CN109553372A - A kind of preparation and application for the ardealite roadbed material that can be recycled - Google Patents
A kind of preparation and application for the ardealite roadbed material that can be recycled Download PDFInfo
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- CN109553372A CN109553372A CN201811598964.5A CN201811598964A CN109553372A CN 109553372 A CN109553372 A CN 109553372A CN 201811598964 A CN201811598964 A CN 201811598964A CN 109553372 A CN109553372 A CN 109553372A
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- ardealite
- roadbed material
- roadbed
- water
- preparation
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Classifications
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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
- C04B28/14—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 calcium sulfate cements
- C04B28/16—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 calcium sulfate cements containing anhydrite, e.g. Keene's cement
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/024—Ingredients added before, or during, the calcining process, e.g. calcination modifiers
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
Abstract
The present invention proposes a kind of preparation and application of ardealite roadbed material that can be recycled, belong to roadbed material field, the ardealite that free moisture content is 7%-20% is added in saturated calcium hydroxide solution and carries out neutralization reaction by the present invention, obtains the ardealite of removal titanium pigment acid group and fluorine ion；Ardealite obtained carries out high-temperature calcination at 170 DEG C -350 DEG C, and dihydrate gypsum therein is made to be changed into type III anhydrous gypsum；Type III anhydrous gypsum obtained is mixed with water, water-reducing agent and waterproofing agent, and the ardealite roadbed material is made.Application method proposed by the present invention is that ardealite roadbed material is first used to subgrade construction after the completion of roadbed is on active service to carry out high-temperature calcination again to ardealite roadbed material, and be re-used for subgrade construction.Ardealite roadbed material obtained by the present invention has good intensity, water stability and volume stability, and under the premise of maintenance ardealite roadbed material property pure property, realization be can be recycled.
Description
Technical field
The invention patent relates to roadbed material field, in particular to a kind of system for the ardealite roadbed material that can be recycled
Standby and application method.
Background technique
Ardealite is the by-product in phosphorous chemical industry production process, and China is that (yield of phosphate fertilizer occupies world head for phosphorous chemical industry big country
Position), discharge about 20,000,000 tons of ardealite year, year utilization rate less than 20%, about 2.5 hundred million tons of ardealite of the stockpiling of current China.Phosphorus
Gypsum mainly becomes dihydrate gypsum (mass fraction is typically larger than 85%), contains a small amount of soluble impurity, such as H simultaneously+, can
Dissolubility P2O5And F ion.The ardealite for not being able to utilize during stockpiling, soluble impurity can with Free water therein to
Subsurface wastewater infiltration system causes water pollution, harm ecology and environment.
That how to expand ardealite utilizes channel, is asking for current urgent need to resolve to alleviate space, environment and ecological pressure
Topic.By carrying out washing or alkali neutralization processing to ardealite, ardealite can be prepared into cement adjustable solidification agent, phosphate fertilizer, building block, gypsum
The materials such as plate and wall coating mortar, but prepare the generation of these materials ardealite consumption amount and ardealite annual output not
Match, still has a large amount of ardealite (80% or so of annual output) stockpiling, need to open up new application approach.
Currently, China is carrying out large-scale Transport Facility Construction, and 2017, the total kilometrage of China's highway was
13.7 ten thousand highways occupy No. 1 in the world, but relative to All population capacities and economy development requirement, the Transport Facility Construction in China is also
Up for lasting promotion.During highway construction, need to consume a large amount of roadbed material, conventional roadbed material includes stone
A large amount of consumption of head, sand and soil etc., these natural resources have resulted in serious ecology and environmental hazard.If phosphorus stone can be used
Industrial by-products as cream replace conventional roadbed material, then can get the situation of two-win.
Roadbed material is used phosphogypsum as, has some scholars and conducts a preliminary study, Wu Shaopeng etc. has studied phosphorus stone
Cream-flyash-quick lime system (mass ratio 8:8:1) is used as the feasibility of roadbed material, and result of study shows to be suitable for pressure
In the case of solidity, which can be used for the preparation of highway subgrade, and (Wu Shaopeng, Shen Weiguo, Zhou Mingkai wait phosphogypsum powder coal ash stone
Research [J] Chinese Highway journal of grey cementing material, 2001,14 (z1): 13-15.)；Zhou Futao etc. has studied ardealite-powder
Coal ash-cement-quick lime system (mass ratio 9:10:2:1) is used as the feasibility of roadbed material, and result of study shows in phosphorus stone
Under conditions of cream volume is suitable for, system can get optimal intensity, and (experiment of Zhou Futao, Shi Zongli's ardealite roadbed material are ground
Study carefully [J] Chinese building material science and technology, 2014,23 (4): 49-52.).
From the studies above result as it can be seen that the thinking that existing research uses phosphogypsum as roadbed material is using hydraulic cement
The hydration reaction of material (such as cement, flyash), by generating water-soluble extremely low C-S-H gel or ettringite come cementing
Ardealite particle simultaneously generates intensity.The advantages of this method is to improve the intensity and water stability of studied composite system, is lacked
Point is the generation of entringite so that system has the risk of late expansion destruction, while the exterior materials such as cement, flyash and lime
Incorporation, change the pure property of ardealite, reduce the feasibility of ardealite regeneration (for example: the phosphorus after hydration and hardening
Gypsum-flyash-cement-lime system is difficult to regenerate and apply as gypsum material).
Summary of the invention
The purpose of the invention is to overcome the shortcoming of prior art, a kind of ardealite road that can be recycled is provided
The preparation and application of sill, the present invention pass through technological means under the premise of holding ardealite material properties pure property
It ensures feasibility of the ardealite as roadbed material, forms a kind of environmentally protective, the ardealite roadbed material that can be recycled.
The roadbed material is meeting intensity, water stability and the volume stability that should have as a kind of construction material of means of transportation
Under the premise of, also have the characteristics that it is environmentally protective, can be recycled.Wherein, intensity show the way sill bear external loads ability,
Water stability shows the way anti-softening ability of the sill under Riddled Condition, and volume stability shows the way ruler of sill during military service
Very little holding capacity.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of ardealite roadbed material that can be recycled proposed by the present invention, which is characterized in that including
Following steps:
(1) ardealite that free moisture content is 7%-20% is added in saturated calcium hydroxide solution and neutralize instead
It answers, until the pH value of leachate is 7.0 ± 0.3, obtains the ardealite of removal titanium pigment acid group and soluble fluoride ion；
(2) ardealite made from step (1) is subjected to high-temperature calcination at 170 DEG C -350 DEG C, makes two water in ardealite
Gypsum is changed into type III anhydrous gypsum；
(3) by type III anhydrous gypsum, water, water-reducing agent and waterproofing agent made from step (2) according to mass percent 60%-
70%:23%-33%:0.5%-1.5%:3.5%-5.5% is mixed, and stirs evenly and the ardealite roadbed material is made
Material.
The present invention also proposes a kind of application method of ardealite roadbed material that above-mentioned preparation method is prepared, feature
It is, it is 180 ± 10mm that the consistency of the ardealite roadbed material obtained, which is controlled in fluidity, then by the ardealite road
Sill is poured into road designated position and forms roadbed, after the completion of roadbed military service, by the ardealite roadbed in the roadbed
Material carries out high-temperature calcination at 170 DEG C -350 DEG C, obtains type III anhydrous gypsum again, is re-used for the construction of roadbed.
The advantages of the present invention
1, in such a way that neutralization reaction-high-temperature calcination combines, the pure property of ardealite roadbed material property is maintained,
And the type III anhydrous gypsum obtained after high-temperature calcination can be used as roadbed material recycling to the ardealite roadbed material again,
Realize the saving of resource and the energy.
2, by the neutralization reaction with calcium hydroxide, water-soluble H in ardealite is eliminated+, phosphate radical and fluorine ion, keep away
Harmfulness of the ardealite as roadbed material to environment is exempted from.
(III) type III anhydrous gypsum is formed by high-temperature calcination, the method that then aquation forms dihydrate gypsum again, benefit
With the interspersed and combination between dihydrate gypsum crystal, the hydration activity of type III anhydrous gypsum is played, has been formed after having ensured aquation
The intensity of solidified body.
3, by mixing water-reducing agent in the system of type III anhydrous gypsum and water, the water consumption of work progress is reduced, is subtracted
The small porosity of solidified body, improve solidified body intensity and anti-water percolating capacity.
4, by mixing waterproofing agent in the system of type III anhydrous gypsum and water, reaching dead-end pore and generating hydrophobic energy
The purpose of power has ensured the water stability of ardealite roadbed material.
To sum up, the ardealite roadbed material prepared through the invention can meet roadbed material and bear vehicle during military service
The performance requirement of load action and environmental attack effect (freeze thawing, drying, aqueous solution infiltration etc.), has good intensity, water steady
Property and volume stability can be recycled under the premise of maintaining the pure property of ardealite roadbed material property, realize money
The saving in source and the energy, and preparation process is simple, production cost is low.
Specific embodiment
To technical solution of the present invention, detailed description are as follows with reference to embodiments:
A kind of preparation method of ardealite roadbed material that can be recycled proposed by the present invention, includes the following steps:
(1) ardealite that free moisture content is 7%-20% is added in saturated calcium hydroxide solution and carries out neutralization reaction,
PH value to leachate is 7.0 ± 0.3, obtains the ardealite of removal titanium pigment acid group and soluble fluoride ion；
(2) ardealite made from step (1) is carried out to high-temperature calcination at 170 DEG C -350 DEG C (calcination time length depends on
In the heat exchange efficiency of calcination process, calcination time can be fluctuated in several minutes-a few hours), change the dihydrate gypsum in ardealite
For type III anhydrous gypsum；
(3) by type III anhydrous gypsum made from step (2), water (quality of water meets standard for drinking), water-reducing agent and
Waterproofing agent is mixed according to mass percent 60%-70%:23%-33%:0.5%-1.5%:3.5%-5.5%, stirring
The ardealite roadbed material is uniformly made.
Preferably, the water-reducing agent in step (3) uses polycarboxylic acid water reducing agent, and solid content is 10% to 40%.
Preferably, waterproofing agent uses containing hydrogen silicone oil in step (3).Further, containing hydrogen silicone oil is that water-based emulsion type is hydrogeneous
Silicone oil.
The present invention also proposes a kind of application method of ardealite roadbed material as made from the above method, by institute obtained
It is 180 ± 10mm (test method of fluidity, referring to GB/ that the consistency for stating ardealite roadbed material, which is controlled in fluidity,
T17669.4-1999), the ardealite roadbed material is then poured into road designated position shape after vibrating, conserving, solidify
At roadbed, being on active service to the roadbed, (military service of so-called roadbed is completed, and whole means of transportation are often as, such as high speed for completion
Highway needs overhaul or builds again, is related to reconstructing for roadbed；The active time of roadbed is generally -50 years 20 years)
Afterwards, the high-temperature calcination at 170 DEG C -350 DEG C is carried out to the ardealite roadbed material in roadbed, obtains type III anhydrous gypsum (its
In, 85%) mass fraction of calcium sulfate is greater than, ardealite roadbed material is mixed to form with water, water-reducing agent and waterproofing agent again, then
The secondary construction for roadbed.
The quality hundred of type III anhydrous gypsum, water, water-reducing agent and waterproofing agent in the ardealite roadbed material of the embodiment of the present invention
Divide ratio are as follows: (60%-70%): (23%-33%): (0.5%-1.5%): (3.5%-5.5%).In application process, use
Raw material composition ratio is as shown in table 1:
The preparation method of 1 ardealite roadbed material of table
When the present invention is particularly applicable in roadbed construction engineering, in road construction site, according to ratio shown in table 1 by object
After material mixing, ardealite roadbed material is formed, the ardealite roadbed material filling of plasticity in place and after consolidation and sclerosis, can be formed
Ardealite roadbed.Detailed process is as follows:
Calcium hydroxide will be used to carry out the ardealite after pH value neutralisation and carry out high-temperature calcination, form the anhydrous stone of type III
Cream transports road construction site after III anhydrous gypsum is sealed packaging.It, will in the mixing plant of road construction site
Type III anhydrous gypsum, water, water-reducing agent and waterproofing agent are loaded into blender after being measured, and are started blender and are stirred and obtain
It is expected that the slurry of consistency, is transported to pouring position for slurry pipeline or hopper and is poured.It can be aided in casting process suitable
Degree vibrates, to ensure the compactness of casting.After casting complete, covering curing is carried out with plastic film to the upper surface of roadbed,
After maintenance 7 days, pass through the construction quality of CBR test and flexure degree testing inspection roadbed, it is ensured that meet engine request.Later, phosphorus
Gypsum roadbed enters the military service stage, after the completion of roadbed military service, carries out high-temperature calcination again to ardealite roadbed material therein
Generate type III anhydrous gypsum, which can be sealed to packaging storage, when it is subsequent in use, by it with water,
Water-reducing agent and waterproofing agent mix in proportion, are re-used for subgrade construction.In addition, the present invention is by way of high-temperature calcination, it can not
It is disconnected to realize from ardealite roadbed material to type III anhydrous gypsum, then arrive the transformation between ardealite roadbed material.
It is proposed using conventional ardealite roadbed material (ardealite: cement: flyash: water=62:6:16:16) and the present invention
Can be recycled ardealite roadbed material (type III anhydrous gypsum: water-reducing agent: waterproofing agent: water=62:1:4:33) preparation examination
As shown in table 2, intensity therein is uniaxial compressive strength for intensity, water stability and the volume stability comparison of sample；Water stability is leaching
Strength retention after water 24 hours, relative to air care sample；It in temperature is 20 DEG C that volume stability, which is sample, relatively wet
In the environment that degree is 60%, the expansion rate of 180 day age.
The conventional ardealite roadbed material of table 2 and ardealite properties of roadbed material proposed by the present invention compare
It is according to the present invention that the reaction mechanism is as follows:
(I) calcium hydroxide is added in ardealite and carries out neutralization reaction, adjust the pH value of system to 7.0 ± 0.3.The neutralization
On the one hand reaction can eliminate H in ardealite+, the acidity of system is reduced, on the other hand may make the soluble phosphoric acid in ardealite
Root and fluorine ion are reacted with calcium ion, generate water-soluble very low calcium phosphate and calcirm-fluoride, reach removal titanium pigment acid group and
The purpose of fluorine ion.
(II) ardealite after neutralization reaction is subjected to high-temperature calcination at 170 DEG C -350 DEG C, so that two in ardealite
Water gypsum is changed into type III anhydrous gypsum.In use process, type III anhydrous gypsum carries out hydration reaction after meeting water, by molten
Solution-crystallization mechanism forms dihydrate gypsum again, and the dihydrate gypsum crystal that hydration reaction is formed is mutually interspersed, forms fine and close solidification
Body, generates intensity and water resistant divides infiltration capacity.
(III) dihydrate gypsum that hydration reaction generation is carried out by type III anhydrous gypsum, it is and outer during roadbed is on active service
During boundary carries out humidity exchange, volume change is small, therefore, has good volume stability.
(IV) to ensure that type III anhydrous gypsum carries out intensity and water stability that hydration reaction forms dihydrate gypsum, in type III
Water-reducing agent and waterproofing agent are mixed in the system that anhydrous gypsum and water are formed.The effect of water-reducing agent be reduce type III anhydrous gypsum and
Water is formed by slurry, the water requirement when reaching desired consistency, thus the porosity of the induration formed after reducing aquation, with
Ensure that intensity and water resistant divide infiltration capacity；The effect of waterproofing agent is to fill the induration hole formed after aquation, and rely on waterproof
The hydrophobicity of agent further repels outside moisture to the migration inside induration, to reach significantly improves induration water stability
Purpose.
(VI) it by the dihydrate gypsum solidified body formed after type III anhydrous gypsum aquation, completes to be on active service as roadbed material
After task, by 170 DEG C -350 DEG C of high-temperature calcination (during calcining, water-reducing agent can be eliminated and two kinds of waterproofing agent organic
Object), regeneration forms type III anhydrous gypsum, prepares to be again introduced into subgrade construction and military service link.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (5)
1. a kind of preparation method for the ardealite roadbed material that can be recycled, which comprises the following steps:
(1) ardealite that free moisture content is 7%-20% is added in saturated calcium hydroxide solution and carries out neutralization reaction, until
The pH value of leachate is 7.0 ± 0.3, obtains the ardealite of removal titanium pigment acid group and soluble fluoride ion；
(2) ardealite made from step (1) is subjected to high-temperature calcination at 170 DEG C -350 DEG C, makes the dihydrate gypsum in ardealite
It is changed into type III anhydrous gypsum；
(3) by type III anhydrous gypsum, water, water-reducing agent and waterproofing agent made from step (2) according to mass percent 60%-70%:
23%-33%:0.5%-1.5%:3.5%-5.5% is mixed, and stirs evenly and the ardealite roadbed material is made.
2. the preparation method of ardealite roadbed material as described in claim 1, which is characterized in that diminishing described in step (3)
Agent is polycarboxylic acid water reducing agent, and solid content is 10% to 40%.
3. the preparation method of ardealite roadbed material as described in claim 1, which is characterized in that waterproof described in step (3)
Agent uses containing hydrogen silicone oil.
4. the preparation method of ardealite roadbed material as described in claim 1, which is characterized in that the containing hydrogen silicone oil is aqueous
Emulsion-type containing hydrogen silicone oil.
5. a kind of ardealite roadbed material being prepared according to preparation method described in any one of Claims 1 to 4 makes
With method, which is characterized in that controlling the consistency of the ardealite roadbed material obtained in fluidity is 180 ± 10mm, so
The ardealite roadbed material is poured into road designated position afterwards and forms roadbed, after the completion of roadbed military service, by the roadbed
Interior ardealite roadbed material carries out high-temperature calcination at 170 DEG C -350 DEG C, obtains type III anhydrous gypsum again, is re-used for
The construction of roadbed.
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| CN201811598964.5A CN109553372B (en) | 2018-12-26 | 2018-12-26 | Preparation and use methods of recyclable phosphogypsum roadbed material |
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| CN201811598964.5A CN109553372B (en) | 2018-12-26 | 2018-12-26 | Preparation and use methods of recyclable phosphogypsum roadbed material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330246A (en) * | 2019-06-21 | 2019-10-15 | 李思言 | The technique that epitaxial blocked method and crystal rearrangement method change new ardealite condensation performance |
| CN110510895A (en) * | 2019-08-27 | 2019-11-29 | 辽宁省产品质量监督检验院（辽宁省建筑材料监督检验院） | A kind of Desulphurization roadbed filling |
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