CN1199908C - Artificial wallastonite and its producing method - Google Patents

Artificial wallastonite and its producing method Download PDF

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Publication number
CN1199908C
CN1199908C CN 99127560 CN99127560A CN1199908C CN 1199908 C CN1199908 C CN 1199908C CN 99127560 CN99127560 CN 99127560 CN 99127560 A CN99127560 A CN 99127560A CN 1199908 C CN1199908 C CN 1199908C
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raw material
furnace
wollastonite
making
artificial
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CN1301677A (en
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张梦显
门兆严
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Dalian Global Mineral Ltd By Share Ltd
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Abstract

The present invention relates to artificial wollastonite which comprises calcium fluoride and the oxide of calcium, silicon, aluminum, magnesium, sodium, boron, barium, etc. After raw materials, such as natural wollastonite, silica, calcite, feldspar, luorite, etc. are crushed and mixed, the raw materials are put into a kiln to be heated by fuel gas and fired at the temperature of 1000 to 1600 DEG C; then, the raw materials are cooled naturally or cooled by a water quenching method and are ground; thus, the artificial wollastonite is formed. The artificial wollastonite can be used as a protecting material for metallurgical casting, a desulfurizing agent and a dephosphorizing agent for refining outside the furnace, a powder solidifying agent, paint for a welding rod, etc.

Description

Artificial tabular spar and method for making thereof
The present invention relates to metallurgical cast protecting materials, is that element oxides such as a kind of calcic, silicon, aluminium are the production technology of master's artificial stone material; Relate to the welding electrode cladding material simultaneously.
Wollastonite is the natural silicate mineral, Calucium Silicate powder CaSiO 3Content is more than 50%.Because its stable physics and chemical property are applied to chemical industry, building materials, field of metallurgy in recent decades.Because it is single that natural wollastonite is formed, its range of application is subjected to certain restriction.Carried out the research of synthetic wollastonite in recent years both at home and abroad: carry out proportioning with the industrial mineral that contains different element compounds, and the experiment of various processes, the oxide compound that facts have proved elements such as containing silicon, calcium, aluminium, magnesium, boron is that the artificial tabular spar of main body has more advantageous property and range of application more widely.Producing this product at present is to be main raw material with the industrial mineral, forms through fusing.Production method is broadly divided into two kinds: the one, and what ZL97116724.9 provided is production unit with the metallurgical shaft furnace, is fuel with coke, the method for firing for raw material with Wingdale, quartzite etc.Because coke is brought ash impurities below 20% into, so the product colour that is fired into is darker, vitreous state is difficult to fully, and product only can be used for the covering slag base-material, and use range is too narrow.Other method is the electric arc furnace method for cooking, many except its operation, power consumption is big, cost high, electrode burns consumption and also brings beavy metal impurity into to product, its difficult quality improves.The obtained product of described these methods can't be more widely used in other respects.
At the defective that above-mentioned prior art exists, the present invention is intended to use the reasonable raw material prescription, and advanced equipment and sintering technology are made high quality, can adapt to the product of artificial tabular spar cheaply of many-sided application.
Contained component still is CaO and SiO in the product of the present invention 2, also can be CaO and Al 2O 3, other components are (as MgO, Na 2O, Fe 2O 3, B 2O 3, BaO, CaF 2Deng) change to some extent along with the purposes difference.Component is with CaO and SiO 2Be main artificial tabular spar as metallurgical continuous casting covering slag base-material, it prevents that secondary oxidation, lubricated, insulation and purification function are all good; Certainly also very suitable as the insulating covering agent in the ladle.Component is with CaO and Al 2O 3The product that is main, less siliceous even does not have silicon can be made furnace external refining agent, the CaO that wherein contains, Al 2O 3The function that all has desulfurization, phosphorus; Contain B 2O 3Product can be used as the powder solidifying agent.
In order to make the product that contains these components, the present invention adopts and contains these components or can participate in sintering procedure that to react the mineral and the compound that change into these components be raw material, for example provides SiO with natural wollastonite, quartzite, water glass 2Wingdale (also name calcite) and natural wollastonite provide CaO; Aluminium vanadine and bauxite all can provide Al 2O 3Magnesite and brucite, light or reburned magnesia can provide MgO; Calcined soda for industry provides Na 2O; Fluorite can provide CaF 2Lithionite, Quilonum Retard provide Li 2O; Barite and barium carbonate provide BaO; Simultaneously can provide Na with feldspar in addition 2O, K 2O, Al 2O 3, SiO 2Rhombspar can provide CaO and MgO etc. simultaneously.
The present invention to the requirement (weight %) of raw material is:
Natural wollastonite CaSiO 3〉=50
Quartzite (silica) SiO 2〉=90
Calcite (Wingdale) CaCO 3〉=90
Feldspar Na 2O+K 2O 〉=13
Aluminium vanadine Al 2O 3〉=80
Bauxite Al 2O 3〉=50
Rhombspar CaMg (CO 3) 2〉=90
Magnesite MgCO 3〉=90
Brucite Mg (OH) 2〉=90
Fluorite CaF 2〉=70
Soda ash Na 2CO 3〉=90
Quilonum Retard Li 2CO 3〉=90
Lithionite Li 2O 〉=5
Barium carbonate BaCO 3〉=90
Barite BaSO 4〉=80
Water glass Na 2SiO 3〉=90
Borax Na 2B 4O 7.10H 2O 〉=90
Can burn out the artificial tabular spar product with shaft furnace, electric arc furnace.It is considered herein that to be more preferably and use tank furnace; (being that the kiln that glaze is used is fired in ceramic industry) is with combustion gas-comprise coal gas, liquefied gas and Sweet natural gas etc.-be the technology of the energy; its specific practice is; all raw materials all need to be crushed to the footpath and are 10cm following grain or powdery; tank furnace needs below the 2mm; its objective is and melt as early as possible and react; one reacts completely to reduce power loss and to make; to calculate and mix in the input tank furnace of back in the ratio of required each component of product through the raw material of metering; fuse with the combustion gas heating, be controlled at 1000-1600 ℃ and fire.In the sintering procedure, carbonate in the raw material and other compounds carry out decarbonation, dehydration reaction, the molten materials that is fired into is almost completely vitreous state, constantly flow out the hydrophthalmia under tank furnace, the refrigerative mode has two kinds: the one, and water quenching, molten mass bursts into granule or fritter with cold water, and preferably particle diameter is 1-5mm grain, piece, from water, separate drying, grinding and screening, packing warehouse-in then; Other method is through cold naturally or air-cooled, broken then, grinding screening.With the molten mass that tank furnace is fired into, it is of light color, is close to translucent body.
The method for making of this artificial tabular spar is: in weight proportion, contain the natural wollastonite of 30-100% in raw materials used, and CaSiO in the natural wollastonite 3Content 〉=wt50%, its step comprises:
A. will put into stove behind the raw material pulverizing mixing;
B. heat stove, under 1000-1600 ℃, fire;
C. with water quenching or air cooling method cooling molten materials, obtain artificial tabular spar after crushing and screening; Wherein said stove is shaft furnace, electric arc furnace, tank furnace, and heating energy source is respectively metallurgical coke, electricity, combustion gas, and when using shaft furnace or electric arc furnace, to particle diameter 10cm, when using tank furnace, raw material pulverizing is to particle diameter 2mm with raw material pulverizing.Wherein raw material can be natural wollastonite, quartz and fluorite; Also can be natural wollastonite, calcite and fluorite; Can also be natural wollastonite and fluorite.Wherein combustion gas is coal gas, liquefied gas or Sweet natural gas.Artificial tabular spar according to the inventive method is produced, in wt%, contain:
CaO 35.20-48.34
SiO 2 43.41-60.01
Al 2O 3 0.98-2.93
Fe 2O 3 0.28-2.0。
Furnace external refining agent of the present invention contains in wt%:
CaO 48.10-49.01％
SiO 2 2.58-4.76％
Al 2O 3?46.82-46.93％
Fe 2O 3?0.87-0.94％
MgO 0.62-0.72％
P 0.03-0.71％
S 0.08-0.13％
The method for making of this furnace external refining agent, its step comprises:
A: will put into stove behind raw material limestone and the bauxitic clay pulverizing mixing;
B: the heating stove, under 1320-1420 ℃, fire;
C:, obtain furnace external refining agent after crushing and screening with water quenching or air cooling method cooling molten materials;
Wherein said stove is shaft furnace, electric arc furnace, tank furnace, and heating energy source is respectively metallurgical coke, electricity, combustion gas, and when using shaft furnace or electric arc furnace, to particle diameter 10cm, when using tank furnace, raw material pulverizing is to particle diameter 2mm with raw material pulverizing.
Raw material of the present invention uses proper, and its prescription rationally; Particularly on manufacture method, select tank furnace for use, with combustion gas particularly Sweet natural gas be that its control of fuel is easy, simple to operate, make good product quality and can produce the product of various compositions and suitable different needs to reduce cost significantly.This is that prior art can't be compared.
Embodiment
Below with example this law is described further.
Example 1: fire artificial tabular spar with tank furnace, become the following powder-material of particle diameter 2mm standby required feedstock production.Get the natural wollastonite 815kg of powder, quartzy 65kg, fluorite 120kg thorough mixing stirs, and the combustion gas tank furnace is preheated to 1320 ± 20 ℃, after constant 10 minutes mixed material is dropped in the kiln from fire door, and the visual fusion situation is constantly replenished reinforced.Slowly moving behind the material melting to the kiln wake flow, further fully fusion in flow process.The molten mass kiln tail water eye place that flows through falls in the cooling basin, bursts the disintegrating slag that becomes to differ in size, and pulls out and is dried to water content below 0.5%, gets 6mm aperture sieve screening pack.
Product through checking its composition (%) is: CaO 43.48, SiO 249.37, Al 2O 32.68, Fe 2O 30.30, F -3.62 MgO 0.45.Granularity 1-6mm accounts for more than 90%.
Example 2: get powder: natural wollastonite 875kg, calcite 25kg, fluorite 100kg, method for making such as example 1 are got 1350 ± 20 ℃ of kiln temperature.
Product detects its composition (%): CaO 48.34, SiO 243.41, Al 2O 32.93, Fe 2O 30.4, F -4.38 MgO 0.7, K 2O 0.3.Granularity 1-6mm accounts for more than 90%.
Example 3: get powder: natural wollastonite 598kg, quartzite 282kg, fluorite 120kg, method for making such as example 1,1440 ± 20 ℃ of kiln temperature.
Product detects its composition (%): CaO 35.2, SiO 260.01, Al 2O 31.22, Fe 2O 30.28, F -2.91 MgO 0.42.
Example 4: get powder: natural wollastonite 900kg, fluorite 100kg, method for making such as example 1,1400 ± 20 ℃ of kiln temperature.
Product detects its composition (%): CaO 46.31, SiO 245.27, Al 2O 31.28, Fe 2O 30.33, F -3.78 MgO 0.46.
Example 5: get natural wollastonite powder entirely, method for making such as example 1,1450 ± 20 ℃ of kiln temperature.Product its composition (%) after testing is: CaO 46.34, SiO 250.49, Al 2O 30.98, Fe 2O 30.34.
Example 1-5 product is suitable for doing the metallurgical protective slag base-material, and 4 are more suitable for covering material, and 4.5 also can be used as the raw material of welding electrode outer layer coating.
Example 6 is got powder: calcite 345kg, fluorite 270kg, rhombspar 280kg, bauxitic clay 105kg, method for making such as example 1,1450 ± 20 ℃ of kiln temperature, not existing together is that melts flows out to ground from the mouth of a river, burst into piece behind the naturally cooling, through fragmentation, the following pack of 20mm is got in screening.
Product composition (%) is after testing: CaO 42.31, SiO 22.36, Al 2O 314.34, Fe 2O 30.46 MgO 11.20, CaF 229.30, H 2O 0.03.Granularity 5-20mm accounts for more than 90%.
Example 7 is got powder: Wingdale 660kg, bauxitic clay 340kg, 1400 ± 20 ℃ of kiln temperature, method for making such as example 6.
Product its composition (%) after testing is: CaO 49.01, SiO 22.58, Al 2O 346.82, Fe 2O 30.94 MgO 0.62, P 0.71, and S 0.08, H 2O 0.076.
The suitable external refining material of doing of the product of example 6,7.
Example 8 is got powder: quartzite 399kg, borax 407kg, soda ash 194kg, method for making such as example 6,1250 ± 20 ℃ of kiln temperature.
Product its composition (%) after testing is CaO 1.47, SiO 252.31, Al 2O 32.55, Na 2O 2.73, B 2O 319.75 MgO 0.54, S 0.011, and P 0.0170, and product sieves below 20 orders, can be used for the solid powdering agent.
Example 9 is produced artificial tabular spar with shaft furnace (1 meter of diameter).Get metallurgical coke 280kg, natural wollastonite 815kg, quartzite 65kg, fluorite 120kg is stirred in it standby together, and the 200kg firewood is put into shaft furnace, light, add the 700kg coke button, treat after the coke button combustion compound to be added gradually, add wind and the kiln temperature control about 1320 ℃, the melt gob flows out from discharge port at the bottom of kiln, becomes piece through shrend, pulls out to be dried to moisture content＜0.05%, through the screening of 6mm hole sizer, pack.
Product detects its composition (%) CaO 42.03, SiO 248.67, Al 2O 32.92, F -3.13 MgO 0.94, Fe 2O 30.79.
Example 10 is got Wingdale 660kg, and bauxitic clay 340kg founds with example 9 methods, and molten mass is crushed to below the 30mm through naturally cooling.
Product is its composition (%) CaO 48.10 after testing, SiO 24.76, Al 2O 346.93 MgO 0.72, Fe 2O 30.87 P 0.03, S 0.13, H 2O 0.01.
Example 11 is produced artificial tabular spar with electric arc furnace.Get natural wollastonite 875kg, calcite 25kg, fluorite 100kg, mixing is fed in the electric furnace that has electrode bar, the energising igniting, furnace temperature reaches 1350 ℃ of material semi-moltens, constantly drips to furnace bottom formation liquid layer, flows out from the mouth of a river, and shrend bursts into fritter.Can temporarily block up the upper water-out mouth when trickling slowly, put its outflow in good time again as molten mass.Pull fragment out, the screening of dry back.
Product is its composition (%) CaO 48.45 after testing, SiO 242.83, Al 2O 33.03 MgO 0.79, Fe 2O 30.48, F -4.74 granularity 1-6mm accounts for more than 90%.
Example 12 is got calcite 345kg, fluorite 270kg, and rhombspar 280kg, bauxitic clay 105kg mixing is founded as example 11 methods.Material dissolves at 1450 ℃, and molten mass flows out naturally cooling, is crushed to the following fritter of 20mm.
The product detected result is: CaO 41.90%, SiO 23.46%, Al 2O 314.58%, MgO 10.37%, Fe 2O 30.43%, CaF 229.02%, H 2O 0.07%.

Claims (6)

1. the method for making of an artificial tabular spar is characterized in that:
In weight proportion, contain the natural wollastonite of 30-100% in raw materials used, and content 〉=wt50% of CaSiO3 in the natural wollastonite, its step comprises:
A: will put into stove behind the raw material pulverizing mixing;
B: the heating stove, under 1000-1600 ℃, fire;
C:, obtain artificial tabular spar after crushing and screening with water quenching or air cooling method cooling molten materials;
Wherein said stove is shaft furnace, electric arc furnace, tank furnace, and heating energy source is respectively metallurgical coke, electricity, combustion gas, and when using shaft furnace or electric arc furnace, to particle diameter 10cm, when using tank furnace, raw material pulverizing is to particle diameter 2mm with raw material pulverizing.
2. method for making according to claim 1 is characterized in that wherein raw material is natural wollastonite, quartz and fluorite.
3. method for making according to claim 1 is characterized in that wherein raw material is natural wollastonite, calcite and fluorite.
4. method for making according to claim 1 is characterized in that wherein raw material is natural wollastonite and fluorite.
5. according to the described method for making of arbitrary claim among the claim 1-4, it is characterized in that wherein combustion gas is coal gas, liquefied gas or Sweet natural gas.
6. according to the artificial tabular spar of the described method for making production of arbitrary claim among the claim 1-5, it is characterized in that: contain in wt%:
CaO 35.20-48.34
SiO 2 43.41-60.01
Al 2O 3 0.98-2.93
Fe 2O 3 0.28-2.0。
CN 99127560 1999-12-29 1999-12-29 Artificial wallastonite and its producing method Expired - Fee Related CN1199908C (en)

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CN102051443A (en) * 2010-12-31 2011-05-11 昆明理工大学 High basicity fluorine-free RH (Ruhrstah-Heraeus) desulfurizer
CN102390839B (en) * 2011-08-17 2013-02-13 四川海吉尔环保科技开发有限公司 Method for producing artificial wollastonite powder by utilizing Bayer red mud
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