CN108046669A - Geo-polymer and its preparation method and application - Google Patents
Geo-polymer and its preparation method and application Download PDFInfo
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- CN108046669A CN108046669A CN201711382031.8A CN201711382031A CN108046669A CN 108046669 A CN108046669 A CN 108046669A CN 201711382031 A CN201711382031 A CN 201711382031A CN 108046669 A CN108046669 A CN 108046669A
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- polymer
- flyash
- shield dregs
- dregs
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- 229920000642 polymer Polymers 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010881 fly ash Substances 0.000 claims abstract description 57
- 239000012190 activator Substances 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000004927 clay Substances 0.000 claims abstract description 18
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 126
- 235000019353 potassium silicate Nutrition 0.000 claims description 40
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 40
- 239000011449 brick Substances 0.000 claims description 18
- 239000004566 building material Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000010883 coal ash Substances 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 33
- 238000004064 recycling Methods 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 3
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000004568 cement Substances 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract description 3
- 239000004571 lime Substances 0.000 abstract description 3
- 235000013339 cereals Nutrition 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 230000006378 damage Effects 0.000 description 20
- 238000010586 diagram Methods 0.000 description 19
- 230000006835 compression Effects 0.000 description 18
- 238000007906 compression Methods 0.000 description 18
- 230000008901 benefit Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 10
- 238000012216 screening Methods 0.000 description 9
- 239000012634 fragment Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002689 soil Substances 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000002956 ash Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- 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
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of geo-polymers and its preparation method and application, above-mentioned geo-polymer is at least prepared by flyash, shield dregs and alkali-activator for raw material, the main component of shield dregs be clay, flyash with drying after shield dregs mass ratio be 1~2: 3；The mixture of shield dregs after flyash and drying and the mass ratio of alkali-activator are 1: 0.14~0.18.High mud containing rate shield dregs is carried out recycling by the geo-polymer, and preparing raw material does not include traditional cementitious material such as any kind of cement and lime, avoids larger carbon emission amount, at low cost；Above-mentioned geo-polymer intensity height and water-tolerant.Alkali-activator is added to by the way of spraying in mixture of the flyash with shield dregs, avoids the occurrence of larger granule by the preparation method of above-mentioned geo-polymer；And mixing wet feed is compressed in a mold so that geo-polymer test specimen has higher-strength and water resistance.
Description
Technical field
The present invention relates to the utilization technology fields of dregs, particularly, are related to a kind of geo-polymer.In addition, this hair
It is bright to further relate to a kind of preparation method and application of geo-polymer.
Background technology
Geo-polymer is a kind of novel green building materials, can use solid waste, mineral and alkali soluble rich in silane agent
Prepared by liquid or alkali metal silicate solutions reaction, particularly metakaolin, flyash or slag the like waste or mineral.At present,
The electric power in China 75% is supplied by heat power station, and coal-fired power plant generates a large amount of flyash, as power consumption increases, power plant row
The flyash removed is also sharply increasing.Flyash source is wide, at low cost, and some performances are better than metakaolin, so using powder
Coal ash, which makes geo-polymer, has extensive development prospect.
With the high speed development of the development of city development construction, especially subway construction in recent years, generate and largely build
Dregs is built, the discharge and disposal of dregs become a great problem that puzzlement urban environment is administered.Shield machine driving is that domestic subway is opened
The construction method generally used is dug, the shield dregs moisture content generated is high, harmfulness is big.Generally speaking, shield dregs is one
The native stone mixture of kind, is made of, each component content is mainly influenced by prime stratum feature rubble, sand, clay and water.Such as,
For shield machine in various micro- weathered rock formation drivings, dregs main component is rubble and mountain flour, either sieves and is dehydrated and all compares
It easily, can recycling by simple process；When silty sand ground and weathered sandstone tunnel, dregs sand factor is higher, through place
Reason can be used as injecting paste material；And in claystone or the soil layer driving of various height weathering, the dregs clay content of generation is higher, by
Big in clod viscosity, recycling difficulty is high.There is enterprise to attempt to fire standard brick, a side with above-mentioned high mud containing rate shield dregs
Face sintering process energy consumption is big, pollution environment, and factory of on the other hand baking bricks is generally in suburb, and large-scale excavation project is all in city, dregs
Transportation cost is big.Therefore, carry out the recycling of high mud containing rate shield dregs, there is important economic benefit and Environmental Effect
Benefit.
The content of the invention
It is difficult to solve high mud containing rate shield dregs the present invention provides a kind of geo-polymer and its preparation method and application
In the recycling the technical issues of.
The technical solution adopted by the present invention is as follows：
A kind of geo-polymer is at least prepared, shield by flyash, shield dregs and alkali-activator for raw material
The main component of structure dregs be clay, flyash with drying after shield dregs mass ratio be 1~2: 3；Flyash and drying
The mixture of shield dregs afterwards and the mass ratio of alkali-activator are 1: 0.14~0.18.
Further, shield dregs is using preceding needing to dry and crush.
Further, shield dregs sieves after crushing, its grain size is made to be less than 2mm.
Further, flyash is respectively less than 3% with the shield dregs moisture content after drying.
Further, alkali-activator is waterglass and the mixed liquor of NaOH solution.
According to another aspect of the present invention, the preparation method of above-mentioned geo-polymer is additionally provided, is comprised the following steps：
(1) by the drying of shield dregs, crush, the shield dregs that obtains that treated；It will treated shield dregs and fine coal
Ash is mixed to get mixture in proportion；
(2) alkali-activator is added to by the way of spraying in the mixture of step (1), stirs, obtain mixing wet
Material；
(3) the mixing wet feed that step (2) obtains is fitted into mold and compressed, demoulded after standing, you can obtained geology and gather
Close object.
Further, in step (1) will shield dregs crush after sieve, take grain size less than 2mm shield dregs with
Flyash mixes.
Further, the grain size of flyash is less than 2mm.
Further, alkali-activator is added in mixture using closed spraying agitating device in step (2).
Further, mixing time is 5~10min in step (2).
Further, step (3) is specially：Mixing wet feed is fitted into mold, side rim compacting, until filling mold；
Then mixing wet feed is compressed on hydraulic dynamometer, the pressure of hydraulic dynamometer unloads after gradually increasing to 10~12MPa, stands
After demould.
Further, time of repose is 20~28h in step (3).
Further, conserved 30~40 days after the demoulding in step (3).
Further, step (2) neutral and alkali exciting agent is the mixed liquor of waterglass and NaOH solution, the concentration of NaOH solution
For 8~12mol/L, the modulus of waterglass is 2.4~3.2.
Further, before mixing wet feed is packed into mold in step (3), mineral oil is smeared in mould inner wall.
Further, the mode of the demoulding is to use soft hammer or static pressure by molding mixing wet feed in step (3)
It releases.
According to another aspect of the present invention, above-mentioned geo-polymer is additionally provided or ground that above-mentioned preparation method is prepared
Matter polymer is in the application of building material product.
Further, building material product for standard brick, pavior brick, garden landscape earth-retaining stone, kerbstone, grass-planting brick, revetment brick,
One or more of prefabricated gutter, retaining wall block.
The invention has the advantages that：
1st, geo-polymer of the invention, uses flyash, high mud containing rate shield dregs and alkali-activator as raw material system
Standby to form, wherein high mud containing rate shield dregs main ingredient is clay, as fine aggregate after drying, flyash is volcanic ash
Material, preparing raw material does not include traditional cementitious material such as any kind of cement and lime, avoids larger carbon emission amount, cost
It is low, recycling is carried out to high mud containing rate shield dregs；Above-mentioned geo-polymer has extremely low porosity and minimum infiltration
Coefficient, intensity height and water-tolerant；Geo-polymer is oxide network structural system, will not aoxidize and decompose, and is had fine
Durability, can be used for building material product, it can also be used to submerged structure, acidproof, alkaline-resisting, high temperature resistant building etc..
2nd, the preparation method of geo-polymer of the invention, has carried out recycling, no to high mud containing rate shield dregs
Shield dregs has only been digested, has reduced the discharge of solid waste, and has generated economic benefit.By alkali-activator using spraying
Mode be added to flyash in the mixture of treated shield dregs so that compound particles uniformly moisten, and avoid out
Existing larger granule；And compress mixing wet feed in a mold, reduce the porosity of mixing wet feed, improve its compactness, from
And make the geo-polymer test specimen of gained that there is higher-strength and good water resistance.
3rd, the preparation method of geo-polymer of the invention, simple for process, reaction condition is mild, reproducible, is suitble to rule
Modelling produces.
4th, the application of geo-polymer of the invention in building material product digests high mud containing rate shield dregs, reduces solid
The discharge of discarded object solves urban environment governing problem, while also generates long-range economic benefit.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to accompanying drawings, the present invention is described in further detail.
Description of the drawings
The attached drawing for forming the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention
Example and its explanation are applied for explaining the present invention, is not constituted improper limitations of the present invention.In the accompanying drawings：
Fig. 1 is the flow diagram of matter method for producing polymer in soil of the present invention；
Fig. 2 is the single compressing stress strain curve schematic diagram of 1 geo-polymer of the preferred embodiment of the present invention；
Fig. 3 is the damage -form schematic diagram of 1 geo-polymer of the preferred embodiment of the present invention.
Fig. 4 is the single compressing stress strain curve schematic diagram of 2 geo-polymer of the preferred embodiment of the present invention；
Fig. 5 is the damage -form schematic diagram of 2 geo-polymer of the preferred embodiment of the present invention.
Fig. 6 is the single compressing stress strain curve schematic diagram of 3 geo-polymer of the preferred embodiment of the present invention；
Fig. 7 is the damage -form schematic diagram of 3 geo-polymer of the preferred embodiment of the present invention.
Fig. 8 is the single compressing stress strain curve schematic diagram of 4 geo-polymer of the preferred embodiment of the present invention；
Fig. 9 is the damage -form schematic diagram of 4 geo-polymer of the preferred embodiment of the present invention.
Figure 10 is the single compressing stress strain curve schematic diagram of 5 geo-polymer of the preferred embodiment of the present invention；
Figure 11 is the damage -form schematic diagram of 5 geo-polymer of the preferred embodiment of the present invention.
Figure 12 is the single compressing stress strain curve schematic diagram of 6 geo-polymer of the preferred embodiment of the present invention；
Figure 13 is the damage -form schematic diagram of 6 geo-polymer of the preferred embodiment of the present invention.
Figure 14 is the single compressing stress strain curve schematic diagram of 7 geo-polymer of the preferred embodiment of the present invention；
Figure 15 is the damage -form schematic diagram of 7 geo-polymer of the preferred embodiment of the present invention.
Figure 16 is the single compressing stress strain curve schematic diagram of 8 geo-polymer of the preferred embodiment of the present invention；
Figure 17 is the damage -form schematic diagram of 8 geo-polymer of the preferred embodiment of the present invention.
Figure 18 is the single compressing stress strain curve schematic diagram of 9 geo-polymer of the preferred embodiment of the present invention；
Figure 19 is the damage -form schematic diagram of 9 geo-polymer of the preferred embodiment of the present invention.
Specific embodiment
It should be noted that in the case where there is no conflict, the feature in embodiment and embodiment in the application can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
The present invention provides a kind of geo-polymers, are original at least by flyash, shield dregs and alkali-activator
Material is prepared, and the main component of shield dregs is clay, and the mass ratio of flyash and the shield dregs after drying is 1~2: 3；
The mixture of shield dregs after flyash and drying is 1: 0.14~0.18 with the mass ratio of the alkali-activator.
Above-mentioned shield dregs for shield machine in claystone or the soil layer driving of various height weathering the clay content that generates compared with
High dregs, since clod viscosity is big, recycling difficulty is high.Above-mentioned shield dregs is applied to the system of geo-polymer
It is standby, shield dregs has not only been digested, has reduced the discharge of solid waste, and has generated economic benefit.
Above-mentioned geo-polymer uses flyash, high mud containing rate shield dregs and alkali-activator to be prepared for raw material,
Wherein high mud containing rate shield dregs main ingredient is clay, and as fine aggregate after drying, flyash is pozzolanic material, system
Standby raw material does not include traditional cementitious material such as any kind of cement and lime, avoids larger carbon emission amount, at low cost, realizes
The recycling of high mud containing rate shield dregs；Above-mentioned geo-polymer has extremely low porosity and minimum infiltration coefficient,
Intensity height and water-tolerant；Geo-polymer is oxide network structural system, will not aoxidize and decompose, and is had durable well
Property, it can be used for building material product, building material product includes standard brick, pavior brick, garden landscape earth-retaining stone, kerbstone, grass-planting brick, shield
One or more in slope brick, prefabricated gutter, retaining wall block, it can also be used to submerged structure, acidproof, alkaline-resisting, high temperature resistant building
Deng.
Preferably, shield dregs is using preceding needing to dry and crush.Above-mentioned shield dregs is high mud containing rate shield dregs, is contained
Water rate is higher, is dried before it is used to prepare geo-polymer；When the shield dregs moisture content used is more than
When 40%, it is dehydrated before drying.It crushes and is conducive to being sufficiently mixed for shield dregs and flyash, and gained can be improved
The intensity of the geo-polymer arrived.
Preferably, shield dregs sieves after crushing, its grain size is made to be less than 2mm.The above-mentioned grain size using shield dregs is less than
On the one hand 2mm contributes to it to be sufficiently mixed with flyash, ensure the uniform properties of mixture, improves the intensity of made test block；Separately
On the one hand local strength declines caused by avoiding bulk walk.
Preferably, flyash is respectively less than 3% with the shield dregs moisture content after drying.It is above-mentioned to be less than 3% using moisture content
Flyash and shield dregs, be on the one hand convenient for above-mentioned raw materials wearing into fine powder, choose the powder that grain size is less than 2mm；The opposing party
Face, relatively low moisture content can be such that flyash is sufficiently mixed uniformly with shield dregs, after addition alkali-activator is mixed and stirred and compressed,
Compactness higher further improves the intensity of gained geo-polymer.
Preferably, alkali-activator is waterglass and the mixed liquor of NaOH solution.Wherein, the concentration of NaOH solution for 8~
12mol/L, the modulus of waterglass is 2.4~3.2.
The inventive concept total as one, the present invention also provides the preparation method of above-mentioned geo-polymer, including following
Step：
(1) by the drying of shield dregs, crush, the shield dregs that obtains that treated；It will treated shield dregs and fine coal
Ash is mixed to get mixture in proportion；
(2) alkali-activator is added to by the way of spraying in the mixture of step (1), stirs, obtain mixing wet
Material；
(3) the mixing wet feed that step (2) obtains is fitted into mold and compressed, demoulded after standing, you can obtained geology and gather
Close object.
After the shield dregs dried, crushing obtains is mixed in proportion with flyash in above-mentioned steps (1), dry mixing 5 minutes,
It is uniformly mixed, obtains mixture.
The preparation method of above-mentioned geo-polymer has carried out recycling to high mud containing rate shield dregs, has not only disappeared
Change shield dregs, reduced the discharge of solid waste, and generate economic benefit.By alkali-activator using the side of spraying
Formula be added to flyash in the mixture of treated shield dregs so that compound particles uniformly moisten, avoid the occurrence of compared with
Big granule；And compress mixing wet feed in a mold, reduce the porosity of mixing wet feed, improve its compactness, so that
Obtained geo-polymer test specimen has higher-strength and good water resistance.The preparation method of above-mentioned geo-polymer, work
Skill is simple, and reaction condition is mild, reproducible, is suitble to large-scale production.
Preferably, sieved after shield dregs is crushed in step (1), the shield dregs and powder that grain size is taken to be less than 2mm
Coal ash mixes.Preferably, the grain size of flyash is less than 2mm.In above-mentioned steps (1) by shield dregs drying, crush obtain it is thin
Particle crosses 2mm sieves, you can obtains the shield dregs that grain size is less than 2mm.Flyash sample pulverized powder simultaneously crosses 2mm sieves, you can obtains
Grain size is less than the flyash of 2mm.The above-mentioned grain size using shield dregs and flyash is respectively less than 2mm, on the one hand contribute to its with
Flyash is sufficiently mixed, and ensures the uniform properties of mixture, improves the intensity of made geo-polymer test block；On the other hand avoid
Local strength caused by bulk walk declines.
Preferably, alkali-activator is added in mixture using closed spraying agitating device in step (2).Using
Closed spraying agitating device, the siccative of side stirring flyash and treated shield dregs, while by exciting agent with mist
It sprays into, avoids moistening uneven, cause agglomerating.
Preferably, mixing time is 5~10min in step (2).It is stirred after adding in alkali-activator in above-mentioned steps (2)
Time cannot it is too short can not be too long, mixing time is too short, and flyash, treated shield dregs and alkali-activator cannot fill
Tap is touched, uneven so as to cause moistening degree；Mixing time is long, and above-mentioned substance has occurred that reaction, is further continued for stirring at this time
The geo-polymer of generation can be destroyed by mixing.
Preferably, step (3) is specially：Mixing wet feed is fitted into mold, side rim compacting, until filling mold；So
Mixing wet feed is compressed on hydraulic dynamometer afterwards, the pressure of hydraulic dynamometer unloads after gradually increasing to 10~12MPa, after standing
The demoulding.It is above-mentioned that mixing wet feed side rim is compacted and when being molded on the forcing press of hydraulic control, using Slow loading, gradually increase
Big pressure after maximum pressure is reached, continues 5s, then unloading pressure to 10~12MPa.Mixing wet feed is improved by static pressure
Compactness, so as to improve the intensity of geo-polymer.During aforesaid operations, application pressure is too small, and mixing wet feed can be caused close
Solidity is inadequate, low strength；It is excessive to apply pressure, then mixes wet feed and is squeezed out from pressure head and die clearance.Above-mentioned mixing wet feed exists
It is stood before the demoulding, the mixing wet feed in mold can be made fully to react at normal temperatures, so that geo-polymer is strong
Degree significantly improves.
Preferably, when time of repose is 20~28 small in step (3).Preferably, 30~40 are conserved in step (3) after the demoulding
My god.Can making mixing wet feed using above-mentioned standing, curing time, the reaction was complete at normal temperatures, so that geo-polymer shaping effect
Fruit is more preferable, intensity higher.
Preferably, step (2) neutral and alkali exciting agent is waterglass and the mixed liquor of NaOH solution, and the concentration of NaOH solution is
8~12mol/L, the modulus of waterglass is 2.4~3.2.Using waterglass and the mixed liquor of NaOH solution as alkali-activator,
The reaction being allowed to flyash is more complete, so as to get geo-polymer intensity higher.
Preferably, before mixing wet feed is packed into mold in step (3), mineral oil is smeared in mould inner wall.Aforesaid operations are favourable
It is demoulded after shaping in mixing wet feed.
Preferably, the mode of the demoulding is to be pushed away molding mixing wet feed using soft hammer or static pressure in step (3)
Go out.Its in above-mentioned mixing wet feed forming process is filled with die clearance, and frictional force is larger, causes the demoulding difficult；Along with ground
The intensity of matter polymer early period is not high, it is impossible to larger load is born, using soft hammer such as wooden stick hammering or static pressure side during the demoulding
Formula will mix wet feed and release, and avoid generating initial damage inside geo-polymer, cause final strength relatively low.
The inventive concept total as one, additionally provides above-mentioned geo-polymer or ground that above-mentioned preparation method is prepared
Matter polymer is in the application of building material product.It is above-mentioned that new building material product is manufactured using geo-polymer, dregs is not only digested, is reduced
Solid waste discharge solves urban environment governing problem, and generates long-range economic benefit.
Preferably, building material product be standard brick, it is pavior brick, garden landscape earth-retaining stone, kerbstone, grass-planting brick, revetment brick, pre-
One or more of gutter processed, retaining wall block.The geology that above-mentioned geo-polymer or above-mentioned preparation method are prepared
Polymer is mainly used in above-mentioned one or more of building material product, not only consumes high mud containing rate shield dregs, environmental protection, and
And remarkable in economical benefits.
In following embodiment, various reagents are commercially available.
Embodiment 1
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 3: 1 mass ratio
It is 0.14: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 1.8: 1, NaOH concentration 8mol/L, modulus of water glass 3.0.Above-mentioned shield dregs is high mud containing rate
Shield dregs, main component are clay.
The preparation method of above-mentioned geo-polymer is as follows：
(1) high mud containing rate shield dregs is dried, then crushed, cross the sieve of 2mm, obtain the shield dregs that grain size is less than 2mm,
That is fine grained soil；Dry flyash is worn into fine powder, and crosses the sieve of 2mm, obtains the flyash that grain size is less than 2mm, i.e. fine ash；It will
Fine grained soil obtained above is mixed with fine ash, dry mixing 5min, until uniformly, obtaining mixture.(2) dress is stirred in closed spraying
It puts and is added to alkali-activator in mixture using spray pattern, stir 10 minutes, until all materials moistening degree connects
It is near to obtain mixing wet feed.(3) above-mentioned mixing wet feed is packed into the iron mold of diameter 50mm, height 100mm, side rim is manually pressed
It is real, then compressed material with the load of 10MPa, stand 24 it is small when after the demoulding obtain above-mentioned geo-polymer, it is then normal in room temperature
It is conserved 35 days under the conditions of wet.With reference to Fig. 1, to prepare the flow chart of geo-polymer.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Fig. 2, three test specimens made of the proportioning, and peak compression intensity point
It Wei not 13.05MPa, 11.785MPa, 13.001MPa.With reference to Fig. 3, the fragment after the test specimen destruction of geo-polymer is shorter, passes through
The general character is not strong, and the destruction cone that top is formed is more apparent.
Embodiment 2
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 3: 1 mass ratio
It is 0.16: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 2: 1, NaOH concentration 10mol/L, modulus of water glass 3.0.Above-mentioned shield dregs is high mud containing rate
Shield dregs, main component are clay.
The method that the present embodiment prepares geo-polymer is same as Example 1.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Fig. 4, three test specimens made of the proportioning, and peak compression intensity point
It Wei not 18.463MPa, 22.235MPa, 20.098MPa.With reference to Fig. 5, after the test specimen destruction of geo-polymer, bottom is formed substantially
Cone.
Embodiment 3
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 3: 1 mass ratio
It is 0.18: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 2.2: 1, NaOH concentration 12mol/L, modulus of water glass 3.0.Above-mentioned shield dregs contains mud to be high
Rate shield dregs, main component are clay.
The method that the present embodiment prepares geo-polymer is same as Example 1.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Fig. 6, three test specimens made of the proportioning, and peak compression intensity point
It Wei not 18.321MPa, 18.192MPa, 16.1MPa.With reference to Fig. 7, after the test specimen destruction of geo-polymer, top is formed significantly
Cone.
Embodiment 4
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 2: 1 mass ratio
It is 0.16: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 1.8: 1, NaOH concentration 12mol/L, modulus of water glass 3.0.Above-mentioned shield dregs contains mud to be high
Rate shield dregs, main component are clay.
The method that the present embodiment prepares geo-polymer is same as Example 1.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Fig. 8, three test specimens made of the proportioning, and peak compression intensity point
It Wei not 24.991MPa, 26.922MPa, 26.624MPa.With reference to Fig. 9, after the test specimen destruction of geo-polymer, fragment connectivity
Good, apparent cone is formed on bottom, shows that intensity gives full play to.
Embodiment 5
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 2: 1 mass ratio
It is 0.18: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 2: 1, NaOH concentration 8mol/L, modulus of water glass 3.0.Above-mentioned shield dregs is high mud containing rate shield
Structure dregs, main component are clay.
The method that the present embodiment prepares geo-polymer is same as Example 1.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Figure 10, three test specimens made of the proportioning, and peak compression intensity
Respectively 21.563MPa, 21.168MPa, 21.129MPa.With reference to Figure 11, after the test specimen destruction of geo-polymer, close to circle
Taper is destroyed, and external fragment connectivity is preferable.
Embodiment 6
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 2: 1 mass ratio
It is 0.14: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 2.2: 1, NaOH concentration 10mol/L, modulus of water glass 3.0.Above-mentioned shield dregs contains mud to be high
Rate shield dregs, main component are clay.
The method that the present embodiment prepares geo-polymer is same as Example 1.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Figure 12, three test specimens made of the proportioning, and peak compression intensity
Respectively 14.510MPa, 13.591MPa, 13.501MPa.With reference to Figure 13, after the test specimen destruction of geo-polymer, close to entirety
Failure by shear, the fragment difference in size of generation is larger, became uneven.
Embodiment 7
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 3: 2 mass ratio
It is 0.18: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 1.8: 1, NaOH concentration 10mol/L, modulus of water glass 3.0.Above-mentioned shield dregs contains mud to be high
Rate shield dregs, main component are clay.
The method that the present embodiment prepares geo-polymer is same as Example 1.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Figure 14, three test specimens made of the proportioning, and peak compression intensity
Respectively 25.988MPa, 25.785MPa, 27.455MPa.With reference to Figure 15, after the test specimen destruction of geo-polymer, periphery is in whole
Body strip and block peels off, and fragment connectivity is fine.
Embodiment 8
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 3: 2 mass ratio
It is 0.14: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 2: 1, NaOH concentration 12mol/L, modulus of water glass 3.0.Above-mentioned shield dregs is high mud containing rate
Shield dregs, main component are clay.
The method that the present embodiment prepares geo-polymer is same as Example 1.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Figure 16, three test specimens made of the proportioning, and peak compression intensity
Respectively 15.848MPa, 18.067MPa, 16.86MPa.It is broken close to shearing after the test specimen destruction of geo-polymer with reference to Figure 17
Bad shape, fragment size are uneven.
Embodiment 9
Geo-polymer is prepared from the following materials：Grain size is respectively less than 2mm and moisture content be respectively less than 3% drying,
Shield dregs after crushing and screening process is carried out being mixed to form mixture, alkali-activator with flyash by 3: 2 mass ratio
It is 0.16: 1 with the mass ratio of mixture, wherein, alkali-activator is waterglass and the mixed liquor of NaOH solution, water glass solution
Mass ratio with NaOH solution is 2.2: 1, NaOH concentration 8mol/L, modulus of water glass 3.0.Above-mentioned shield dregs is high mud containing rate
Shield dregs, main component are clay.
The method that the present embodiment prepares geo-polymer is same as Example 1.
The test specimen end face of above-mentioned geo-polymer is polished flat smooth, carried out using Instron rigidity matchings uniaxial
Compression experiment measures its Complete stress-strain curve, with reference to Figure 18, three test specimens made of the proportioning, and peak compression intensity
Respectively 15.216MPa, 17.068MPa, 15.641MPa.With reference to Figure 19, after the test specimen destruction of geo-polymer, close to shearing
Failure mode, fragment size are uneven.
Each parameter is obtained by orthogonal test conceptual design in the preparation method of 1~9 geo-polymer of above-described embodiment, will just
Experimental result is handed over to be analyzed, obtains table 1.As seen from the results in Table 1, each factor polymers intensity effect over the ground：Alkali-activator with
The mixture quality ratio of shield dregs after flyash and drying>Waterglass and NaOH solution mass ratio>NaOH concentration>Flyash with
Shield dregs mass ratio after drying, optimal alkali-activator/mixture quality is than 0.18, optimal waterglass/NaOH solution matter
Amount is than for 1.8, optimum N aOH concentration 12mol/L, optimal flyash and the shield dregs mass ratio 1/2 after drying, and can be with
Find out that the molar concentration of NaOH solution is smaller more than being influenced after 10mol/L.
1 Orthogonal Experiment and Design of table and result
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (13)
1. a kind of geo-polymer, which is characterized in that
The geo-polymer is at least prepared by flyash, shield dregs and alkali-activator for raw material, the shield
The main component of dregs be clay, the flyash with drying after the shield dregs mass ratio be 1~2: 3；The powder
The mixture of the shield dregs after coal ash and drying is 1: 0.14~0.18 with the mass ratio of the alkali-activator.
2. geo-polymer according to claim 1, which is characterized in that
The shield dregs is using preceding needing to dry and crush.
3. geo-polymer according to claim 2, which is characterized in that
The shield dregs sieves after crushing, its grain size is made to be less than 2mm.
4. geo-polymer according to claim 1, which is characterized in that
The flyash is respectively less than 3% with the shield dregs moisture content after drying；And/or
The alkali-activator is waterglass and the mixed liquor of NaOH solution.
5. a kind of preparation method of Claims 1-4 any one of them geo-polymer, which is characterized in that including following step
Suddenly：
(1) by shield dregs drying, crush, the shield dregs that obtains that treated；It will treated the shield slag
It is native to be mixed to get mixture in proportion with the flyash；
(2) alkali-activator is added to by the way of spraying in the mixture of the step (1), stirs, obtain mixing wet
Material；
(3) the mixing wet feed that the step (2) obtains is fitted into mold and compressed, demoulded after standing, you can obtain describedly
Matter polymer.
6. the preparation method of geo-polymer according to claim 5, which is characterized in that
It is sieved after the shield dregs is crushed in the step (1), takes the shield dregs of the grain size less than 2mm and institute
State flyash mixing；And/or
The grain size of the flyash is less than 2mm.
7. the preparation method of geo-polymer according to claim 5, which is characterized in that
The alkali-activator is added in the mixture using closed spraying agitating device in the step (2)；With/
Or
Mixing time is 5~10min in the step (2).
8. the preparation method of geo-polymer according to claim 5, which is characterized in that
The step (3) is specially：The mixing wet feed is fitted into mold, side rim compacting, until filling mold；Then exist
The mixing wet feed is compressed on hydraulic dynamometer, the pressure of the hydraulic dynamometer unloads after gradually increasing to 10~12MPa, quiet
Postpone the demoulding.
9. the preparation method of geo-polymer according to claim 5, which is characterized in that
Time of repose is 20~28h in the step (3)；And/or
It is conserved 30~40 days after the demoulding in the step (3).
10. the preparation method of geo-polymer according to claim 5, which is characterized in that
Step (2) the neutral and alkali exciting agent for waterglass and NaOH solution mixed liquor, the concentration of the NaOH solution for 8~
12mol/L, the modulus of the waterglass is 2.4~3.2.
11. the preparation method of geo-polymer according to claim 5, which is characterized in that
Before mixing wet feed is packed into mold in the step (3), mineral oil is smeared in mould inner wall；And/or
The mode of the demoulding is to be released the molding mixing wet feed using soft hammer or static pressure in the step (3).
12. Claims 1-4 any one of them geo-polymer or claim 5 to 9 any one of them preparation method system
Application of the standby obtained geo-polymer in building material product.
13. the preparation method of geo-polymer according to claim 12, which is characterized in that
The building material product is standard brick, pavior brick, garden landscape earth-retaining stone, kerbstone, grass-planting brick, revetment brick, prefabricated draining
One or more of ditch, retaining wall block.
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