CN113264699A - Q/P phase cement clinker containing calcium aluminate - Google Patents

Q/P phase cement clinker containing calcium aluminate Download PDF

Info

Publication number
CN113264699A
CN113264699A CN202110399377.9A CN202110399377A CN113264699A CN 113264699 A CN113264699 A CN 113264699A CN 202110399377 A CN202110399377 A CN 202110399377A CN 113264699 A CN113264699 A CN 113264699A
Authority
CN
China
Prior art keywords
phase
calcium aluminate
cement clinker
calcium
mineral
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.)
Granted
Application number
CN202110399377.9A
Other languages
Chinese (zh)
Other versions
CN113264699B (en
Inventor
王守德
袁俊刚
颜景华
黄永波
程新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN202110399377.9A priority Critical patent/CN113264699B/en
Publication of CN113264699A publication Critical patent/CN113264699A/en
Application granted granted Critical
Publication of CN113264699B publication Critical patent/CN113264699B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C04B7/32—Aluminous 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
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • 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
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
    • 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
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
    • 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
    • Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods

Abstract

The invention particularly relates to a Q/P phase cement clinker containing calcium aluminate phosphate, belonging to the technical field of building materials. The cement clinker is prepared from Q/P phase-calcium phosphoaluminate (C)8A6P) -Calcium Aluminate (CA) -dicalcium silicate (C)2S) -Tetracalcium aluminoferrite (C)4AF) five mineral phases. The invention is realized by adding a certain amount of P into the system2O5Not only promotes the generation of Q/P phase, but also reduces the cement firing temperature due to the introduction of the iron phase and promotes the generation of calcium phosphoaluminate, so that part of calcium aluminate is converted into calcium phosphoaluminate to replace part of C2S to ensure later strength growth. The cement clinker prepared by the invention has the advantages of low sintering temperature, good hydration performance and high early strengthAnd the later strength is not shrunk.

Description

Q/P phase cement clinker containing calcium aluminate
Technical Field
The invention particularly relates to a Q/P phase cement clinker containing calcium aluminate phosphate, belonging to the technical field of building materials.
Background
When T ∙ W ∙ Parker researches on high alumina cement, the findings are moreColor minerals (pleochrote). Later, this type of mineral was called P phase, whose molecular composition was 6CaO ∙ 4Al2O3∙FeO∙SiO2Abbreviated as C6A4F '' S, and conclude that P phase may exist in the following system: CA-P phase-C12A7-C2S; CA-P phase-C2S-C2An AS; CA-P phase-C2AS-FeO. If MgO in the system is used for replacing FeO, the P phase is converted into the Q phase.
The Q-phase mineral is a stable phase formed at 1260 ℃ to 1300 ℃ by a CaO-MgO-Al2O3-SiO2 quaternary system, and is originally considered to be C6A4MS, 6CaO ∙ 4Al2O3∙MgO∙SiO2Later, Kapralik I and Hanic F et al have made new studies on the composition and structure of phase Q. The composition of the Q phase is considered to be C6A4The deviation of MS is that Q is corresponding to various solid solutions, and the molecular formula can be abbreviated as Ca20 Al32-2VMg VSiVO 68Wherein V is the same as (2.5, 3.5), for research convenience, the composition of Q phase is still taken as Ca20Al26 Mg3 Si3O68Or C6A4MS。
Mineral C in phase Q and portland cement of Jiang Fenghua et al2S、C4The Q phase-C was obtained in the study of the coexistence conditions of AF2S-C4AF-C12A7And (4) preparing the system. The system has low cement firing temperature and can save energy; the raw material can utilize limestone with high magnesium and low calcium, and can fully utilize limited natural resources; the content of calcium is lower than that of ordinary silicate cement, and CO is reduced during firing2The cement system has the advantages of fast hydration heat release, short setting time, high early strength and the like. But due to C2S is slowly hydrated and cannot meet the requirement of later strength increase of cement, so that the research and development of the Q-phase cement clinker with excellent performance has important significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a Q/P phase cement clinker containing calcium aluminate phosphate, which can fully utilize industrial raw materials of high-magnesium limestone, bauxite and phosphorus ashThe stone is prepared into a product with the dominant Q/P phase and CPA, C2S，C4AF and other minerals.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the invention provides a Q/P phase cement clinker containing calcium aluminate, which is prepared from Q/P phase-calcium aluminate phosphate (C)8A6P) -Calcium Aluminate (CA) -dicalcium silicate (C)2S) -Tetracalcium aluminoferrite (C)4AF) five mineral phases.
Further, the mineral phase composition of the cement clinker is as follows:
Q/P phase 40-60%
20 to 40 percent of calcium phosphoaluminate
5 to 20 percent of calcium aluminate
0 to 10 percent of dicalcium silicate
0-5% of tetracalcium aluminoferrite.
Further, the P-phase mineral is 6CaO ∙ 4Al2O3∙FeO∙SiO2Abbreviated as C6A4F' S; the Q-phase mineral is C6A4MS, 6CaO ∙ 4Al2O3∙MgO∙SiO2Or C20A16-vM v S v，v∈(2.5-3.5)。
The invention also provides a preparation method of the calcium aluminate phosphate-containing Q/P phase cement clinker, which is characterized in that the raw materials are weighed according to the mineral proportion, the raw materials are sieved by a standard sieve, stirred by a ball mill, dried, prepared into a sample, placed into a low-temperature oven for drying, and then placed into a high-temperature calcining furnace for high-temperature calcining.
Further, the aperture of the standard sieve is 200 meshes.
Further, the high-temperature calcination is carried out for 2 hours at 1300 ℃ and 1350 ℃.
The Q/P phase mineral used in the invention can be prepared by synthesis between oxides, and can also be formed by solid phase reaction of calcium aluminate and phases containing silicon, magnesium and iron, namely calcium aluminate and C are formed firstly under different alkalinity2S、C2AS, which then reacts with MgO/FeO to form the Q/P phase. Calcining water by adopting industrial raw materialsIn the case of clinker, the inevitable introduction of large amounts of silicon, in the form of C2The form of AS exists in the clinker ore phase, C2As an inert material, the hydration activity is extremely low, and the hydration activity is along with C in clinker2The increase of AS content seriously affects the hydration activity of cement. Therefore, limestone with high magnesium and low calcium, fly ash and apatite are selected as raw materials, redundant silicon in the raw materials is combined with calcium aluminate and magnesium/iron contained in the raw materials, and the raw materials are calcined at high temperature. Because the industrial raw material contains partial small amount of iron, Q/P phase and C4AF can coexist at low temperature, and a small amount of C in clinker4The presence of AF lowers the cement firing temperature and, with Fe2O3 The content of the Q/P phase is increased when the doping amount is increased. But at higher temperatures C4AF partially dissolves MgO in a solid state, so that the content of MgO for forming the Q phase is reduced, and the generation of the Q phase is suppressed, so that Fe is contained in a large amount2O3The formation of the Q phase is adversely affected. When higher Fe2O3When mixing, the amount of C is added4MgO with AF content of about 1/30 can be supplemented with C4The content of MgO in AF solid solution is not affected and the forming temperature is greatly reduced, therefore, the Q phase can be generated only under the condition of rich magnesium.
The invention is realized by adding a certain amount of P into the system2O5Not only promotes the generation of Q/P phase, but also reduces the cement firing temperature due to the introduction of the iron phase and promotes the generation of calcium phosphoaluminate, so that part of calcium aluminate is converted into calcium phosphoaluminate to replace part of C2S to ensure later strength growth.
The invention has the beneficial effects that; the cement clinker prepared by the invention has the advantages of low sintering temperature, good hydration performance, high early strength and no reverse shrinkage of later strength.
Detailed Description
The technical solution of the present invention is further explained and illustrated by the following specific embodiments.
A Q/P phase phosphoaluminate cement clinker comprises the following cement minerals in percentage by mass and sintering conditions:
the experimental raw materials adopted by the invention are as follows: high-magnesium limestone, bauxite, apatite, slag powder and fly ash are all industrial raw materials, and specific mineral oxide compositions are shown in tables 1-3.
Example 1
The raw materials are calculated and weighed according to the mineral proportion, the raw materials are 200g, the granularity is that the raw materials pass through a standard sieve of 200 meshes, and the residue on the sieve is 6-10%. And then stirring by using a ball mill, drying and preparing a sample. The sample is a cake-shaped sample with the diameter of 40mm, is put into a low-temperature oven for drying, is then placed into a high-temperature calcining furnace for sintering at 1350 ℃, and is kept warm for 2 hours.
The clinker minerals comprise the following components in percentage by weight:
Q/P phase: 40 percent of
Calcium aluminophosphate: 35 percent of
Calcium aluminate: 10 percent of
Dicalcium silicate: 10 percent of
Tetracalcium aluminoferrite: 5 percent.
Example 2
The raw materials are calculated and weighed according to the mineral proportion, the raw materials are 200g, the granularity is that the raw materials pass through a standard sieve of 200 meshes, and the residue on the sieve is 6-10%. And then stirring by using a ball mill, drying and preparing a sample. The sample is a cake-shaped sample with the diameter of 40mm, is put into a low-temperature oven for drying, is then placed into a high-temperature calcining furnace for sintering at 1350 ℃, and is kept warm for 2 hours.
The clinker minerals comprise the following components in percentage by weight:
Q/P phase: 45 percent of
Calcium aluminophosphate: 40 percent of
Calcium aluminate: 10 percent of
Dicalcium silicate: 3 percent of
Tetracalcium aluminoferrite: 2 percent.
Example 3
The raw materials are calculated and weighed according to the mineral proportion, the raw materials are 200g, the granularity is that the raw materials pass through a standard sieve of 200 meshes, and the residue on the sieve is 6-10%. And then stirring by using a ball mill, drying and preparing a sample. The sample is a cake-shaped sample with the diameter of 40mm, is put into a low-temperature oven for drying, is then placed into a high-temperature calcining furnace for sintering at 1350 ℃, and is kept warm for 2 hours.
The clinker minerals comprise the following components in percentage by weight:
Q/P phase: 50 percent of
Calcium aluminophosphate: 35 percent of
Calcium aluminate: 8 percent of
Dicalcium silicate: 5 percent of
Tetracalcium aluminoferrite: 2 percent.
Comparative example 1
The raw materials of apatite, bauxite and fly ash are ground to be fine and pass through a standard sieve with 200 meshes, and the screen residue is 6-10%. The raw materials are calculated and weighed according to the mineral proportion to be 200g, and then stirred by a ball mill, dried and prepared into samples. The sample is a round cake-shaped sample with the diameter of 40mm, the round cake-shaped sample is placed into a low-temperature oven for drying, then the round cake-shaped sample is placed into a high-temperature calcining furnace for calcining at 1300 ℃, the temperature is kept for 2 hours, and the round cake-shaped sample is taken out and then is quenched to obtain the cement clinker.
The clinker minerals comprise the following components in percentage by weight:
calcium aluminophosphate: 60 percent of
Calcium aluminate: 10 percent of
E, gehlenite: 20 percent of
Dicalcium silicate: 8 percent of
Tetracalcium aluminoferrite: 2 percent.
TABLE 1 apatite mineral oxide composition
Figure DEST_PATH_IMAGE001
TABLE 2 bauxite oxide composition
Figure 406155DEST_PATH_IMAGE002
TABLE 3 high-magnesium limestone oxide composition
Figure DEST_PATH_IMAGE003
TABLE 4 fly ash oxide composition
Figure 995399DEST_PATH_IMAGE004
Effect embodiment: test for compressive Strength
And (3) putting the clinker and the steel balls into a ball milling tank, milling to a certain fineness, sieving by a 200-mesh sieve, and controlling the screen residue to be 0.2-0.5% to obtain the Q-phase cement. The mold is molded by 2cm × 2cm × 2cm, the water-cement ratio is 0.35, the mold is maintained in a room temperature curing chamber for 24 hours, the mold is removed, then the samples prepared in the embodiments and the comparative examples are placed in a curing box, the samples are cured for 3 d, 7 d and 28 d respectively under the standard conditions of constant temperature and constant humidity, and then the compression strength test is carried out respectively, and the specific results are shown in table 5.
TABLE 5 mechanical Properties of samples of examples and comparative examples at different ages
Figure DEST_PATH_IMAGE005

Claims (6)

1. A Q/P phase cement clinker containing calcium aluminate, characterized in that the cement clinker is prepared from Q/P phase-calcium aluminate phosphate (C)8A6P) -Calcium Aluminate (CA) -dicalcium silicate (C)2S) -Tetracalcium aluminoferrite (C)4AF) five mineral phases.
2. The calcium aluminate-containing Q/P phase cement clinker as claimed in claim 1, characterized in that the mineral phase composition of said cement clinker is:
Q/P phase 40-60%
20 to 40 percent of calcium phosphoaluminate
5 to 20 percent of calcium aluminate
0 to 10 percent of dicalcium silicate
0-5% of tetracalcium aluminoferrite.
3. The calcium alumino-phosphate containing Q/P phase cement clinker according to claims 1 or 2, characterized in that said P phase mineral is 6CaO ∙ 4Al2O3∙FeO∙SiO2Abbreviated as C6A4F' S; the Q-phase mineral is C6A4MS, 6CaO ∙ 4Al2O3∙MgO∙SiO2Or C20A16-vM v S v，v∈(2.5-3.5)。
4. A process for the preparation of a Q/P phase cement clinker containing calcium aluminate phosphates, as defined in any of the claims from 1 to 3, characterized by the following steps: weighing raw materials according to the mineral proportion, sieving the raw materials by a standard sieve, stirring the raw materials by a ball mill, drying, preparing a sample, putting the sample into a low-temperature oven for drying, and then putting the sample into a high-temperature calcining furnace for high-temperature calcining.
5. The method of claim 4, wherein the standard sieve has a pore size of 200 mesh.
6. The method according to claim 4 or 5, wherein the high-temperature calcination is performed by holding at 1300-1350 ℃ for 2 h.
CN202110399377.9A 2021-04-14 2021-04-14 Q/P phase cement clinker containing calcium aluminate Active CN113264699B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110399377.9A CN113264699B (en) 2021-04-14 2021-04-14 Q/P phase cement clinker containing calcium aluminate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110399377.9A CN113264699B (en) 2021-04-14 2021-04-14 Q/P phase cement clinker containing calcium aluminate

Publications (2)

Publication Number Publication Date
CN113264699A true CN113264699A (en) 2021-08-17
CN113264699B CN113264699B (en) 2022-09-16

Family

ID=77228909

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110399377.9A Active CN113264699B (en) 2021-04-14 2021-04-14 Q/P phase cement clinker containing calcium aluminate

Country Status (1)

Country Link
CN (1) CN113264699B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115784653A (en) * 2022-12-20 2023-03-14 江苏容汇通用锂业股份有限公司 Preparation method of phosphoaluminate cement clinker and phosphoaluminate cement clinker

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1198457A (en) * 1966-10-03 1970-07-15 James Reid Cattanach Improvements in and relating to Compositions for Producing Air-Entrained Concrete
CN1600727A (en) * 2004-10-22 2005-03-30 济南大学 Aluminate cement material of containing mineral in Q phase
CN102910851A (en) * 2012-10-22 2013-02-06 济南大学 Q-phase aluminate cement expanding agent and preparation method thereof
CN107986655A (en) * 2017-12-25 2018-05-04 济南大学 A kind of phosphor aluminate cement is modified sulphoaluminate cement clinker
CN108117289A (en) * 2017-12-25 2018-06-05 济南大学 A kind of aluminophosphates base sea work cementitious material
CN108658485A (en) * 2018-07-09 2018-10-16 深圳大学 A kind of hydraulic cement clinker and preparation method thereof, hydraulic cement and its application
CN108726906A (en) * 2018-07-09 2018-11-02 深圳大学 A kind of cementitious material and the preparation method and application thereof, a kind of ocean supporting material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1198457A (en) * 1966-10-03 1970-07-15 James Reid Cattanach Improvements in and relating to Compositions for Producing Air-Entrained Concrete
CN1600727A (en) * 2004-10-22 2005-03-30 济南大学 Aluminate cement material of containing mineral in Q phase
CN102910851A (en) * 2012-10-22 2013-02-06 济南大学 Q-phase aluminate cement expanding agent and preparation method thereof
CN107986655A (en) * 2017-12-25 2018-05-04 济南大学 A kind of phosphor aluminate cement is modified sulphoaluminate cement clinker
CN108117289A (en) * 2017-12-25 2018-06-05 济南大学 A kind of aluminophosphates base sea work cementitious material
CN108658485A (en) * 2018-07-09 2018-10-16 深圳大学 A kind of hydraulic cement clinker and preparation method thereof, hydraulic cement and its application
CN108726906A (en) * 2018-07-09 2018-11-02 深圳大学 A kind of cementitious material and the preparation method and application thereof, a kind of ocean supporting material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
程新: "《新型胶凝材料》", 31 October 2018, 中国建材工业出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115784653A (en) * 2022-12-20 2023-03-14 江苏容汇通用锂业股份有限公司 Preparation method of phosphoaluminate cement clinker and phosphoaluminate cement clinker

Also Published As

Publication number Publication date
CN113264699B (en) 2022-09-16

Similar Documents

Publication Publication Date Title
CN101525217B (en) Environmental-friendly clinker-free cement and preparation method thereof
Aziz et al. Physico-chemical and mechanical characteristics of pozzolanic cement pastes and mortars hydrated at different curing temperatures
US5509962A (en) Cement containing activated belite
CN108178536B (en) Method for preparing low-clinker cement by calcining coal gasification slag step by step
CN110799472A (en) Concrete composition and method for producing same
EP2878585B1 (en) Method for the manufacturing of cementitious C-S-H seeds
CN113582608A (en) Low-carbon cement and preparation method thereof
CN113264699B (en) Q/P phase cement clinker containing calcium aluminate
KR100968073B1 (en) Slag cement composition
CN115724602A (en) Low-carbon multi-element cement clinker for efficiently utilizing high-magnesium limestone and preparation method thereof
CN112341010B (en) Portland cement clinker and preparation method thereof
CN114455904A (en) Shrinkage compensation composite material based on modified alunite tailings and preparation method thereof
Chandara Study of pozzolanic reaction and fluidity of blended cement containing treated palm oil fuel ash as mineral admixture
CN112279529A (en) Method for improving silicon and aluminum content in sintered cement by using converter steel slag
KR101366835B1 (en) Cement composition using desulphurizing dust
Li et al. Preparation of sulphoaluminate-alite composite mineralogical phase cement clinker from high alumina fly ash
CN113185161B (en) Phosphoaluminate cement clinker containing Q/P phase
CN113896494B (en) Ferronickel slag building material and preparation method thereof
CN109020397A (en) A kind of phase-change energy-storage mortar and preparation method thereof
JP5855902B2 (en) Alumina cement
JP6953787B2 (en) Environmental load reduction clinker, cement composition and its manufacturing method, and ground improvement method
CN113929324B (en) High-iron high-silicon sulphoaluminate cement clinker prepared from molten steel slag and preparation method thereof
CN115838250B (en) Red mud-based admixture, clinker, and preparation method and application thereof
KR20190121539A (en) Process for the preparation of initialcompression improving agent for hydraulic cement
CN115340305B (en) Silicate cement for low-aluminum-acid tricalcium communication prepared from rare earth tailings and preparation method thereof

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