CN107354583B - The high-valued comprehensive utilization process of dead catalyst slag - Google Patents
The high-valued comprehensive utilization process of dead catalyst slag Download PDFInfo
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- CN107354583B CN107354583B CN201710556575.5A CN201710556575A CN107354583B CN 107354583 B CN107354583 B CN 107354583B CN 201710556575 A CN201710556575 A CN 201710556575A CN 107354583 B CN107354583 B CN 107354583B
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4218—Glass fibres
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/04—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/026—Obtaining nickel or cobalt by dry processes from spent catalysts
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
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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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention discloses a kind of high-valued comprehensive utilization process of dead catalyst slag, it stirs and evenly mixs dead catalyst slag and adhesive to obtain mixed material in blender, mixed material granulating and forming in ball press, spherical material is placed in electric arc furnaces with the agent of metal supplementary set, cosolvent and is sufficiently reacted to being completely melt, electric arc furnaces molten bath include the liquid of cobalt nickel with containing AL2O3、SiO2Slag liquid formed layering, the liquid alloy of the nickel containing cobalt is located at lower layer, slag liquid is on upper layer, aluminium alloy flows out to obtain cobalt-nickel alloy from the discharge port of electric arc furnaces, and slag liquid is discharged from the slag notch of electric arc furnaces, obtains the slag liquid that temperature is not less than 1300 DEG C, slag liquid acts on forming filamentary fibers by tumbling machine high speed centrifugation power, filamentary fibers collect to obtain blanket semi-finished product by condensers negative pressure, and blanket semi-finished product drying, needle thorn, cutting, packaging obtain finished product.Present invention process process is short, and recovery efficiency is high, no waste residue, waste water output, is suitble to industrialization large-scale production.
Description
Technical field
The invention belongs to spent catalyst recovery technical fields, more particularly, to a kind of high-valued synthesis of dead catalyst slag
Utilize technique.
Background technique
During the industry productions such as petrochemical industry, chemical industry, catalyst is usually used to accelerate reaction process, with the increasing of time
Add catalyst that can eventually lead to catalyst failure because the reasons such as carbon distribution, poisoning gradually lose activity in use, becomes useless
Catalyst.The dead catalyst main ingredient of these inactivations is AL2O3、SiO2, Mo, W, V, Ni, Co etc..It is valuable in dead catalyst
There is metal very high recovery value to form largely after enterprise is to the recycling of valuable metal Mo, W, V with AL2O3、SiO2For
Alloy Ni, Co dead catalyst slag of carrier, dead catalyst slag material composition are as follows: AL2O3 40~55%, SiO2 35~45%, Ni 5
~10%, Co 3~8%.Currently, above-mentioned dangerous dead catalyst slag can only do waste material stacking, landfill disposal, there is only illegal
Behavior, and environment is caused seriously to pollute.
Summary of the invention
To solve the above problems, the object of the present invention is to provide a kind of high-valued comprehensive utilization process of dead catalyst slag,
So that dangerous waste gurry is successfully become two kinds of alloy products and industrial heat preservation cotton, realizes change and give up to protect, not only simple process, process
Short and secondary resource resource recovery is high.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of high-valued comprehensive utilization process of dead catalyst slag comprising following steps:
Step 1, be in mass ratio by dead catalyst slag and adhesive 1:0.1~0.2 ratio stirred in blender it is mixed
It is even to obtain mixed material；
Step 2, the mixed material for obtaining step 1 are sent into granulating and forming in ball press by belt conveyor, obtain grain
Degree is less than the spherical material of 5cm；
Step 3 sets spherical material and the agent of metal supplementary set, cosolvent according to mass ratio 1:0.05~0.1:0.15~0.2
In in 1200~1600 DEG C of 60~120min of reaction, sufficiently reaction is to being completely melt in electric arc furnaces；Due to close in electric arc furnaces molten bath
The liquid of difference nickel containing cobalt of degree with contain AL2O3、SiO2Slag liquid form layering, the liquid alloy of the nickel containing cobalt is located at lower layer, contains
AL2O3、SiO2Slag liquid on upper layer, aluminium alloy flows out to obtain cobalt-nickel alloy from the discharge port of electric arc furnaces；It is provided on electric arc furnaces small
For external crucible for slagging tap, small external crucible is equipped with electrode assembly, contains AL2O3、SiO2Slag liquid flowed out out of electric arc furnaces molten bath after fall into
Small external crucible, electrode assembly, which is in, contains AL2O3、SiO2Slag liquid in；Small external crucible slag notch bottom is equipped with the internal cone with cavity
Shape guide shell, guide shell is corresponding with the position of wire swaying roller on tumbling machine and guide shell bottom end away from wire swaying roller distance is 1.2~1.5
Meter, the slag liquid liquid level in small external crucible is 40~50cm, contains AL2O3、SiO2Slag liquid through slag notch, guide shell be discharged, obtain
Temperature contains AL not less than 1300 DEG C2O3、SiO2Slag liquid；
Slag liquid of the temperature that step 4, step 3 obtain not less than 1300 DEG C flows on the high-speed rotating wire swaying roller of tumbling machine,
It acts on forming filamentary fibers through high speed centrifugation power, the revolving speed of centrifugal drying silk is 1300~1500r/min；Filamentary fibers are by getting rid of silk
Machine and the air-introduced machine of condensers junction installation are blowed to condensers negative pressure via the delivery conduit of 750~900mm of diameter and are collected
Obtain blanket semi-finished product；
The blanket semi-finished product that step 5, step 4 obtain enter dry drying in Drying unit, and drying temperature is 800~1200
℃；For blanket product after drying by needing machine needling shape at needle punched blanket, the blanket product after making drying has toughness；
The needle punched blanket that step 6, step 5 obtain is cut via filling machine, packaging unit is packed, and obtains finished product.
Further, in above-mentioned step 1, adhesive is one or both of waterglass, spent pulping liquor.
Further, in above-mentioned step 3, metal supplementary set agent is one of iron family element, preferably iron powder.
Further, in above-mentioned step 3, cosolvent is calcium oxide, magnesia, fluorite, any one in aluminium oxide
Or two or more mixtures.
Further, in above-mentioned step 3, guide shell material is tungsten material.
The high-valued comprehensive utilization process of above-mentioned dead catalyst, the fibre diameter of glass heat-insulating cotton obtained are 18~50
μm, adaptive temperature is -44 DEG C~100 DEG C, and density is 24~28kg/ m3, thermal coefficient≤0.034, combustion rating is fire retardant
Grade, thermal resistance value >=2.5.
The high-valued comprehensive utilization process of above-mentioned dead catalyst, the cobalt-nickel alloy rate of recovery are greater than 99.95%, and slag liquid is whole
Industrial glass heat-preservation cotton is made.
The above-mentioned high-valued comprehensive utilization process of dead catalyst slag, material composition is by weight percentage in dead catalyst slag
Are as follows: AL2O3 57~70%, SiO2 12~25%, Ni5~10%, Co3~8%.
Due to the adoption of the technical scheme as described above, the present invention has the following advantages:
The high-valued comprehensive utilization process of dead catalyst slag, process flow is short, and production cost is low, easy to operate, recycling
High-efficient, no waste residue, waste water output meet environmental requirement, have both been able to achieve dead catalyst metal in the dreg cobalt nickel to more environment-friendly
Secondary recovery, and dreg liquid can be made industrial heat preservation material realize economic value, be suitble to industrialization large-scale production.
Specific embodiment
Technical solution of the present invention is described in further detail below with reference to embodiment.
The high-valued comprehensive utilization process of dead catalyst slag of the present invention comprising step in detail below:
Step 1, be in mass ratio by dead catalyst slag and adhesive 1:0.1~0.2 ratio stirred in blender it is mixed
It is even to obtain mixed material；
Step 2, the mixed material for obtaining step 1 are sent into granulating and forming in ball press by belt conveyor, obtain grain
Degree is less than the spherical material of 5cm；Spherical material can be improved the gas permeability of the bed of material in electric arc furnaces molten bath and improve furnace charge smelting property
Energy；
Step 3 sets spherical material and the agent of metal supplementary set, cosolvent according to mass ratio 1:0.05~0.1:0.15~0.2
In in 1200~1600 DEG C of 60~120min of reaction, to being completely melt, metal supplementary set agent effect is to mend for sufficiently reaction in electric arc furnaces
Collect valuable metal and form alloy, cosolvent effect is fluxing and the viscosity in adjustment electric arc furnaces molten bath；In electric arc furnaces molten bath due to
The liquid of difference nickel containing cobalt of density with contain AL2O3、SiO2Slag liquid form layering, the liquid alloy of the nickel containing cobalt is located at lower layer, contains
AL2O3、SiO2Slag liquid on upper layer, aluminium alloy flows out to obtain cobalt-nickel alloy from the discharge port of electric arc furnaces；It is provided on electric arc furnaces small
For external crucible for slagging tap, small external crucible is equipped with electrode assembly, contains AL2O3、SiO2Slag liquid flowed out out of electric arc furnaces molten bath after fall into
Small external crucible, electrode assembly, which is in, contains AL2O3、SiO2Slag liquid in, by electrode assembly guarantee slag tap when slag liquid temperature；Before small
Bed slag notch bottom is equipped with the internal conical flow guiding cylinder with cavity, and guide shell is corresponding with the position of wire swaying roller on tumbling machine
And guide shell bottom end is 1.2~1.5 meters away from wire swaying roller distance, the slag liquid liquid level in small external crucible is 40~50cm, can be true
Protecting slag liquid, continuous, smooth, flow and flow velocity are consistent through guide shell outflow, contain AL2O3、SiO2Slag liquid through slag notch, guide shell arrange
Out, it obtains temperature and contains AL not less than 1300 DEG C2O3、SiO2Slag liquid；
Slag liquid of the temperature that step 4, step 3 obtain not less than 1300 DEG C flows on the high-speed rotating wire swaying roller of tumbling machine,
It acts on forming filamentary fibers through high speed centrifugation power, the revolving speed of centrifugal drying silk is 1300~1500r/min；Filamentary fibers are by getting rid of silk
Machine and the air-introduced machine of condensers junction installation are blowed to condensers negative pressure via the delivery conduit of 750~900mm of diameter and are collected
Obtain blanket semi-finished product；
The blanket semi-finished product that step 5, step 4 obtain enter dry drying in Drying unit, and drying temperature is 800~1200
℃；For blanket product after drying by needing machine needling shape at needle punched blanket, the blanket product after making drying has toughness；
The needle punched blanket that step 6, step 5 obtain is cut via filling machine, packaging unit is packed, and obtains finished product.
In above-mentioned step 1, adhesive is one or both of waterglass, spent pulping liquor.
In above-mentioned step 3, metal supplementary set agent is one of iron family element, preferably iron powder.
In above-mentioned step 3, cosolvent be calcium oxide, magnesia, fluorite, in aluminium oxide any one or it is two or more
Mixture.
In above-mentioned step 3, guide shell material is tungsten material, and high temperature resistant increases service life, guarantees going out for small external crucible
The combination of cinder notch and tumbling machine.
The high-valued comprehensive utilization process of above-mentioned dead catalyst, the fibre diameter of glass heat-insulating cotton obtained are 18~50
μm, adaptive temperature is -44 DEG C~100 DEG C, and density is 24~28kg/ m3, thermal coefficient≤0.034, combustion rating is fire retardant
Grade, thermal resistance value >=2.5.
The high-valued comprehensive utilization process of dead catalyst of the present invention, the cobalt-nickel alloy rate of recovery are greater than 99.95%, and slag liquid is whole
Industrial glass heat-preservation cotton is made.
The high-valued comprehensive utilization process of dead catalyst slag of the present invention, material composition is by weight percentage in dead catalyst slag
Are as follows: AL2O3 57~70%, SiO2 12~25%, Ni5~10%, Co3~8%.
The foregoing is merely presently preferred embodiments of the present invention, rather than limitation of the present invention, is not departing from essence of the invention
In the case where mind and range, equivalent changes and modifications made according to the patent scope of the present invention should all belong to of the invention special
Within sharp protection scope.
Claims (7)
1. a kind of high-valued comprehensive utilization process of dead catalyst slag, it is characterized in that: itself the following steps are included:
Step 1 stirs and evenly mixs the ratio that dead catalyst slag and adhesive are 1:0.1~0.2 in mass ratio in blender
To mixed material；
Step 2, the mixed material for obtaining step 1 are sent into granulating and forming in ball press by belt conveyor, and it is small to obtain granularity
In the spherical material of 5cm；
Spherical material and metal traps, cosolvent are placed in electricity according to mass ratio 1:0.05~0.1:0.15~0.2 by step 3
In 1200~1600 DEG C of 60~120min of reaction in arc furnace, sufficiently react to being completely melt；Due to density in electric arc furnaces molten bath
The liquid alloy of difference nickel containing cobalt with contain AL2O3、SiO2Slag liquid form layering, the liquid alloy of the nickel containing cobalt is located at lower layer, contains
AL2O3、SiO2Slag liquid on upper layer, the liquid alloy of the nickel containing cobalt flows out to obtain cobalt-nickel alloy from the discharge port of electric arc furnaces；Electric arc furnaces
On be provided with small external crucible for slagging tap, small external crucible is equipped with electrode assembly, contains AL2O3、SiO2Slag liquid out of, electric arc furnaces molten bath
Small external crucible is fallen into after outflow, electrode assembly, which is in, contains AL2O3、SiO2Slag liquid in；Small external crucible slag notch bottom is equipped with internal tool
There is the conical flow guiding cylinder of cavity, guide shell is corresponding with the position of wire swaying roller on tumbling machine and guide shell bottom end is away from wire swaying roller distance
It is 1.2~1.5 meters, the slag liquid liquid level in small external crucible is 40~50cm, contains AL2O3、SiO2Slag liquid through slag notch, water conservancy diversion
Cylinder discharge obtains temperature not less than 1300 DEG C and contains AL2O3、SiO2Slag liquid；
Slag liquid of the temperature that step 4, step 3 obtain not less than 1300 DEG C flows on the high-speed rotating wire swaying roller of tumbling machine, through height
Fast centrifugal force acts on forming filamentary fibers, and the revolving speed of centrifugal drying silk is 1300~1500r/min；Filamentary fibers by tumbling machine with
The air-introduced machine of condensers junction installation, then blow via the delivery conduit of 750~900mm of diameter to condensers, negative pressure is collected
Obtain blanket semi-finished product；
The blanket semi-finished product that step 5, step 4 obtain enter dry drying in Drying unit, and drying temperature is 800~1200 DEG C；
For blanket product after drying by needing machine needling shape at needle punched blanket, the blanket product after making drying has toughness；
The needle punched blanket that step 6, step 5 obtain via filling machine cut, packaging unit packaging, obtain industrial glass heat-preservation cotton at
Product.
2. the high-valued comprehensive utilization process of dead catalyst slag according to claim 1, it is characterized in that: in its step 3, metal
Trapping agent is one of iron family element.
3. the high-valued comprehensive utilization process of dead catalyst slag according to claim 1, it is characterized in that: in its step 3, hydrotropy
Agent is calcium oxide, magnesia, fluorite, any one or two or more mixtures in aluminium oxide.
4. the high-valued comprehensive utilization process of dead catalyst slag according to claim 1, it is characterized in that: in its step 3, water conservancy diversion
Cylinder material is tungsten material.
5. the high-valued comprehensive utilization process of dead catalyst slag according to claim 1, it is characterized in that: its industrial glass obtained
The fibre diameter of glass heat-preservation cotton is 18~50 μm, and adaptive temperature is -44 DEG C~100 DEG C, and density is 24~28kg/ m3, thermally conductive system
Number≤0.034, combustion rating are fire retardant grade, thermal resistance value >=2.5.
6. the high-valued comprehensive utilization process of dead catalyst slag according to claim 1, it is characterized in that: its cobalt-nickel alloy recycles
Rate is greater than 99.95%, and industrial glass heat-preservation cotton is all made in slag liquid.
7. the high-valued comprehensive utilization process of dead catalyst slag according to claim 1, it is characterized in that: in its dead catalyst slag
Material composition is by weight percentage are as follows: AL2O3 57~70%, SiO2 12~25%, Ni5~10%, Co3~8%.
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| RU2306325C1 (en) * | 2006-01-18 | 2007-09-20 | Общество с ограниченной ответственностью "Базальтопластик" | Polymeric protective barrier coating |
| DE102006011303A1 (en) * | 2006-03-11 | 2007-09-13 | Johns Manville Europe Gmbh | New composite material |
| CN102531375B (en) * | 2012-01-06 | 2014-08-13 | 山西国际电力科技有限公司 | Method for preparing inorganic refractory fiber product from thermal-state pulverized fuel ash or slag |
| CN103290223B (en) * | 2013-05-28 | 2015-03-04 | 北京矿冶研究总院 | Comprehensive recovery method for multiple metals of waste catalyst |
| CN106367554B (en) * | 2016-08-30 | 2018-05-29 | 宝钢发展有限公司 | Iron and useful metal and the method for producing slag wool are extracted in a kind of secondary resource |
| CN106673453A (en) * | 2016-12-19 | 2017-05-17 | 江苏省冶金设计院有限公司 | Utilization method of red mud slag |
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