CN108863122B - Natural hydraulic lime and preparation method thereof - Google Patents
Natural hydraulic lime and preparation method thereof Download PDFInfo
- Publication number
- CN108863122B CN108863122B CN201810846163.XA CN201810846163A CN108863122B CN 108863122 B CN108863122 B CN 108863122B CN 201810846163 A CN201810846163 A CN 201810846163A CN 108863122 B CN108863122 B CN 108863122B
- Authority
- CN
- China
- Prior art keywords
- mass
- sio
- tailings
- limestone
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- C04B7/00—Hydraulic cements
- C04B7/34—Hydraulic lime cements; Roman cements ; natural cements
-
- 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
- C04B2/00—Lime, magnesia or dolomite
- C04B2/02—Lime
- C04B2/04—Slaking
-
- 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
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
Abstract
The invention provides natural hydraulic lime and a preparation method thereof, belonging to the field of constructionThe technical field of building materials. According to the invention, limestone tailings are subjected to presintering and roasting in sequence to obtain a roasted product; the limestone tailings comprise the following components in percentage by mass: CaCO365～89％；SiO26-28%; the balance of MgCO3、Al2O3And Fe2O3One or more of; the SiO2Middle active SiO2The content of the limestone tailings is 4-16%; and carrying out a digestion reaction on the obtained limestone tailings and water to obtain the natural hydraulic lime. The invention takes limestone tailings as raw materials, is economic and environment-friendly; and the natural hydraulic lime with better performance is obtained through the processes of pre-burning, roasting and digesting.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to natural hydraulic water cement and a preparation method thereof.
Background
Natural Hydraulic Lime (NHL) is produced by roasting, crushing and digesting argillaceous limestone with various clay contents or siliceous limestone with various silica contents. The natural hydraulic lime has the self-repairing characteristic that after the natural hydraulic lime is contacted with water, a water hardening process is generated firstly and a gas hardening process is generated later, namely the water hardening process is generated after the natural hydraulic lime is contacted with water in the early stage and is rapidly solidified, the strength of the process is rapidly increased, the generated gas hardening process has good self-repairing effect, the strength is gradually increased, and the process enables the hydraulic lime to generate multiple pores and to have good water and gas permeability.
The natural hydraulic lime is a natural inorganic material different from the traditional lime material and cement material, and has the advantages of low shrinkage, sulfate resistance, moderate bending strength and compressive strength, and the like. The production process has no any external additive and low water soluble salt content. The natural hydraulic lime has both hydraulic property and air hardness. The air hardening component is mainly Ca (OH)2The hydraulic component is mainly 2 CaO. SiO2(C2S), and a small amount of 2 CaO. Al2O3·SiO2、3CaO·SiO2、3CaO·Al2O3And 4 CaO. Al2O3·Fe2O3And the like. It is composed ofThe hydraulicity depends mainly on the amount of dicalcium silicate bound to silica and calcium oxide produced by the decomposition of calcium carbonate.
According to European standards BS EN459 and BS EN-196, according to 28d compressive strength and Ca (OH)2The natural hydraulic lime is classified into three grades, NHL2, NHL3.5, NHL5, according to the content. The 28d compressive strength of the NHL2, NHL3.5 and NHL5 products is 2-7 MPa, 3.5-10 MPa and 5-15 MPa respectively.
Ca (OH) in NHL2 product2Content is not less than 35%, Ca (OH) in NHL3.5 product2The content is not less than 25 percent, and Ca (OH) in NHL5 product2The content is not less than 15%, wherein the grade difference of the natural hydraulic lime is as follows: 1) the content of dicalcium silicate formed in the lime calcination; 2) ca (OH) after lime digestion2The content of (a). The higher the grade, the more hydraulic components and the less air-setting components of the product.
Chinese patent CN104724953A discloses a method for preparing natural hydraulic lime by using limestone or quartz powder, wherein the raw material is limestone or quartz powder, the price is relatively high, and active SiO in the quartz powder2The amount is extremely low.
Disclosure of Invention
In view of the above, the present invention aims to provide a natural hydraulic lime and a preparation method thereof, and the preparation method of the natural hydraulic lime provided by the present invention has the advantages of wide raw material source, economy and environmental protection.
The invention provides a preparation method of natural hydraulic lime, which comprises the following steps:
1) sequentially pre-burning and roasting limestone tailings to obtain a roasted product;
the limestone tailings comprise the following components in percentage by mass:
CaCO365～89％；
the balance of MgCO3、Al2O3And Fe2O3One or more of;
the SiO2Middle active SiO2The mass of the limestone is 4-16% of that of limestone tailings;
2) and (2) carrying out a digestion reaction on the roasted product obtained in the step 1) and water to obtain the natural hydraulic lime.
Preferably, the particle size of the limestone tailings in the step 1) passes through a 180-mesh sieve, and the sieve residue is not more than 2%.
Preferably, the temperature of the pre-sintering in the step 1) is 900 ℃, and the time of the pre-sintering is 2 hours.
Preferably, the roasting temperature in the step 1) is 1100-1300 ℃, and the roasting time is 3-10 h.
Preferably, the mass of the water in the step 2) is 1-5 times of the mass of the free calcium oxide in the roasted product.
Preferably, the mass of free calcium oxide in the calcined product is determined by the ethylene glycol method.
Preferably, the temperature of the digestion reaction is room temperature, and the time of the digestion reaction is 0.5-5 h.
The invention also provides the natural hydraulic lime prepared by the preparation method, which is characterized in that the fineness of the natural hydraulic limestone is 0.2mm, the balance of the screen is not more than 2% of the total mass of the screened materials, and the balance of the screen with the size of 0.09mm is not more than 15% of the total mass of the screened materials.
The beneficial technical effects are as follows: the invention provides natural hydraulic lime and a preparation method thereof, limestone tailings are subjected to presintering and roasting in sequence to obtain a roasted product; the limestone tailings comprise the following components in percentage by mass: CaCO365～89％；SiO26-28%; the balance of MgCO3、Al2O3And Fe2O3One or more of; the SiO2Middle active SiO2The content of the limestone tailings is 4-16%; and carrying out a digestion reaction on the obtained roasted product and water to obtain the natural hydraulic lime. The invention takes limestone tailings as raw materials, is economic and environment-friendly; and the natural hydraulic lime meeting the BS.EN459-2015 standard is obtained through the processes of pre-burning, roasting and digesting.
Drawings
FIG. 1 reactive SiO2Content is the same as naturalA component relation diagram of hydraulic lime;
FIG. 2 is a schematic diagram of a dicalcium silicate reaction model.
Detailed Description
The invention provides a preparation method of natural hydraulic lime, which comprises the following steps:
1) sequentially pre-burning and roasting limestone tailings to obtain a roasted product;
the limestone tailings comprise the following components in percentage by mass:
CaCO365～89％；
the balance of MgCO3、Al2O3And Fe2O3One or more of;
the SiO2Middle active SiO2The mass of the limestone is 4-16% of that of limestone tailings;
2) carrying out a digestion reaction on the roasted product obtained in the step 1) and water to obtain the natural hydraulic lime.
According to the invention, limestone tailings are subjected to presintering and roasting in sequence to obtain a roasted product;
the limestone tailings comprise the following components in percentage by mass:
CaCO365～89％；
the balance of MgCO3、Al2O3And Fe2O3One or more of;
the SiO2Middle active SiO2The content of the limestone tailings is 4-16%.
In the present invention, the particle size of the limestone tailings is preferably 180 mesh sieve with the balance of the sieve not greater than 2%.
The invention preferably sequentially crushes and ball-mills the limestone tailings raw materials to obtain the limestone tailings meeting the granularity requirement.
In the present invention, the particle size after crushing is preferably less than 1 cm.
The method of crushing in the present invention is not particularly limited, and a crushing method known to those skilled in the art may be selected. In the present invention, crushing is preferably performed using a jaw crusher.
The method of ball milling is not particularly limited in the present invention, and a ball milling method known to those skilled in the art may be used.
The invention preferably determines the grade of the prepared natural hydraulic lime by measuring the content of active silicon dioxide in the obtained limestone tailings.
In the present invention, the method of measurement is preferably a gravimetric method.
In the present invention, the preparation of natural hydraulic lime from the limestone tailings occurs as follows:
CaCO3→CaO+CO2Δ H178.34 kJ/mol (in the standard state)
2CaO+SiO2→β-2CaO·SiO2Δ H-126.318 kJ/mol (in the standard state)
CaO+H2O→Ca(OH)2Δ H ═ 65.23kJ/mol (in the standard state).
In the present invention, dicalcium silicate C is added according to the reaction product2S component requirement, first determining the active SiO2Content, assuming C in the product2S and Ca (OH)2The total weight of (1) is 100%, soluble SiO2With s-SiO2The theoretical mass of the hydraulic component and the mass of the air-hardening component are calculated according to the following formula:
by measuring active SiO2And formula I and formula II2S and pozzolanic component Ca (OH)2And with reference to fig. 1, the grade of the natural hydraulic lime finally obtained is judged:
FIG. 1 shows a schematic view of aAs active SiO2The content is related to the components in the natural hydraulic lime.
When active SiO is in tailings2At a content of 4% to 8%, namely the hydraulic component C2S is between 13.7 and 25.0 percent and is used for preparing NHL 2;
when active SiO is in tailings2At a content of 8-12%, a hydraulic component C2S is 25.0 to 34.4 percent and is used for preparing NHL 3.5;
when active SiO is in tailings2When the content is 12-16%, the hydraulic component C2S is 34.4-42.3% and is used for preparing NHL 5.
In the invention, the pre-burning temperature is preferably 900 ℃, and the pre-burning time is preferably 2 hours.
The temperature of the present invention is preferably raised from room temperature to the pre-firing temperature. The temperature rise rate is not particularly limited in the present invention, and any temperature rise rate known in the art may be selected.
In the invention, the roasting temperature is preferably 1100-1300 ℃, more preferably 1150-1250 ℃, and the roasting time is preferably 3-10 hours, more preferably 5-8 hours.
The temperature of the present invention is preferably raised from the calcination temperature to the calcination temperature. The temperature rising rate is not particularly limited in the present invention, and a temperature rising rate known to those skilled in the art may be selected.
Specifically, in the present invention, the reaction principle of the calcination is as follows:
in the roasting process, dicalcium oxide is generated, a reaction model of the dicalcium oxide generation process is a spherical shape by adopting a Ginsterlinger equation, a reaction model diagram is shown in FIG. 2, a calcium oxide particle layer surrounds a silica layer, the whole reaction calcium oxide is a diffusion phase, the reaction is carried out along the surface of silica particles, and in the binary heterogeneous chemical reaction, the relationship between the silica conversion rate α and the reaction time is as follows:
1-2α/3-(1-α)2/3＝Ae-Ea/RTt formula III
Wherein α is SiO2The conversion rate, T is the holding time, T is the roasting temperature, R is the molar gas constant 8.3145J mol-1·K-1，EaFor apparent activation energy, the experimental derivation was 168.37KJ/mol, A is a pre-exponential factor, and the experimental derivation was 16.19.
In the present invention, the SiO2The conversion is the mass ratio of active silica to total silica.
In the present invention, the roasting preferably further comprises grinding the roasted product to obtain a roasted product.
In the present invention, the fineness of the ground roasted product is preferably such that the amount of the sieve residue of 0.2mm is not more than 2% of the total mass of the sieved material, and the amount of the sieve residue of 0.09mm is not more than 15% of the total mass of the sieved material.
After the roasted product is obtained, the obtained roasted product and water are subjected to digestion reaction to obtain the natural hydraulic lime.
In the present invention, the mass of the water is preferably 1 to 5 times, and more preferably 2 to 3 times, the mass of the free calcium oxide in the calcined product. The water consumption for digestion can ensure complete digestion of free calcium oxide and prevent hydration of dicalcium silicate.
In the present invention, the mass of free calcium oxide in the calcined product is preferably determined by the ethylene glycol method.
The invention obtains the air hardening component Ca (OH) in the natural hydraulic lime through a digestion reaction2。
In the invention, the time of the digestion reaction is preferably 0.5-2 h, more preferably 1-1.5 h, the condition of the digestion reaction is room temperature, and the reaction temperature can be 50-80 ℃.
In the present invention, the digestion reaction further comprises ball milling.
In the invention, the fineness after ball milling is that the 0.2mm sieve residue is not more than 2% of the total mass of the sieved materials, and the 0.09mm sieve residue is not more than 15% of the total mass of the sieved materials.
The method of ball milling is not particularly limited in the present invention, and a ball milling method known to those skilled in the art may be selected.
The invention also provides the natural hydraulic limestone prepared by the preparation method, wherein the fineness of the natural hydraulic limestone is that the 0.2mm screen allowance is not more than 2% of the total mass of the screened materials, and the 0.09mm screen allowance is not more than 15% of the total mass of the screened materials.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
CaCO consisting of limestone and tailing minerals387% of SiO2The content of the other components is 9 percent, and the other components are MgCO3Or Al2O3. Determination of its active SiO2The maximum conversion of the content was calculated to be 78%, and the theoretical hydraulic component C was found from the formula I and the formula II2S22.4%, air hardening Ca (OH)2It was 77.6%. Crushing and ball milling, keeping the temperature of the raw materials at 900 ℃ for 2h in a muffle furnace at the temperature rise stage, keeping the temperature of the raw materials at 1100 ℃ for 5.0h in a hydraulic component generation stage according to a formula III, cooling the raw materials under natural conditions, digesting the roasted products with 5 times of water amount after ball milling, ball milling the digested products until the fineness reaches 0.2mm, the residue on a sieve is not more than 2 percent of the total mass of the sieved materials, and the residue on a sieve with the fineness of 0.09mm is not more than 15 percent of the total mass of the sieved materials, thus obtaining NHL2 with the whiteness of 55.4 and the density of 2.32g/cm3The standard thick water-cement ratio is 0.48, the initial setting time is 5h, the final setting time is 14h, and the volume stability is qualified. The 28d compressive strength is 2.3MPa, the 28d elastic modulus is 8000MPa, the 180d compressive strength can reach 7.0MPa, and the 28d shrinkage rate is 0.53.
Example 2
CaCO consisting of limestone and tailing minerals 380% of SiO2The content of the other components is 14 percent and MgCO is used as the other component3Or Al2And O3. Determination of its active SiO2The maximum conversion of the content was calculated to be 82%, and the theoretical hydraulic component C was found from the above formula I and formula II2S is 32.2%, and the air hardening component is Ca (OH)2The content was 67.8%. Crushing and ball milling, maintaining the temperature of 900 deg.C for 2h in muffle furnace, setting the calcination temperature at 1200 deg.C according to formula III in hydraulic component generation stage, maintaining the temperature for 2.2h, cooling under natural condition,ball milling the roasted product, digesting with 4 times of water, ball milling the digested product to obtain the product with fineness of 0.2mm and the balance not more than 2% of the total mass of the sieved material, and ball milling the digested product to obtain NHL3.5 with the balance not more than 15% of the total mass of the sieved material, and the prepared NHL3.5 has whiteness value of 67.3 and density of 2.42g/cm3The standard thick water-cement ratio is 0.43, the initial setting time is 4h, the final setting time is 10h, and the volume stability is qualified. The 28d compressive strength is 2.3MPa, the 28d elastic modulus is 10000MPa, the 180d compressive strength can reach 9.2MPa, and the 28d shrinkage rate is 0.40.
Example 3
CaCO consisting of limestone and tailing minerals376% of SiO2The content of the other components is 19 percent and MgCO is used as the other component3Or Al2O3. Determination of its active SiO2The content was 16.7%, and the maximum conversion was 88% as calculated from the formula I and the formula II, and the theoretical hydraulic component C was found to be2S42.3%, air hardening Ca (OH)2The content was found to be 56.8%. After crushing and ball milling, the raw materials are kept warm for 2h at 900 ℃ in a muffle furnace in a temperature rise stage, and the roasting time t is 1.14h when the roasting temperature is 1300 ℃ in a hydraulic component generation stage according to a formula III. Cooling under natural conditions, ball-milling the roasted product, digesting with 3 times of water, ball-milling the digested product to obtain a product with fineness of 0.2mm and the balance of the sieve not more than 2% of the total mass of the sieved material, and ball-milling the digested product to obtain NHL5 with the balance of the sieve of 0.09mm not more than 15% of the total mass of the sieved material, wherein the prepared NHL5 has a whiteness value of 65.1 and a density of 2.63g/cm3The standard thick water-cement ratio is 0.39, the initial setting time is 3h, the final setting time is 10h, and the volume stability is qualified. The 28d compressive strength is 5.6MPa, the 28d elastic modulus is 12000MPa, the 180d compressive strength can reach 16MPa, and the 28d shrinkage rate is less than 0.15.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of natural hydraulic lime comprises the following specific steps:
1) sequentially pre-burning and roasting limestone tailings to obtain a roasted product;
the limestone tailings comprise the following components in percentage by mass:
CaCO365～89％；
SiO26～28％；
the balance of MgCO3、Al2O3And Fe2O3One or more of;
the SiO2Middle active SiO2The mass of the limestone tailings is 4-16% of that of the limestone tailings;
the natural hydraulic lime comprises a hydraulic component and an air-hardening component;
the mass percentages of the hydraulic component and the pneumatic component are calculated by formula I and formula II, wherein the active SiO2With s-SiO2Represents:
when the active SiO is in the tailings2When the content is 4-8%, the mass percent of the hydraulic component is 13.7-25.0%;
when the active SiO is in the tailings2When the content is 8-12%, the mass percent of the hydraulic component is 25.0-34.4%;
when the active SiO is in the tailings2When the content is 12-16%, the mass percentage of the hydraulic component is 34.4-42.3%;
the pre-sintering temperature is 900 ℃, and the pre-sintering time is 2 hours;
the roasting temperature is 1100-1300 ℃, and the roasting time is 3-10 h;
2) carrying out a digestion reaction on the roasted product obtained in the step 1) and water to obtain the natural hydraulic lime.
2. The preparation method of claim 1, wherein the particle size of the limestone tailings in the step 1) is 180-mesh sieve, and the sieve residue is not more than 2%.
3. The preparation method according to claim 1, wherein the mass of the water in the step 2) is 1 to 5 times of the mass of the free calcium oxide in the roasted product.
4. The production method according to claim 1, wherein the mass of free calcium oxide in the calcined product is measured by an ethylene glycol method.
5. The preparation method according to claim 1, wherein the temperature of the digestion reaction is room temperature, and the time of the digestion reaction is 0.5-5 h.
6. The natural hydraulic lime prepared by the preparation method of any one of claims 1 to 5, wherein the fineness of the natural hydraulic lime is that the 0.2mm screen residue is not more than 2% of the total mass of the screened materials, and the 0.09mm screen residue is not more than 15% of the total mass of the screened materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810846163.XA CN108863122B (en) | 2018-07-27 | 2018-07-27 | Natural hydraulic lime and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810846163.XA CN108863122B (en) | 2018-07-27 | 2018-07-27 | Natural hydraulic lime and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108863122A CN108863122A (en) | 2018-11-23 |
| CN108863122B true CN108863122B (en) | 2020-06-30 |
Family
ID=64306242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810846163.XA Active CN108863122B (en) | 2018-07-27 | 2018-07-27 | Natural hydraulic lime and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108863122B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348846A (en) * | 2018-12-21 | 2020-06-30 | 西南科技大学 | Hydraulic cementing material and preparation method thereof |
| CN111348850A (en) * | 2018-12-21 | 2020-06-30 | 西南科技大学 | Hydraulic lime and production method thereof |
| CN110950556B (en) * | 2019-12-26 | 2020-12-18 | 中国矿业大学(北京) | High-activity belite-containing natural hydraulic lime and preparation method thereof |
| CN113666652B (en) * | 2021-08-23 | 2022-07-12 | 中国矿业大学(北京) | Natural hydraulic lime and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100595427B1 (en) * | 2004-07-16 | 2006-06-30 | 한일시멘트 (주) | The manufacturing method and composition of nonsintering natural hydraulic lime mortar |
| GB201002223D0 (en) * | 2010-02-10 | 2010-03-31 | Gibson Robin | Hydraulic lime composition |
| CN103466968B (en) * | 2013-08-23 | 2015-01-21 | 西安建筑科技大学 | Method for preparing natural hydraulic lime with lead and zinc mine tailings |
| CN104016652A (en) * | 2014-05-30 | 2014-09-03 | 中国矿业大学(北京) | Autoclaved aerated concrete and preparation method thereof |
| CN104724953B (en) * | 2015-03-12 | 2017-03-01 | 北京工业大学 | A kind of method that natural hydraulic lime prepared by utilization limestone and silica flour |
-
2018
- 2018-07-27 CN CN201810846163.XA patent/CN108863122B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108863122A (en) | 2018-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108863122B (en) | Natural hydraulic lime and preparation method thereof | |
| CN105330180B (en) | Early-strength low-heat portland cement and preparation method thereof | |
| CN107021654B (en) | A kind of sulphur calcium silicates sulphate aluminium cement and preparation method thereof | |
| JP6175081B2 (en) | Method for producing auxiliary cementitious materials (SCMs) | |
| CN110104998B (en) | Micro-fine particle high-silicon tailing grouting material | |
| CN102092976B (en) | Mass eco-concrete expansive agent and preparation method thereof | |
| CN101643333B (en) | and application of concrete expansion agent for compensating concrete dry shrinkage | |
| CN108191364B (en) | Modification method of phosphogypsum building gypsum product | |
| Gómez-Casero et al. | Physical, mechanical and thermal properties of metakaolin-fly ash geopolymers | |
| CN102674723B (en) | Cementing material made of earthy yellow malm and used for repairing masonry cultural relics | |
| CN104230243A (en) | Non-fired and non-steamed tailing brick and preparation method thereof | |
| CN101684675B (en) | Autoclaved phosphogypsum brick and method for preparing same | |
| CN107522501B (en) | Aerated concrete and preparation method thereof | |
| CN110436907A (en) | A method of utilizing preparing mullite from gangue | |
| CN104045294A (en) | Preparation method of inorganic gelling material for reinforcing brick-material culture relic | |
| CN103288371A (en) | Tungsten tailing concrete admixture and application thereof | |
| CN110963764A (en) | Waterproof concrete and preparation method thereof | |
| EP2878585B1 (en) | Method for the manufacturing of cementitious C-S-H seeds | |
| US7537653B2 (en) | Microsilica materials with improved pozzolanic activity | |
| CN112592145A (en) | Preparation method of early-strength phosphogypsum expansion mortar | |
| CN103466968B (en) | Method for preparing natural hydraulic lime with lead and zinc mine tailings | |
| CN104961363B (en) | A kind of method of the active ground-slag of use shaft kiln factory and office reason discarded concrete system and aggregate | |
| CN110790539A (en) | Preparation method of new material for reinforcing sandstone grotto cultural relics | |
| CN107382107B (en) | Method for preparing sulphoaluminate cement clinker by using magnesium slag and manganese slag | |
| CN101531476A (en) | A preparation method for producing aluminate gelled material by ferro vanadium waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |