CN106007632B - A kind of method that utilization gangue prepares high intensity binder materials - Google Patents
A kind of method that utilization gangue prepares high intensity binder materials Download PDFInfo
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- CN106007632B CN106007632B CN201610340328.7A CN201610340328A CN106007632B CN 106007632 B CN106007632 B CN 106007632B CN 201610340328 A CN201610340328 A CN 201610340328A CN 106007632 B CN106007632 B CN 106007632B
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of method that utilization gangue prepares high intensity binder materials, the gel that the present invention is prepared using discarded gangue is based on silicon, alumina gel, with very high intensity and workability, wherein add calcium stearate and be used as stabilizer, C S H gels are easily formed, cementing effect is played, further increases the intensity of gel, the present invention takes full advantage of discarded gangue, substantial amounts of to have saved resource.
Description
Technical field
High intensity binder materials is prepared the invention mainly relates to binder materials field, more particularly to a kind of utilization gangue
Method.
Background technology
Gangue is the solid waste discharged during coal mining process and coal washing, be one kind in coalification course with coal seam companion
A kind of relatively low, harder than the coal black gray expandable rock of raw phosphorus content.Including the digging gangue during tunnelling, mining process
In the spoil that is produced in top plate, bottom plate and interlayer and choose during coal washing wash spoil.Its main component is Al2 O3 、
SiO2 , the Fe not waited containing quantity also in addition2 O3 、CaO、MgO、Na2 O、K2 O、P2 O5 、SO3 With micro rare element；
Gangue is thrown aside, takes tract.Sulfide effusion or leaching in gangue can pollute air, farmland
And water body.Hillock can also spontaneous combustion occur fire, or in rainy season avalanche, silt river up and cause disaster.China accumulates gangue and reached
More than 1000000000 tons, 100,000,000 tons of gangue will be also discharged every year.In order to eliminate pollution, from the sixties, many countries start to pay attention to coal
The processing and utilization of spoil.
Coal gangue subculture replaces fuel：Change iron；Burning boiler；Burnt lime；Reclaim coal.Produce cement：Produce normal silicate water
Mud；Produce special cement；Produce clinker-free cement.Produce construction material：Coal gangue baked brick, preferably, color is uniform for quality；Coal
Spoil produce lightweight aggregate, lightweight aggregate be for the relative density of less concrete, and select a class porous aggregate；Produce bastard coal
Asbestos, using gangue and lime as raw material, through high temperature melt, a kind of construction material of injection.Produce chemical products：System knot
Brilliant alchlor, using gangue and chemical engineering industry by-product hydrochloric acid as primary raw material, by broken, roast, grind, acidleach, precipitation,
Condensing crystallizing and dehydration etc. production technology and be made, be a kind of new water purification agent；Waterglass processed；Produce ammonium sulfate, gangue
Interior iron sulfide produces SO at high temperature2 , reoxidize and produce SO3 , meet aquatic production sulfuric acid, and with the production of chemicals sulphur of ammonia
Sour ammonium.
Utilization ways have following several：
1. coal and pyrite are reclaimed：By Simple process, washing has gone out coal from gangue, is therefrom selected by screening
Colm, while sorting out pyrite.Or from the jigging machine of coal separation -- in plane shaking table flow reclaim pyrite, wash mixed coal and
Middle coal.The coal of recovery can be used as power the fuel of boiler, and construction material can be made by washing cash, and pyrite can make industrial chemicals.
2. it is used to generate electricity：It is main to be generated electricity with washing middle coal and wash cash multifuel combustion.China washes middle coal with boiling furnace combustion and washes cash
Mixture（The kilocalorie of caloric value per kilogram about 2000）Generate electricity.Clinker can produce cinder brick and blast furnace cement.Japan has more than 10
This power plant；The mixture of middle coal and spoil used, general per kilogram caloric value is 3500 kilocalories；When firepower is not enough, heavy oil is used
It is combustion-supporting.The Federal Republic of Germany and Holland build the personal power plant in colliery and coal preparation plant together in, with coal, coal slime and coal in utilization
Spoil generates electricity.
The caloric value of test gangue should use special instrument to carry out, and microcomputer calorimeter can meet the survey of caloric value
Examination.
3. construction material is manufactured：Instead of clay as brick-making raw material, good farmland can be dug less.When baking bricks, gangue sheet is utilized
The combustible of body, can save coal.
Coal gangue sintering hollow brick, refers to that gangue or flyash are primary raw material, and fired has with shale
Vertical hole（Hole ratio is not less than 25%, and the size in hole is small and quantity is more）Brick.Its appearance and size, length is 290,240,
190mm, width is 240,190,180,175,140,115mm, is highly 90mm. by top surface facing each other, big face and bar face
Right angle hexahedron is constituted, at least two evenly distributed bar holes are offered at middle part, bar is separated by between hole by rib, bar Kong Yu great
Face, bar face are parallel, are therebetween outer wall, and two openings in bar hole are located on two top surfaces respectively, divide between described bar hole and bar face
The less side row hole in some apertures is not offered, is rib between side row hole side row hole adjacent thereto or adjacent bar hole.
Gangue partly or entirely can replace clay composition to produce ordinary cement.The bastard coal that spontaneous combustion or hand-firing cross
Stone, with certain activity, can as cement active addition, production Portland cement (volume is less than 20%), volcano
Grey matter cement（Volume 20~50%）And cement with little clinker（Volume is more than 50%）.Directly it can also be matched somebody with somebody with lime, gypsum with appropriate
Than wearing into clinker-free cement, can making aggregate as cementitious matter with boiling furnace slag or make coarse-fine aggregate system with stone, boiling furnace slag
Into the construction material such as concrete segment or concrete hollow block.The state-owned special gangue such as Britain, Belgium replaces siliceous original
The factory of material production cement.
Gangue can be used to sinter lightweight aggregate.Japan manufactured lightweight aggregate with gangue in 1964 as primary raw material, was used for
Build high-rise building, building weight saving 20%.
Crystal aluminum chloride can be obtained with hydrochloric acid leaching.Residue after leaching, predominantly silica, can make production rubber filling
The raw material of material and wet production waterglass.Contained rare element in remaining mother liquor（Such as germanium, gallium, vanadium, uranium）, determined depending on content
It extracts value.
In addition, gangue can also be used to produce low-heat value gas, manufacture is ceramic, making soil conditioner, or for paving the way,
Underground filling, ground filling make ground.Also careless afforestation can be planted on hillock after spontaneous combustion, is beautified the environment.
Up to the present the utilization dynamics of gangues is big not enough.Technology imperfection, regional development is uneven, to environment
Influence it is still very serious, be mainly manifested in following several aspects.
1st, it is located at the utilization coal gangue storage yard of influence land resource near well head more, mostly close to residential block, gangue
On the one hand a large amount of stack take substantial amounts of land area, is on the other hand also affecting the land resource bigger than stacking area,
So that the arable land of surrounding becomes barren, it is impossible to be utilized.
2nd, pollution air gangue air storage can produce a large amount of airborne dusts, and this is mainly due to the bastard coal in ground stacking
After stone is exposed to the sun and rain for a long time, it will weathering is crushed；In addition, can be disintegrated after gangue water suction, so as to be easy to produce
Dust.Under the action of the forces of the wind, it will deteriorate the quality of mining area air.In addition, containing residual coal, carbonaceous mudstone and being given up in gangue
The combustibles such as timber, wherein C, S may make up the material base of gangue spontaneous combustion.Gangue business air storage, accumulates over a long period, cash
Heat inside tor is gradually accumulated.When temperature reaches the burning point of combustible, the residual coal in Gangue just can spontaneous combustion.Spontaneous combustion
Afterwards, hillock internal temperature is 800-1000 DEG C, makes spoil molten bonding and releases substantial amounts of CO, CO2, SO2, H2Harmful gas such as S, NOx
Body, wherein with SO2Based on.One spontaneous combus tion of waste heap is more than ten years to decades.The discharge of these pernicious gases, not only drops
Ambient air quality around low hillock, healthy, the ecological environment also usually around influence of influence Residents in Mining Area, makes
Arboreal growth is slow, pest and disease damage increases, crop production reduction, to death.
3rd, harm water and soil gangue, which is removed, contains dust, SiO2 , A12 O3 And outside the macroelement such as Fe, Mn, also have other
Trace heavy metal element, such as Pb, Sn, As, Cr etc., these elements are toxic heavy-metal elements.When the coal gangue hill of air storage
After drenching erosion through rainwater, acid water is produced, Shangdi and the water body of surrounding is polluted.When the spoil in spoil stockyard stacks unreasonable, cash
Slope instability easily occurs for clitter, so as to cause the avalanche of Gangue, sliding, especially in heavy rain season, this phenomenon is outstanding in mountain area
To be common, easily occurs mud-rock flow, so as to bring disaster to the farmland in downstream, river and personal security.
Therefore in order to further improve the resource utilization of gangue, it is necessary to study its being applicable in different field
Property.
The content of the invention
The object of the invention is exactly high-strength in order to make full use of discarded Coal Gangue Resource to be prepared there is provided one kind using gangue
Spend the method for binder materials.
The present invention is achieved by the following technical solutions：
A kind of method that utilization gangue prepares high intensity binder materials, comprises the following steps：
（1）Dry Coal Refuse is taken, fine powder is ground to form, 100-170 mesh sieves, the sulphur with its weight 1-2% is crossed
Sour aluminium ammonium mixing, calcines 40-50 minutes at 200-300 DEG C, is cooled to normal temperature, adds compound weight 10-14% activation breast
Liquid, 80-100 revs/min is stirred 16-20 minutes, in the oil bath of 150-200 DEG C of feeding, insulated and stirred 7-10 minutes, discharging cooling,
It is filtered to remove filtrate；
（2）Obtained filter residue is washed 3-4 times, is sent in Muffle furnace, is calcined 30-40 minutes at 800-900 DEG C, cooling
To normal temperature, its weight 20-30%, concentration are added to in 3-5mol/l sodium hydroxide solution, magnetic agitation 1-2 minutes, mistake
Filter, obtains secondary filtrate, secondary filter residue；
（3）Add in its weight 0.6-1% absolute ethyl alcohol, stir in above-mentioned secondary filtrate, rise temperature is
60-70 DEG C, the sulfuric acid that concentration is 97-98% is added dropwise, regulation pH is 1-3, insulation reaction 1-2 hours at the temperature disclosed above, much silicon
Colloidal sol；
（4）By above-mentioned secondary filter residue be added to its weight 70-80%, concentration for 10-15mol/l hydrochloric acid solution in, stir
Mixing 40-50 minutes is mixed, filter residue is filtered to remove, sodium hydroxide is added dropwise in filtrate, regulation pH is 7-8, stands 20-30 minutes,
The deionized water of 10-13 times of filtrate weight is added, magnetic agitation 2.6-3 minutes is mixed with above-mentioned many Ludox, add compound
Weight 2-3% stabilizer, 0.7-1% emulsifying agent, 600-1000 revs/min is stirred 10-14 minutes, is produced.
A kind of method that utilization gangue prepares high intensity binder materials, described activation emulsion is by following weight parts
Raw material mixing composition：
Prodan 7-10, sodium chloride 0.1-0.2, sp-80 0.1-0.2, sodium carboxymethylcellulose 1-2, deionized water
100-130。
A kind of method that utilization gangue prepares high intensity binder materials, described stabilizer is calcium stearate, described
Emulsifying agent is sodium carboxymethylcellulose.
It is an advantage of the invention that：
The gel that the present invention is prepared using discarded gangue is based on silicon, alumina gel, with very high intensity and construction
Performance, wherein adding calcium stearate as stabilizer, easily forms C-S-H gels, plays cementing effect, further carry
The high intensity of gel, the present invention takes full advantage of discarded gangue, substantial amounts of to have saved resource.
Embodiment
Embodiment 1
A kind of method that utilization gangue prepares high intensity binder materials, comprises the following steps：
（1）Dry Coal Refuse is taken, fine powder is ground to form, 170 mesh sieves, the alum with its weight 2% are crossed
Mixing, is calcined 50 minutes at 300 DEG C, is cooled to normal temperature, adds the activation emulsion of compound weight 14%, 100 revs/min of stirrings
20 minutes, in the oil bath of 200 DEG C of feeding, insulated and stirred 10 minutes, discharging cooling was filtered to remove filtrate；
（2）Obtained filter residue is washed 3 times, is sent in Muffle furnace, is calcined 40 minutes at 900 DEG C, is cooled to normal temperature, plus
Enter in the sodium hydroxide solution that to its weight 30%, concentration is 3mol/l, magnetic agitation 1 minute, filtering obtains secondary filtrate, two
Secondary filter residue；
（3）Add in the absolute ethyl alcohol of its weight 0.6%, stir in above-mentioned secondary filtrate, rise temperature is 70
DEG C, the sulfuric acid that concentration is 98% is added dropwise, regulation pH is 3, at the temperature disclosed above insulation reaction 1 hour, much Ludox；
（4）Above-mentioned secondary filter residue is added to its weight 80%, concentration in 15mol/l hydrochloric acid solution, stirring is mixed
50 minutes, filter residue is filtered to remove, sodium hydroxide is added dropwise in filtrate, regulation pH is 8, stands 20 minutes, adds filtrate weight 13
Deionized water again, magnetic agitation 2.6 minutes is mixed with above-mentioned many Ludox, the stabilizer of addition compound weight 2%, 0.7%
Emulsifying agent, 1000 revs/min stir 14 minutes, produce.
A kind of method that utilization gangue prepares high intensity binder materials, described activation emulsion is by following weight parts
Raw material mixing composition：
Prodan 10, sodium chloride 0.2, sp-80 0.2, sodium carboxymethylcellulose 1, deionized water 130.
A kind of method that utilization gangue prepares high intensity binder materials, described stabilizer is calcium stearate, described
Emulsifying agent is sodium carboxymethylcellulose.
Claims (1)
1. a kind of method that utilization gangue prepares high intensity binder materials, it is characterised in that comprise the following steps：
（1）Dry Coal Refuse is taken, fine powder is ground to form, 100-170 mesh sieves, the aluminum sulfate with its weight 1-2% is crossed
Ammonium is mixed, and is calcined 40-50 minutes at 200-300 DEG C, is cooled to normal temperature, adds compound weight 10-14% activation emulsion,
80-100 revs/min is stirred 16-20 minutes, in the oil bath of 150-200 DEG C of feeding, insulated and stirred 7-10 minutes, discharging cooling, filtering
Remove filtrate；Described activation emulsion is made up of the raw material mixing of following weight parts：Prodan 7-10, sodium chloride 0.1-
0.2nd, sp-80 0.1-0.2, sodium carboxymethylcellulose 1-2, deionized water 100-130；
（2）Obtained filter residue is washed 3-4 times, is sent in Muffle furnace, is calcined 30-40 minutes at 800-900 DEG C, is cooled to often
Temperature, is added to its weight 20-30%, concentration in 3-5mol/L sodium hydroxide solution, magnetic agitation 1-2 minutes is filtered,
Obtain secondary filtrate, secondary filter residue；
（3）Its weight 0.6-1% absolute ethyl alcohol is added in above-mentioned secondary filtrate, is stirred, rise temperature is 60-70 DEG C,
The sulfuric acid that concentration is 97-98% is added dropwise, regulation pH is 1-3, insulation reaction 1-2 hours at the temperature disclosed above, much Ludox；
（4）Above-mentioned secondary filter residue is added to its weight 70-80%, concentration in 10-15mol/L hydrochloric acid solution, stirring is mixed
Close 40-50 minutes, be filtered to remove filter residue, sodium hydroxide is added dropwise in filtrate, regulation pH is 7-8, stands 20-30 minutes, adds
The deionized water of 10-13 times of filtrate weight, magnetic agitation 2.6-3 minutes is mixed with above-mentioned many Ludox, adds compound weight
2-3% stabilizer, 0.7-1% emulsifying agent, 600-1000 revs/min is stirred 10-14 minutes, is produced；Described stabilizer is hard
Resin acid calcium, described emulsifying agent is sodium carboxymethylcellulose.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1170703A (en) * | 1997-07-30 | 1998-01-21 | 谢业坤 | Gangue building powder and its producing method |
| CN101172632A (en) * | 2007-10-11 | 2008-05-07 | 刘成长 | Technique for producing hydroted alumina and silicic acid with coal gangue |
| TW200920695A (en) * | 2007-11-09 | 2009-05-16 | Pingshuo Ind Ltd | Process for recovery of silica followed by alumina from coal fly ash |
| CN102126735A (en) * | 2011-01-21 | 2011-07-20 | 万载县金洲化工厂 | Method for extracting tschermigite from coal gangue or stone coal |
| CN104891855A (en) * | 2015-05-19 | 2015-09-09 | 河北工程大学 | A method of extracting rare earth sulfate from coal gangue and applying the rare earth sulfate as a concrete additive |
-
2016
- 2016-05-21 CN CN201610340328.7A patent/CN106007632B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1170703A (en) * | 1997-07-30 | 1998-01-21 | 谢业坤 | Gangue building powder and its producing method |
| CN101172632A (en) * | 2007-10-11 | 2008-05-07 | 刘成长 | Technique for producing hydroted alumina and silicic acid with coal gangue |
| TW200920695A (en) * | 2007-11-09 | 2009-05-16 | Pingshuo Ind Ltd | Process for recovery of silica followed by alumina from coal fly ash |
| CN102126735A (en) * | 2011-01-21 | 2011-07-20 | 万载县金洲化工厂 | Method for extracting tschermigite from coal gangue or stone coal |
| CN104891855A (en) * | 2015-05-19 | 2015-09-09 | 河北工程大学 | A method of extracting rare earth sulfate from coal gangue and applying the rare earth sulfate as a concrete additive |
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