CN110066182A - Utilize the method for pyrite cinder preparation magnesium-ferrum-aluminum composite material - Google Patents
Utilize the method for pyrite cinder preparation magnesium-ferrum-aluminum composite material Download PDFInfo
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- CN110066182A CN110066182A CN201910450939.0A CN201910450939A CN110066182A CN 110066182 A CN110066182 A CN 110066182A CN 201910450939 A CN201910450939 A CN 201910450939A CN 110066182 A CN110066182 A CN 110066182A
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- pyrite cinder
- ferrum
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- 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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
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- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Materials Engineering (AREA)
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- Dispersion Chemistry (AREA)
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Abstract
The present invention relates to a kind of methods with pyrite cinder preparation magnesium-ferrum-aluminum composite material, belong to fire resisting material field；Specifically: 1) add water to be ground into slurry after mixing evenly pyrite cinder, material A is obtained after magnetic method, then obtain material B after washing desliming；2) material B and magnesite are worn into fine powder, is ground altogether after mixing, bonding agent is added, is pressed into adobe, obtain material C through keeping the temperature under high temperature oxidative atmosphere after drying；3) material C is crushed, and is mixed with magnesia, magnesium aluminate spinel, corundum, additional bonding agent, and compression moulding, kiln drying first is being dried, then the Yu Baowen in hyperthermia tunnel Kiln；Product of the present invention has the excellent performances such as intensity height, good thermal shock stability, refractoriness under load are high, high temperature creep is good, corrosion resistance and resistance to flaking are good, extension kliner coating is good, anti-oxidant reducing power is strong, pyrite cinder can be turned waste into wealth, realize its renewable resources.
Description
Technical field
The present invention relates to a kind of cement kiln preparation methods of magnesium-ferrum-aluminum composite material, belong to fire resisting material field.
Background technique
Pyrite cinder is the waste residue generated in gas washing in SA production factory and phosphate fertilizer plant's production sulfuric acid process.According to statistics, every 1 ton of production
Sulfuric acid, which is paid, produces about 0.8 ton of slag and a small amount of flue dust.Since the raw material of production industrial sulphuric acid is troilite, so containing in pyrite cinder
There are a large amount of iron and other valuable non-ferrous metals.According to the grade of various regions troilite and Coexisting component difference, iron in usual slag
Content account for about the 33-57% of slag total weight, silica accounts for 10-24%, additionally with Cu, Zn, Pb and a small amount of noble metal,
These are all valable starting materials required for metallurgy and other industry.However, most of pyrite cinder and flue dust are arbitrarily stacked in the past,
Not plus processing, this not only serious ground contamination environment, but also the waste of a large amount of useful metals is caused, therefore, research is from pyrite cinder
Middle recycling iron and valuable metal can not only eliminate pyrite cinder bring environmental pollution, but also resource can be made full use of to become useless
For treasured, make waste renewable resources.
In recent years, with the development of sulfuric acid industry, the processing of pyrite cinder has caused the note of domestic and international chemist
Meaning, and have accumulated many successful experiences.It such as rushes and recycles useful metal and noble metal in pyrite cinder, or directly use pyrite cinder
Make cement additive or even someone directly using pyrite cinder as the material of sewage treatment, waste recycling.But as sulfuric acid
Main ingredient in slag -- iron is but chiefly used in making additive in manufacture of cement, or sinter supplying blast fumance iron is made.With
The continuous development of sulfuric acid industry, pay produce pyrite cinder waste it is more and more.It is reported that China's sulfuric acid industry is discharged every year
Pyrite cinder have reached more than 1,000 ten thousand tons.Therefore, how to handle has seemed very urgent using pyrite cinder.
Summary of the invention
The present invention aiming at the problems existing in the prior art, is disclosed and is answered using the magnesium-ferrum-aluminum that pyrite cinder is prepared as raw material
Condensation material is applied to cement kiln clinkering zone, with biography using the excellent extension kliner coating performance of magnesium-ferrum-aluminum composite material and Structural flexibility
The Periclase-hercynite brick of system is compared, and big, the at high cost problem of hercynite synthesis difficulty, while this hair are avoided
Have very strong adaptability, the qualification rate of product high different redox conditions in bright product sintering process, can be realized
Waste residue of sulfuric acid is turned waste into wealth, and promoting has good Social benefit and economic benefit.
The present invention is implemented as follows:
A method of magnesium-ferrum-aluminum composite material is prepared using pyrite cinder, which is characterized in that specific step is as follows:
Step 1: adding water to grind pyrite cinder, it is ground to slurry after mixing evenly, material A, material are obtained after magnetic method
A obtains material B after washing desliming again；
Step 2: material B and magnesite are worn into fine powder respectively, 6h~18h is ground after mixing in proportion altogether, is added 1.5%~3.5%
Bonding agent is pressed into adobe, through held for some time under 1450 DEG C~1730 DEG C oxidizing atmospheres after drying, obtains material C；The step
By mill altogether and high-temperature atmosphere sintering in rapid, FeO is realizednHigh uniformity dispersion in MgO.Oxygen in FeOn and clinker
Change calcium reaction and generate highly viscous calcium ferrite and ferrous acid aluminium phase, one layer of stable kliner coating can be formed, play protection refractory material
Effect；
Step 3: material C is broken into different grain size, and mixed in proportion with granularity magnesia, magnesium aluminate spinel, corundum not etc.
It closes, additional bonding agent mixing, and compression moulding；The bonding agent of step 2 and step 3 can be identical or not identical, generally
It is divided into inorganic bonding agent and organic bond.The fusing point of magnesium aluminate spinel is high, wearability is good, plays the role of strengthening matrix, make
Obtaining product has excellent corrosion resistance and resistance to flaking.Corundum is introduced in the form of bulky grain, can be anti-with the magnesia of surrounding
A magnesium aluminate spinel band should be formed.
Step 4: the material of above-mentioned compression moulding is first dried 24-72h at 80-150 DEG C in dry kiln, then in height
Magnesium-ferrum-aluminum composite material can be prepared into 1500 DEG C of -1720 DEG C of heat preservation 6-12h in warm tunnel oven.The composite material being prepared
Product have intensity height, good thermal shock stability, refractoriness under load height, high temperature creep is good, corrosion resistance and resistance to flaking are good,
The excellent performances such as kliner coating is good, anti-oxidant reducing power is strong are hung, can satisfy the use environment of cement kiln processing different material,
It is a kind of novel non-chrome product, while pyrite cinder is turned waste into wealth, realize its renewable resources, promoting has positive meaning
Justice.
Further, in the step two material B and magnesite additional proportion are as follows: w (B): w (magnesite)=(7~
15) %:(86~94) %；Granularity after the material B and magnesite are ground is 240 mesh~325 mesh.
Further, the bonding agent is the combination of one or both of pulp solution, dextrin, calcium lignosulfonate.
Further, the mass percent of material C is 30%~73% in the step three, the mass percent 20% of magnesia
~50%, magnesium aluminate spinel 3%~15%, the mass percent of corundum is 3%~10%.The mass percent of additional bonding agent is upper
State the 2.5%~5.5% of substance summation.
Further, the particle size range and adding proportion of the magnesia, magnesium aluminate spinel, corundum are as follows:
3≤granularity≤5mm:6%~13%；
1≤granularity≤3mm:35%~55%；
0≤granularity≤1mm:20%~30%；
0≤granularity≤0.088mm:26%~38%.
It further, include FeO in the pyrite cindernComponent；It include MgO component in the magnesite.
The beneficial effect of the present invention compared with prior art is:
1) it by magnetic method, extracts the FeO in pyrite cindern, realize the renewable resources of pyrite cinder；Pass through total mill and high temperature
Atmosphere sintering realizes FeOnHigh uniformity dispersion in MgO, FeOn is reacted with the calcium oxide in clinker generates high viscosity
Calcium ferrite and ferrous acid aluminium phase, one layer of stable kliner coating can be formed, play the role of protect refractory material；
2) thermal expansion coefficient of magnesium aluminate spinel is low, about the half of periclase, and it is excellent that the difference of the two has product
Thermal shock resistance；The fusing point of magnesium aluminate spinel is high, wearability is good, plays the role of strengthening matrix, so that product is with excellent
Corrosion resistance and resistance to flaking；Corundum is introduced in the form of bulky grain, can react to form a magnalium point with the magnesia of surrounding
Spar band, the reaction can continue to carry out in the use process of material by ion diffusion, the process along with volume expansion,
Be conducive to improve the high temperature creep of material in use；
3) Periclase-hercynite material is widely used in cement kiln at present, is using hercynite as source of iron；Hercynite
Higher cost, synthesis difficulty be larger, it is more sensitive to redox condition, cannot stablize under high temperature or atmosphere change condition and deposit
The qualification rate for further resulting in product is low, and product of the present invention is highly dissolved using FeOn in MgO, avoids using synthesis
Hercynite, product will not crack in sintering process because of the variation of firing atmosphere, and can adapt to water extensively
The use environment of stall processing different material；
4) by specific test data the result shows that: product of the present invention has excellent performance indicator, specific data are as follows: aobvious
Porosity 14-18%, bulk density 2.85-3.15g/cm3, cold crushing strength 60-85MPa, refractoriness under load be greater than 1680
DEG C, (1100 DEG C, water cooling) of thermal shock resistance are greater than 10 times, and have excellent corrosion resistance, oxidation-reduction resistance, anti-strip
Property, hang kliner coating and high temperature creep, be able to satisfy the requirement of the Trend of Chrome-free of cement kiln refractory.
Specific embodiment
It is clear to keep the purpose of the present invention, technical solution and effect clearer, example is exemplified below to the present invention into one
Step is described in detail.It should be understood that specific implementation described herein is not intended to limit the present invention only to explain the present invention.
Embodiment 1
(1) water is added to be ground to certain particle size pyrite cinder, slurry after mixing evenly, obtains material A, material after magnetic method
A obtains material B after washing desliming again.Material B and magnesite are worn into fine powder, granularity is 325 mesh, wherein w (B): w (magnesite
Mine)=(7~15) %:(86~94) %, additional 1% dextrin dry powder grinds 6h~18h altogether, 3% bonding agent is added, is pressed into after mixing
Adobe obtains material C through held for some time under 1450 DEG C~1730 DEG C oxidizing atmospheres after drying；
(2) by mass percentage, 70% material C, 20% magnesia, 7% electric melting magnesium aluminum spinel, 3% plate diamond spar press than
Example mixing, additional 3% pulp solution are bonding agent, when production, first weigh various raw materials according to the ratio, are uniformly mixed, through being kneaded
To pug, then rubbed press machine compression moulding first dries 10-25h, then at 1550 DEG C -1700 DEG C at 120-250 DEG C
High temperature sintering 5-12h；
The material C has 5-3mm, 3-1mm, 1-0mm and≤tetra- kinds of granularities of 0.088mm, the magnesia have 1-0mm and≤
Two kinds of granularities of 0.088mm, the electric melting magnesium aluminum spinel are 3-1mm, and the granularity of the plate diamond spar is 3-1mm.
The performance indicator of products obtained therefrom are as follows: apparent porosity 15.6%, bulk density 3.03g/cm3, cold crushing strength
77MPa, refractoriness under load be greater than 1680 DEG C, thermal shock resistance (1100 DEG C, water cooling) 12 times, corrosion resistance, it is anti-oxidant also
Originality, creep resistance and extension kliner coating performance are preferable.
Embodiment 2
The production technology and embodiment 1 of the present embodiment are identical, the difference is that:
By mass percentage, 60% material C, 25% magnesia, 12% electric melting magnesium aluminum spinel, 3% plate diamond spar, additional 3%
Pulp solution be bonding agent.
The material C has 5-3mm, 3-1mm, 1-0mm and≤tetra- kinds of granularities of 0.088mm, the magnesia have 1-0mm and≤
Two kinds of granularities of 0.088mm, the electric melting magnesium aluminum spinel are 3-1mm, and the granularity of the plate diamond spar is 3-1mm.
The performance indicator of products obtained therefrom are as follows: apparent porosity 15.8%, bulk density 3.01g/cm3, cold crushing strength
73MPa, refractoriness under load be greater than 1680 DEG C, thermal shock resistance (1100 DEG C, water cooling) 15 times, corrosion resistance, it is anti-oxidant also
Originality, creep resistance and extension kliner coating performance are preferable.
Embodiment 3
Production technology and embodiment 1 are identical, the difference is that:
By mass percentage, 50% material C, 32% magnesia, 13% electric melting magnesium aluminum spinel, 5% plate diamond spar, additional 3%
Pulp solution be bonding agent.
The material C has 5-3mm, 3-1mm, 1-0mm and≤tetra- kinds of granularities of 0.088mm, and the magnesia has 3-1mm, 1-0mm
With≤two kinds of granularities of 0.088mm, the electric melting magnesium aluminum spinel is 3-1mm, and the granularity of the plate diamond spar is 3-1mm.
The performance indicator of products obtained therefrom are as follows: apparent porosity 16.3%, bulk density 3.0g/cm3, cold crushing strength
70MPa, refractoriness under load be greater than 1680 DEG C, thermal shock resistance (1100 DEG C, water cooling) 14 times, corrosion resistance, it is anti-oxidant also
Originality, creep resistance and extension kliner coating performance are preferable.
Embodiment 4
Production technology and embodiment 1 are identical, the difference is that:
By mass percentage, 48% material C, 36% magnesia, 10% alumina magnesium aluminate spinel, 6% plate diamond spar, additional 3%
Pulp solution be bonding agent.
The material C has 5-3mm, 3-1mm, 1-0mm and≤tetra- kinds of granularities of 0.088mm, and the magnesia has 3-1mm, 1-0mm
With≤two kinds of granularities of 0.088mm, the alumina magnesium aluminate spinel is 3-1mm, and the granularity of the plate diamond spar is 3-1mm.
The performance indicator of products obtained therefrom are as follows: apparent porosity 16.0%, bulk density 3.03g/cm3, cold crushing strength
68MPa, refractoriness under load be greater than 1680 DEG C, thermal shock resistance (1100 DEG C, water cooling) 13 times, corrosion resistance, it is anti-oxidant also
Originality, creep resistance and extension kliner coating performance are preferable.
Embodiment 5
Production technology and embodiment 1 are identical, the difference is that:
By mass percentage, 45% material C, 37% magnesia, 12% alumina magnesium aluminate spinel, 6% plate diamond spar, additional 3%
Pulp solution be bonding agent.
The material C has 5-3mm, 3-1mm, 1-0mm and≤tetra- kinds of granularities of 0.088mm, and the magnesia has 3-1mm, 1-0mm
With≤two kinds of granularities of 0.088mm, the alumina magnesium aluminate spinel is 3-1mm, the granularity of the plate diamond spar be 3-1mm and≤
Two kinds of granularities of 0.088mm.
The performance indicator of products obtained therefrom are as follows: apparent porosity 16.6%, bulk density 2.98g/cm3, cold crushing strength
65MPa, refractoriness under load be greater than 1680 DEG C, thermal shock resistance (1100 DEG C, water cooling) 16 times, corrosion resistance, it is anti-oxidant also
Originality, creep resistance and extension kliner coating performance are preferable.
Embodiment 6
Production technology and embodiment 1 are identical, the difference is that:
By mass percentage, 73% material C, 20% magnesia, 3% electric melting magnesium aluminum spinel, 4% plate diamond spar, additional 3%
Pulp solution be bonding agent.
The material C has 5-3mm, 3-1mm, 1-0mm and≤tetra- kinds of granularities of 0.088mm, and the magnesia has 3-1mm, 1-0mm
With≤two kinds of granularities of 0.088mm, the electric melting magnesium aluminum spinel is 3-1mm, and the granularity of the plate diamond spar is 3-1mm.
Embodiment 7
Production technology and embodiment 1 are identical, the difference is that:
By mass percentage, 30% material C, 50% magnesia, 10% alumina magnesium aluminate spinel, 10% plate diamond spar are additional
2.5% pulp solution is bonding agent.
The material C has 5-3mm, 3-1mm, 1-0mm and≤tetra- kinds of granularities of 0.088mm, and the magnesia has 3-1mm, 1-0mm
With≤two kinds of granularities of 0.088mm, the alumina magnesium aluminate spinel is 3-1mm, and the granularity of the plate diamond spar is 3-1mm.
Embodiment 8
Production technology and embodiment 1 are identical, the difference is that:
By mass percentage, 50% material C, 25% magnesia, 15% alumina magnesium aluminate spinel, 10% plate diamond spar are additional
5.5% pulp solution is bonding agent.
The material C has 5-3mm, 3-1mm, 1-0mm and≤tetra- kinds of granularities of 0.088mm, and the magnesia has 3-1mm, 1-0mm
With≤two kinds of granularities of 0.088mm, the alumina magnesium aluminate spinel is 3-1mm, the granularity of the plate diamond spar be 3-1mm and≤
Two kinds of granularities of 0.088mm；According to specific needs, can be with particle size range and adding proportion 3≤granularity≤5mm:6%~
13%；1≤granularity≤3mm:35%~55%；0≤granularity≤1mm:20%~30%；0≤granularity≤0.088mm:26%~38%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as of the invention
Protection scope.
Claims (6)
1. a kind of method using pyrite cinder preparation magnesium-ferrum-aluminum composite material, which is characterized in that specific step is as follows:
Step 1: adding water to grind pyrite cinder, it is ground to slurry after mixing evenly, material A, material are obtained after magnetic method
A obtains material B after washing desliming again；
Step 2: material B and magnesite are worn into fine powder respectively, 6h~18h is ground after mixing in proportion altogether, is added 1.5%~3.5%
Bonding agent is pressed into adobe, through held for some time under 1450 DEG C~1730 DEG C oxidizing atmospheres after drying, obtains material C；
Step 3: material C is crushed, and mixed in proportion with granularity magnesia, magnesium aluminate spinel, corundum not etc., additional combination
Agent mixing, and compression moulding；
Step 4: the material of above-mentioned compression moulding is first dried 24-72h in dry kiln at 80-150 DEG C, then in high temperature tunnel
Magnesium-ferrum-aluminum composite material can be prepared into 1500 DEG C of -1720 DEG C of heat preservation 6-12h in road kiln.
2. a kind of method using pyrite cinder preparation magnesium-ferrum-aluminum composite material according to claim 1, which is characterized in that
The additional proportion of material B and magnesite in the step two are as follows: %:(86~94 w (B): w (magnesite)=(7~15)) %；Institute
Granularity after material B and the magnesite grinding stated is 240 mesh~325 mesh.
3. a kind of method using pyrite cinder preparation magnesium-ferrum-aluminum composite material according to claim 1, which is characterized in that
The bonding agent is the combination of one or both of pulp solution, dextrin, calcium lignosulfonate.
4. a kind of method using pyrite cinder preparation magnesium-ferrum-aluminum composite material according to claim 1, which is characterized in that
The mass percent of material C is 30%~73% in the step three, the mass percent 20%~50% of magnesia, magnesium aluminate spinel
3%~15%, the mass percent of corundum is 3%~10%；Additional bonding agent mass percent is 2.5%~5.5%.
5. a kind of method using pyrite cinder preparation magnesium-ferrum-aluminum composite material according to claim 4, which is characterized in that
The particle size range and adding proportion of the magnesia, magnesium aluminate spinel, corundum are as follows:
3≤granularity≤5mm:6%~13%；
1≤granularity≤3mm:35%~55%；
0≤granularity≤1mm:20%~30%；
0≤granularity≤0.088mm:26%~38%.
6. a kind of method using pyrite cinder preparation magnesium-ferrum-aluminum composite material according to claim 1, which is characterized in that
It include FeO in the pyrite cindernComponent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215637A (en) * | 2022-07-19 | 2022-10-21 | 湖南有色金属研究院有限责任公司 | Preparation method of sulfuric acid cinder micro-electrolysis filler and micro-electrolysis filler |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215637A (en) * | 2022-07-19 | 2022-10-21 | 湖南有色金属研究院有限责任公司 | Preparation method of sulfuric acid cinder micro-electrolysis filler and micro-electrolysis filler |
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