8份的腐殖酸钠。乙基纤维素、明胶和腐殖酸钠三者复配使得薄膜具有一定粘结性，更好地附着于混粒A表面，同时具有 良好的形变韧性，提高球团的落下强度和抗压强度；而焦炭的添加则使该薄膜层具有一定的空隙率，进一步改善还原动力学条件。
进一步的，所述包裹混粒A的薄膜厚度为0.5～3mm。
进一步的，所述再混料的复合粘结剂包括质量份数为10～50份的膨润土、5～20份的酚醛树脂、5～20份的液体石腊、3～12份的粘木粉。
更进一步的，所述复合粘结剂还包括质量份数为8～25份的沥青以及3～20份的聚乙烯亚胺。
进一步的方案中，所述复合粘结剂由质量份数为35～44份的膨润土、8～12份的酚醛树脂、8～12份的液体石腊、7～10份的粘木粉、12～20份的沥青以及8～12份的聚乙烯亚胺复合而成。
进一步的，所述复合粘结剂的制备方法为：
1)、称取所述重量份数的膨润土、粘木粉和聚乙烯亚胺，加入适量的水，混合均匀制成液体a；
2)、称取所述重量份数的酚醛树脂加入氢氧化钠水溶液，于40～45℃加热熔化，再加入甲醛，继续加热至95℃，保温30～40min后，冷却降温，即得酚醛树脂溶液；
3)、称取所述重量份数的沥青加热至200摄氏度，得到熔融态沥青，加入液体石蜡混合均匀，随后将与所述液体a、酚醛树脂溶液加入，再次混合均匀，即制得所述复合粘结剂。
上述方案中，通过膨润土、粘木粉、酚醛树脂等各种粘结剂的共同作用形成的复合粘结剂，膨润土和粘木粉具有有很强的亲合粘结功能，而粘木粉与高分子聚合物聚乙烯亚胺共同使用相容性佳，聚乙烯亚胺基体与粘木粉粘接可促进木粉的分散，防止粒子团聚，提高球团产品的强度，能使生球在受 到冲击作用时，使球团球粒之间相互滑动，从而产生塑性变形不至于破碎，提高了生球的落下强度。此外，采用粘木粉还可改善再混料的亲水性，促使球团迅速生成，提高球团产量。聚乙烯亚胺与各粘接剂的复配还进一步提高粘结剂的弹性和韧性，显著提高复合粘结剂的性能，保证原料球团的入炉要求和生产过程中的热强度要求。
进一步的，所述步骤(7)的高温固结过程中的温度为1100～1250℃，时间为35～50min。
再进一步的，所述步骤(6)中制成的复合球团大小为30～45mm。
本发明所述方法制备的自熔性复合球团同时具有含碳球团和熔剂性球团两者的优点，改善球团矿的高温冶金性能。该球团矿具有粘结剂添加量极少、粘结性好、球团矿铁品位高；同时还具有优良的抗压强度，本发明的制备方法制备的自熔性复合球团的冷态抗压强度增大。实验证明，根据本发明的制备方法制备的自熔性复合球团的冷态抗压强度高于2440N/个，落下强度大于8次/个，完全满足高炉炼铁炉料的使用要求。另外，其高温抗压强度明显高于现有技术生产出的球团，可实现高效冶炼。
具体实施方式
下文参照附图对本发明的具体实施例进行详细说明。
实施例1薄膜的制备
本发明所述的自熔性复合球团薄膜料由质量份数为1份的乙基纤维素、1份的明胶、1份的焦炭和1份的腐殖酸钠混合均匀后加入适量水，制成薄膜溶剂。
实施例2薄膜的制备
本发明所述的自熔性复合球团薄膜料10份的乙基纤维素、10份的明胶、 10份的焦炭和8份的腐殖酸钠混合均匀后加入适量水，制成薄膜溶剂。
实施例3薄膜的制备
本发明所述的自熔性复合球团薄膜料5份的乙基纤维素、5份的明胶、6份的焦炭和4份的腐殖酸钠混合均匀后加入适量水，制成薄膜溶剂。
实施例4复合粘结剂的制备
原料：10份的膨润土、5份的酚醛树脂、5份的液体石腊、3份的粘木粉；
制备方法：
1)、称取所述重量份数的膨润土、粘木粉，加入适量的水，混合均匀制成液体a；
2)、称取所述重量份数的酚醛树脂加入氢氧化钠水溶液，于40～45℃加热熔化，再加入甲醛，继续加热至95℃，保温30～40min后，冷却降温，即得酚醛树脂溶液；
3)、将所述液体a、酚醛树脂溶液加入，再次混合均匀，即制得所述复合粘结剂。
实施例5复合粘结剂的制备
原料：40份的膨润土、10份的酚醛树脂、10份的液体石腊、8份的粘木粉；
制备方法同实施例4所述。
实施例6复合粘结剂的制备
原料：25份的膨润土、11份的酚醛树脂、10份的液体石腊、5份的粘木粉、8份的沥青以及3份的聚乙烯亚胺；
制备方法：
1)、称取所述重量份数的膨润土、粘木粉，加入适量的水，混合均匀制 成液体a；
2)、称取所述重量份数的酚醛树脂加入氢氧化钠水溶液，于40～45℃加热熔化，再加入甲醛，继续加热至95℃，保温30～40min后，冷却降温，即得酚醛树脂溶液；
3)、称取所述重量份数的沥青加热至200摄氏度，得到熔融态沥青，加入液体石蜡混合均匀，随后将与所述液体a、酚醛树脂溶液加入，再次混合均匀，即制得所述复合粘结剂。
实施例7复合粘结剂的制备
原料：20份的膨润土、9份的酚醛树脂、11份的液体石腊、6份的粘木粉、25份的沥青以及20份的聚乙烯亚胺
制备方法同实施例6所述。
实施例8复合粘结剂的制备
原料：35份的膨润土、8份的酚醛树脂、8份的液体石腊、7份的粘木粉、12份的沥青以及8份的聚乙烯亚胺。
制备方法同实施例6所述。
实施例9复合粘结剂的制备
原料：44份的膨润土、12份的酚醛树脂、12份的液体石腊、10份的粘木粉、20份的沥青以及12份的聚乙烯亚胺。
制备方法同实施例6所述。
实施例10复合粘合剂的制备
原料：40份的膨润土、10份的酚醛树脂、10份的液体石腊、8份的粘木粉、16份的沥青以及10份的聚乙烯亚胺；
制备方法同实施例6所述。
实施例11
一种自熔性复合球团的制备方法，包括下述步骤：
(1)制备混合料A：混合料A的原料组成包括质量份数为15份的焦炭、8份的肥煤和50份的生石灰，混合均匀；
(2)混合料A造粒：将混合料A加水混匀，随后用造粒机制成颗粒状的混粒A，其中，所述混粒A的颗粒大小为5mm；
(3)制备薄膜料：将实施例1制备的薄膜原料混合适量的水搅拌至液态状；
(4)混粒A裹膜：将混粒A置于滚圆机上，采用喷洒方式将薄膜料粘附于混粒A表面，静置干燥；
(5)制备再混料：包裹薄膜后的混粒A与精铁矿、镁石粉和实施例4制备的复合粘结剂混合均匀，制成再混料；其中，按照质量份数计算，所述混粒A为80份、精铁矿为100份、镁石粉为20份，复合粘结剂为20份，同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；
(6)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团；
(7)干燥后的复合球团在还原窑内经过高温固结，其中温度1100～1250℃，时间35～50min，得到高温还原的自熔性复合球团。
对成品球团矿的冶金性能进行监测，如表1所示。
实施例12
自熔性复合球团的制备方法，包括下述步骤：
(1)制备混合料A：混合料A的原料组成包括质量份数为25份的焦炭、 20份的肥煤和100份的生石灰，混合均匀；
(2)混合料A造粒：将混合料A加水混匀，随后用造粒机制成颗粒状的混粒A，其中，所述混粒A的颗粒大小为12mm；
(3)制备薄膜料：将实施例3薄膜原料混合适量的水搅拌至液态状；
(4)混粒A裹膜：将混粒A置于滚圆机上，采用喷洒方式将薄膜料粘附于混粒A表面，静置干燥；
(5)制备再混料：包裹薄膜后的混粒A与精铁矿、镁石粉和实施例5制备的复合粘结剂混合均匀，制成再混料；其中，按照质量份数计算，所述混粒A为200份、精铁矿为300份、镁石粉为50份，复合粘结剂为80份，同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；
(6)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团，大小为30mm；
(7)干燥后的复合球团在还原窑内经过高温固结，得到高温还原的自熔性复合球团，其中温度1100～1250℃，时间35～50min。
对成品球团矿的冶金性能进行监测，如表1所示。
实施例13
自熔性复合球团的制备方法，包括下述步骤：
(1)制备混合料A：混合料A的原料组成包括质量份数为25份的焦炭、20份的肥煤、100份的生石灰，混合均匀；
(2)混合料A造粒：将混合料A加水混匀，随后用造粒机制成颗粒状的混粒A，其中，所述混粒A的颗粒大小为12mm；
(3)制备薄膜料：将实施例3制备的薄膜原料混合适量的水搅拌至液态 状；
(4)混粒A裹膜：将混粒A置于滚圆机上，采用喷洒方式将薄膜料粘附于混粒A表面，静置干燥；
(5)制备再混料：包裹薄膜后的混粒A与精铁矿、镁石粉和实施例10制备的复合粘结剂混合均匀，制成再混料；其中，按照质量份数计算，所述混粒A为200份、精铁矿为300份、镁石粉为50份，复合粘结剂为80份，同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；
(6)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团，大小为30mm；
(7)干燥后的复合球团在还原窑内经过高温固结，得到高温还原的自熔性复合球团；其中温度1100～1250℃，时间35～50min。
对成品球团矿的冶金性能进行监测，如表1所示。
实施例14
自熔性复合球团的制备方法，包括下述步骤：
(1)制备混合料A：混合料A的原料组成包括质量份数为25份的焦炭、20份的肥煤、100份的生石灰和1份的膨润土，混合均匀；
(2)混合料A造粒：将混合料A加水混匀，随后用造粒机制成颗粒状的混粒A，其中，所述混粒A的颗粒大小为10mm；
(3)制备薄膜料：将实施例3制备的薄膜原料混合适量的水搅拌至液态状；
(4)混粒A裹膜：将混粒A置于滚圆机上，采用喷洒方式将薄膜料粘附于混粒A表面，静置干燥；
(5)制备再混料：包裹薄膜后的混粒A与精铁矿、镁石粉和实施例10制备的复合粘结剂混合均匀，制成再混料；其中，按照质量份数计算，所述混粒A为200份、精铁矿为300份、镁石粉为50份，复合粘结剂为80份，同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；
(6)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团，大小为35mm；
(7)干燥后的复合球团在还原窑内经过高温固结，得到高温还原的自熔性复合球团；其中温度1100～1250℃，时间35～50min。
对成品球团矿的冶金性能进行监测，如表1所示。
实施例15
自熔性复合球团的制备方法，包括下述步骤：
(1)制备混合料A：混合料A的原料组成包括质量份数为22份的焦炭、12份的肥煤、75份的生石灰、10份的水泥，混合均匀；
(2)混合料A造粒：将混合料A加水混匀，随后用造粒机制成颗粒状的混粒A，其中，所述混粒A的颗粒大小为15mm；
(3)制备薄膜料：将实施例2制备的薄膜原料混合适量的水搅拌至液态状；
(4)混粒A裹膜：将混粒A置于滚圆机上，采用喷洒方式将薄膜料粘附于混粒A表面，静置干燥；
(5)制备再混料：包裹薄膜后的混粒A与精铁矿、镁石粉和实施例7制备的复合粘结剂混合均匀，制成再混料；其中，按照质量份数计算，所述混粒A为150份、精铁矿为250份、镁石粉为35份，复合粘结剂为60份， 同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；
(6)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团，大小为40mm；
(7)干燥后的复合球团在还原窑内经过高温固结，得到高温还原的自熔性复合球团，其中，温度1100～1250℃，时间35～50min，
对照实施例1
一种自熔性复合球团的制备方法，包括下述步骤：
(1)制备混合料A：混合料A的原料组成包括质量份数为15份的焦炭、8份的肥煤和50份的生石灰，混合均匀；
(2)混合料A造粒：将混合料A加水混匀，随后用造粒机制成颗粒状的混粒A，其中，所述混粒A的颗粒大小为5mm；
(3)制备再混料：混粒A与精铁矿、镁石粉和实施例4制备的复合粘结剂混合均匀，制成再混料；其中，按照质量份数计算，所述混粒A为80份、精铁矿为100份、镁石粉为20份，复合粘结剂为20份，同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；
(6)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团；
(7)干燥后的复合球团在还原窑内经过高温固结，其中温度1100～1250℃，时间35～50min，得到高温还原的自熔性复合球团。
对成品球团矿的冶金性能进行监测，如表1所示。
对照实施例2
一种自熔性复合球团的制备方法，包括下述步骤：
(1)称取质量份数为焦炭15份、肥煤8份、生石灰50份、精铁矿100份、镁石粉20份、实施例4制备的复合粘结剂20份，同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.6-1.2；
(2)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团；
(3)干燥后的复合球团在还原窑内经过高温固结，其中温度1100～1250℃，时间35～50min，得到高温还原的自熔性复合球团。
对成品球团矿的冶金性能进行监测，如表1所示。
对上述实施例和对照实施例所制成的成品球团矿的冶金性能进行测试，如表1所示。
表1 冶金性能
Figure PCTCN2018116833-appb-000001
需要说明的是，在本文中，术语“包括”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括哪些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。
上述内容是对本发明优选的具体实施方式和实施例作了详细说明，但是本发明并不限于上述实施方式和实施例，在本领域技术人员所具备的知识范围内，还可以在不脱离本发明构思的前提下做出各种变化。

Claims (10)

  1. 一种自熔性复合球团的制备方法，其特征在于，包括下述步骤：
    (1)制备混合料A：混合料A的原料组成包括质量份数为15～25份的焦炭、8～20份的肥煤和50～100份的生石灰，混合均匀；
    (2)混合料A造粒：将混合料A加水混匀，随后用造粒机制成颗粒状的混粒A，其中，所述混粒A的颗粒大小为5-15mm；
    (3)制备薄膜料：将薄膜原料混合适量的水搅拌至液态状；
    (4)混粒A裹膜：将混粒A置于滚圆机上，采用喷洒方式将薄膜料粘附于混粒A表面，静置干燥；
    (5)制备再混料：包裹薄膜后的混粒A与精铁矿、镁石粉和复合粘结剂混合均匀，制成再混料；其中，按照质量份数计算，所述混粒A为80～200份、精铁矿为100～300份、镁石粉为20～50份，复合粘结剂为20～80份，同时调整混粒A和镁石粉的用量使所述球团三元碱度(CaO 2+MgO)/SiO 2为0.8-1.2；
    (6)制备球团：将再混料置于造粒机上，加入少量水分润湿后静置45min，进行圆盘或圆筒造球，静置干燥，制成复合球团；
    (7)干燥后的复合球团在还原窑内经过高温固结，得到高温还原的自熔性复合球团。
  2. 如权利要求1所述的自熔性复合球团的制备方法，其特征在于，所述混合料A还包括质量份数为1～10份的膨润土或水泥。
  3. 如权利要求1所述的自熔性复合球团的制备方法，其特征在于，所述薄膜料还包括质量份数为1～10份的乙基纤维素、1～10份的明胶、1～10份 的焦炭和1～8份的腐殖酸钠。
  4. 如权利要求1所述的自熔性复合球团的制备方法，其特征在于，所述包裹混粒A的薄膜厚度为0.5～3mm。
  5. 如权利要求1所述的自熔性复合球团的制备方法，其特征在于，所述再混料的复合粘结剂包括质量份数为10～50份的膨润土、5～20份的酚醛树脂、5～20份的液体石腊、3～12份的粘木粉。
  6. 如权利要求5所述的自熔性复合球团的制备方法，其特征在于，所述复合粘结剂还包括质量份数为8～25份的沥青以及3～20份的聚乙烯亚胺。
  7. 如权利要求6所述的自熔性复合球团的制备方法，其特征在于，所述复合粘结剂由质量份数为35～44份的膨润土、8～12份的酚醛树脂、8～12份的液体石腊、7～10份的粘木粉、12～20份的沥青以及8～12份的聚乙烯亚胺复合而成。
  8. 如权利要求6～7任一项所述的自熔性复合球团的制备方法，其特征在于，所述复合粘结剂的制备方法为：
    1)、称取所述重量份数的膨润土、粘木粉和聚乙烯亚胺，加入适量的水，混合均匀制成液体a；
    2)、称取所述重量份数的酚醛树脂加入氢氧化钠水溶液，于40～45℃加热熔化，再加入甲醛，继续加热至95℃，保温30～40min后，冷却降温，即得酚醛树脂溶液；
    3)、称取所述重量份数的沥青加热至200摄氏度，得到熔融态沥青，加入液体石蜡混合均匀，随后将与所述液体a、酚醛树脂溶液加入，再次混合均匀，即制得所述复合粘结剂。
  9. 如权利要求1所述的自熔性复合球团的制备方法，其特征在于，所述步骤(7)的高温固结过程中的温度为1100～1250℃，时间为35～50min。
  10. 如权利要求1所述的自熔性复合球团的制备方法，其特征在于，所述步骤(6)中制成的复合球团大小为30～45mm。
PCT/CN2018/116833 2018-10-29 2018-11-22 自熔性复合球团的制备方法 Ceased WO2020087593A1 (zh)

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