CN115747485B - A metallurgical pellet bentonite bonding enhancer composite and its application - Google Patents
A metallurgical pellet bentonite bonding enhancer composite and its applicationInfo
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- CN115747485B CN115747485B CN202211594137.5A CN202211594137A CN115747485B CN 115747485 B CN115747485 B CN 115747485B CN 202211594137 A CN202211594137 A CN 202211594137A CN 115747485 B CN115747485 B CN 115747485B
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Abstract
本发明提供一种冶金球团膨润土粘结增强剂复合物及应用，所述复合物按重量份计，包括以下原料：正磷酸铵盐类10‑15份、多聚磷酸铵盐类15‑20份、缩聚磷酸铝盐类15‑20份、氢氧化铝40‑50份和煅烧硼镁石10‑15份；所述正磷酸铵盐类的通式为(NH4)nH3‑nPO4，式中n≤3；所述多聚磷酸铵盐类的通式为H(n‑m)+2(NH4)mPnO3n+1，式中4≤n≤10，m≤n+2；所述缩聚磷酸铝盐类为具有以下通式的线型链状聚磷酸铝盐：式中4≤n≤10。将复合物与球团膨润土粉混合得到冶金球团膨润土粘结增强剂，本发明增强剂显著提高球团膨润土的湿球强度、高温强度和抗暴温度，球团膨润土用量大幅度降低、球团铁品级大幅度升高。The present invention provides a metallurgical pellet bentonite bonding enhancer composite and application. The composite comprises the following raw materials, measured in parts by weight: 10-15 parts of ammonium orthophosphate salts, 15-20 parts of ammonium polyphosphate salts, 15-20 parts of condensed aluminum phosphate salts, 40-50 parts of aluminum hydroxide, and 10-15 parts of calcined johnsonite. The ammonium orthophosphate salts have a general formula of ( NH4 ) nH3 -nPO4 , where n is less than or equal to 3; the ammonium polyphosphate salts have a general formula of H (n-m)+2 ( NH4 ) mPnO3n +1 , where 4 is less than or equal to n and m is less than or equal to n+2; and the condensed aluminum phosphate salts are linear chain aluminum polyphosphate salts having the following general formula: Wherein 4≤n≤10. The composite material is mixed with pelletized bentonite powder to obtain a metallurgical pelletized bentonite bonding enhancer. The enhancer of the present invention significantly improves the wet bulb strength, high temperature strength, and burst temperature of the pelletized bentonite, significantly reduces the amount of pelletized bentonite used, and significantly improves the iron grade of the pellets.
Description
Technical Field
The invention belongs to the technical field of metallurgical raw material pretreatment, and relates to a metallurgical pellet bentonite bonding enhancer compound and application thereof.
Technical Field
The oxidized pellet has the advantages of uniform granularity, high cold strength, high iron grade, good reducibility and the like, and is a high-quality blast furnace burden. In order to improve the pelletization performance of the pellets and improve the product quality, a plurality of binders are usually added in pellet production, and a series of inorganic binders such as clay, diatomite, lime, cement, water glass, borate and the like are used. However, all inorganic binders have some side effects so that the metallurgical properties of the pellets are poor, forcing people to develop and research new binders, and finally, bentonite is found to be the most suitable pellet binder. The bentonite can improve the falling strength of green pellets on one hand and can obviously improve the burst temperature of the green pellets on the other hand. The technical and economic index of the pellet mill can be obviously improved after bentonite is added into the pellets.
Bentonite is mainly clay composed of montmorillonite minerals. It has the properties of expansibility, suspension property, dispersibility and hydrophilicity. Since the montmorillonite has small particle size, the negative charges in the internal unit cells have the same number, the homopolar charges repel each other, and the montmorillonite has good suspension property, and meanwhile, has strong hydrophilicity and dispersibility. In addition, bentonite is a high-dispersivity substance, and the bonding property of the pelleting material is improved after the bentonite is added, so that the capillary diameter in the green pellets is reduced, and the capillary force is increased. On the other hand, the bentonite is filled among the particles of the green pellets in the form of colloid particles after absorbing water, so that the cohesive force among the particles is increased, and the strength of the green pellets can be improved. The bentonite is added into the pellet production, so that the compressive strength of the pellet is improved, and sliding can be generated among particles when the green pellets are impacted by external force. Therefore, the falling strength of the green ball is obviously improved.
The improvement of the anti-cracking temperature of the green pellets is another reason for selecting bentonite in the pellet industry. The drying time of green pellets often accounts for more than one quarter of the total firing time. The final quality of pellets is also affected to some extent by the quality of green pellets. Thus, the drying speed of the green pellets is always attempted to be improved without affecting the drying burst of the green pellets. The bursting temperature of green pellets is mainly determined by the evaporation rate and diffusion rate of water, and pellets are easy to burst when the diffusion rate is slower than the evaporation rate. Because the bentonite has strong binding force with the special affinity of water, the water in the green pellets gradually migrates to the surfaces of the green pellets for evaporation, and the water loss is slower when the pellets are dried, so that the evaporation speed of the water is reduced, the bursting temperature of the green pellets is improved, and the bursting possibility when the green pellets are dried is greatly weakened. According to the production experience of pellet production, from adding slaked lime to adding bentonite, the bursting temperature of the green pellets is increased from 450 ℃ to more than 700 ℃, the quality of the pellets is improved, and the yield is increased by more than 60%.
The bentonite is adopted as a pellet binder to bring adverse effects. The main component of bentonite is SiO 2, the content of which is above 60 percent, and excessive addition of bentonite can reduce the growth speed of the green pellets and the iron grade of pellets, thereby bringing adverse effects to blast furnace ironmaking. Experience proves that every 1 percent of bentonite proportion is increased, the grade of pellets is reduced by 0.6 percent, and the SiO 2 content of the corresponding finished ore is also greatly increased. SiO 2 as a harmful component in pellet smelting is reduced as much as possible when the strength of a certain pellet is ensured.
However, according to the production data statistics of decades in China, the bentonite dosage of foreign pellet production enterprises is within 1%, and the bentonite average dosage of the pellet production enterprises in China is about 2.5-3.5%, and the difference is obvious compared with foreign levels. Therefore, the company performs a series of experimental researches on the pelletization of domestic iron ore powder pellets, and discovers that the bentonite dosage is generally about 1% when using American wyoming pellet bentonite for pelletization, each index of the pellets meets the requirements, and the bentonite dosage is more than 2% when using Tianzheng company to purify bentonite and match CMC, PAA, HPAM and other various additives for performing corresponding pelletization experiments. Even when experiments were carried out using wyoming pure natural sodium bentonite and the above-mentioned various additives, the level of 1% of the amount of the additive to be added was not reached. The pellet ore product produced in this way has low iron grade, high SiO 2 content and far from international level, and the main reason is that the bentonite dosage is too high during pelletizing. According to data statistics, the bentonite consumption of the current domestic pellet mill is generally about 2.5-3.5%, and the difference is obvious compared with the foreign level (1%), even if the Ping Shahai bentonite mining area built by the company is a domestic accepted pellet and cast high-quality bentonite, the bentonite consumption can only reach the level of 2% when the iron ore pellets are formed. And with the increasing shortage of iron ore resources in recent years, the quality of the iron concentrate for pelletization is deteriorated, and the use amount of bentonite tends to increase. The use amount of bentonite is too high, so that the production cost of pellets is increased, the iron grade of the pellets is reduced, the pellets are used for smelting in a blast furnace, the pig iron yield is reduced, the coke ratio is increased, and the economic benefit is seriously influenced.
The addition of a certain amount of bentonite in the pelletizing process of the metallurgical pellets can obviously improve the falling strength, the compressive strength, the bursting temperature and the dry pellet strength of green pellets. However, bentonite contains a large amount of SiO 2、Al2O3 and other impurities, and the quality of pellets is affected due to the reduction of the grade of pellet iron caused by adding the bentonite into the pellets. For many years, research and development of organic binders have been focused on, and the purpose of the organic binders is to reduce the dosage of bentonite, even cancel bentonite, and improve the iron grade of pellets by utilizing the characteristic that the organic binders have few impurities. From the 80 s of the 20 th century, research on the use of organic binders for pellet preparation has been initiated both at home and abroad. However, despite the research of organic binders for decades, the binder that has been the absolute dominator in pellet production to date remains bentonite. Organic binders have not been widely used for a variety of reasons including uniformity of addition and mixing, pelletization kinetics, green pellet thermal performance, pellet firing, cost, and the like.
The bentonite addition rate in pellet ore production in China is generally high, and one of the main reasons is caused by iron ore powder raw materials. The domestic iron grade is generally about 62-63%, which is 2-3% lower than the international advanced level. Meanwhile, compared with foreign iron ore powder raw materials, the foreign iron ore powder has finer granularity and the content of less than 0.074mm is generally more than 85 percent. The granularity of the domestic iron ore powder raw material is coarse, the content of less than 0.074mm is generally below 75%, and the difference is large compared with foreign materials. The iron concentrate is used for pelletizing, and bentonite (2.5-3.5% or even higher) with higher proportion is needed to meet the requirements of pellet strength index, antiknock temperature and the like. The bentonite addition rate in pellet production in China is generally higher, and is also more important because the bentonite gap for pellets is large, and particularly because the bentonite gap between the bentonite for pellets and foreign countries exists, the bentonite must be added in a large proportion to ensure the index requirements of pellet strength, anti-cracking temperature and the like, and as a result, the impurity contents of SiO 2, al 2O3 and the like of the pellets are increased, and the grade of the finished pellets is greatly reduced. Therefore, under the condition that the content grade and granularity condition of the existing domestic iron ore powder raw material cannot be changed, the aim of improving the pellet quality and reducing the bentonite blending proportion can only be broken through from the point of developing the pellet bentonite additive. Therefore, domestic pellet and pellet bentonite manufacturers are actively taking various measures to strive to reduce the bentonite proportion on the basis of meeting the pellet production requirements. The pellet bentonite reinforcing agent is researched and developed to improve the bentonite binding property, and has very important practical significance for replacing the conventional bentonite to reduce the bentonite blending proportion.
Disclosure of Invention
Accordingly, the applicant has invented a metallurgical pellet bentonite adhesion enhancer and used it to perform related research and production verification of partial replacement bentonite.
The invention aims to provide a metallurgical pellet bentonite bonding enhancer which is used for partially replacing pellet bentonite to supplement the defects of the pellet bentonite such as self bonding strength and the like, so that the aim of achieving indexes such as pellet strength, bursting temperature and the like by using a lower bentonite proportion is fulfilled. The use of the metallurgical pellet bentonite adhesion enhancer can obviously reduce the mixing proportion of bentonite in the pellets, avoid bringing about impurities in the metallurgical pellets caused by the massive use of bentonite, further bring about the improvement of the iron grade of the pellets, and effectively save the production cost of the iron ore pellets.
It has been found that the incorporation of certain combinations of inorganic compounds having the specific elemental composition and molecular structure described below, such as ammonium orthophosphate, ammonium polyphosphate, aluminum hydroxide, and calcined boron magnesium, into pellet bentonite has a significant effect on improving the wet bulb strength, dry bulb strength, and burst temperature of metallurgical pellets. A metallurgical pellet bentonite adhesion enhancer composite of the invention comprises a combination of these inorganic compounds.
The technical scheme of the invention is as follows:
The metallurgical pellet bentonite adhesion enhancer compound comprises the following raw materials in parts by weight:
10-15 parts of ammonium orthophosphate, 15-20 parts of ammonium polyphosphate, 15-20 parts of condensed aluminum phosphate, 40-50 parts of aluminum hydroxide and 10-15 parts of calcined boron magnesium stone;
The general formula of the ammonium orthophosphate is (NH 4)nH3-nPO4, wherein n is less than or equal to 3, and the general formula of the ammonium polyphosphate is H (n-m)+2(NH4)mPnO3n+1, wherein n is more than or equal to 4 and less than or equal to 10, and m is more than or equal to n+2;
The condensed aluminum phosphate is a linear chain aluminum polyphosphate having the general formula:
Wherein n is more than or equal to 4 and less than or equal to 10.
Ammonium orthophosphate is one or more of NH 4H2PO4、(NH4)2HPO4 and (NH 4)3PO4), ammonium orthophosphate is an unstable compound, hydrolysis reaction is carried out when water is encountered, decomposition, dehydration condensation and other chemical reactions are carried out when heat is encountered, H 3PO4 is generated under normal temperature conditions, such as NH 4H2PO4, corresponding chemical reactions are carried out, NH 4H2PO4→NH3+H3PO4, new H 3PO4 and another component Al (OH) 3 of the invention are subjected to neutralization reaction to generate Al (H 2PO4)3), the generated Al (H 2PO4)3 is slowly condensed at room temperature to gradually generate cohesive Al 2(H2P2O7)3, the generated Al (H 2PO4)3 and Al 2(H2P2O7)3) can also react with curing agent calcined magnesite to generate Mg (H 2PO4)2、MgH2P2O7, mgB (H 2PO4)5 and the like).
As noted above, the primary factor considered in the selection of ammonium orthophosphate salts in the present invention should be that they provide as much nascent H 3PO4 as possible for the neutralization reaction with Al (OH) 3, while also providing as low ammonia release as possible from the selected ammonium orthophosphate salts. Therefore, NH 4H2PO4 is preferred in the present invention.
The molecular structure of the ammonium polyphosphate is long-chain or branched-chain compound formed by connecting-P-O-P-chains, and the molecular weight of the ammonium polyphosphate can be very large and can be more than hundred thousand. These ammonium polyphosphates are also thermally unstable compounds, and particularly can undergo chemical reactions such as decomposition, dehydration, deamination, condensation, etc. upon exposure to high temperatures to produce various larger molecular weight ammonium polyphosphates. The temperature continues to rise, the generated ammonium polyphosphate with larger molecular weight can be decomposed to generate polyphosphoric acid, ammonia and water are removed, the process of ammonia removal and water can reduce the temperature inside the pellets, ammonia and water can come out through the existing pore channels of the pellets, at the moment, the pellets have certain strength, and a small amount of ammonia and water are led out from the inside of the pellets and cannot damage the pellets. Meanwhile, the generated high molecular weight polyphosphoric acid reacts with Al (OH) 3 to generate aluminum polyphosphate with better bonding effect, so that the compressive strength of the pellets is further increased. The macromolecular ammonium polyphosphate which does not participate in the reaction is decomposed completely at about 750 ℃ and almost no residues remain in the pellets.
Because the high polymerization degree ammonium polyphosphate salt has better thermal stability than the low polymerization degree ammonium polyphosphate salt, for example, the ammonium polyphosphate salt with n more than or equal to 20 is decomposed in a large amount at the temperature of more than 350 ℃, namely, the ammonium polyphosphate salt can provide bonding strength for the pellets at the temperature of more than 350 ℃, the invention preferably selects the low polymerization degree ammonium polyphosphate salt with n=4-10, the hydrogen atoms on the chain of which are not completely replaced by ammonium, particularly the low molecular weight ammonium polyphosphate salt with the hydrogen atoms at the end group part, which is more easy to generate a series of reactions of deamination, dehydration, condensation and the like to generate bonding substances under the conditions of pelletizing and drying and sintering of metallurgical pellets. The low molecular weight ammonium polyphosphate salts with hydrogen atoms at the end groups are:
(NH4)4H2P4O13、(NH4)3H3P4O13、(NH4)2H4P4O13、NH4H5P4O13、(NH4)5H2P5O16、(NH4)4H3P5O16、(NH4)3H4P5O16、(NH4)2H5P5O16、NH4H6P5O16、(NH4)6H2P6O19、(NH4)5H3P6O19、(NH4)4H4P6O19、(NH4)3H5P6O19、(NH4)2H6P6O19、(NH4)H7P6O19、(NH4)7H2P7O22、(NH4)6H3P7O22、(NH4)5H4P7O22、(NH4)4H5P7O22、(NH4)3H6P7O22、(NH4)2H7P7O22、(NH4)H8P7O22、(NH4)8H2P8O25、(NH4)7H3P8O25、(NH4)6H4P8O25、(NH4)5H5P8O25、(NH4)4H6P8O25、(NH4)3H7P8O25、(NH4)2H8P8O25、(NH4)H9P8O25、(NH4)9H2P9O28、(NH4)8H3P9O28、(NH4)7H4P9O28、(NH4)6H5P9O28、(NH4)5H6P9O28、(NH4)4H7P9O28、(NH4)3H8P9O28、(NH4)2H9P9O28、(NH4)H10P9O28、(NH4)10H2P10O31、(NH4)9H3P10O31、(NH4)8H4P10O31、(NH4)7H5P10O31、(NH4)6H6P10O31、(NH4)5H7P10O31、(NH4)4H8P10O31、(NH4)3H9P10O31、(NH4)2H10P10O31 And (one or more of NH 4)H11P10O31).
The ammonium polyphosphate salt with the end group containing hydrogen atoms and low molecular weight is white crystal or amorphous fine powder, has lower solubility in water and proper thermal stability, starts to slowly decompose into polyphosphoric acid at about 150 ℃, and gradually generates cohesive aluminum polyphosphate.
The polycondensed aluminum phosphate according to the present invention is an equilibrium mixture of aluminum pyrophosphate and higher chain type aluminum polyphosphate, and may contain a very small amount of aluminum orthophosphate as an impurity. Condensed aluminium phosphate is two or more anionsTetrahedral groups, connected by their tips, undergo polycondensation to form relatively complex mixtures of polymers, i.e. mixtures having a reproducible tetrahedral structureWhileThe two are connected through oxygen atoms shared at the top corner by P-O-P bonds.
The phosphorus atom in the polycondensed aluminum phosphate according to the invention is in a completely oxidized state, so that its chemical properties are relatively stable. However, it is well known that condensed aluminum phosphates are not sufficiently stable to hydrolysis and that in the presence of water and other suitable conditions, all P-O-P bonds may be broken and react with themselves or with other materials to form materials having cohesive properties.
The hydrolysis path and speed of the condensed aluminum phosphate are different according to the anion of the condensed aluminum phosphate, and the condensed aluminum phosphate contains more connected aluminum phosphateTetrahedral condensed aluminum phosphate structure with relatively few interconnectionsThe tetrahedral condensed aluminium phosphate hydrolyzes much faster, and in particular the aluminium superphosphate salts containTetrahedra are numerous and always have branched structures and are therefore the least stable class of condensed aluminum phosphates. One of the main factors considered in the selection of condensed aluminium phosphate salts in metallurgical pellets according to the present invention is that they are not expected to react too fast, so that linear condensed aluminium phosphate salts with a degree of polymerization of n=4-10 are preferred in the present invention, and the hydrogen atoms in the chain are not completely substituted, and the terminal group is a low molecular weight condensed aluminium phosphate salt of two hydrogen atoms. The specific low molecular weight polycondensed aluminum phosphate salts preferred in the present invention are as follows:
Al4(H2P4O13)3、AlH3P4O13、Al2(H4P4O13)3、Al(H5P4O13)3、Al5(H2P5O16)3、Al4(H3P5O16)3、AlH4P5O16、Al2(H5P5O16)3、Al(H6P5O16)3、Al2H2P6O19、Al5(H3P6O19)3、Al4(H4P6O19)3、AlH5P6O19、Al2(H6P6O19)3、Al(H7P6O19)3、Al7(H2P7O22)3、Al2H3P7O22、Al5(H4P7O22)3、Al4(H5P7O22)3、AlH6P7O22、Al2(H7P7O22)3、Al(H8P7O22)3、Al8(H2P8O25)3、Al7(H3P8O25)3、Al2H4P8O25、Al5(H5P8O25)3、Al4(H6P8O25)3、AlH7P8O25、Al2(H8P8O25)3、Al(H9P8O25)3、Al3H2P9O28、Al8(H3P9O28)3、Al7(H4P9O28)3、Al2H5P9O28、Al5(H6P9O28)3、Al4(H7P9O28)3、AlH8P9O28、Al2(H9P9O28)3、Al(H10P9O28)3、Al10(H2P10O31)3、Al3H3P10O31、Al2H4P10O31、Al7(H5P10O31)3、Al2H6P10O31、Al5(H7P10O31)3、Al4(H8P10O31)3、AlH9P10O31、Al2(H10P10O31)3 And Al (one or more of H 11P10O31)3).
Compared with orthophosphate, the condensed aluminum phosphate has acidic group-POO -, and the main chain-type poly-phosphoric acid-PO-O-PO-, thus has the own uniqueness, the condensed aluminum phosphate salt which is shown in the chemical reaction has strong dehydration condensation property, gradually polymerizes into condensed aluminum phosphate with larger molecular weight from smaller molecules, the condensed property is that the condensed aluminum phosphate with high content P 2O5 is more than the condensed aluminum phosphate with low content P 2O5, and the reaction speed of hydrolysis and the like of the condensed aluminum phosphate salt can be accelerated by heating.
The aluminum hydroxide related to the metallurgical pellet bentonite adhesion enhancer is aluminum hydroxide trihydrate A1 (OH) 3, the appearance is white powder, and both crystallization and amorphous can be realized. The crystal structure of alumina trihydrate is composed of closely packed hydroxyl ions in the form of AB bilayers, while aluminum ions are among the above-mentioned stacked hydroxyl ions, and in the octahedral voids formed, 2/3 of the voids are occupied by aluminum ions, and the remaining voids are empty. Each aluminum ion coordinates six-OH ions, and the closely packed hydroxyl ions form a layered structure, and two adjacent layers are connected by hydrogen bonds formed by the hydroxyl ions. This layered structure is highly susceptible to wetting and penetration by the above-mentioned phosphoric acid and condensed phosphoric acid produced by decomposition of ammonium orthophosphate and ammonium polyphosphate salts and reacts to form the corresponding cohesive species of aluminum.
The calcined paigeite related to the metallurgical pellet bentonite adhesion enhancer is prepared by calcining and crushing natural paigeite ore at 700-850 ℃, and has an alkaline reaction in water, and the calcined paigeite mainly contains MgO, B 2O3 and a boron magnesium two-element compound thereof, and the compound can be a main component. The latest research shows that the calcined paigeite is used as the curing agent of aluminum phosphate binders, has higher activity than calcined magnesia, and can be used for curing at normal temperature and high temperature. Considering that the metallurgical pellet not only relates to wet-ball strength in the pelletizing stage, but also relates to high-temperature strength in the drying and sintering stage, the invention adopts calcined boron-magnesium stone as a normal-temperature curing agent and a high-temperature curing agent of the metallurgical pellet bentonite bonding reinforcing agent.
From the effect of each component of the metallurgical pellet bentonite bonding enhancer, the effect of the ammonium orthophosphate is mainly to provide wet-bulb strength for the pellets. The main functions of the components ammonium polyphosphate and aluminum polyphosphate are to provide high temperature strength and anti-explosion temperature for the pellets. The components aluminum hydroxide and calcined boron-magnesium stone can react with the three components to generate adhesive substances under the conditions of normal temperature and high temperature, so that the components can be said to provide wet bulb strength and high temperature strength for the pellets.
The metallurgical pellet bentonite adhesion enhancer compound consists of ammonium orthophosphate, ammonium polyphosphate, condensed aluminum phosphate, calcined boron magnesium stone and aluminum hydroxide. According to the action mechanism of each component of the metallurgical pellet bentonite adhesion enhancer compound, some components can be singly decomposed and condensed to generate adhesion, some components react with each other to provide adhesion, some components react with calcined boron-magnesium stone or aluminum hydroxide to provide adhesion, some reactions generate and generate adhesion under normal temperature conditions, and some reactions generate and generate high-temperature adhesion under high temperature conditions. Therefore, the reinforcing system composed of all the five components has multiple substance types, wherein a plurality of components can provide low-temperature strength and high-temperature strength at the same time, the components in the composition have mutual synergistic and mutual complementary effects, the interference resistance is strong, and the components still can play a role in reinforcing when the pelletizing condition fluctuates to a certain extent.
The invention is preferably a tackifying system composed of ammonium orthophosphate, ammonium polyphosphate, condensed aluminum phosphate, calcined boron magnesium and aluminum hydroxide, and the mass ratio of the components is as follows:
Aluminum hydroxide, calcined boron magnesium stone, ammonium orthophosphate, ammonium polyphosphate, condensed aluminum phosphate=40-50:10-15:10-15:15-20:15-20:
wherein the ammonium polyphosphate preferably has a degree of polymerization of 4 to 10, and the aluminum polyphosphate preferably has a degree of polymerization of 4 to 10.
The five components are evenly mixed and sealed and packaged, and the metallurgical pellet bentonite bonding enhancer compound is obtained.
The metallurgical pellet bentonite binding enhancer of the invention provides additional (auxiliary) binding effect for the pellet bentonite to bind iron ore powder, and is realized by the following chemical processes.
(1) The mechanism of providing wet bulb strength to the pellets by the metallurgical pellet bentonite bond enhancer complex is approximately as follows:
The ammonium polyphosphate, especially ammonium orthophosphate, as the component of the iron ore pellet adhesion enhancer compound dispersed in the pellet bentonite will self-hydrolyze to produce phosphoric acid when contacting with water sprayed from pelletizing, and the phosphoric acid reacts with aluminum hydroxide to produce a series of adhesive matters to provide strength for wet pellets. Reaction to form H 3PO4 by hydrolysis of NH 4H2PO4:
NH4H2PO4→H3PO4+NH3↑
The nascent H 3PO4 undergoes a neutralization reaction with another component Al (OH) 3 in the adhesion enhancer to yield Al (H 2PO4)3:
Al(OH)3+3H3PO4→Al(H2PO4)3+3H2O
The newly formed Al (H 2PO4)3 has cohesiveness, and it can also slowly condense to gradually form Al 2H2P6O19 with cohesiveness, etc.
The Al (H 2PO4)3, al 2H2P6O19 and the like) can also react with MgO in the calcined magnesite to generate Mg (H 2PO4)2, mgAlHP 6O19 and MgB (H 2PO4)5), and the substances generated by the reactions can provide normal-temperature strength for the pellets.
Certain components in the aluminum polyphosphate in the reinforcing agent compound can also dissociate chelating groups when meeting water to complex with iron elements in iron powder, so that the pellets generate normal temperature strength. When the component AlH 6P7O22 is contacted with water sprayed by pelletizing, alH 4P7O22 2- ions with strong complexing ability are dissociated:
AlH6P7O22→AlH4P7O22 2-++2H+
The AlH 4P7O22 2- ions penetrate the iron oxide powder surface and combine with the iron to form FeAlH 4P7O22, and these FeAlH 4P7O22 gradually form a bond between the iron powder particles:
AlH4P7O22 2-+Fe2+→FeAlH4P7O22
The reaction products Al (H 2PO4)3、FeAlH4P7O22 and the like all play a role in binding, provide binding for iron powder except for the role in binding pellet bentonite, and increase the wet bulb strength of the iron ore pellets.
(2) The mechanism for providing high-temperature strength for the pellets by the metallurgical pellet bentonite bonding enhancer is as follows:
the aluminum phosphate polycondensate in the metallurgical pellet bentonite adhesion enhancer compound has a unique structure, namely contains an acidic group-POO - and a longer chain type main chain-PO-O-PO-, so that the aluminum phosphate polycondensate has strong dehydration condensation property in the pellet drying and sintering processes, gradually polymerizes into aluminum phosphate polycondensate with good adhesion performance and larger molecular weight from smaller molecules, and further improves the high-temperature strength and bursting temperature of the pellets. In the process of drying and sintering the pellets, along with the rise of temperature, each polycondensed aluminum phosphate molecule in the metallurgical pellet bentonite bonding enhancer compound can possibly generate intermolecular dehydration polymerization reaction under the action of high temperature. For example, each of the "O" and "OH" on each AlH 4P5O16 molecule can form a water molecule with the "OH" and "O" on another adjacent AlH 4P5O16 molecule or other condensed aluminum phosphate molecules of different types, respectively, and the water molecule is subjected to the glycidyl polymerization reaction. The AlH 4P5O16 performs a glycidyl polymerization reaction on the plane and space to form long-chain or space three-dimensional netlike macromolecules, and generates binding force among ferric oxide powder particles, so that the high-temperature strength and the anti-explosion capability of the iron ore pellets are improved.
The aluminum polyphosphate in the metallurgical pellet bentonite adhesion enhancer compound can also dissociate complexing groups to complex with iron elements on the surface of iron powder to enhance pellets when water is heated. According to the metallurgical pellet bentonite bonding reinforcing agent, one component AlH 4P5O16 can dissociate AlH 2P5O2- 16 ions with complexation capacity when heated:
AlH4P5O16→AlH2P5O2- 16++2H+
The AlH 2P5O2- 16 ions penetrate the iron oxide powder surface and combine with the iron to form FeAlH 2P5O16, and these FeAlH 2P5O16 gradually form a bond between the iron powder particles:
AlP3O10 2-+Fe2+→FeAlH2P5O16
The reaction products FeAlH 2P5O16 and the like play a role in binding, provide binding force for the iron powder except for the bentonite pellets, and provide a certain degree of assistance for the high-temperature strength of the pellets.
The ammonium polyphosphate in the metallurgical pellet bentonite adhesion enhancer compound can be subjected to chemical reactions such as dehydration, deamination, condensation and the like when the pellets are dried and sintered at high temperature, so that polyphosphoric acid is generated, and the polyphosphoric acid reacts with Al (OH) 3 to generate aluminum polyphosphate with good adhesion, so that the high-temperature strength of the pellets is improved, and the burst temperature of the pellets is increased. For example:
(NH4)H7P6O19→NH3+H8P6O19
H8P6O19+Al(OH)3→AlH5P6O19+3H2O
The above-mentioned Al (H 2PO4)3, al 2H2P6O19, etc.) can be reacted with MgO in calcined paigeite to produce Mg (H 2PO4)2, mgAlHP 6O19 and MgB (H 2PO4)5), these substances produced by these reactions can provide normal-temp. strength for pellets, and the mechanism of that many phosphates and polyphosphate can be used as bond reinforcing agent for bentonite pellets in the invention, and the phosphate ion contained in the polyphosphate component in the reinforcing agent compound can be undergone the process of polycondensation reaction to produce large molecule, at initial stage, PO 4 3- existed in phosphate binder can be undergone the process of curing agent calcination of paigeite, and gradually undergone the process of polycondensation reaction to produce PO 4 2- so as to form chain-like polymerized end point, and as the reaction advances, PO 4 2- ion can be reacted again into PO 4 -, and many PO 4 - end portions can be combined together to form a series of linear polyphosphate.
Since the polycondensed aluminum phosphate and ammonium polyphosphate salts according to the present invention are complex compounds, they undergo various other chemical reactions under pellet conditions, and these reaction products are beneficial to pellet strength as a whole.
The invention has one of the remarkable characteristics that the wet bulb strength of pellets manufactured in the metallurgical pellet bentonite bonding enhancer compound is mainly provided by bentonite, and the enhancer compound has a certain effect on the wet bulb strength, so that the wet bulb strength of the pellets is improved. The pellet bentonite has good dispersibility due to the effect of the mutual repulsion of the homopolarity among particles due to the small particle size of the montmorillonite and negative charge in the internal unit cell. After the bentonite is added, the cohesive property of the pelletizing material is improved, so that the capillary diameter in the green pellets is reduced and the capillary force is increased. On the other hand, after the bentonite absorbs water, the bentonite is filled among the particles of the green pellets in a colloidal particle manner, so that the connection condition among the particles of the materials can be improved, the transfer effect among the particles is realized, the binding force among the particles is increased, and the mechanical strength of the green pellets is increased as the binding capacity is increased. The bentonite is added into the pellet production to improve the compressive strength of the pellet, and when the green pellets are impacted by external force, sliding can be generated between the particles, so that the falling strength of the green pellets is improved more obviously. In the metallurgical pellet bentonite adhesion enhancer compound, H 3PO4 generated by hydrolysis of NH 4H2PO4 at room temperature reacts with Al (OH) 3, alH 2PO4 and condensate thereof are generated, the aluminum polyphosphate is hydrolyzed at room temperature and has good adhesion performance with iron powder reaction products and other room temperature, and the wet bulb strength of the pellets is further increased.
The invention is also characterized in that the high temperature strength and the anti-cracking temperature of the pellets are derived from two parts, one part is derived from the strength generated by bentonite, but the invention is not enough, the requirement can be met by singly using the bentonite with the addition of 2 to 2.5 percent or even higher proportion, and the other part is derived from the metallurgical pellet bentonite bonding enhancer compound. Bentonite is a substance with large specific surface area and high dispersity, and the addition of bentonite changes the surface property of the mixture, so that a high-temperature sintered glass phase exists between iron powder in the pellets, and the high-temperature strength of the pellets is improved. The bentonite can be used as a binder to greatly improve the bursting temperature because the bentonite and water have special affinity, so that the moisture in the pellets can be slowly migrated to the surface of the green pellets for evaporation, but the moisture in the pellets is not excessively fast released, and the bursting of the pellets due to the excessive internal vapor pressure is avoided. The contribution of the metallurgical pellet bentonite bonding enhancer compound to the high-temperature strength of the pellets is as described above, because certain components in the metallurgical pellet bentonite bonding enhancer react to generate substances with high-temperature bonding strength before and during the pellet drying and sintering process, thereby obviously improving the high-temperature strength and bursting temperature of the pellets.
Pellets produced using the metallurgical pellet bentonite bonding enhancer composite of the present invention continue to produce cementitious substances other than bentonite from the beginning of pelletization, which is a further significant feature of the present invention. These cementitious substances continue to play a role in pellet strength. As the drying and sintering temperature of the pellets increases, new adhesive substances appear, and the high-temperature strength of the pellets is acted. The reinforcing effect of the reinforcing agent compound is another auxiliary effect on the basis of the bonding strength of bentonite on the pellets, and the high-temperature bonding effect of the reinforcing agent compound is still exerted after the bentonite loses the bonding effect after the temperature is increased to 600-700 ℃ and the structural water is no longer bonded. So the pellets can bear greater antiknock stress than pellets bonded with bentonite alone. The metallurgical pellet bentonite bonding enhancer compound is beneficial to the performance of continuously increasing the heat intensity of the iron ore pellets in the heating process, so that the dry heat intensity of the pellets is rapidly increased in the heating process, larger antiknock stress can be borne, and particularly the performance of maintaining or increasing the heat intensity after 600-900 ℃ bentonite bonding is lost is more noble.
The invention also provides a specific preparation method of the metallurgical pellet bentonite bonding enhancer, and another technical problem to be solved is to provide a method for preparing the metallurgical pellet bentonite bonding enhancer. Because the metallurgical pellet bentonite bonding enhancer compound is small in dosage, the grinding processing of the pellet bentonite is continuous operation, and in order to ensure that the metallurgical pellet bentonite bonding enhancer compound is uniformly added and distributed in the bentonite, a large amount of carriers are needed to be used, and the bonding enhancer compound is mixed and diluted in the carriers. The specific preparation method of the metallurgical pellet bentonite bonding enhancer comprises the steps of feeding and uniformly mixing aluminum hydroxide trihydrate, calcined boron magnesium stone, ammonium orthophosphate, ammonium polyphosphate and condensed aluminum phosphate according to a proportion to obtain a metallurgical pellet bentonite bonding enhancer compound, and uniformly mixing the compound and pellet bentonite powder serving as a carrier according to a mass ratio of 1:1-5 to obtain the metallurgical pellet bentonite bonding enhancer.
The pellet bentonite adhesion enhancer is a turquoise powder, and industrial experiments prove that the pellet bentonite adhesion enhancer has good adhesion enhancement effect on bentonite with low blue absorption and bentonite with high blue absorption. Particularly, the bentonite with low blue absorption widely existing in the nature can be used for the production and processing of the pellet bentonite, which is significant for fully utilizing bentonite resources and reducing the production cost of the pellet bentonite. The carrier pellet bentonite is not an inert carrier, and the main function of the carrier pellet bentonite is as a carrier of the pellet bentonite adhesion enhancer, and the carrier pellet bentonite are uniformly mixed with each other so as to be beneficial to the uniform addition and dispersion of the metallurgical pellet bentonite adhesion enhancer in the pellet bentonite. In addition, the carrier is the pellet bentonite, and the pellet bentonite has a bonding effect on the iron powder. That is, the non-inert carrier in the invention does not affect the quality of the cast bentonite and does not have adverse effects.
The invention has the most remarkable beneficial effects that:
(1) Remarkably improves the wet bulb strength of the pellet bentonite
The reaction product of the metallurgical pellet bentonite adhesion enhancer has adhesion performance and has good effect on improving the compressive strength of green pellets. Under the condition that the total amount of bentonite is 1.3%, as the dosage of the reinforcing agent is increased from 0.1% to 0.3%, the falling strength and the compressive strength of magnetite green pellets are respectively increased from 2.4 times/each to 6.0 times/each, and the compressive strength is increased from 10.30N/each to 14.20N/each. This is because the bonding component generated by the reaction of the reinforcing agent is in a viscous state at an early stage, and a liquid-bonding bridge is formed between the iron powder particles. With the increase of the proportion of the metallurgical pellet bentonite bonding reinforcing agent, the viscosity of the bridge liquid is increased so as to improve the inter-particle viscous action energy, the dislocation amplitude of particles can be obviously increased under the condition that bridge liquid bonds are not broken, the anti-plastic deformation energy among the particles is increased, and the drop strength and the compressive strength of green balls are increased greatly.
(2) The high-temperature strength and the anti-explosion temperature of the pellets are obviously improved
The use of the iron ore pellet bentonite adhesion enhancer also brings about a great improvement in the high-temperature strength and the anti-riot temperature of the pellets. Pellet bentonite alone requires 2.0% of the dosage of pellet anti-burst temperature to reach 600 ℃, while 0.1%, 0.2% and 0.3% of reinforcing agent are respectively doped on the basis of 1.3% of bentonite, and the pellet anti-burst temperature exceeds 650 ℃, 700 ℃ and 850 ℃ respectively. The main reason for the good high temperature strength and antiknock performance of the iron ore pellets using the metallurgical pellet bentonite adhesion enhancer is that in the process of drying and sintering the pellets, as the temperature rises, the reaction products of certain components of the metallurgical pellet bentonite adhesion enhancer, such as Al (H 2PO4)3、FeAl(H6P10O31) and the like, are subjected to intermolecular dehydration polymerization under the action of high temperature, and undergo glycidyl polymerization on the plane and space to form a long-chain or space three-dimensional reticular macromolecular chain or reticular structure, finally form solid gel, generate binding force among iron oxide powder particles, and increase the high temperature strength and antiknock performance of the iron ore pellets.
(3) The dosage of the pellet bentonite is greatly reduced and the grade of the pellet iron is greatly increased
When no binder is added, the grade of the pellet iron is 64.36%, and when 2.0% of bentonite is added, the grade of the pellet iron is only 62.26%, and the grade is reduced by 2.10%. When 0.10 percent of reinforcing agent and 1.30 percent of pellet bentonite are added for partial replacement, the pellet iron grade is 63.74 percent, which is improved by 1.48 percent compared with the pellet bentonite. The metallurgical pellet bentonite bonding enhancer can provide extra low-temperature and high-temperature strength for pellets, the blending amount of the pellet bentonite is greatly reduced from 2.0% to 1.3%, the physicochemical properties and the pelletizing performance of raw materials are improved, the introduction of harmful impurities such as silicon dioxide is further reduced, and the quality of finished pellets is obviously improved.
Detailed Description
The following examples are given to further illustrate the features of the present invention and are provided for illustrative purposes only and in no way limit the scope of the invention.
The present invention (NH 4)3H7P8O25 -based ammonium polyphosphate and Al 8(H2P8O25)3 -based aluminum polyphosphate polycondensates) is commercially available.
Example-preparation of Metallurgical pellet Bentonite adhesion enhancer example
The metallurgical pellet bentonite bonding enhancer A is prepared by uniformly mixing five components of industrial aluminum hydroxide, calcined boron magnesium stone, industrial ammonium dihydrogen phosphate, poly ammonium phosphate mainly comprising NH 4)3H7P8O25 and poly aluminum phosphate mainly comprising Al 8(H2P8O25)3 according to the mass ratio of 45:12.5:12:17.5:17.5 to obtain a pellet bentonite bonding enhancer compound, and uniformly mixing the compound with pellet bentonite according to the mass ratio of 1:5.
Example preparation of a Metallurgical pellet Bentonite adhesion enhancer example
The metallurgical pellet bentonite bonding enhancer B is prepared by uniformly mixing five components of industrial aluminum hydroxide, calcined boron magnesium stone, industrial ammonium dihydrogen phosphate, poly ammonium phosphate mainly comprising NH 4)3H7P8O25 and polycondensed aluminum phosphate mainly comprising Al 8(H2P8O25)3 according to the mass ratio of 40:10:10:15:15, and uniformly mixing the mixture with pellet bentonite according to the mass ratio of 1:5.
Example preparation of Trimetallurgical pellet Bentonite adhesion enhancer
The metallurgical pellet bentonite bonding enhancer C is prepared by uniformly mixing five components of industrial aluminum hydroxide, calcined boron magnesium stone, industrial ammonium dihydrogen phosphate, poly ammonium phosphate mainly comprising NH 4)3H7P8O25 and poly aluminum phosphate mainly comprising Al 8(H2P8O25)3 according to the mass ratio of 50:15:15:20:20, and uniformly mixing the mixture with pellet bentonite according to the mass ratio of 1:5.
Example four Metallurgical pellet Bentonite bond enhancer substituting for high blue absorbing Bentonite example
The water content of the magnetite powder is controlled to be 8.4-8.6% after the magnetite powder is dried. 5kg of magnetite powder is weighed, and the metallurgical pellet bentonite bonding enhancer A and the blue absorbing amount 32 of pellet bentonite H prepared in the first embodiment are mixed into a certain proportion to be used as pellet bonding agents. And pelletizing on a disc pelletizer with the diameter of 800mm, the rotating speed of 25r/min and the inclination angle of 49 degrees, weighing 500g after pelletizing, measuring the moisture of the green pellets, and taking the green pellets with the diameter of 10-15 mm for measuring the burst temperature, the falling strength and the compressive strength of the green pellets. The green pellets are dried in an iron-chromium-aluminum wire resistance furnace with the hearth diameter of 50mm at 120 ℃ and then baked in a silicon-carbon tube resistance furnace. The compressive strength of pellets was measured using an intelligent pellet press. The results of the pelletization experiments are shown in Table 1.
Table 1 Experimental results of the combination of enhancer A and high blue absorption Bentonite
| Enhancer A/% | Bentonite H/% | Drop Strength/(times/0.5 m) | Compressive Strength/(N/N) | Burst temperature/°c |
| 0 | 2.0 | 3.3 | 9.10 | >600 |
| 0 | 1.3 | 2.4 | 5.6 | 542 |
| 0.1 | 1.3 | 4.4 | 10.30 | >650 |
| 0.2 | 1.3 | 5.2 | 12.01 | >700 |
| 0.3 | 1.3 | 6.0 | 14.20 | >850 |
The green pellets of the pellets produced by the reinforcing agent A have good thermal performance and the burst temperature is above 650 ℃. When 0.10% of the reinforcing agent A is added, the dosage of bentonite is reduced to 1.3%, and the green strength requirement can be met, and the green strength requirement can reach 4.4 times/(0.5 m). From the viewpoint of pelletization effect, when the reinforcing agent A is adopted, the dosage of the reinforcing agent A with the dosage of 0.10 percent can be reduced by 0.7 percent of bentonite for the iron ore concentrate tested. The replacement efficiency of the reinforcing agent A is higher.
Example five metallurgical pellet Bentonite adhesion enhancer instead of Low blue absorbing Bentonite example
All operations are the same as in example four except that the blue-absorbing amount of 32 bentonite H is replaced by the blue-absorbing amount of 24 bentonite M. The results of the pelletization experiments are shown in Table 2.
Table 2 Experimental results of the combination of reinforcing agent A and Low-absorption blue ball bentonite
| Enhancer A/% | Bentonite M/% | Drop Strength/(times/0.5 m) | Compressive Strength/(N/N) | Burst temperature/°c |
| 0 | 3.5 | 3.0 | 8.42 | >600 |
| 0 | 1.7 | 1.6 | 4.4 | 530 |
| 0.1 | 1.7 | 4.2 | 8.78 | >600 |
| 0.2 | 1.7 | 4.7 | 10.32 | >650 |
| 0.3 | 1.7 | 5.3 | 12.74 | >750 |
When the low blue (24) absorbing pellet bentonite is used alone for pelletizing, the bentonite doping amount needs to reach 3.5% burst temperature to exceed 600 ℃. When the reinforcing agent A is added in 0.10%, the dosage of the low blue-absorbing bentonite is reduced to 1.7%, the green ball strength requirement can be met, the green ball strength requirement can be reached to 4.2 times/(0.5 m), and the bursting temperature is above 600 ℃. From the viewpoint of pelletizing effect, when the reinforcing agent A is adopted, low blue-absorbing amount of inferior bentonite can be used for the pellet binder.
Example six iron grade of pellets when the reinforcing agent B was substituted for bentonite
The high-grade furnace burden is the fundamental guarantee for realizing high yield and low consumption of the blast furnace, and is also the target for long-term pursuit of metallurgical workers. The pellet world has been devoted to research and development of various binders for many years, and the purpose of the pellet world is to reduce the dosage of bentonite, even cancel the bentonite, and improve the iron grade of pellets. Therefore, the iron grade of the pellets is a main basis for verifying the advantages and disadvantages of the pellet bentonite additive.
Table 3 shows the results of the grade analysis of the iron pellets with different reinforcing agents B. When no binder is added, the grade of the pellet iron is 64.36%, and when 2.0% of bentonite H (32) with high blue absorption is added, the grade of the pellet iron is only 62.26%, and the grade is reduced by 2.10%. When 0.30% of the reinforcing agent B is added to completely replace bentonite, the grade of the pellet iron is 63.57%, which is lower than that of the pellet without the binder by 0.79%, but is improved by 1.31% compared with that of the bentonite pellet. When 0.10% of reinforcing agent B and 1.30% of bentonite are added for partial replacement, the grade of pellet iron is 63.74%, and the grade of pellet iron is improved by 1.48% compared with that of bentonite pellets. Therefore, when the reinforcing agent B is adopted to replace bentonite, the effect of obviously improving the grade of the pellet iron is achieved.
TABLE 3 iron grade of reinforcing agent B pellets in different proportions
| Bentonite amount/% | Reinforcing agent B | W(TFe)% |
| 0 | 0 | 64.36 |
| 2.0 | 0 | 62.26 |
| 0 | 0.3 | 63.57 |
| 1.3 | 0.1 | 63.74 |
Example influence of seven Metallurgical pellet Bentonite bond enhancer C on the pelletization Property of iron concentrate
When the metallurgical pellet bentonite adhesion enhancer is not added and only the high blue absorption amount bentonite H2.0% is used, the growth rate of the pellets is 1.46mm/min, and the 1.3% bentonite is compounded with 0.2% metallurgical pellet bentonite adhesion enhancer C, so that the growth rate of the pellets is reduced to 1.52mm/min. This is due to the fact that the metallurgical pellet bentonite bonding enhancer C is added to the pellet raw material to reduce the bentonite doping amount, which results in a slight increase in the growth rate of the pellets.
Claims (3)
1. The metallurgical pellet bentonite adhesion enhancer compound is characterized by comprising, by weight, 10-15 parts of ammonium orthophosphate, 15-20 parts of ammonium polyphosphate, 15-20 parts of polycondensate aluminum phosphate, 40-50 parts of aluminum hydroxide and 10-15 parts of calcined boron-magnesium stone;
The general formula of the ammonium orthophosphate is (NH 4)nH3-nPO4, wherein n is less than or equal to 3, and the general formula of the ammonium polyphosphate is H (n-m)+2(NH4)mPnO3n+1, wherein n is more than or equal to 4 and less than or equal to 10, and m is more than or equal to n+2;
The condensed aluminum phosphate is a linear chain aluminum polyphosphate having the general formula:
wherein n is more than or equal to 4 and less than or equal to 10;
the calcined paigeite is prepared by calcining natural paigeite ore at 700-850 ℃ and crushing, and reacts with ammonium polyphosphate and condensed aluminum phosphate at normal temperature and high temperature to generate bonding effect and solidify, so that the calcined paigeite is used as a normal temperature solidifying agent and a high temperature solidifying agent of a metallurgical pellet bentonite bonding reinforcing agent.
2. The metallurgical pellet bentonite bonding enhancer complex of claim 1, wherein the ammonium orthophosphate is one or more of NH 4H2PO4、(NH4)2HPO4 and (NH 4)3PO4).
3. A preparation method of a metallurgical pellet bentonite bonding enhancer is characterized in that the metallurgical pellet bentonite bonding enhancer compound as defined in claim 1 and pellet bentonite powder as a carrier are uniformly mixed according to a mass ratio of 1:1-5 to obtain the metallurgical pellet bentonite bonding enhancer.
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