CN114804671A - Method for preparing nodular cast iron grinding ball from iron-rich nickel slag and preparing cementing material in cooperation with nodular cast iron grinding ball - Google Patents
Method for preparing nodular cast iron grinding ball from iron-rich nickel slag and preparing cementing material in cooperation with nodular cast iron grinding ball Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 174
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000002893 slag Substances 0.000 title claims abstract description 144
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 77
- 238000000227 grinding Methods 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 55
- 229910001141 Ductile iron Inorganic materials 0.000 title claims abstract description 53
- 238000010791 quenching Methods 0.000 claims abstract description 51
- 230000000171 quenching effect Effects 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000002054 inoculum Substances 0.000 claims abstract description 27
- 238000003723 Smelting Methods 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 238000005266 casting Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 238000011081 inoculation Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910001563 bainite Inorganic materials 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 12
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000010079 rubber tapping Methods 0.000 claims description 8
- 230000002195 synergetic effect Effects 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005279 austempering Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 4
- NCJRLCWABWKAGX-UHFFFAOYSA-N [Si].[Ca].[Ba] Chemical compound [Si].[Ca].[Ba] NCJRLCWABWKAGX-UHFFFAOYSA-N 0.000 claims description 3
- OOJQNBIDYDPHHE-UHFFFAOYSA-N barium silicon Chemical compound [Si].[Ba] OOJQNBIDYDPHHE-UHFFFAOYSA-N 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical group [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 27
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- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 12
- 239000004568 cement Substances 0.000 description 8
- 239000004567 concrete Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
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- 229910000519 Ferrosilicon Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- 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
Abstract
The invention discloses a method for preparing a cementing material by the cooperation of nodular cast iron grinding balls prepared from iron-rich nickel slag. The method comprises the following steps: adding a reducing agent and a modifying agent into the iron-rich nickel slag, and carrying out reduction smelting to obtain molten iron and molten secondary slag; adding a nodulizer and an inoculant into the molten iron, performing nodulizing and inoculation treatment, and casting into balls; carrying out heat treatment on the cast ball to obtain a nodular cast iron grinding ball; and (3) quenching the molten secondary slag, drying and performing ball milling to obtain the active micro powder cementing material. According to the invention, the iron-rich nickel slag is used as a raw material, the cast iron grinding balls prepared by extracting metal from the iron-rich nickel slag are combined with the cementing material prepared by synchronously modifying molten slag, so that the process flow of nickel slag treatment is optimized, the cost is reduced, the production efficiency is improved, the added value of the product is high, and the market competition advantage is achieved; by means of full component utilization, the utilization rate of the nickel slag can be effectively improved, and the recycling and harmless utilization of the iron-rich nickel slag are promoted.
Description
Technical Field
The invention relates to the technical field of nickel slag treatment, in particular to a comprehensive nickel slag treatment process, and particularly relates to a method for preparing a cementing material by cooperating ductile cast iron grinding balls prepared from iron-rich nickel slag.
Background
The nickel slag is produced by FeO and SiO in the ferronickel smelting process 2 And industrial waste slag formed by water quenching the molten material with MgO as the main component. According to the difference of ore sources (oxidized ore or sulfide ore) and smelting processes (a flash furnace method, an oxygen-enriched top-blown method, a rotary kiln direct reduction method or a rotary kiln-submerged arc furnace combined method), 6-16 tons of nickel slag can be discharged when 1 ton of nickel is produced, and the nickel slag becomes the fourth major smelting industrial waste slag after iron slag, steel slag and red mud in China.
According to different production raw materials and processes, the chemical components of the nickel slag are different, but the TFe content is about 40 percent, which is far higher than the average grade of iron ore in China, and the nickel slag also contains a small amount of alloy elements such as nickel, copper and the like and 25 to 35 percent of SiO 2 1-5% of CaO and 5-10% of MgO, which are resources with valuable metal recycling value and used for developing cementing materials. On the other hand, China has become the largest world-wide iron ore import country from 2003, the import quantity is on the rise year by year, the external dependence of the iron ore in China is kept above 80% in six years, the import quantity reaches 11.7 hundred million tons in 2020, the external dependence is 80.6%, and the non-renewable property of the iron ore is combined, so that the seeking of alternative resources of the iron ore is bound to be a necessary way for promoting the healthy development of the iron and steel industry. Therefore, resource utilization of nickel slag is an urgent need for solving land waste and environmental pollution caused by large accumulation of nickel slag, and is also an important way for changing waste into valuable, seeking available steel production raw materials, reducing cost, improving efficiency and promoting resource recycling.
The current utilization direction of iron-rich nickel slag mainly comprises the following steps: (1) valuable metals are extracted, for example, CN104988302A discloses a nickel slag treatment method for efficiently recovering iron resources; (2) as a filling material; (3) preparing microcrystalline glass, such as CN109399940A discloses a method for preparing nickel slag microcrystalline glass; (4) for producing building materials such as cement, concrete, building blocks, autoclaved products and the like, for example, CN 112608043A discloses a high-strength nickel slag-based solid waste cementing material and a preparation method thereof; CN 111559901A discloses alkali-activated recycled nickel slag cement concrete; CN104671825A discloses a nickel slag autoclaved aerated concrete block and a preparation method thereof. However, the above utilization modes of nickel slag are parallel to each other, the product line is single, for example, if valuable metals in nickel slag are simply extracted, the nickel slag can be used as a raw material in the steel industry, but a large amount of secondary slag is generated in the nickel slag, the nickel slag is directly used as a cementing material without any treatment, the valuable metal resources in the nickel slag are wasted, the value of the nickel slag cannot be fully exerted by the two slag, and the comprehensive utilization degree of the nickel slag is low.
In conclusion, the treatment method for iron-rich nickel slag in the prior art has single function, cannot fully utilize valuable components of nickel slag, has low economic benefit, and simultaneously extracts metal elements in the nickel slag in the stage of preparing raw materials for steel production, rarely relates to the process flow of subsequent product production, and has unclear practical application value.
Disclosure of Invention
Based on the above, the invention aims to provide a method for preparing a cementing material by the cooperation of nodular cast iron grinding balls prepared from iron-rich nickel slag, so as to solve the problems of low comprehensive utilization degree of nickel slag, complex operation flow of nickel slag utilization, single product, low added value and the like in the prior art.
The above object of the present invention can be achieved by the following technical solutions:
the invention provides a method for preparing a nodular cast iron grinding ball from iron-rich nickel slag to prepare a cementing material in a synergistic manner, which comprises the following steps: adding a reducing agent and a modifying agent into the iron-rich nickel slag, and carrying out reduction smelting to obtain molten iron and molten secondary slag; adding a nodulizer and an inoculant into the molten iron, performing nodulizing and inoculation treatment, and casting into balls; carrying out heat treatment on the cast ball to obtain a nodular cast iron grinding ball; and (3) quenching the molten secondary slag, drying and performing ball milling to obtain the active micro powder cementing material.
Optionally, the molten iron comprises the following components: 3 to 3.8 percent of C, 2 to 3.5 percent of Si, 0.5 to 2.5 percent of Mn, less than or equal to 0.1 percent of P, less than or equal to 0.03 percent of S, 0 to 0.5 percent of Cu and the balance of Fe.
Optionally, the mass ratio of the iron-rich nickel slag, the reducing agent and the modifying agent is 100: 2-15: 10-30 parts; wherein the reducing agent is a carbon-containing raw material, and the modifying agent is a CaO-containing raw material.
Optionally, during reduction smelting, the smelting temperature is 1350-1550 ℃.
Optionally, the tapping temperature is 1460-1520 ℃ during tapping.
Optionally, in the step of adding a nodulizer and an inoculant into the molten iron, performing nodulizing and inoculating treatment and casting into balls, adding the nodulizer and the inoculant into the molten iron in a mode of flushing along with flow; the mass ratio of the molten iron to the inoculant to the nodulizer is 100: 0.3-1: 1 to 2. Optionally, the inoculant is a ferrosilicon inoculant, a silicon barium inoculant or a silicon barium calcium inoculant. The nodulizer is a magnesium alloy nodulizer. Optionally, the casting is performed to form a sphere, and the casting temperature is more than or equal to 1420 ℃.
Optionally, in the step of performing heat treatment on the cast ball to obtain the ductile iron grinding ball, the heat treatment is performed by performing isothermal quenching before aging treatment.
Optionally, the austempering is performed in a temperature interval of bainite transformation.
Optionally, the austempering comprises: polishing and cleaning the cast ball, and austenitizing; moving to an isothermal quenching device for isothermal quenching and introducing a bainite structure.
Optionally, austempering, comprising: keeping the cast ball after polishing and cleaning at 880-940 ℃ for 60-150 min for austenitizing; quickly moving the steel plate to an isothermal quenching device for isothermal quenching to introduce a bainite structure, wherein the isothermal temperature is 220-350 ℃, and the heat preservation time is 60-180 min; and air cooling after isothermal quenching.
Optionally, the step of austempering is followed by an aging treatment. The aging treatment comprises the following steps: and (3) placing the cast ball subjected to isothermal quenching in an aging treatment device, preserving the temperature for 20-26 h, for example 24h, at 130-160 ℃, and air-cooling to room temperature to obtain the nodular cast iron grinding ball.
Optionally, the surface hardness of the nodular cast iron grinding ball is more than or equal to 50 HRC.
Optionally, in the ball milling step, the nodular cast iron grinding balls are used as a ball milling medium.
Optionally, quenching and drying the molten secondary slag, and performing ball milling to obtain the active micro powder cementing material: quenching by adopting a water spraying cooling mode or a mode of quickly pouring water into the water and stirring simultaneously to obtain water quenching wet slag. And drying the water quenching wet slag by adopting drying equipment until the water content is less than 1 percent to obtain water quenching dry slag. The nodular cast iron grinding balls are used as a ball milling medium, and the water quenched dry slag is ground in ball milling equipment until the specific surface area is more than 400m 2 And/kg, discharging to obtain the active micro powder cementing material.
Optionally, the density of the active micro powder cementing material is more than 2.83g/cm3, the standard curing 7d activity index of the mortar test block is more than 72%, and the standard curing 28d activity index is more than 88%.
Has the advantages that: according to the invention, the iron-nickel-rich slag metal is extracted to prepare the cast iron grinding ball and the molten slag is synchronously modified to prepare the cementing material for combination, namely, the valuable metal iron-containing material extracted from the iron-nickel-rich slag is used for preparing the nodular cast iron grinding ball, and the molten secondary slag in the iron extraction process is used for preparing the cementing material, so that a process route from waste slag to various finished products is opened, and the added value of the product is high; the nickel slag treatment process is optimized, and the cost is reduced; realizes the full component utilization of the nickel slag, improves the utilization rate of the nickel slag and promotes the recycling harmless utilization of the iron-rich nickel slag.
Compared with the prior art, the invention also has the following advantages and beneficial effects:
(1) the method adopts a mode of valuable metal component reduction and slag thermal state synchronous modification to prepare the nodular cast iron grinding ball and the cementing material, and realizes the full-component high-value development of the iron-rich nickel slag through combined production and utilization.
(2) The invention carries out quenching on the molten secondary slag of reduction smelting to obtain a large amount of glass phase, improves the activity of the glass phase, can directly prepare the active micro powder cementing material for the cement admixture and the concrete admixture without adding other materials, has simple process flow and effectively improves the utilization rate of the nickel slag.
(3) Furthermore, a bainite structure is introduced into the nodular cast iron grinding ball through a heat treatment process of isothermal quenching and then aging treatment, so that residual stress is eliminated, the strength and the wear resistance are improved, the additional value of the grinding ball product is improved, and the method has market competitiveness. The method solves the problem that the bainite structure can not be completely obtained in the conventional quenching and low-temperature tempering heat treatment mode.
(4) Furthermore, the method can also introduce the prepared nodular cast iron grinding balls as a ball milling medium into the step of preparing the cementing material by using the secondary slag, thereby realizing the composite cross application of preparing metal products and building products by using the nickel slag and providing a reliable path for the high-value utilization of nickel slag resources; the product interaction and the co-production are combined, so that the cost reduction, the efficiency improvement and the comprehensive utilization are really realized.
Drawings
Fig. 1 is a process flow chart of a method for preparing a nodular cast iron grinding ball and a cementing material by using the iron-rich nickel slag in an embodiment of the invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for preparing a nodular cast iron grinding ball from iron-rich nickel slag to prepare a cementing material in a synergistic manner, which comprises the following steps: carrying out reduction smelting on the iron-rich nickel slag to obtain molten iron and secondary slag; preparing a nodular cast iron grinding ball by casting and heat treatment by using the molten iron; the active micro powder gel material is prepared by quenching, drying and ball milling secondary slag.
The combined mode of 'preparing nodular cast iron grinding balls by reducing valuable metal components and preparing cementing materials by thermal state synchronous modification of slag' of the iron-rich nickel slag provided by the invention provides a feasible path for full-component high-value utilization of the iron-rich nickel slag by optimizing the process flow; the added value of the product is high, the utilization rate of the nickel slag is effectively improved, and the recycling and harmless utilization of the iron-rich nickel slag is promoted.
In the process of preparing the active micro-powder cementing material from the secondary slag, the nodular cast iron grinding balls prepared by the method are preferably used as a ball milling medium during ball milling; therefore, the composite cross application of the metal products and the building products prepared from the nickel slag is realized, and the cost reduction, the efficiency improvement and the comprehensive utilization are really realized through the product interaction and the co-production combined use.
In a preferred embodiment, in the step of preparing the nodular cast iron grinding ball by casting and heat treatment by using the molten iron, the heat treatment is carried out by carrying out isothermal quenching and then aging treatment, and a bainite structure is introduced into the nodular cast iron grinding ball by an isothermal quenching heat treatment process, so that the strength and the wear resistance are improved, the additional value of a grinding ball product is improved, and the grinding ball has market competitiveness; after isothermal quenching, aging treatment is carried out, so that residual stress is further eliminated, cracking of the workpiece is prevented, the bainite ductile iron grinding ball is obtained, and the bainite structure is guaranteed to be obtained.
Fig. 1 schematically shows a process flow of a method for preparing a nodular cast iron grinding ball and a cementing material by using iron-rich nickel slag in an embodiment of the invention. As shown in figure 1, the method for preparing the nodular cast iron grinding ball from the iron-nickel-rich slag to prepare the cementing material in a synergistic way comprises the following steps:
(1) reducing and smelting to extract iron: adding a reducing agent and a modifying agent in a certain proportion into the iron-rich nickel slag, uniformly mixing, then sending into a smelting furnace for reduction smelting to generate molten iron and secondary slag, wherein the melt of the secondary slag is on the upper layer of the molten iron, and discharging molten iron and slag irregularly.
The smelting furnace adopted by the reduction smelting can be a side-blown smelting furnace, an electric arc furnace, an ore smelting furnace, an intermediate frequency furnace and the like. Preferably, the molten pool is fully stirred in the smelting process, so that the reaction process can be accelerated; the stirring mode can adopt one or more of gas stirring, electromagnetic stirring and mechanical stirring.
In the invention, the iron-rich nickel slag: reducing agent: hardening and tempering agent is 100: 2-15: 10-30; so as to obtain molten iron with required components and regulate the components of the secondary slag. Wherein the reducing agent is a carbon-containing raw material, such as coal powder, coke powder and the like. The modifying agent preferably adopts CaO-rich raw materials, such as one or more of limestone, quicklime, dolomite and the like, so that the obtained active micro powder can meet the content requirement of each component when the active micro powder is used for preparing building materials such as cement and the like. The invention adjusts the alkalinity and the composition of the secondary slag by the CaO-rich modifier to obtain the active micro powder. Further, the C/S of the secondary slag is adjusted to be approximately equal to 1.0, such as 0.9, 1.0, 1.2 and the like, by adopting the conditioning agent, so that the obtained micro powder has good gelling activity.
In the reduction smelting process, materials in the furnace are heated to 1350-1550 ℃ to form a molten pool, and then reduction iron extraction and slagging processes are carried out for 30-150 min. And (4) tapping after the molten iron components are detected to be qualified in front of the furnace, wherein the temperature is 1460-1520 ℃, and slag stopping is required during tapping. The obtained molten iron comprises the following components: 3-3.8% of C, 3-3.5% of Si2, 0.5-2.5% of Mn, less than or equal to 0.1% of P, less than or equal to 0.03% of S, 0-0.5% of Cu and the balance of Fe. In the embodiment of the invention, the iron-rich nickel slag is used as an iron-producing raw material; meanwhile, a method of reducing and extracting iron and adjusting components for modification is adopted, so that the possibility of preparing the cementing material from the slag powder is improved.
(2) Preparing a nodular cast iron grinding ball: adding an inoculant and a nodulizer into the molten iron obtained in the step (1) in a certain proportion, carrying out inoculation and spheroidization, then carrying out casting molding, cooling and drawing to obtain a cast ball; and after polishing and cleaning the obtained cast ball, carrying out a heat treatment process of isothermal quenching and then aging treatment to obtain the bainite ductile iron grinding ball.
Wherein, the process of casting the molten iron into the cast ball adopts die casting with simple process to cast the ball, for example, sand die casting or metal die casting process can be selected, the casting temperature is more than or equal to 1420 ℃, and slag blocking needs to be paid attention to during casting.
Preferably, the nodulizer and the inoculant are added into the molten iron in a mode of flushing with the flow during pouring, and the mechanical strength of the nodular cast iron can be ensured by adopting the mode. Wherein, molten iron: inoculant: nodulizer 100: 0.3-1: 1 to 2. Wherein the inoculant can be selected from one of silicon iron grain inoculant, silicon barium inoculant and silicon barium calcium inoculant. The inoculant is adopted to promote graphitization, improve graphite morphology and distribution conditions, increase the number of eutectic clusters, refine matrix tissues and have good effects in a short time (about 5-8 min) after inoculation. The nodulizer can be selected from magnesium alloy nodulizers. The nodulizer can promote graphite in the structure to crystallize into a spherical shape and keep the spherical shape for a long time without deformation, and has the functions of deoxidation and desulfurization while improving the mechanical strength.
The structure obtained after the molten iron is cast is easy to be uneven, and the service life of the cast ball can be prolonged by carrying out heat treatment on the cast ball after casting. The heat treatment process comprises the following steps:
first, austempering is performed in the temperature range of bainite transformation: keeping the temperature of the cast ball at 880-940 ℃ for 60-150 min for austenitizing, then quickly moving the cast ball to an isothermal quenching device for keeping the temperature for a period of time, and then air-cooling; wherein the isothermal temperature is 220-350 ℃, and the heat preservation time is 60-180 min. And then carrying out isothermal treatment and aging treatment, namely, keeping the temperature at 130-160 ℃ for 20-26 h, carrying out air cooling to room temperature after the aging treatment is finished, further eliminating residual stress through the aging treatment, and preventing the workpiece from cracking.
The isothermal quenching device can be selected from a medium-frequency quenching furnace, a high-frequency quenching furnace, a power-frequency quenching furnace, a mesh-belt type isothermal quenching furnace, a vertical quenching furnace, a salt bath furnace and the like. The salt bath medium can be selected from sodium nitrate, potassium nitrate, sodium chloride, etc. The aging treatment device is provided with drying functional equipment, such as an optional oven, a drying box and the like.
According to the invention, through the bainite structure introduced by the isothermal quenching and then the aging treatment, the impact toughness, the fracture toughness, the wear resistance and the service life of the grinding ball can be obviously improved, the surface hardness of the bainite type nodular cast iron grinding ball is more than or equal to 50HRC, the standard of GB/T17445 plus 2009 casting grinding ball is met, the production cost is low, and the method is a suitable choice of grinding ball materials. The heat treatment of the invention adopts isothermal quenching and aging treatment, and the temperature is constant in the temperature interval of bainite transformation, so that the room temperature structure of the obtained grinding ball is guaranteed to be bainite, and the grinding ball has higher hardness and simultaneously the toughness is improved. The method solves the problem that the bainite structure can not be completely obtained in the conventional quenching and low-temperature tempering heat treatment mode.
(3) Preparing active micro powder: after iron extraction, the molten secondary slag is quenched, dried and ball milled to obtain the active micro powder cementing material for cement and concrete. The cast iron grinding balls prepared after iron extraction can be used as a ball milling medium to grind secondary slag, so that the effective utilization of products is realized.
The molten secondary slag is quenched by adopting a water spraying cooling mode or a cooling mode of directly pouring into water. Further, in the cooling process, the secondary slag is stirred in time so as to improve the cooling rate. The formation of a large amount of active glass phase is ensured by quenching the molten secondary slag.
The water quenching wet slag obtained after quenching is dried before preparing the active micro powder to obtain water quenching dry slag with the water content of less than 1 percent, thereby avoiding the problem that the water quenching wet slag can generate hydration reaction in the grinding process. Wherein, the drying device can be used without an oven, a drying oven and the like.
And (3) feeding the dried water quenched dry slag into ball milling equipment for grinding, wherein the ball milling equipment can be a drum-type ball mill, a conical ball mill, a horizontal ball mill, a planetary ball mill and the like, the bainite type nodular cast iron grinding ball prepared by the method is used as a ball milling medium, the water quenched dry slag is ground to a required specific surface area, and then discharging is carried out, so that the active micro powder cementing material for cement and concrete is obtained. The prepared nodular cast iron grinding ball is introduced into a cementing material for preparing the ball, and the product is combined in an interactive and joint production manner, so that the cost is reduced, the efficiency is improved, and the comprehensive utilization degree is high.
The obtained active micro powder has a specific surface area of more than 400m 2 Kg, density > 2.83g/cm 3 The standard curing 7d activity index of the mortar test block is more than 72 percent, the standard curing 28d activity index is more than 88 percent, and the standard curing is in accordance with JC/T2503-The technical index requirements of the powder.
According to the invention, a large amount of glass phase is obtained by quenching the molten secondary slag obtained by reduction smelting, so that the activity of the glass phase is improved, and the active micro powder cementing material for the cement admixture and the concrete admixture can be directly prepared without adding other materials, so that the process flow is simple, and the utilization rate of nickel slag is effectively improved.
According to the invention, the slag is thermally modified while valuable metal components are extracted from the iron-rich nickel slag through reduction smelting to prepare the nodular cast iron grinding balls, and the obtained secondary slag can be used for cement admixture and concrete admixture only through a simple way of grinding to the required specific surface area without adding an exciting agent during preparation of the active micro powder auxiliary cementing material, so that the process flow of nickel slag treatment is optimized, the cost is reduced, the production efficiency is improved, and the full-component high-value utilization of the iron-rich nickel slag can be realized.
The technical scheme of the invention is further explained by combining the specific embodiment as follows:
example 1
The method for preparing the nodular cast iron grinding ball from the iron-rich nickel slag to prepare the cementing material in a synergistic way comprises the following steps:
1) iron extraction from iron-rich nickel slag
The device comprises the following steps: and (4) a side-blown smelting furnace.
Iron-rich nickel slag: coal powder: quick lime is 100: 4: 20.
heating the materials in the furnace to 1400 ℃ to form a molten pool, then carrying out reduction iron extraction and slagging for 40min, and raising the temperature to 1480 ℃ during tapping, and stopping slag and tapping. The obtained molten iron comprises the following components: 3.08 percent of C, 2.56 percent of Si, 1.26 percent of Mn, 0.06 percent of P, 0.01 percent of S, 0.24 percent of Cu and the balance of Fe.
2) Ball casting
The grinding ball is formed by adopting an iron mold sand-lined casting process, the casting temperature is 1460 ℃, a magnesium alloy nodulizer and a ferrosilicon grain inoculant are flushed along with the flow, and molten iron: inoculant: nodulizer 100: 0.3: 1.2, the diameter of the sphere is phi 30 mm.
3) Thermal treatment
And carrying out isothermal heat treatment on the obtained cast ball, keeping the temperature of the cast ball at 920 ℃ for 120min for austenitizing, then quickly moving the cast ball to a salt bath furnace with the temperature of 320 ℃ for heat preservation for 120min, and then carrying out air cooling, wherein the salt bath medium is a 1:1 mixture of potassium nitrate and sodium nitrate. And (4) placing the grinding balls subjected to isothermal treatment in an oven at 140 ℃ for heat preservation for 24 hours, and air-cooling to room temperature.
4) Preparation of active micro powder
Pouring the tapped slag into water for quenching to ensure that the slag is vitrified, drying and grinding the slag in a ball mill, wherein the specific surface area of the ground slag is 428m 2 Kg, density 2.916g/cm 3 The standard curing 7d activity index of the mortar test block is 82%, and the standard curing 28d activity index is 106%.
The description of the present invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to practitioners skilled in this art. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
Claims (10)
1. A method for preparing a cementing material by the cooperation of a nodular cast iron grinding ball prepared from iron-rich nickel slag is characterized by comprising the following steps:
adding a reducing agent and a modifying agent into the iron-rich nickel slag, and carrying out reduction smelting to obtain molten iron and molten secondary slag;
adding a nodulizer and an inoculant into the molten iron, performing nodulizing and inoculation treatment, and casting into balls; carrying out heat treatment on the cast ball to obtain a nodular cast iron grinding ball;
and (3) quenching the molten secondary slag, drying and performing ball milling to obtain the active micro powder cementing material.
2. The method for preparing the nodular cast iron grinding ball and preparing the cementing material by the cooperation of the iron-rich nickel slag and the nodular cast iron grinding ball according to claim 1, wherein the molten iron comprises the following components: 3 to 3.8 percent of C, 2 to 3.5 percent of Si, 0.5 to 2.5 percent of Mn, less than or equal to 0.1 percent of P, less than or equal to 0.03 percent of S, 0 to 0.5 percent of Cu and the balance of Fe.
3. The method for preparing the nodular cast iron grinding ball synergistic preparation cementitious material by using the iron-nickel-rich slag according to claim 1,
the mass ratio of the iron-rich nickel slag to the reducing agent to the tempering agent is 100: 2-15: 10-30; wherein the reducing agent is a carbon-containing raw material, and the modifying agent is a CaO-containing raw material;
during reduction smelting, the smelting temperature is 1350-1550 ℃;
when tapping, the tapping temperature is 1460-1520 ℃.
4. The method for preparing the nodular cast iron grinding ball and preparing the cementing material cooperatively according to the iron and nickel-rich slag of claim 1, wherein in the steps of adding a nodulizer and an inoculant into molten iron, performing nodulizing and inoculation treatment and casting into balls,
adding a nodulizer and an inoculant into molten iron in a mode of flushing with flow; the mass ratio of the molten iron to the inoculant to the nodulizer is 100: 0.3-1: 1-2; the inoculant is a silicon-iron grain inoculant, a silicon-barium inoculant or a silicon-barium-calcium inoculant; the nodulizer is a magnesium alloy nodulizer;
the casting is carried out to form balls, and the pouring temperature is more than or equal to 1420 ℃.
5. The method for preparing the nodular cast iron grinding ball and preparing the cementing material cooperatively according to the iron-nickel-rich slag of claim 1, wherein in the step of obtaining the nodular cast iron grinding ball by carrying out heat treatment on the casting ball, the heat treatment is carried out by carrying out isothermal quenching firstly and then carrying out aging treatment;
wherein the austempering is performed within a bainite transformation temperature interval, and comprises:
keeping the cast ball after polishing and cleaning at 880-940 ℃ for 60-150 min for austenitizing;
quickly moving the steel plate to an isothermal quenching device for isothermal quenching to introduce a bainite structure, wherein the isothermal temperature is 220-350 ℃, and the heat preservation time is 60-180 min;
and (5) air cooling after isothermal quenching.
6. The method for preparing the nodular cast iron grinding ball synergistic preparation cementitious material by using the iron-nickel-rich slag according to claim 5,
the aging treatment comprises the following steps: and (3) placing the cast ball subjected to isothermal quenching in an aging treatment device, preserving the temperature for 20-26 h at 130-160 ℃, and cooling in air to room temperature.
7. The method for preparing the nodular cast iron grinding ball synergistic preparation cementitious material through the iron-nickel-rich slag according to claim 1, wherein the surface hardness of the nodular cast iron grinding ball is more than or equal to 50 HRC.
8. The method for preparing the nodular cast iron grinding balls and preparing the cementing material cooperatively according to the iron-nickel-rich slag as claimed in claim 1, wherein in the step of ball milling, the nodular cast iron grinding balls are used as a ball milling medium.
9. The method for preparing the cementing material by the synergism of the nodular cast iron grinding balls and the nickel-rich slag according to claim 8, is characterized in that in the step of quenching and drying the molten secondary slag and obtaining the active micro powder cementing material by ball milling,
quenching by adopting a water spraying cooling or rapid pouring into water while stirring to obtain water quenching wet slag;
drying the water quenching wet slag by adopting drying equipment until the water content is less than 1% to obtain water quenching dry slag;
the nodular cast iron grinding balls are used as a ball milling medium, and the water quenched dry slag is ground in ball milling equipment until the specific surface area is more than 400m 2 And/kg, discharging to obtain the active micro powder cementing material.
10. The method for preparing the nodular cast iron grinding ball synergistic preparation cementitious material by using the iron-nickel-rich slag according to claim 9, wherein the density of the active micro powder cementitious material is more than 2.83g/cm 3 The standard curing 7d activity index of the mortar test block is more than 72 percent, and the standard curing 28d activity index is more than 88 percent.
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