CN106927737A - A kind of preparation method of lime ground mass high-intensity building materials - Google Patents
A kind of preparation method of lime ground mass high-intensity building materials Download PDFInfo
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- CN106927737A CN106927737A CN201710127422.9A CN201710127422A CN106927737A CN 106927737 A CN106927737 A CN 106927737A CN 201710127422 A CN201710127422 A CN 201710127422A CN 106927737 A CN106927737 A CN 106927737A
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- China
- Prior art keywords
- cullet
- lime stone
- building materials
- sample
- lime
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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
- C04B28/006—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/22—Glass ; Devitrified glass
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Civil Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a kind of preparation method of lime ground mass high-intensity building materials.First using cullet and lime stone as raw material, after being crushed, 100 mesh sieves are crossed respectively and is dried；Cullet is measured with mass percent again：Lime stone=30%~60%：40%~70%, the 5%~10% of cullet and lime stone gross weight water or sodium hydroxide solution is measured again, the concentration of sodium hydroxide solution is 2~5mol/L, after each raw material is well mixed, bulk sample and the demoulding are pressed under the briquetting pressure of 30MPa, under the conditions of 140 DEG C~240 DEG C, hydrothermal hardening 1~24h is carried out, rupture strength is obtained after drying up to 25MPa high-intensity building materials.Present invention process is simple, energy-conserving and environment-protective, realizes zero CO2 emission of the lime stone in construction material preparation process, and cullet cycling and reutilization.
Description
Technical field
The present invention relates to a kind of preparation method of lime ground mass high-intensity building materials, belong to Wall or floor tile, pavior brick, square
The construction material preparing technical fields such as brick, ceiling and rivers bank protection, specifically using lime stone be aided with cullet prepare it is high-strength
The method for spending lime stone building materials.
Background technology
At present, the construction material such as Wall or floor tile, pavior brick, square brick, ceiling and rivers bank protection mainly still uses soil
High-temperature firing is formed after shaping, but, the observable index of the technique is higher, and land resource is extremely limited.China's lime
Stone resource very abundant, accounts for more than the 64% of global gross storage capacity, and lime stone has turned into the main of material particularly construction material
Raw material.Traditional lime stone prepares quick lime and there is high temperature, while having discharged substantial amounts of CO2The problems such as.
In addition, China's glassware discarded every year is more than 7,000,000 tons, but the rate of recovery is only 13%, far below the rate of recovery
It is 50% world standard.At present, relatively advanced cullet treatment technology is glass pumice technology, and one is prepared using cullet
Porous light inorganic material (patent No. 201310281305.X) is planted, but its intensity is relatively low, is mainly used in functional material, for example
Can be used for the occasions such as the heat-insulated, water filtration of wall thermal insulating, while CO cannot be realized2Quasi-zero emission.
The content of the invention
It is an object of the invention to provide a kind of technology is simple, the high intensity lime stone building materials of low cost systems
Preparation Method.
In order to achieve the above object, lime stone is aided with cullet and prepares height by the present invention by hydrothermal hardening mode
Intensity lime stone building materials.Reaction temperature of the invention is well below common ceramic firing temperature so that energy consumption
Substantially reduce, while the decomposition of calcium carbonate is it also avoid, thus more energy-conserving and environment-protective.The anti-folding of product obtained using the method is strong
Degree reaches 25MPa or so, can meet the aspects such as Wall or floor tile, pavior brick, square brick, ceiling and rivers bank protection material
The use requirement of construction timber.
Comprise the following steps that：
First using cullet and lime stone as raw material, after being crushed, 100 mesh sieves are crossed respectively and is dried.Again with quality hundred
Ratio is divided to measure cullet：Lime stone=30%~60%：40%~70%, then measure cullet and lime stone gross weight 5%
~10% water or sodium hydroxide solution, the concentration of sodium hydroxide solution is 2~5mol/L, and the above-mentioned raw material for measuring is mixed
After uniform, bulk sample and the demoulding are pressed under the briquetting pressure of 30MPa, under the conditions of 140 DEG C~240 DEG C, carry out hydro-thermal
1~24h of solidification, is obtained high-intensity building materials bulk cured article after drying.By detection, the product rupture strength for obtaining reaches
25MPa or so is arrived, the building of the aspects such as Wall or floor tile, pavior brick, square brick, ceiling and rivers bank protection material can be met
With the use requirement of material.
Advantages of the present invention and effect are：
1, during the present invention prepares high-intensity building materials using lime stone and cullet, used is that temperature is less than
240 DEG C of hydrothermal hardening method, compared with temperature after being molded using soil is higher than 1000 DEG C of traditional handicrafts of firing, energy consumption
About its 1/5, therefore energy consumption is small, and product preparation cost is low.
2, (140~240 DEG C) decomposition temperatures far below lime stone of solidification temperature of the present invention, thus the lime stone (carbonic acid
Calcium) material will not discharge substantial amounts of CO in process of production2, it is possible to achieve zero (accurate zero) discharge of greenhouse gases.
3, the present invention cullet of extremely difficult decomposition is realized as a kind of main additive for preparing high-intensity building materials
To the cycling and reutilization of cullet, not only technology is simple, low cost, it is thus also avoided that human body is damaged, and reduces soil money
Source wastes, and mitigates carrying capacity of environment.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Fig. 2 is the rupture strength of the sample of different watering quantities in embodiment 1.
Fig. 3 is the rupture strength of the sample of addition various concentrations NaOH in embodiment 2.
Fig. 4 is the rupture strength of the sample of different hardening times in embodiment 3.
Fig. 5 is the XRD spectrum of the sample of different hardening times in embodiment 3.
Fig. 6 is the infared spectrum of the sample of different hardening times in embodiment 3.
Fig. 7 is the rupture strength of the sample of different solidification temperatures in embodiment 4.
Fig. 8 is the SEM photograph of hydrothermal hardening preceding sample in embodiment 4.
Fig. 9 be embodiment 4 in it is hydrothermal hardening after sample SEM photograph.
Specific embodiment
It is raw material from cullet and lime stone, after being crushed, 100 mesh sieves is crossed respectively and is dried, after obtaining grinding
Lime stone and cullet.The present invention is further illustrated by embodiment 1-4.
Embodiment 1
The embodiment is with watering quantity as variable, so that the rupture strength for observing solidified sample under the conditions of different watering quantities becomes
Change, and be analyzed.First, grinding is weighed according to mass percent to sieve and lime stone (40~70%) and useless glass after drying
Glass (30~60%), 0~20% different quality containing that cullet and lime stone two raw material gross weights are then measured again is gone
Ionized water, mixes and is well mixed respectively, then respectively by the compound of different watering quantities, in FW-4 type desk type powder tablet press machines
Under it is compressing, briquetting pressure is 30MPa, and the sample after the demoulding is put into water heating kettle carries out hydrothermal hardening, hydrothermal temperature 180
DEG C, hydro-thermal time 15h.Sample (40mm × 15mm × 6mm) after solidification dries 24h in 60 DEG C of baking ovens, and system shown in Fig. 2 is obtained
The sample of row.
Figure it is seen that during without water, its sample strength is almost nil, and when this is due to not water mixing, difficult forming
Cause.With the increase of watering quantity, the rupture strength of the sample after solidification increased, maximum intensity when watering quantity is 10%
9.3MPa is reached, because adding the appropriate water can to accelerate the mass transfer rate in sample between solid particle, promotes reaction to carry out
Cause.When watering quantity is more than 15%, sample pressing process has water to ooze out, and shaping becomes difficult again so that under rupture strength
Drop.Therefore, the watering quantity for selecting 10% is the optimum value of the series embodiment.
Embodiment 2
The embodiment with the naoh concentration of extra addition be variable, so as to observe the addition bar of different NaOH
The rupture strength change of solidified sample under part, and be analyzed.
First, weigh grinding to sieve and lime stone (40%~70%) and cullet (30%~60%) after drying, so
Mix the sodium hydroxide solution of various concentrations (2~5mol/L) respectively afterwards, the molten incorporation of NaOH is cullet and lime
Two the 10% of raw material gross weight, stone, is well mixed, and the NaOH that various concentrations (2~5mol/L) will be then mixed respectively is molten
The compound of liquid, compressing under FW-4 type desk type powder tablet press machines, briquetting pressure is 30MPa, and the sample after the demoulding is put into
Hydrothermal hardening, 180 DEG C of hydrothermal temperature, hydro-thermal time 15h are carried out in water heating kettle.Sample (40mm × 15mm × 6mm) after solidification
24h is dried in 60 DEG C of baking ovens, the sample of series as shown in Figure 3 is obtained.
From figure 3, it can be seen that with the increase of concentration of sodium hydroxide solution, the rupture strength of solidified sample gradually strengthens,
The maximum intensity when concentration of sodium hydroxide solution is 5mol/L, rupture strength is close to 21MPa.Because at this concentration, sample resists
Folding intensity is sufficiently high, and product cost can be improved accordingly during concentration increase, therefore, with reference to rupture strength and economic benefit, I
By naoh concentration the embodiment series in optimum value be chosen to be 5mol/L.
Embodiment 3
The embodiment is with hardening time as variable, so as to observe the rupture strength of solidified sample under the conditions of different hardening times
Change, and be analyzed.First, weigh grinding sieve and after drying lime stone (40%~70%) and cullet (30%~
60%), then addition cullet and lime stone two sodium hydroxide solutions of raw material gross weight 10% (concentration is 5mol/L) and
It is well mixed, the compound of certain mass is then weighed, compressing under FW-4 type desk type powder tablet press machines, briquetting pressure is
30MPa, the sample after the demoulding is put into water heating kettle carries out hydrothermal hardening, 180 DEG C of hydrothermal temperature, 0~18h of hydro-thermal time.Solidification
Sample (40mm × 15mm × 6mm) afterwards dries 24h in 60 DEG C of baking ovens, and that 0~18h of hydro-thermal time shown in Fig. 4 is obtained is
The sample of row.
As can be seen from Figure 4, curing reaction initial stage (1h was in the past), sample strength increases sharply, and reaches after 1h, and intensity increases
Slowly.15h intensity reaches maximum, and close to 21MPa, after 15h, intensity declines rupture strength, therefore its optimum reacting time is 15h
Left and right.Fig. 5 be curing process before and after sample XRD spectrum, it can be found that the thing of lime stone mutually be calcite, when solidified between be
During 6h, the peak of calcium silicate hydrate (C-S-H systems) is occurred in that, illustrate that cullet generates calcium silicate hydrate with CaCO3 reactions
(C-S-H systems).Extension over time, the characteristic peak of calcium silicate hydrate (C-S-H systems) exists and increases always at 30 °
By force, having at 15h near 7 ° in addition has new diffraction maximum to generate, and this is the characteristic peak of tobermorite.Fig. 6 be curing process not
With the infared spectrum of time sample.It will be appreciated from fig. 6 that 3447cm-1The vibration peak at place is the stretching vibration of adsorbed water O-H,
1436cm-1,876cm-1And 713cm-1Vibration peak be CO3 2-Vibration, 876cm-1Vibration peak also demonstrates calcium carbonate ore deposit
Thing is calcite.Due to silicon dioxde reaction generation sodium metasilicate in sodium hydroxide solution and cullet, there is less silica during 0h
Vibration peak, with the growth in reaction time, the intensity of silica vibration peak is significantly increased, and illustrates that 15h generates more calcium silicates
Hydrate (C-S-H systems) and tobermorite.Understood with reference to the variation trends of Fig. 4, raw material cullet and lime stone with
The calcium silicate hydrate (C-S-H systems) and tobermorite of sodium hydroxide solution reaction generation cause that sample strength increases.
Embodiment 4
The embodiment is with solidification temperature as variable, so that the rupture strength for observing solidified sample under condition of different temperatures becomes
Change, and be analyzed.First, in the same manner as in Example 3, grinding is weighed to sieve and the lime stone (40%~70%) after drying and useless
Glass (30%~60%), then the sodium hydroxide solution (10%) of incorporation of concentration 5mol/L and is well mixed, and then weighs one
Determine the compound of quality, compressing under FW-4 type desk type powder tablet press machines, briquetting pressure is 30MPa, the sample after the demoulding
Being put into water heating kettle carries out hydrothermal hardening, 100 DEG C~220 DEG C of hydrothermal temperature, hydro-thermal time 15h.After solidification sample (40mm ×
15mm × 6mm) 24h is dried in 60 DEG C of baking ovens, the sample of Fig. 7 series is obtained.
From figure 7 it can be seen that with the raising of reaction temperature, probe intensity is dramatically increased, at 200 DEG C, intensity is reached
25MPa or so.Temperature continues to raise, and rupture strength decreases.It is its curing mechanism of labor, to the sample before and after solidification
SEM photograph is carried out, Fig. 8 and 9 is as a result seen.As shown in Figure 8, before processing, larger particle is loose to be packed together, between particle between
Gap is larger.Fig. 9 shows to generate a large amount of needle-likes between bulky grain and on large particle surface after solidification and the tobermorite of sheet is brilliant
Body, these crystal are filled with the gap of original particle, increase substantially firming body consistency, and thus intensity increase.
The rupture strength of the sample after cured above is to test rupture strength using XQ-106A universal testing machines.
Claims (1)
1. a kind of preparation method of lime ground mass high-intensity building materials, its feature is as follows：
First using cullet and lime stone as raw material, after being crushed, 100 mesh sieves are crossed respectively and is dried；Again with mass percent
Measure cullet：Lime stone=30%~60%：40%~70%, then measure cullet and lime stone gross weight 5%~
10% water or sodium hydroxide solution, the concentration of sodium hydroxide solution is 2~5mol/L, after above-mentioned raw materials are well mixed,
Bulk sample and the demoulding are pressed under the briquetting pressure of 30MPa, under the conditions of 140 DEG C~240 DEG C, carry out hydrothermal hardening 1~
24h, is obtained high-intensity building materials bulk cured article after drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002840A (en) * | 2019-03-25 | 2019-07-12 | 同济大学 | A method of automatic humidifying material is prepared using calcium chloride |
| CN110550932A (en) * | 2019-09-11 | 2019-12-10 | 上海海顾新材料科技有限公司 | method for hydrothermal preparation of high-strength building material from siliceous tailings by steam |
| CN117361915A (en) * | 2023-08-16 | 2024-01-09 | 浙江大学 | Method for preparing hydrothermal curing body based on relative content of active calcium and active silicon |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674729A (en) * | 2012-05-17 | 2012-09-19 | 同济大学 | Method for curing urban building waste at low temperature and normal pressure to produce building material |
| CN104743998A (en) * | 2015-03-06 | 2015-07-01 | 同济大学 | Method for wet-type burning sea sand to produce high strength building material |
-
2017
- 2017-03-06 CN CN201710127422.9A patent/CN106927737B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674729A (en) * | 2012-05-17 | 2012-09-19 | 同济大学 | Method for curing urban building waste at low temperature and normal pressure to produce building material |
| CN104743998A (en) * | 2015-03-06 | 2015-07-01 | 同济大学 | Method for wet-type burning sea sand to produce high strength building material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002840A (en) * | 2019-03-25 | 2019-07-12 | 同济大学 | A method of automatic humidifying material is prepared using calcium chloride |
| CN110002840B (en) * | 2019-03-25 | 2021-09-24 | 同济大学 | Method for preparing automatic humidity adjusting material by using calcium chloride |
| CN110550932A (en) * | 2019-09-11 | 2019-12-10 | 上海海顾新材料科技有限公司 | method for hydrothermal preparation of high-strength building material from siliceous tailings by steam |
| CN117361915A (en) * | 2023-08-16 | 2024-01-09 | 浙江大学 | Method for preparing hydrothermal curing body based on relative content of active calcium and active silicon |
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