CN106927737B - 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 PDF

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CN106927737B
CN106927737B CN201710127422.9A CN201710127422A CN106927737B CN 106927737 B CN106927737 B CN 106927737B CN 201710127422 A CN201710127422 A CN 201710127422A CN 106927737 B CN106927737 B CN 106927737B
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cullet
lime stone
building materials
lime
sample
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CN106927737A (en
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景镇子
裘鹏程
刘子系
祁郁捷
苗嘉俊
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Tongji University
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Tongji University
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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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Civil Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The present invention relates to a kind of preparation methods of lime ground mass high-intensity building materials.First using cullet and lime stone as raw material, after being crushed, sieves with 100 mesh sieve and dry respectively；Cullet: lime stone=30%~60%:40%~70% is measured with mass percent again, 5%~10% water or sodium hydroxide solution of cullet and lime stone total weight are measured again, the concentration of sodium hydroxide solution is 2~5mol/L, after mixing by each raw material, it is pressed into bulk sample under the briquetting pressure of 30MPa and demoulds, under the conditions of 140 DEG C~240 DEG C, progress hydrothermal hardening 1~flexural strength is made for 24 hours, after drying up to 25MPa high-intensity building materials.Present invention process is simple, energy conservation and environmental protection, realizes the cycling and reutilization of zero CO2 emission and cullet of the lime stone in construction material preparation process.

Description

A kind of preparation method of lime ground mass high-intensity building materials
Technical field
The present invention relates to a kind of preparation methods of lime ground mass high-intensity building materials, belong to Wall or floor tile, pavement brick, square The construction materials preparation technical fields such as brick, ceiling and rivers bank protection, specifically using lime stone be aided with cullet prepare it is high-strength Spend the method for lime stone building materials.
Background technique
Currently, the construction materials such as Wall or floor tile, pavement brick, square brick, ceiling and rivers bank protection are mainly or using soil High temperature is fired after molding, and still, the energy consumption of the technique is relatively high, and land resource is extremely limited.China's lime Stone resource very abundant, 64% or more of Zhan Quanqiu gross storage capacity, lime stone has become the main of material especially construction material Raw material.Traditional lime stone prepares quick lime, and there are high temperature, while having discharged a large amount of CO2The problems such as.
In addition, the glassware that China discards every year is more than 7,000,000 tons, but the rate of recovery is only 13%, is far below the rate of recovery For 50% world standard.Currently, relatively advanced cullet processing technique is glass pumice technology, cullet preparation one is utilized The porous light inorganic material (patent No. 201310281305.X) of kind, but its intensity is lower, is mainly used for functional material, such as It can be used for the occasions such as the heat-insulated, water filtration of wall thermal insulating, while cannot achieve CO2Quasi-zero emission.
Summary of the invention
A kind of system of the object of the present invention is to provide technologies high-intensitive lime stone building materials simple, at low cost Preparation Method.
In order to achieve the above object, lime stone is aided with cullet by hydrothermal hardening mode height is prepared by the present invention Intensity lime stone building materials.Reaction temperature of the invention is well below common ceramic firing temperature, so that production energy consumption It substantially reduces, while also avoiding the decomposition of calcium carbonate, thus be more energy-saving and environmentally friendly.The anti-folding of product obtained using this method is strong Degree reaches 25MPa or so, can satisfy such as Wall or floor tile, pavement brick, square brick, ceiling and rivers bank protection material etc. The requirement of construction timber.
Specific step is as follows:
First using cullet and lime stone as raw material, after being crushed, sieves with 100 mesh sieve and dry respectively.Again with quality hundred Divide than measurement cullet: lime stone=30%~60%:40%~70%, then measure the 5% of cullet and lime stone total weight ~10% water or sodium hydroxide solution, the concentration of sodium hydroxide solution are 2~5mol/L, and the above-mentioned raw material measured is mixed After uniformly, it is pressed into bulk sample under the briquetting pressure of 30MPa and demoulds, under the conditions of 140 DEG C~240 DEG C, carries out hydro-thermal Solidification 1~for 24 hours, high-intensity building materials bulk cured article is made after drying.After testing, the product flexural strength obtained reaches 25MPa or so is arrived, can satisfy the building of such as Wall or floor tile, pavement brick, square brick, ceiling and rivers bank protection material etc. With the 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 lower than 240 DEG C of hydrothermal hardening method, compared with the traditional handicraft made of temperature after soil molding is higher than 1000 DEG C of firings, energy consumption About its 1/5, therefore production energy consumption is small, and product preparation cost is low.
2, (140~240 DEG C) of the solidification temperature of the present invention decomposition temperatures far below lime stone, thus the lime stone (carbonic acid Calcium) material will not discharge a large amount of CO in process of production2, zero (standard zero) discharge of greenhouse gases may be implemented.
3, the present invention uses the cullet of extremely difficult decomposition as a kind of main additive for preparing high-intensity building materials, realizes It is not only technically simple, at low cost to the cycling and reutilization of cullet, it is thus also avoided that cause harm to the human body, reduce soil money Source waste, mitigates carrying capacity of environment.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is the flexural strength of the sample of different watering quantities in embodiment 1.
Fig. 3 is the flexural strength that the sample of various concentration sodium hydroxide is added in embodiment 2.
Fig. 4 is the flexural strength of the sample of different curing times in embodiment 3.
Fig. 5 is the XRD spectrum of the sample of different curing times in embodiment 3.
Fig. 6 is the infared spectrum of the sample of different curing times in embodiment 3.
Fig. 7 is the flexural 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
Selecting cullet and lime stone is raw material, after being crushed, sieves with 100 mesh sieve and dries respectively, after obtaining grinding Lime stone and cullet.The present invention is further illustrated by embodiment 1-4.
Embodiment 1
The embodiment is using watering quantity as variable, so that the flexural strength for observing solidified sample under the conditions of different watering quantities becomes Change, and is analyzed.Firstly, weighing lime stone (40~70%) and useless glass after grinding is sieved and dries according to mass percent Glass (30~60%) then measures going for 0~20% different quality containing of two raw material gross weights of cullet and lime stone again Ionized water is mixed respectively and is uniformly mixed, then respectively by the mixture of different watering quantities, in FW-4 type desk type powder tablet press machine Lower compression moulding, briquetting pressure 30MPa, the sample after demoulding, which is put into water heating kettle, carries out hydrothermal hardening, hydrothermal temperature 180 DEG C, hydro-thermal time 15h.For 24 hours, obtained Fig. 2 is shown to be sample (40mm × 15mm × 6mm) after solidification for drying in 60 DEG C of baking ovens The sample of column.
Figure it is seen that sample strength is almost nil when not adding water, this is because when not water mixing, difficult forming Caused by.With the increase of watering quantity, the flexural strength of the sample after solidification be increased, maximum intensity when watering quantity is 10% Reach 9.3MPa, this is because suitable water, which is added, can accelerate mass transfer rate in sample between solid particle, reaction is promoted to carry out Caused by.When watering quantity is more than 15%, sample pressing process has water exudation, and molding becomes difficult again, so that under flexural strength Drop.Therefore, 10% watering quantity is selected as the optimum value of the series embodiment.
Embodiment 2
The embodiment is using the naoh concentration additionally added as variable, to observe the additive amount item of different sodium hydroxides The flexural strength variation of solidified sample under part, and analyzed.
Firstly, weighing the lime stone (40%~70%) after grinding is sieved and dries and cullet (30%~60%), so Mix the sodium hydroxide solution of various concentration (2~5mol/L) respectively afterwards, the molten incorporation of sodium hydroxide is cullet and lime The 10% of two raw material gross weights of stone is uniformly mixed, and the sodium hydroxide that then will mix various concentration (2~5mol/L) respectively is molten The mixture of liquid, the compression moulding under FW-4 type desk type powder tablet press machine, briquetting pressure 30MPa, the sample after demoulding are put into Progress is hydrothermal hardening in water heating kettle, and 180 DEG C of hydrothermal temperature, hydro-thermal time 15h.Sample (40mm × 15mm × 6mm) after solidification For 24 hours, the sample of series as shown in Figure 3 is made in drying in 60 DEG C of baking ovens.
From figure 3, it can be seen that the flexural strength of solidified sample gradually increases with the increase of concentration of sodium hydroxide solution, The maximum intensity when concentration of sodium hydroxide solution is 5mol/L, flexural strength is close to 21MPa.Since at this concentration, sample is anti- It is sufficiently high to roll over intensity, and product cost can correspondingly increase when concentration increases, therefore, in conjunction with flexural 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 using curing time as variable, to observe the flexural strength of solidified sample under the conditions of different curing times Variation, and analyzed.Firstly, weigh the lime stone (40%~70%) after grinding is sieved and dries and cullet (30%~ 60%), then the sodium hydroxide solution (concentration 5mol/L) of two raw material gross weights 10% of cullet and lime stone is added simultaneously It is uniformly mixed, then weighs the mixture of certain mass, the compression moulding under FW-4 type desk type powder tablet press machine, briquetting pressure is 30MPa, the sample after demoulding be put into water heating kettle carry out it is hydrothermal hardening, 180 DEG C of hydrothermal temperature, 0~18h of hydro-thermal time.Solidification For 24 hours, a system of 0~18h of hydro-thermal time shown in Fig. 4 is made in the drying in 60 DEG C of baking ovens of sample (40mm × 15mm × 6mm) afterwards The sample of column.
As can be seen from Figure 4, curing reaction initial stage (1h was in the past), sample strength increases sharply, and after reaching 1h, intensity increases Slowly.15h intensity reaches maximum value, and flexural strength is close to 21MPa, after 15h, intensity decline, therefore its optimum reacting time is 15h Left and right.Fig. 5 is the XRD spectrum of sample before and after curing process, it can be found that the object of lime stone is mutually calcite, when solidified between be When 6h, there is the peak of calcium silicate hydrate (C-S-H system), illustrates that cullet is reacted with CaCO3 and generate calcium silicate hydrate (C-S-H system).With the extension of time, the characteristic peak of calcium silicate hydrate (C-S-H system) always exists and increases at 30 ° By force, furthermore nearby having at 15h at 7 ° has new diffraction maximum to generate, 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 mine Object is calcite.Since silicon dioxde reaction generates sodium metasilicate in sodium hydroxide solution and cullet, there is lesser silicon oxygen in when 0h Vibration peak, with the growth in reaction time, the intensity of silicon oxygen vibration peak is significantly increased, and illustrates that 15h generates more calcium silicates Hydrate (C-S-H system) and tobermorite.In conjunction with Fig. 4 variation trends it is found that raw material cullet and lime stone with The calcium silicate hydrate (C-S-H system) and tobermorite that sodium hydroxide solution reaction generates increase sample strength.
Embodiment 4
The embodiment is using solidification temperature as variable, so that the flexural strength for observing solidified sample under condition of different temperatures becomes Change, and is analyzed.Firstly, in the same manner as in Example 3, weighing the lime stone (40%~70%) after grinding is sieved and dries and giving up Glass (30%~60%) then the sodium hydroxide solution (10%) of incorporation of concentration 5mol/L and is uniformly mixed, then weighs one The mixture for determining quality, the compression moulding under FW-4 type desk type powder tablet press machine, briquetting pressure 30MPa, the sample after demoulding It is hydrothermal hardening to be put into progress in water heating kettle, 100 DEG C~220 DEG C of hydrothermal temperature, hydro-thermal time 15h.After solidification sample (40mm × 15mm × 6mm) it is dried in 60 DEG C of baking ovens for 24 hours, the sample of Fig. 7 series is made.
From figure 7 it can be seen that probe intensity dramatically increases with the raising of reaction temperature, at 200 DEG C, intensity is reached 25MPa or so.Temperature continues to increase, and flexural strength decreases.For its curing mechanism of detailed analysis, to the sample for solidifying front and back SEM photograph is carried out, as a result sees Fig. 8 and 9.As shown in Figure 8, before processing, biggish particle is loose to be packed together, between particle between Gap is larger.Fig. 9 shows to produce a large amount of needle-shaped and sheet tobermorites crystalline substances after solidifying between bulky grain and on large particle surface Body, these crystal are filled with the gap of original particle, increase substantially solidified body consistency, thus intensity increases.
The flexural strength of sample after cured above is to test flexural strength using XQ-106A universal testing machine.

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, sieves with 100 mesh sieve and dry respectively；Again with mass percent Measure cullet: lime stone=30%~60%:40%~70%, then measure cullet and lime stone total weight 5%~ 10% water or sodium hydroxide solution, the concentration of sodium hydroxide solution are 2~5mol/L, after mixing by above-mentioned raw materials, It is pressed into bulk sample under the briquetting pressure of 30MPa and demoulds, under the conditions of 140 DEG C~240 DEG C, progress hydrothermal hardening 1~ For 24 hours, high-intensity building materials bulk cured article is made after drying.
CN201710127422.9A 2017-03-06 2017-03-06 A kind of preparation method of lime ground mass high-intensity building materials Active CN106927737B (en)

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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

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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

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