CN101555147A - Flexible periclase compound spinel brick - Google Patents
Flexible periclase compound spinel brick Download PDFInfo
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- CN101555147A CN101555147A CNA2009100115911A CN200910011591A CN101555147A CN 101555147 A CN101555147 A CN 101555147A CN A2009100115911 A CNA2009100115911 A CN A2009100115911A CN 200910011591 A CN200910011591 A CN 200910011591A CN 101555147 A CN101555147 A CN 101555147A
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Abstract
A flexible periclase compound spinel brick solves the problems of the structure spalling and the environmental pollution of the generated sexivalence chromium salt which are always existed in the traditional magnesia-chromite brick. The manufacturing process thereof comprises sand making and brick making; firstly, a solid solution, the inner core of the body of which contains Al2O3, Cr2O3 and MgO, is prepared; the outer edge of the body is special synthesized solid solution sand formed by layer belts containing magnesium aluminate spinel; and then ynthesized solid solution sand used as one of brick making ingredient, prefabricated magnesite clinker, and periclase spinel selected according to the requirements are made into the periclase compound spinel brick according to the requirements of the set technological conditions. The brick conditionally retains a defined amount of chromium and has good hanging kliner coating performance, and obviously reduces the capability of generating sexivalence chromium salt owing to changing the mode of existence of Cr2O3 in the brick. When the brick is used, a metamorphic zone belt does not appear, thus fundamentally eliminating the recurring illness of the structure spalling generation in the use course and prolonging the service life.
Description
Technical field
The present invention relates to a kind of refractory materials, is that a kind of non-structure that is specifically designed to the cement kiln clinkering zone peels off specifically, and the flexible periclase compound spinel brick of sexavalence chromic salts is grown, can effectively be reduced to the life-span.
Background technology
Mainly there are two big technical barriers in the magnesia chrome brick that existing cement kiln clinkering zone is used:
First magnesia chrome brick produces human body and the deleterious sexavalence chromic salts of environment in producing and using.
German doctor E. popularize law Ilyushin in 1931 is found the many lung cancer of the chromic acid worker of saltworks, further discovers, the water-soluble sexavalence chromic salts that enters human body infiltrates and is reduced to trivalent chromium behind the cell and constitutes carcinogens, and then causes the sudden change and the canceration of cell.The harm and the protection of sexavalence chromic salts all paid much attention in countries in the world, in China's " drinking water sanitary standard " " industrial design hygienic standard " all regulation tap water sexavalence chromic salts be no more than 0.05mg/l, a chromic maximum permissible concentration is 0.0015mg/l in the atmosphere of Residential areas, the highest permissible discharge concentration of trade effluent 0.5mg/l.
The cement kiln magnesia chrome brick is cement industry, the chromic source of pollution of fire-resistant industry, and it is the highest Cr of the residual brick of kiln down
+ 6Content reaches 2577mg/kg.Produce cement 12～1,300,000,000 ton per year to the various model cement kilns of 2007 China in the end of the year, year consume nearly 400,000 tons of magnesia chrome brick, this means that producing the sexavalence chromic salts gets over kiloton.The sexavalence chromic salts is water-soluble, is easy to differentiate that promptly looking unfamiliar into thick yellow-green colour salt efflorescence at brick after the residual brick of following kiln makes moist is exactly the sexavalence chromic salts.Because of the sexavalence chromic salts water-soluble, especially big to the hazardness of environment.Discover the chrome ore (Cr in the magnesia chrome brick
2O
3), magnesia chrome spinel (MgOCr
2O
3) and cement clinker, fuel in potassium (K
2O), sodium (Na
2O), calcium (CaO) has generated Cr
+ 6Salt or double salt, be stored in the pore of chrome ore, this means that changing chrome ore exists form just can stop generation sexavalence chromic salts.
Although since the Japanese magnesia chrome brick that is used for cement kiln first with the replacement of periclasite spinel brick in 1975 is attempted to reduce the harm of sexavalent chrome salt pair human body and environment, had tested once with the periclasite spinel brick countries in the world, dolomite brick, magnesia calcium zirconium bricks etc. replace magnesia chrome brick, China introduces six large-scale decomposition kilns from the eighties in last century, the kiln-lining brick of initial import is with regard to useful periclasite spinel brick, dolomite brick replaces magnesia chrome brick, but all because of the periclasite spinel brick kliner coating of losing control of one's feelings, reasons such as dolomite brick peels off all can't be achieved success the effort that reduces the sexavalence chromic salts.Thisly will eliminate Cr in the brick
2O
3As the research direction of eliminating the harm of sexavalence chromic salts, though go through the effort in year surplus in the of 30, all less than the original intention that realizes stopping the sexavalence chromic salts, even to this day, magnesia chrome brick is still the principal item that is used for the various cement kiln clinkering zones of China.
It two is that magnesia chrome brick in use peels off and becomes the persistent ailment that can't eliminate.
As everyone knows, the structure metamorphic belt of the wide 20-40mm of reaching in use appears in magnesia chrome brick.The major cause that causes magnesia chrome brick to peel off is: the mineral structure of magnesia chrome brick is periclasite and magnesia chrome spinel system, be higher than the firing temperature (1500 ℃) of cement with cement slurry eutectic temperature mutually, so it is big that cement slurry is invaded the degree of depth mutually, rotten bandwidth, the physics of this metamorphic belt, mechanical property are different with former brick, occur peeling off under the effect of mechanical stress and thermal stresses, reduce more than 40% work-ing life.
Major reason is arranged in addition in addition, i.e. chrome ore (Cr in use
2O
3) to distance hot side 15～40mm place's enrichment,, but not coincidence with the rarefied zone position consistency of magnesia chrome brick, enriching quantity is chromium content (Cr in the brick
2O
39%) 2.5～3.0 times, maximum enriching quantity reaches 29%.Cr
2O
3Fusing point up to 2400 ℃ about, Cr
2O
3The impossible sintering of zone of enrichment so make zone of enrichment tissue looseness, causes structure spalling.Even more serious is Cr
2O
3This enrichment also strengthened the growing amount of sexavalence chromic salts with same multiple.Fire-resistant factory uses gives birth to chrome ore making magnesia chrome brick, a small amount of chrome ore (Cr
2O
3) when burning till and periclasite (MgO) reaction generate magnesia chrome spinel, the overwhelming majority exists with state of nature, this just makes chrome ore produce enrichment in use inevitably, causes the magnesia chrome brick structure spalling and generates the sexavalence chromic salts.
Summary of the invention
The purpose of this invention is to provide a kind of flexible periclase compound spinel changes, it has solved the structure spalling that traditional magnesia chrome brick exists always and has generated problem such as sexavalent chrome salt pollution environment, its reasonable in design, this brick have not only changed Cr in it when having kept an amount of chromium conditionally
2O
3Have a form, reduce the ability that generates the sexavalence chromic salts significantly, but also realized that the extension kliner coating is functional, use back non-structure metamorphic belt, fundamentally eliminated the persistent ailment of structure spalling, prolonged work-ing life.
The technical essential of the technical solution adopted in the present invention is:
The used batching of flexible periclase compound spinel brick comprises that body is close greater than 3.25g/cm
3Synthetic Solid solution sand and body close greater than 3.25g/cm
3Magnesite clinker, the weight ratio of each component is in the batching: synthetic sosoloid sand: magnesite clinker=(4～6): (15～12); The brickmaking operation steps is as follows: will prepare burden respectively through the broken back of pulverizing by the grade screening, magnesite clinker be ground into 4-2mm, 2-1mm, 1-0mm ,≤0mm level Four granularity, synthesize sosoloid sand be ground into 2-0mm ,≤0mm two-stage granularity; Size composition major controls at different levels in the batching: the 2-1mm grade accounts for 16-20%, and the 1-0mm grade accounts for 15-24%, and≤0mm grade accounts for 32-38%, and surplus is the 4-2mm grade; Granularities at different levels will accurately be made sreen analysis in the course of processing, finish batching according to sreen analysis; Be equipped with proportion 1.2-1.25g/cm again
3Paper pulp as wedding agent, in edge runner-wet mill, be mixed into pug, order of addition(of ingredients) is to add particulate material earlier, treat particulate material by paper pulp wetting evenly after, add fine powder again, the mixing time after fine powder adds can not be less than 10 minutes; The mud material forming that mixes is the close 3.0～3.1g/cm of body
3Work in-process, work in-process are dry down 90～110 ℃ of temperature, 16～24 hours time of drying, make residual water-content less than 0.5%; Dried work in-process burn till under 1670～1690 ℃ in tunnel furnace, are incubated 6-8 hour; The temperature fall time of controlling 1650 ℃ to 1400 ℃ is no less than 6 hours, is incubated 2 hours down at 1400 ℃, and the kiln discharge passed examination is the finished product flexible periclase compound spinel brick.
Contain Al in the batching of above-mentioned flexible periclase compound spinel brick in addition
2O
358～66% body is close greater than 3.20g/cm
3Sintering periclasite spinel sand, the weight ratio of each component is in the described batching: synthetic sosoloid sand: magnesite clinker: sintering periclasite spinel sand=(4～6): (15～12): (0.1～2), except that sintering periclasite spinel is sieved into the 2-0mm one-level granularity by grade after fragmentation, all the other brickmaking operation stepss are identical with above-mentioned brickmaking operation steps in its brickmaking operation steps.
The body kernel of above-mentioned synthetic Solid solution sand is to contain Al
2O
3, Cr
2O
3With the Solid solution of MgO, the outer rim of body is the layer band that contains magnesium-aluminium spinel; Used batching comprises the calcined wagnerite powder, gives birth to chromite ore fine and high alumina raw bauxite powder, and its weight ratio is: the calcined wagnerite powder: give birth to chromite ore fine: high alumina raw bauxite powder=(20～43): (32～27): (32～28); System sand operation steps is as follows: with calcined wagnerite, give birth to chrome ore and high alumina raw bauxite and be milled down to the percent of pass that equals or be not more than 0.088mm respectively after crushed greater than 95%; Powder is done chemical analysis determine various raw material consumptions; The batching that to determine is with proportion 1.05g/cm then
3Rare paper pulp make wedding agent and in sand mill, mix; Mixed fine powder is pressed into the waste base of standard type on press, waste base through 90～110 ℃ dry after residual water-content less than 0.5%; In the high temperature kiln, burn till under the 1750-1770C, be incubated 6～8 hours; The cooling rate of control in the tunnel furnace drops to 1400 ℃ by 1650 ℃ and can not be less than 6 hours, and wherein 1400 ℃ of insulations are at least 2 hours; The control component target of synthetic Solid solution sand is:
SiO
2Equal or be not more than 2.5%, Al
2O
320～35%, Cr
2O
312～18%, body is close＞3.25g/cm
3
Also contain aluminium hydrate powder in the batching of above-mentioned synthetic Solid solution sand, the weight ratio of each component is in the used batching: the calcined wagnerite powder: give birth to chromite ore fine: aluminium hydrate powder: high alumina raw bauxite powder=(20～43): (32～27): (16～2): (32～28); All the other system sand operation stepss are identical with above-mentioned system sand operation steps.
In the system sand operation steps of above-mentioned synthetic Solid solution sand, when described waste base was burnt till in rotary kiln, firing temperature equaled or is not more than 1800 ℃, and all the other system sand operation stepss are identical with above-mentioned system sand operation steps.
Advantage and positively effect that the present invention has are: because this flexible periclase compound spinel brick adopted a kind of special synthetic Solid solution sand in batching, specially be that its kernel is to contain Al
2O
3, Cr
2O
3With the Solid solution of MgO etc., outer rim is to be rich in Al
2O
3Magnesium-aluminium spinel (MgOAl
2O
3) layer band.The formation of this special construction is that the temperature that has made full use of when Solid solution is separated out in the silicic acid salt face with magnesium-aluminium spinel is different, the temperature height that Solid solution is separated out (about 1600-1500 ℃), separate out in advance, and the temperature that magnesium-aluminium spinel is separated out low (about 1500-1400 ℃), separate out behind the quilt, thereby the layer band of magnesium-aluminium spinel be enclosed in the Solid solution outer rim, makes synthetic Solid solution sand form a kind of special construction of very science.Reasonable in design because of this brick structure, in batching, kept an amount of chromium content conditionally, but this Cr
2O
3Be changed and had form, so the chrome ore (Cr in the body of synthetic Solid solution sand
2O
3) no longer be the chrome ore of state of nature, but and MgO, Al
2O
3The synthetic Solid solution is because of having changed chrome ore (Cr
2O
3) in magnesia chrome brick, there is a form, so stay the activity that oxide compounds such as having changed it and potassium, sodium, calcium generate the sexavalence chromic salts.Because the outer rim of synthetic Solid solution is a magnesium-aluminium spinel layer band, and magnesium-aluminium spinel and cement eutectic point low (about 1400 ℃) at first produce (trace) liquid phase when contacting with the cement clinker of semi-melting state.Liquid phase has been sealed the pore of brick, has stoped the intrusion of cement phase; It is flexible that liquid phase makes the hot junction of brick produce simultaneously, improved the ability of anti-shearing stress rupture, so the responding layer of flexible periclase compound spinel brick and cement has only the thick (responding layer 15～20mm) of magnesia chrome brick of 3-5mm, thereby realized that the extension kliner coating is functional, do not form the structure metamorphic belt after using, overcome structure spalling.Again because liquid phase has stoped the invasion of cement slurry phase, correspondingly reduced Cr in oxide compound such as potassium in the cement clinker, sodium, calcium and the Solid solution
2O
3Contact, also just reduced the possibility that generates the sexavalence chromic salts.
Synthetic Solid solution sand has been given brick with flexibility and eliminated the structure metamorphic belt, make flexible periclase compound spinel brick possess the performance that magnesia chrome brick is hung kliner coating, solve the structure spalling that traditional magnesia chrome brick exists always again and generated problem such as sexavalent chrome salt pollution environment, fundamentally eliminate the persistent ailment of structure spalling, prolonged work-ing life.
The characteristic water-soluble with the sexavalence chromic salts can judge above-mentioned positively effect:
Will be directly in conjunction with magnesia chrome brick (Cr
2O
39%) and flexible periclase compound spinel brick (Cr
2O
33.5%) be broken into respectively less than each 500g of 1.0mm particle, contain in the 2500ml cup, pour clear water into, contain direct cup in conjunction with magnesia chrome brick and turn green at once, wash 12 times (precipitate 2 hours and pour out clear water), water in the cup remains strong green; Contain the cup of flexible periclase compound spinel brick, have only the green of extremely light extremely light (being difficult to identification), after water in the cup is displayed half a year, because of the MgO aquation becomes oyster white.From the soluble test result as can be seen, changing chrome ore exists form to reduce later the growing amount of sexavalence chromic salts very effectively.In the flexible periclase compound spinel brick non-hexavalent chromium salt is arranged on earth for further determining, the following residual brick of kiln is made diffraction analysis, in flexible periclase compound spinel brick, add pure Na in addition
2O, K
2O each 7.5%, burn till and make diffraction after the 1450 ℃ * 4h and identify, in these two kinds of diffraction qualification results, all do not find the sexavalence chromic salts.
Flexible periclase compound spinel brick shows that through practical application the life-span can extend to (on average) more than 10 months, and wherein quite a few brick has been created China's furnace campaign the highest (18.5 months) service recorder, and normal loss is not more than the 7mm/ month.Through check, the equal non-structure metamorphic belt of residual brick of all large-scale decomposition kiln exhausted flexible periclase compound spinel bricks.
Embodiment
Describe concrete structure of the present invention in detail below in conjunction with embodiment.The manufacturing process of this flexible periclase compound spinel brick is made up of system sand and brickmaking two portions, promptly at first Solid solution sand is synthesized in preparation, to synthesize Solid solution sand again as one of brickmaking batching and ready-formed magnesite clinker and the sintering periclasite spinel of selection as required, prepare burden by the processing condition of setting and the control component target of requirement, make required flexible periclase compound spinel brick.The concrete operations step is as follows:
Step 1 system sand
As the formulation science of the synthetic Solid solution sand of one of brickmaking batching, structure is special, and its main component is Al
2O
3, Cr
2O
3, and MgO, wherein MgO is the integral part in the synthetic Solid solution sand, but it does not belong to the control composition, the major control composition is Al
2O
3, Cr
2O
3, SiO
2, the index of control composition is: SiO
2Equal or be not more than 2.5%, Al
2O
320～35%, Cr
2O
312～18%, density＞3.25g/cm
3The body kernel that should synthesize Solid solution sand is to contain Al
2O
3, Cr
2O
3With the Solid solution of MgO, Cr
2O
3No longer primary chrome ore (Cr in Solid solution
2O
3), the outer rim of body is to contain magnesium-aluminium spinel (MgOAl
2O
3) layer band.
The used batching of system sand comprises the calcined wagnerite powder, gives birth to chromite ore fine and high alumina raw bauxite powder, and its weight ratio is: the calcined wagnerite powder: give birth to chromite ore fine: high alumina raw bauxite powder=(20～43): (32～27): (32～28).System sand operation steps is as follows: with calcined wagnerite (MgO 〉=90%, igloss≤5%), living chrome ore Cr
2O
3〉=35% and high alumina raw bauxite (Al
2O
3〉=70%, SiO
2≤ 5%, igloss≤15%) is milled down to the percent of pass that equals or be not more than the 0.088mm fine powder respectively after crushed greater than 95%; Powder is done chemical analysis determine various raw material consumptions; The batching that to determine is with proportion 1.05g/cm then
3Rare paper pulp make wedding agent and in sand mill, mix; Mixed fine powder is pressed into the waste base of standard type on press, waste base through 90～110 ℃ dry after residual water-content less than 0.5%; In the high temperature kiln, burn till under 1750-177 ℃, be incubated 6～8 hours; In order fully to form the special construction of synthetic sosoloid, the cooling rate in must the control tunnel furnace drops to 1400 ℃ by 1650 ℃ and can not be less than 6 hours, and wherein 1400 ℃ of insulations are at least 2 hours; The control component target of the synthetic Solid solution sand of making after testing, must reach: SiO
2Equal or be not more than 2.5%, Al
2O
320～35%, Cr
2O
312～18%, body is close＞3.25g/cm
3, be salable product, standby.
If in batching, only can not satisfy the SiO that synthesizes in the Solid solution sand with high alumina raw bauxite powder
2Content requirement is so just added a part of aluminium hydroxide (Al
2O
3〉=65%, igloss≤35%), with SiO
2Lower, make and contain in the batching through being milled down to the percent of pass that equals or be not more than the 0.088mm fine powder greater than 95% aluminium hydrate powder.Like this, the weight ratio of each component can be in system sand batching: calcined wagnerite powder: give birth to chromite ore fine: aluminium hydrate powder: high alumina raw bauxite powder=(20～43): (32～27): (16～2): (32～28), all the other system sand operation stepss are identical with above-mentioned system sand operation steps.
In the system sand operation steps of above-mentioned synthetic Solid solution sand, can also place rotary kiln to burn till waste base, firing temperature equals or is not more than 1800 ℃, and all the other system sand operation stepss are identical with above-mentioned system sand operation steps.
Calcined wagnerite powder in the batching can adopt MgO 90～93%, and igloss is not more than 5% calcined wagnerite and processes.
Give birth to chromite ore fine and can adopt Cr
2O
3Living chrome ore greater than 35% processes.
Aluminium hydrate powder can adopt Al
2O
3Aluminium hydroxide greater than 65% processes.
High alumina raw bauxite powder can adopt Al
2O
3Greater than 70%, SiO
2Less than 5%, igloss processes less than 15% raw bauxite.
Make detailed description below in conjunction with the synthetic Solid solution sand of one～four pair of preparation of embodiment.
Embodiment one
Adopt raw bauxite, living chrome ore, the synthetic Solid solution sand of three kinds of feedstock production of calcined wagnerite.
Raw bauxite, give birth to chrome ore, calcined wagnerite through jaw crusher, to the rod crusher machine after, in Lei Meng Mo, break into and be not more than the 0.088mm fine powder, chemical analysis is made in sampling to the powder after levigate.Various material compositions are: raw bauxite chemical ingredients (only accuse and make branch, down together): SiO
23.0%, Al
2O
372.0%, igloss 15.0%; Give birth to chrome ore chemical ingredients: SiO
20.8%, Al
2O
315%, Cr
2O
345.0%, igloss 0%; Calcined wagnerite chemical ingredients: SiO
20.4%, MgO 93.0%, igloss 5.0%.Determine that proportion scheme is: raw bauxite add-on 31%, give birth to chrome ore add-on 29%, calcined wagnerite add-on 40%.Wet basis composition according to batching is converted into calcination based component (being a kind of necessary verification step, down together), and the calcination based component of this batching (being the composition of Solid solution sand) is:
SiO
21.59%, Al
2O
328.57%, Cr
2O
313.98%, MgO 39.64%, meets technical requirements.
Determine after the ratio of components, make wedding agent, three kinds of fine powder wet mixings in sand mill with rare paper pulp; The material that mixes on 400～630 tons of press moulding mark type (230 * 114 * 65mm) waste bases, the control of waste base tolerance of dimension is not tight, but the thickness direction tolerance of dimension is to be not more than 2mm for well, the excessive agglomerating homogeneity that influences of tolerance of dimension; The waste base of work in-process in 90～110 ℃ of moisture eliminators dry 16～24 hours, residual water-content is not more than 0.5%; Klining is gone in dry good waste base entrucking, and 1750～1770 ℃ of firing temperatures are incubated 6～8 hours; Want 1650 ℃ of cooling rates of reducing to 1400 ℃ of strict control, can not be less than 6 hours, 1400 ℃ are incubated 2 hours.
Quality test emphasis to synthetic Solid solution sand is the composition and the volume density of control, and chemical ingredients will meet the requirements, and volume density is greater than or equals 3.25g/cm
3Each batch sand (120～200 tons) should be made lithofacies appraise, checks MgO, Al
2O
3, Cr
2O
3Gu whether the Solid solution outer rim structure of melting range degree and formation is abundant.This structure is abundant more good more, but as long as chemical ingredients is up to specification and burn till by the processing condition of setting, will fully form Solid solution its specific structure of the present invention.
Embodiment two
SiO in the synthetic Solid solution sand in embodiment one
21.59%, be lower than the set upper limit value, illustrated and reduced the raw materials cost space.New materials scheme is, with the living chrome ore among time one-level raw bauxite, inferior one-level calcined wagnerite powder, the embodiment one.
Used raw bauxite, give birth to chrome ore, calcined wagnerite through jaw crusher, to the rod crusher machine after Raymond mill beat powder, chemical analysis is made in levigate powder sampling.Various material chemical components are: raw bauxite: SiO
25.0%, Al
2O
369.0%, igloss 15.0%; Give birth to chrome ore: SiO
20.8%, Al
2O
315%, Cr
2O
345%, igloss 0%; Calcined wagnerite: SiO
21.0%, MgO 90.0%, igloss 5.0%.The proportion scheme of determining is: raw bauxite add-on 32%, give birth to chrome ore add-on 29%, calcined wagnerite add-on 39%.The wet basis composition of this batching is converted into the calcination based component:
SiO
22.38%, Al
2O
328.34%, Cr
2O
314.00%, MgO 37.64%, meets technical requirements.
Compare with embodiment one, the used raw bauxite price of present embodiment reduces about 40%, and the calcined wagnerite price reduces about 20%, and promptly the materials total cost reduces nearly 20%.But synthetic Solid solution sand SiO
2Do not exceed standard, mineral composition and embodiment one are just the same.
Determine that the later operation steps of proportion scheme is identical with embodiment one with requirement.
Embodiment three
Adopt giving birth to chrome ore, aluminium hydroxide, calcined wagnerite is synthesis material, give birth to chrome ore, calcined wagnerite through jaw crusher, to the rod crusher machine after, Raymond mill is beaten powder, aluminium hydroxide is through the ball mill abrasive dust.Chemical analysis is done in living chromite ore fine, calcined wagnerite powder, aluminium hydrate powder sampling, and each material chemical component is: give birth to chrome ore composition: SiO
25.0%, Al
2O
318.0%, Cr
2O
335.0%; Aluminium hydroxide composition: Al
2O
384.0%, igloss 15.0%; Calcined wagnerite: SiO
21.0%, MgO 90.0%, igloss 5.0%.The proportion scheme of determining is: give birth to chrome ore add-on 34%, aluminium hydroxide add-on 18%, calcined wagnerite add-on 48%.The wet basis composition of this batching is converted into the calcination based component:
SiO
22.30%, Al
2O
321.23%, Cr
2O
312.54%, MgO 45.52%, meets technical requirements.
Operation steps after the batching and requirement are with embodiment one.
Embodiment four
Adopting living chrome ore, high alumina raw bauxite, aluminium hydroxide, calcined wagnerite is raw material.Give birth to chrome ore, high alumina raw bauxite, calcined wagnerite through jaw crusher, to the rod crusher machine after thunder cover and beat powder, aluminium hydroxide is abrasive dust in ball mill, to four kinds of powder sampling analysis.Each material chemical component is: give birth to chrome ore composition: SiO
20.8%, Al
2O
315%, Cr
2O
345%, igloss 0%; High alumina raw bauxite composition: SiO
25.0%, Al
2O
369.0%, igloss 15.0%; Aluminium hydroxide composition: Al
2O
384.0%, igloss 15.0%; Calcined wagnerite composition: SiO
21.0%, MgO 90.0%, igloss 5.0%.Proportion scheme is: give birth to chrome ore add-on 37.%, raw bauxite add-on 37%, aluminium hydroxide 2%, calcined wagnerite add-on 24%.The wet basis composition of this batching is converted into the calcination based component:
SiO
22.39%, Al
2O
335.24%, Cr
2O
317.91%, MgO 23.24%, meets technical requirements.
Operation steps after the batching and requirement are with embodiment one.
Step 2 brickmaking
The emphasis of brickmaking batching is to guarantee that product chemical constitution and batching size composition meet the requirements.Control to the product chemical constitution remains SiO
2, Al
2O
3, Cr
2O
3Batching size composition influences quality product and processability, and the emphasis of control is: less than or be not more than 0.088mm level granularity (fine powder), 1-0mm level granularity (intermediate particle), 2-1mm level granularity.Two kinds of raw materials of the main employing of brickmaking batching, it comprises that body is close greater than 3.25g/cm
3Step 1 preparation synthetic Solid solution sand and to contain the body of MgO 95-97% close greater than 3.25g/cm
3Magnesite clinker.The weight ratio of each component is in the batching: synthetic sosoloid sand: magnesite clinker=(4～6): (15～12).
The brickmaking operation steps is as follows: will prepare burden respectively through the broken back of pulverizing by the grade screening, magnesite clinker be ground into 4-2mm, 2-1mm, 1-0mm ,≤0mm level Four granularity, synthesize sosoloid sand be ground into 2-0mm ,≤0mm two-stage granularity.Size composition major controls at different levels are in the batching: the 2-1mm grade accounts for 16-20%, and the 1-0mm grade accounts for 15-24%, and≤0mm grade accounts for 32-38%, and surplus is the 4-2mm grade.Particle greater than 2mm can not controlled, as long as 0～2mm granularities at different levels are controlled well, 2～4mm granulometric composition is rationally inevitable.And then be equipped with proportion 1.2-1.25g/cm
3Paper pulp as wedding agent, in edge runner-wet mill, be mixed into pug.Order of addition(of ingredients) is to add particulate material earlier, treat combined dose of paper pulp of particulate material wetting evenly after, add fine powder again, the mixing time after fine powder adds can not be less than 10 minutes.The mud material forming that mixes is the close 3.0～3.1g/cm of body
3Work in-process, moulding press with 630～1000 tons for well.Work in-process are dry down 90～110 ℃ of temperature, 16～24 hours time of drying, make residual water-content less than 0.5%.Dried work in-process burn till under 1670～1690 ℃ in tunnel furnace, are incubated 6-8 hour, for guaranteeing the quality of brick, control the cooling from 1650 ℃ to 1400 ℃, and temperature fall time is no less than 6 hours, is incubated 2 hours down at 1400 ℃.The kiln discharge passed examination is the finished product flexible periclase compound spinel brick.
Be flexibility and the antistripping ability of guaranteeing brick, in the batching of system flexible periclase compound spinel brick, can add and contain Al
2O
358～66% body is close greater than 3.20g/cm
3Sintering periclasite spinel sand, to regulate Al in the brick
2O
3Content, its effect are the toughness that increases product, further improve the ability of its anti-thermal shock.The weight ratio of each component is in the batching: synthetic sosoloid sand: magnesite clinker: sintering periclasite spinel sand=(4～6): (15～12): (0.1～2), except that sintering periclasite spinel is sieved into the 2-0mm level granularity by grade after broken the pulverizing, all the other brickmaking operation stepss are identical with above-mentioned brickmaking operation steps in its brickmaking operation steps.
Magnesite clinker in the batching can adopt the magnesite clinker of MgO 95%～97% to process.
Sintering periclasite spinel sand can adopt Al
2O
358～66% sintering periclasite spinel processes.
Must take into account the chemical constitution of product during batching, the controlling index of flexible periclase compound spinel brick finished product requires:
SiO
2≤1.8％，Al
2O
3?6～12％，Cr
2O
3?2～5％，MgO≥70％。
Void content 15～18%,
Volume density 〉=2.98g/cm
3,
Loading softening begins texturing temperature (be called for short lotus soft or softening temperature) 〉=1700 ℃,
Thermal shock (1100 ℃ * water, inferior) 〉=12,
Folding strength (1350 ℃ * 0.5 o'clock, Mpa) 〉=4.0,
Thermal conductivity (1200 ℃, w/mk)≤3.1
Make detailed description below in conjunction with five～seven pairs of preparations of embodiment flexible periclase compound spinel brick.
Embodiment five
Adopt synthetic sosoloid sand, two kinds of raw material brickmaking of magnesite clinker.
Magnesite clinker chemical ingredients: SiO
20.8%, MgO 97%,
Be processed into 4-2,2-1,1-0 ,≤4 sections granularities of 0mm, form after each section sreen analysis and be:
In the 4-2 section granularity:＞4mm 3.8%, and 4-3mm 45.5%, and 3-2mm 34.8%, and 2-1mm 14.2, and 1-0mm 0.6%
In the 2-1 section granularity: 3-2mm 1.4%, and 2-1mm 95%, and 1-0.5mm 2.4%, and 0.5-0mm 1.4%
In the 1-0 section granularity: 2-1mm 9.1%, and 1-0.5mm 33.8%, and 0.5-0mm 47.6%, and＜0mm 8.4%
Powder particle size is formed: 0.5-0mm 5%, and＜0mm 95%
The chemical ingredients of synthetic Solid solution sand: SiO
21.59%, Al
2O
328.57%, MgO 39.64%, Cr
2O
313.98% be processed into 2-0 ,≤two sections granularities of 0mm, composition is:
In the 2-0 section particle: 3-2mm 0.9%, and 2-1mm 49.9%, and 1-0.5mm 17.9%, and 0.5-0mm 18.5%,＜0mm8.3%
Powder particle size is formed: 0.5-0mm 5%, and＜0mm 95%
The ratio of components of determining according to sreen analysis is:
The magnesia add-on: 4-2 section granularity 34%, 2-1 section granularity 5%, 1-0 section granularity 17%, fine powder 19%,
Synthetic Solid solution sand add-on: 2-0 section granularity 10%, fine powder 15%.
The pug size composition of calculating batching according to said ratio is:
＞4mm?1.29％，4-3mm?15.47％，3-2mm?11.99％，2-1mm?16.12％，1-0mm?19.57％，＜0mm34.56％。Size composition meets the requirements.
(being product) chemical constitution of batching is: SiO
21.15%, Al
2O
37.14%, MgO 81.91%, Cr
2O
33.5%.Meet the requirements.
By ratio of components, the batch truck automatic blending is with proportion 1.2～1.25g/cm
3Paper pulp is made wedding agent, and batch mixing in mixing pan adds particulate material and paper pulp earlier, treats that particulate material is added fine powder by even wetting back, does time discharging only 10 minutes.Pug moulding on 630～1000 tons of press, work in-process volume density 〉=3.0g/cm
3, work in-process under 90～110 ℃ of temperature dry 16～24 hours, residual water-content≤0.5% advances klining and becomes 1670～1690 ℃, constant temperature time 6～8 hours, reducing to 1400 ℃ of times to 1650 ℃ can not be less than 6 hour, 1400 ℃ of insulations 2 hours.The kiln discharge product carries out quality inspection, and the product that conforms to quality requirements is a finished product.
Embodiment six
Adopting magnesite clinker, synthetic Solid solution sand, sintering spinel sand is brick-making raw material.
The magnesite clinker chemical ingredients is: SiO
20.8%, Mg O97%,
Be processed into 4-2,2-1,1-0 ,≤0mm4 section granularity, size composition is:
4-2 section granularity:＞4mm 4.0%, and 4-3mm 40.0%, and 3-2mm 42.7%, and 2-1mm 10%, and 1-0.5mm 3%
2-1 section granularity: 3-2mm 2.0%, and 2-1mm 93.5%, and 1-0.5mm 3.1%
1-0 section granularity: 2-1mm 7.8%, and 1-0.5mm 35.3%, and 0.5-0mm 48.5%, and＜0mm 8.0%
Fine powder: 0.5-0mm 5%,＜0mm 95%.
Synthetic Solid solution sand chemical ingredients, SiO
22.3%, Al
2O
321.31%, MgO 45.52%, Cr
2O
312.54%
Only use its fine powder, size composition in the brickmaking batching: 0.5-0mm 5%, and＜0mm 95%
Sintering spinel sand chemical ingredients: SiO
21.0%, Al
2O
365%, MgO 32%
2-0mm size composition 2-1mm 10%, 1-0.5mm 70%, and 0.5-0mm 19%
The ratio of components that draws as calculated is:
Magnesia add-on: 4-2mm 33%, 2-1mm 10%, and 1-0mm 18%, and＜0mm 14%,
Synthetic Solid solution sand＜0mm fine powder add-on: 20%,
Sintering spinel sand 2-0mm particle add-on: 5%.
The pug size composition of calculating batching according to proportioning is:
＞4mm?1.32％，4-3mm?13.2％，3-2mm?14.3％，2-1mm?15.8％，1-0mm?21.3％，＜0mm33.74％。
The product chemical ingredients is: SiO
21.26%, Al
2O
37.51%, MgO 81.95%, Cr
2O
32.53%.
Batching granularity and chemical ingredients all meet the requirements.
Following operation steps and requirement are with embodiment 5.
Embodiment seven
Adopting two kinds of magnesite clinkers 1,2, synthetic Solid solution sand, sintering periclasite spinel sand is the brickmaking material.
Magnesite clinker 1 chemical ingredients: SiO
21.8%, MgO 95%.
Be processed into two sections granularities of 4-2,2-1mm, composition is:
4-2 section granularity: 4-3mm 48%, and 3-2mm 37.5%, and 2-1mm 10.2%, and 1-0.5mm 4%
2-1 section granularity: 3-2mm 1.4%, and 2-1mm 90%, and 1-0.5mm 7.4%, and 0.5-0mm 1.0%
Magnesite clinker 2 chemical ingredientss: SiO
20.8%, MgO 97%.
Be processed into 1-0 ,≤two sections granularities of 0mm, composition is:
1-0 section granularity: 2-1mm 7.0%, and 1-0.5mm 40.8%, and 0.5-0mm 42.1%, and＜0mm 9.5%.
Powder particle size is formed: 0.5-0mm 5%, and＜0mm 95%
Synthetic Solid solution sand chemical ingredients: SiO
22.57%, Al
2O
335.24%, MgO 23.24%, Cr
2O
317.91%.
Be processed into 2-0 ,≤two sections granularities of 0mm, composition is:
2-0 section granularity: 3-2mm 0.9%, and 2-1mm 55.0%, and 1-0.5mm 21.4%, and 0.5-0mm 12.6%, and＜0mm 10.3%
Powder particle size is formed, and 0.5-0mm 5%, and＜0mm 95%.
Sintering periclasite spinel sand chemical ingredients is: SiO
21.0%, Al
2O
365%, MgO 32%.
Be processed into 2-0 section granularity, composition is: 2-1mm 10%, and 1-0.5mm 70%, and 0.5-0mm 19%.
According to the ratio of components that calculates be:
Magnesite clinker 1 add-on: 4-2mm 29%, and 2-1mm 10%
Magnesite clinker 2 add-ons: 1-0mm 7%, and＜0mm 19%
Synthetic Solid solution sand add-on: 2-0mm 10%, and＜0mm 15%
Sintering periclasite spinel sand add-on: 2-0mm 10%.
Calculate the pug size composition of batching according to proportioning: 4-3mm 13.92%, and 3-2mm 11.12%, and 2-1mm 18.8%, and 1-0mm 21.5%, and＜0mm 34.32%
The product chemical ingredients is: SiO
21.59%, Al
2O
312.06%, MgO 69.68%, Cr
2O
34.48%.
Size composition and chemical ingredients all meet the requirements.
Following operation steps and requirement are with example 5.
Claims (5)
1, a kind of flexible periclase compound spinel brick is characterized in that: used batching comprises that body is close greater than 3.25g/cm
3Synthetic Solid solution sand and body close greater than 3.25g/cm
3MgO greater than 95% magnesite clinker, the weight ratio of each component is in the described batching: synthetic sosoloid sand: magnesite clinker=(4～6): (15～12); The brickmaking operation steps is as follows: with described batching respectively through the broken back of pulverizing by the grade screening, synthetic sosoloid sand be ground into 2-0mm ,≤0mm two-stage granularity, magnesite clinker break be ground into 4-2mm, 2-1mm, 1-0mm ,≤0mm level Four granularity; Size composition major controls at different levels in the described batching: the 2-1mm grade accounts for 16-20%, and the 1-0mm grade accounts for 15-24%, and≤0mm grade accounts for 32-38%, and surplus is the 4-2mm grade; Granularities at different levels will accurately be made sreen analysis in the course of processing, finish batching according to sreen analysis, are equipped with proportion 1.2-1.25g/cm again
3Paper pulp as wedding agent, in edge runner-wet mill, be mixed into pug, order of addition(of ingredients) is to add particulate material earlier, treat combined dose of paper pulp of particulate material wetting evenly after, add fine powder again, the mixing time after described fine powder adds can not be less than 10 minutes; The mud material forming that mixes is the close 3.0～3.1g/cm of body
3Work in-process; Work in-process are dry down 90～110 ℃ of temperature, 16～24 hours time of drying, make residual water-content less than 0.5%; Dried work in-process burn till under 1670～1690 ℃ in tunnel furnace, are incubated 6-8 hour; Control 1650 ℃ to 1400 ℃ cooling, temperature fall time is no less than 6 hours, is incubated 2 hours down at 1400 ℃, and the kiln discharge passed examination is the finished product flexible periclase compound spinel brick.
2, flexible periclase compound spinel brick according to claim 1 is characterized in that: contain Al in the batching of described flexible periclase compound spinel brick in addition
2O
358～66% body is close greater than 3.20g/cm
3Sintering periclasite spinel sand, the weight ratio of each component is in the described batching: synthetic sosoloid sand: magnesite clinker: sintering periclasite spinel sand=(4～6): (15～12): (0.1～2), except that sintering periclasite spinel is sieved into the 2-0mm one-level granularity by the grade requirement after broken the pulverizing, all the other brickmaking operation stepss are identical with described brickmaking operation steps in its brickmaking operation steps.
3, flexible periclase compound spinel brick according to claim 1 is characterized in that: the body kernel of described synthetic Solid solution sand is to contain Al
2O
3, Cr
2O
3With the Solid solution of MgO, the outer rim of body is the layer band of magnesium-aluminium spinel; Used batching comprises the calcined wagnerite powder, gives birth to chromite ore fine and high alumina raw bauxite powder, and its weight ratio is: the calcined wagnerite powder: give birth to chromite ore fine: high alumina raw bauxite powder=(20～43): (32～27): (32～28); System sand operation steps is as follows: with calcined wagnerite, give birth to chrome ore and high alumina raw bauxite and be milled down to the percent of pass that equals or be not more than 0.088mm respectively after crushed greater than 95%; Powder is done chemical analysis determine various raw material consumptions; The batching that to determine is with proportion 1.05g/cm then
3Rare paper pulp make wedding agent and in sand mill, mix; Mixed fine powder is pressed into the waste base of standard type on press; Waste base through 90～110 ℃ dry after residual water-content less than 0.5%; In the high temperature kiln, burn till under the 1750-1770C, be incubated 6～8 hours; The cooling rate of control in the tunnel furnace drops to 1400 ℃ by 1650 ℃ and can not be less than 6 hours, and wherein 1400 ℃ of insulations are at least 2 hours; The control component target of synthetic Solid solution sand is: SiO
2Equal or be not more than 2.5%, Al
2O
320～35%, Cr
2O
312～18%, body is close＞3.25g/cm
3
4, flexible periclase compound spinel brick according to claim 3, it is characterized in that: also contain aluminium hydrate powder in the batching of described synthetic Solid solution sand, the weight ratio of each component is in the used batching: the calcined wagnerite powder: give birth to chromite ore fine: aluminium hydrate powder: high alumina raw bauxite powder=(20～43): (32～27): (16～2): (32～28); All the other system sand operation stepss are identical with described system sand operation steps.
5, flexible periclase compound spinel brick according to claim 3, it is characterized in that: in the system sand operation steps of described synthetic Solid solution sand, described waste base is burnt till in rotary kiln, firing temperature equals or is not more than 1800 ℃, and all the other system sand operation stepss are identical with described system sand operation steps.
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| CN102336539A (en) * | 2011-09-02 | 2012-02-01 | 浙江铭德新材科技有限公司 | Waste utilization regeneration baking-free magnesia chrome brick and preparation method thereof |
| CN102351552A (en) * | 2011-07-22 | 2012-02-15 | 武汉钢铁(集团)公司 | Compact calcium hexaluminate-magnesia alumina spinel composite refractory material |
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| CN116332660A (en) * | 2023-03-29 | 2023-06-27 | 巩义通达中原耐火技术有限公司 | Periclase-spinel raw material for enhancing kiln coating performance and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102351552A (en) * | 2011-07-22 | 2012-02-15 | 武汉钢铁(集团)公司 | Compact calcium hexaluminate-magnesia alumina spinel composite refractory material |
| CN102336539A (en) * | 2011-09-02 | 2012-02-01 | 浙江铭德新材科技有限公司 | Waste utilization regeneration baking-free magnesia chrome brick and preparation method thereof |
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| CN114929646A (en) * | 2020-02-20 | 2022-08-19 | 里弗雷克特里知识产权两合公司 | Particles for producing sintered refractory products, batch for producing sintered refractory products, method for producing sintered refractory products and sintered refractory products |
| CN111960805A (en) * | 2020-07-28 | 2020-11-20 | 河南工业大学 | Thermal shock resistant magnesium sliding brick and production method thereof |
| CN116332660A (en) * | 2023-03-29 | 2023-06-27 | 巩义通达中原耐火技术有限公司 | Periclase-spinel raw material for enhancing kiln coating performance and preparation method thereof |
| CN116332660B (en) * | 2023-03-29 | 2024-03-12 | 巩义通达中原耐火技术有限公司 | Periclase-spinel raw material for enhancing kiln coating performance and preparation method thereof |
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