本文關(guān)鍵詞： 高貝利特-硫鋁酸鹽水泥 貝利特 外摻離子 活化 工業(yè)試生產(chǎn)　出處：《武漢理工大學(xué)》2013年博士論文　論文類型：學(xué)位論文

【摘要】：水泥熟料生產(chǎn)的CO2排放約有65%來自石灰石的碳酸鹽分解,僅有35%來自燃料的燃燒排放,基于材料本征的排放特點(diǎn),通過優(yōu)化工藝提高能效、輔助膠凝材料使用等措施減排的潛力日益減小,而從水泥基材料組成本身進(jìn)行創(chuàng)新成為全球研究的焦點(diǎn)。 本文通過對(duì)熟料礦物的形成溫度、形成焓、單位礦物CO2排放量等多重因素進(jìn)行低鈣低碳優(yōu)化設(shè)計(jì),實(shí)現(xiàn)了不含高鈣礦物-阿利特(C3S)、以貝利特(C2S)和硫鋁酸鹽(C4A3S)為主導(dǎo)礦物的低能耗、低CO2排放C2S-C4A3S-C4AF三元熟料體系(Belite Calcium Sulfo-Aluminate, BCSA)。通過礦物組成優(yōu)化匹配及晶體的穩(wěn)定與活化,制備出性能優(yōu)于但能耗和排放遠(yuǎn)低于普通硅酸鹽水泥的BCSA水泥。與普通硅酸鹽水泥相比,BCSA水泥生產(chǎn)過程中可節(jié)約石灰石28%和標(biāo)煤約16%以上,減少CO2排放20%以上,實(shí)現(xiàn)了通過水泥基材料創(chuàng)新達(dá)到節(jié)能降耗的目的。 本文利用XRD、紅外光譜IR和SEM等方法,圍繞BCSA的礦物組成設(shè)計(jì)、離子摻雜作用機(jī)理、工業(yè)試生產(chǎn)及其水泥混凝土性能,主要研究了以下內(nèi)容： (1)熟料低鈣組成設(shè)計(jì)和高溫礦相形成研究 確定了熟料低鈣低碳礦物組成的原則。由C2S-C4A3S-C4AF三元礦物組成的熟料體系里,CaA3S和C2S分別是熟料的早期強(qiáng)度和中后期強(qiáng)度的來源。 研究了C2S、C4A3S和C4AF三種礦物的形成溫度和最佳范圍,闡明了三種礦物的共存溫度區(qū)間1250-1350℃。研究了熟料的易燒性、主要熟料礦物C4A3S和C2S的形成和結(jié)晶發(fā)育狀況、以及熟料的物理性能。研究表明,BCSA熟料的最佳燒成溫度范圍是1280-1320℃,在該溫度范圍內(nèi)燒制的熟料具有良好的工作性和物理力學(xué)性能。 (2) BCSA熟料礦物優(yōu)化匹配和熟料／石膏作用機(jī)理 確定了BCSA熟料礦物組成范圍為C2S36-56%, C4A3S32-42%和C4AF5-9%。在上述礦物組成范圍內(nèi),BCSA熟料具有最佳的物理性能,3天和28天抗壓強(qiáng)度分別達(dá)到34.3MPa和55.1MPa。 研究了BCSA熟料與石膏的相互作用機(jī)理。石膏摻量顯著影響B(tài)CSA水泥的性能,確定了石膏最佳摻量范圍為12.5-15%。石膏主要是與C4A3S發(fā)生反應(yīng)形成鈣礬石。在漿體結(jié)構(gòu)中,鈣礬石與其他水化產(chǎn)物一起形成密實(shí)的空間網(wǎng)架結(jié)構(gòu)。 (3)離子摻雜對(duì)熟料礦物晶體的穩(wěn)定與活化機(jī)理研究 p晶型C2S水化速率慢,早期強(qiáng)度低,一直影響著這種礦物在熟料中的作用。本文著重研究了提高β-C2S活性的方法和作用機(jī)理。研究表明,外摻離子Ba2+、P5+和Zn2+等離子均可進(jìn)入p-C2S晶格,引起晶格畸變,并且在礦物表面發(fā)生富集,使得礦物晶體細(xì)化,增強(qiáng)了p-C2S的水化反應(yīng)活性。同時(shí)發(fā)現(xiàn)在多種礦物共存的熟料體系中,部分外摻離子進(jìn)入CSA礦物晶格中,引起晶格畸變,提高了CSA水硬性。β-C2S和C4A3S兩種礦物共存時(shí),外摻離子影響其活性的顯著性依次為：Ba2+P5+Zn2+B3+。 摻入Ba2+的熟料制得的水泥,其28d抗壓強(qiáng)度達(dá)到69.7MPa,比未摻雜空白樣強(qiáng)度提高了15MPa(26.5%)。 (4) BCSA水泥工業(yè)試生產(chǎn)關(guān)鍵技術(shù)的研究 利用現(xiàn)有水泥工藝設(shè)備和工業(yè)原燃料,全球首次在帶五級(jí)預(yù)熱器窯的新型干法生產(chǎn)線上進(jìn)行了BCSA水泥工業(yè)化試生產(chǎn)的關(guān)鍵技術(shù)研究,實(shí)現(xiàn)了該水泥在新型干法生產(chǎn)線的工業(yè)化試生產(chǎn)。確定了工業(yè)化制備的主要工藝參數(shù),所生產(chǎn)水泥的3d強(qiáng)度達(dá)43.7MPa,28d強(qiáng)度達(dá)66.9MPa。 (5) BCSA水泥混凝土力學(xué)性能及耐久性研究 結(jié)果表明,BCSA水泥配制混凝土具有良好的力學(xué)性能(抗折抗壓強(qiáng)度、劈拉強(qiáng)度、軸心抗壓強(qiáng)度等)和耐久性能(包括抗?jié)B性、抗凍性、氯離子滲透性、抗硫酸鹽侵蝕性、抗碳化性能、體積穩(wěn)定性等)。這些性能均優(yōu)于普通水泥配制的混凝土性能。分析表明,BCSA水泥需水量少,漿體內(nèi)部孔隙率較低,且水化產(chǎn)物中鈣礬石形成過程伴隨的微膨脹增加硬化漿體結(jié)構(gòu)的致密度。這是BCSA水泥混凝土具有良好的力學(xué)性能和耐久性能的主要原因。
[Abstract]:The emission of CO2 cement clinker production of about 65% from the limestone decomposition of carbonate, only 35% from fuel combustion emissions, emissions based on the intrinsic characteristics of the material, by optimizing the process to improve the energy efficiency and emission reduction of auxiliary cementitious materials using measures such as the potential is reduced, and from the cement-based material composition itself has become the focus of global innovation research.
Based on the formation of clinker temperature, enthalpy of formation, unit of mineral CO2 emissions of multiple factors such as low calcium and low carbon optimization design, to achieve a high calcium containing minerals - Alite (C3S), Baillet (C2S) and sulphoaluminate (C4A3S) for low energy consumption dominant mineral, low emission of CO2 C2S-C4A3S-C4AF three Clinker System (Belite Calcium Sulfo-Aluminate yuan, BCSA). The stability and activation by mineral composition and optimized matching crystal, preparation superior performance but the energy consumption and emissions is much lower than that of ordinary portland cement BCSA cement. Compared with ordinary portland cement, BCSA cement production process can save 28% limestone and coal for about 16% above. To reduce CO2 emissions by more than 20%, to achieve the purpose of saving energy through innovation of cement-based materials.
In this paper, we use XRD, infrared spectroscopy IR and SEM to study the mineral composition design of BCSA, the mechanism of ion doping, industrial trial production and the performance of cement concrete.
(1) study on the design of low calcium composition of clinker and formation of high temperature ore phase
The principle of composition of low calcium and low carbon minerals is determined. CaA3S and C2S are the sources of early strength and mid and late strength of clinker in C2S-C4A3S-C4AF three mineral system.
Study on the formation of C2S, temperature and the best range of C4A3S and C4AF three kinds of minerals, the coexistence of three kinds of mineral temperature range of 1250-1350 C was studied. The clinker burnability, formation and development status of the main C4A3S and C2S clinker mineral crystallization, and clinker physical properties. The results show that the optimum BCSA of clinker burning the temperature range of 1280-1320 DEG C, clinker firing in the temperature range and has good physical and mechanical properties.
(2) optimum matching of mineral mineral in BCSA clinker and mechanism of clinker / gypsum
The mineral composition range of BCSA clinker is C2S36-56%, C4A3S32-42% and C4AF5-9%.. In the above mineral composition range, BCSA clinker has the best physical properties, and the compressive strength reaches 34.3MPa and 55.1MPa. on the 3 day and the 28 day respectively.
The interaction mechanism of BCSA clinker and gypsum. Gypsum significantly affect the properties of BCSA cement, gypsum to determine the optimal dosage range of 12.5-15%. gypsum is mainly reacted to form ettringite and C4A3S. The structure of slurry, ettringite and other hydration products together to form a space truss structure compact.
(3) study on the stability and activation mechanism of ion doping on the crystal of clinker mineral
P crystal C2S hydration rate is slow, low early strength, has influenced the effect of the mineral in clinker. This paper focuses on the methods to improve the effect and mechanism of beta -C2S activity. The study shows that the addition of P5+ and Ba2+ ions, Zn2+ plasma can enter into the p-C2S lattice, cause the distortion of crystal lattice, and the mineral surface the contents of mineral crystal refinement, enhance the hydration activity of p-C2S. At the same time found in a variety of minerals clinker system, part of doped ions into CSA crystal lattice, caused by lattice distortion, improve the CSA hard water. Beta -C2S and C4A3S two kinds of minerals, with significant ion effect the activity is as follows: Ba2+P5+Zn2+B3+.
The compressive strength of the cement prepared by the clinker doped with Ba2+ is 69.7MPa, which is 15MPa (26.5%) higher than that of the undoped blank sample.
(4) research on key technology of test production in BCSA cement industry
Use of the existing cement production equipment and industrial raw fuel, for the first time in the world with five stage preheater kiln NSP production line is carried out research on the key technology of BCSA cement production industrialization, realize the industrialization of the cement in the new dry production line production. The main process parameters for industrial preparation were determined, the production intensity of 3D cement reached 43.7MPa, 28d strength of 66.9MPa.
(5) study on mechanical properties and durability of BCSA cement concrete
The results show that the BCSA cement concrete has good mechanical properties (flexural and compressive strength, splitting tensile strength, axial compressive strength) and durability (including impermeability, frost resistance, chloride ion permeability, sulfate resistance, carbonation resistance, volume stability, etc.). These properties are the properties of concrete better than ordinary cement. The analysis shows that BCSA need less water cement slurry, low porosity, and the hydration products of ettringite formation process with the increase of the density of the micro expansion structure of hardened paste. This is the main reason of BCSA cement concrete has good mechanical properties and durability.

【學(xué)位授予單位】：武漢理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2013
【分類號(hào)】：TQ172.7

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