CN100457661C - 一种铝酸钙-硫铝酸钙水泥熟料及其膨胀剂的制造方法 - Google Patents
一种铝酸钙-硫铝酸钙水泥熟料及其膨胀剂的制造方法 Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 33
- 239000011575 calcium Substances 0.000 title claims description 16
- 229910052791 calcium Inorganic materials 0.000 title claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims description 13
- 239000004568 cement Substances 0.000 title abstract description 31
- 230000008961 swelling Effects 0.000 title abstract 3
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 15
- 239000011707 mineral Substances 0.000 claims abstract description 15
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 12
- 239000010440 gypsum Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 235000019738 Limestone Nutrition 0.000 claims abstract description 8
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 8
- 239000006028 limestone Substances 0.000 claims abstract description 8
- 229910052925 anhydrite Inorganic materials 0.000 claims abstract description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 239000011411 calcium sulfoaluminate cement Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000002956 ash Substances 0.000 claims description 2
- 239000002802 bituminous coal Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 6
- 238000001354 calcination Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000000227 grinding Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 239000004574 high-performance concrete Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229910001653 ettringite Inorganic materials 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 230000018199 S phase Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000010424 alunite Substances 0.000 description 2
- 229910052934 alunite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052661 anorthite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0042—Powdery mixtures
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/44—Thickening, gelling or viscosity increasing agents
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00215—Mortar or concrete mixtures defined by their oxide composition
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明涉及一种水泥熟料的生产技术和混凝土膨胀剂的生产技术。所述熟料的原料配合比为：铝矾土——50-65%、石灰石——30-40%、石膏——5-15%，对原材料品质要求为：铝矾土——Al2O3＞70%、SiO2＜10%；石灰石——CaO＞54%、SiO2＜10%；石膏——SO3＞45%；烟煤——灰份＜10%、挥发份25-32%、发热量＞26000KJ/kg，所述熟料的矿物组成范围为CA：30～37%、C4A3S：20～25%、CA2：25～30%、C2S：5～10%。熟料的煅烧温度为1320℃-1380℃。用35～40%的熟料和60～65%的硬石膏磨细(0.8mm筛余：10～12%)制成膨胀剂。
Description
技术领域
本发明涉及一种水泥熟料的生产技术和混凝土膨胀剂的生产技术。
技术背景
国内外高铝水泥矿物组成主要在CA-CA2-C2AS相区，其次在CA-C2AS-C2S相区和CA-C12A7-C2S相区。我国以一级矾土和石灰石配制成生料，在旋窑中经1360～14lO℃煅烧成熟料，经粉磨至300～400m2/kg成为高铝水泥或低钙铝酸盐耐火水泥。
一般高铝水泥熟料中，不可避免要带入5～10％SiO2，SiO2被视为有害矿物。由于它形成钙黄长石C2AS是惰性矿物，难以水化。SiO2含量越高，熟料煅烧温度范围越狭窄，烧成不易掌握。根据矿物组成计算公式，在CA-CA2-C2AS相区中全部形成C2AS，C2AS＝4.56×SiO2(％)，我国高铝水泥熟料一般含有SiO2＝5～8％，由此形成C2AS约有22.8～36.5％，这种惰性矿物占总矿物的25～35％，制约了高铝水泥的活性。
发明内容
本发明是在高铝水泥生料中加入一定量的石膏矿化剂，在高温煅烧过程中，CaSO4可以阻碍C2AS形成，使其转化为CA和C2S，与此同时，CaSO4与CA化合成无水硫铝酸钙3CA·CaSO4。这样，熟料中形成较多的CA、CA2、
和C2S有益矿物，减少隋性矿物C2AS的生成数量。从而大大提高水泥的活性，熟料煅烧温度也可以下降至1320～1380℃。研究表明，这是一种以
为主的铝酸钙-硫铝酸钙水泥(Alumina-sulphoaluminate clinker)，我们命名为ASC熟料，在国内外文献中尚无记载。
国内外混凝土膨胀剂主要有日本的硫铝酸钙(CSA)膨胀剂，石灰系膨胀剂；我国有U型膨胀剂、铝酸钙膨胀剂、复合膨胀剂、硅铝酸盐膨胀剂和明矾石膨胀剂等。它们分别以高铝水泥熟料、硫铝酸盐水泥熟料、石灰系熟料、煅烧明矾石、煅烧高岭土和高铝煤矸石作为膨胀熟料，并掺入其它辅助原料磨制而成，这些膨胀剂以10％～15％掺入水泥中，经水化形成钙矾石或氢氧化钙产生体积膨胀。本发明中的低碱高效膨胀剂就是用本发明的铝酸钙—硫铝酸钙水泥熟料与石膏磨制而成的，其膨胀源为钙矾石，碱含量≤0.3％，掺量6～8％，是一种新型低碱高性能膨胀剂，在国内外文献中尚无记载。
本发明的目的在于提供一种铝酸钙—硫铝酸钙水泥熟料的化学组分和生产工艺，以达到提高其水泥熟料活性的目的，并用该水泥熟料制造高性能混凝土膨胀剂。
本发明是涉及一种新型的水泥熟料，它是一种以铝酸一钙(CA)、铝酸二钙(CA2)和无水硫铝酸钙(C3A·CaSO4)为主的铝酸钙—硫铝酸钙水泥熟料(以下简称ASC熟料)。
本发明是在高铝水泥生料中掺入适量石膏矿化剂，CaSO4可以阻止C2AS的生成，使C2AS分解为CA和C2S，与此同时，CaSO4与CA结合成无水硫铝酸钙
从而大大增加高铝水泥的活性。同时，CaSO4矿化剂可以使高铝水泥熟料的煅烧温度降低至1320～1380℃，扩大其烧成范围，在旋窑中更易烧成熟料。
本发明的ASC熟料的化学成分与一般高铝水泥的不同之处是根据水熟料中SiO2的含量，加入适量的石膏矿化剂，并调整CA和CA2的矿物比例，这是本发明的核心技术，另外则是该熟料在旋窑中的烧成技术，如何控制石膏不被分解，在阻止形成C2AS的同时，使CaSO4与CaO、Al2O3结合成
ASC熟料粉磨至比表面积300～400m2/kg成为早强快硬水泥，在常温下水化，主要形成水化铝酸钙CAH10、C2AH8和铝胶AH3。
本发明的膨胀剂是以ASC熟料与石膏共同粉磨可以制成低碱低掺的高性能混凝土膨胀剂，碱含量≤0.3％。它以6～8％掺入硅酸盐水泥中水化生成钙矾石(C3A·3CaSO4·32H2O)，使混凝土产生适度体积膨胀，达到抗裂防渗的补偿收缩目的。
本发明的ASC熟料是用铝矾土、石灰石和石膏制成水泥生料，在回转窑中经1320℃-1380℃煅烧而成。ASC熟料对原材料品质要求为：铝矾土——Al2O3＞70％、SiO2＜10％；石灰石——CaO＞54％、SiO2＜10％；石膏——SO3＞45％；烟煤——灰份＜10％、挥发份25-32％、发热量＞26000KJ/kg。ASC熟料的原料配合比为：铝矾土——50-65％、石灰石——30-40％、石膏——5-15％。本发明的铝酸钙—硫铝酸钙熟料的主要矿物组成范围的重量百分比为：
CA：30～37％
CA2：25～30％ C2S：5～10％
本发明所述的高性能混凝土膨胀剂工艺配方的重量百分比为：
铝酸钙—硫铝酸钙熟料：35～40％；
硬石膏：60～65％
膨胀剂中SO3：30～35％
膨胀剂的细度(0.8mm筛余)：10～12％
具体实施方式
实施例
(1)ASC熟料的制造
表1ASC熟料的原料化学成分
| 原料 | 烧失量 | SiO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> | Fe<sub>2</sub>O<sub>3</sub> | TiO<sub>2</sub> | CaO | MgO | SO<sub>3</sub> |
| 石灰石 | 42.75 | 1.36 | 0.41 | 0.76 | —— | 52.02 | 1.56 | —— |
| 矾土 | 13.77 | 5.18 | 75.56 | 1.33 | 3.20 | 0.52 | 0.54 | —— |
| 石膏 | 1.25 | 2.12 | 0.38 | 0.17 | —— | 39.71 | 0.39 | 49.21 |
| 煤灰 | —— | 55.50 | 21.64 | 10.63 | —— | 1.86 | 2.44 | —— |
原料的化学成分见表1，根据设计的熟料矿物组成，进行配料计算得：石灰石30.5％，矾土58.4％，石膏8.1％，煤灰3％。配制的ASC生料在回转窑中经1350℃煅烧而成ASC熟料，其化学成分见表2，ASC熟料的计算矿物组成见表3，ASC水泥的物理性能见表4。
表2ASC水泥熟料的化学成分(％)
| Loss | SiO<sub>2</sub> | Al<sub>2</sub>O<sub>3</sub> | Fe<sub>2</sub>O<sub>3</sub> | CaO | MgO | TiO<sub>2</sub> | SO<sub>3</sub> |
| 0.31 | 5.44 | 55.26 | 1.08 | 32.35 | 0.04 | 1.49 | 3.50 |
表3ASC熟料矿物组成(％)
| CA | CA<sub>2</sub> | C<sub>4</sub>A<sub>3</sub>S | C<sub>2</sub>S | CT | C<sub>2</sub>F | MA |
| 30.34 | 27.25 | 25.41 | 12.53 | 2.50 | 1.83 | 0.14 |
表4ASC水泥的物理性
(2)高性能混凝土膨胀剂制造
用上述制造的ASC熟料与硬石膏共同粉磨成膨胀剂，其工艺参数见表5。
表5高性能混凝土膨胀剂生产工艺
| ASC熟料(％) | 硬石膏(％) | 比表面积m<sup>2</sup>/kg) | SO<sub>3</sub>(％) |
| 35 | 65 | 310 | 32.5 |
在42.5号普通水泥中分别掺入6％和8％膨胀剂，按从《混凝土膨胀剂》建材行业标准JC476-2001进行检验，其物理性能见表6。
表6高性能混凝土膨胀剂的物理性能
本发明的ASC水泥熟料，磨制成改性高铝水泥，具有快硬早强特性，1d抗压强度为28d的70％以上，安定性良好。用该熟料磨制的高性能混凝土膨胀剂，以6％和8％掺入水泥中，7d膨胀率达0.040～0.048％，14d膨胀率为0.05～0.06％，比目前市售膨胀剂(一般掺量为10～12％)的膨胀效能更高，与空白水泥砂浆相比，强度有所提高，28d强度持续增长。可以说，它是目前国内最先进一种混凝土膨胀剂。
Claims (3)
1.一种铝酸钙-硫铝酸钙水泥熟料，其特征在于：所述熟料的矿物组成范围的重量百分比为CA：30～37％、C4A3S：20～25％、CA2：25～30％、C2S：5～12.53％、CT：2.5％、C2F：1.83％、MA：0.14％。
2.一种制造权利要求1所述熟料的方法，其特征在于：所述熟料的原料配合比的重量百分比为：铝矾土50-65％、石灰石30-40％、石膏5-15％，对原材料品质要求为：铝矾土Al2O3＞70％、SiO2＜10％：石灰石CaO＞54％、SiO2＜10％：石膏SO3＞45％；烟煤灰份＜10％、挥发份25-32％、发热量＞26000KJ/kg，将所述原料在回转窑中经1320℃-1380℃煅烧即成所述熟料。
3.一种用权利要求1所述熟料制造的膨胀剂，其特征在于：铝酸钙-硫铝酸钙水泥熟料的重量百分比为：35～40％，硬石膏的重量百分比为：60～65％，膨胀剂中SO3的重量百分比为：30～35％，该膨胀剂0.8mm筛余的细度为：10～12％。
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| Publication Number | Publication Date |
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| CN1374266A CN1374266A (zh) | 2002-10-16 |
| CN100457661C true CN100457661C (zh) | 2009-02-04 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2849440B1 (fr) * | 2002-12-27 | 2005-07-15 | Lafarge Aluminates | Accelerateur de prise liquide pour composition comprenant du ciment portland. |
| CN100427563C (zh) * | 2006-06-27 | 2008-10-22 | 武汉理工大学 | 一种高温储热材料的制备方法 |
| CN102241411A (zh) * | 2011-03-31 | 2011-11-16 | 遵义市恒新化工有限公司 | 高铝低钙铝酸钙粉生产配方及工艺 |
| CN103232179A (zh) * | 2012-04-28 | 2013-08-07 | 中国建筑材料科学研究总院 | 一种高镁硫铝酸钙改性硅酸盐水泥熟料及其生产方法 |
| CN105669058B (zh) * | 2014-11-18 | 2017-11-10 | 登封电厂集团有限公司 | 一种用铝型材污泥生产硫铝酸盐水泥的方法 |
| CN109095802B (zh) * | 2018-08-27 | 2021-11-09 | 广东睿住住工科技有限公司 | 混凝土用膨胀剂、混凝土及其制备方法 |
| CN109437625A (zh) * | 2018-12-21 | 2019-03-08 | 嘉华特种水泥股份有限公司 | 一种白色硫铝酸盐水泥及其生产方法 |
| CN111847929A (zh) * | 2019-12-25 | 2020-10-30 | 尧柏特种水泥技术研发有限公司 | 一种新型干法预分解窑生产硫铝酸盐水泥熟料的方法 |
| CN112851159B (zh) * | 2021-02-02 | 2022-09-13 | 郑州市建文特材科技有限公司 | 一种硫铝酸钙改性硅酸盐水泥的制备方法 |
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