CN1229404A - 硫酸盐水泥或硫酸盐水泥集料的制造方法 - Google Patents
硫酸盐水泥或硫酸盐水泥集料的制造方法 Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 7
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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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
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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
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
- C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
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- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
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- 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
Abstract
本发明涉及一种制造硫酸盐水泥或硫酸盐水泥集料的方法,其中,矿渣碱度CaO/SiO2为1.35—1.6的水凝活性合成炉渣,例如废物煅烧渣和/或混有金属氧化物还原后的熔融钢渣的高炉矿渣,该合成矿渣还含有10—20%(重量)的Al2O3和低于2.5%(重量)的氧化铁,该合成矿渣与占总混合物5—20%(重量)的碱土金属硫酸盐,如磨碎状的生石膏、尾气石膏、烟气脱硫装置的石膏、石膏或无水石膏相混合。
Description
本发明涉及一种制造硫酸盐水泥或硫酸盐水泥集料的方法。
本世纪初已经发现，粒状高矿渣不但可由石灰或波特兰水泥引发水凝性硬化，这种炉渣亦可由掺合10-15％(重量)的石膏引发硬化。虽然有了这种认识，但在技术上的应用有限。石膏作为这类硫酸盐的代表，随之带来一种石膏膨化的危险。石膏膨化时出现饱含结晶水的反应产物就地所需的空间会产生爆裂作用。这种现象首先发生在普通硫酸盐矿渣水泥中，后者恰好是由波特兰水泥熟料混合物作为含石灰载体引发最初的硬化。已知的硫酸盐矿渣水泥是将高炉渣和15％(重量)以生石膏的形式的硫酸钙磨碎，再加约2％(重量)的波特兰水泥。在硬化的早期阶段，熟石灰的存在是必需的，否则在硫酸盐时效硬化发生之前就会生成一种致密的凝胶层。
正因为如此，硫酸盐矿渣水泥的硬化机制才不能与波特兰水泥的水合作用过程的碱引发相比较。在矿渣水泥的情况下熟石灰的存在引发水合作用，相反，在已知的硫酸盐矿渣水泥的情况下，则应发生一种真正的反应，在该反应过程中石膏转化为硫代铝酸钙。在已知矿渣水泥的情况下，只有在其磨碎细度至少为4000-6000cm2/g的条件下才能使硫代铝酸盐达到所要求的硬化，同时安全地避免石膏膨化。此外还表明，大多数高炉渣不适宜制造硫酸盐矿渣水泥。这对高炉渣尤其如此，因为通常的高炉渣矾土含量较低，因而所需硫代铝酸盐的生成量达不到或仅达不足量的程序，以致石膏膨化的危险仍然存在。最后，高石灰含量是必需的，而通常高炉渣中却不具这样高的含量。由于上述原因，硫酸盐矿查水泥在建筑作业中没有得到应用。
本发明之目的在于，提供发明前言中所提及的方法，籍助于该方法可使水泥或水泥集料具有极好的抗硫酸盐和海水的性能，而且使其用作钻孔水泥，同时还可安全地避免石膏膨化的危险。为达到上述目的，本发明之方法实质在于：矿渣碱度CaO/SiO2为1.35-1.6的水凝活性合成矿渣，例如废物煅烧渣和/或混有金属氧化物还原后的熔融钢渣的高炉矿渣，该合成矿渣还含有10-20％(重量)的Al2O3，和低于2.5％(重量)的氧化铁，该合成矿渣与占总混合物5-20％(重量)的碱土金属硫酸盐如磨碎状的生石膏、尾气石膏、烟气脱硫装置的石膏、石膏或无水石膏相混合。由于采用水凝活性合成矿渣代替通常完全不符合要求的天然矿渣，才可实现完全排除石膏膨化和制造一种水泥或水泥集料的前提条件，此种水泥或水泥集料的突出优点是高的抗海水和抗硫酸盐的能力。由于采用一种合成矿渣，才有可能在合成的矿渣时将矿渣碱度调节到通常高炉矿渣不能达到的矿渣碱度1.35-1.6，例如，这可通过将废物煅烧渣与钢渣混合并将这种钢渣中所含的金属氧化物还原的办法来达到。只要所选择的起始矿渣还不完全合乎要求时，可在熔体中将Al2O3含量调到10-20％(重量)的预定值，同时通过液态矿渣的还原，不仅能使重金属的含量，而且还应能使氧化铁的含量降到低于2.5％(重量)，为其后不产生任何不良副作用。由于采用这种纯度甚高的合成矿渣，则一系列难于处置的材料，诸如，烟气除硫装置的石膏、生石膏、废气石膏以及石膏和无水石膏皆可用作碱土金属载体使用。其中，矿渣的磨碎细度远不如已知的硫酸盐矿渣水泥的细度大，特别是不要求矿渣与石膏一道磨碎，而过去为保证良好的均匀混合却是这样做的。在硫酸盐矿渣水泥制造过程中，通常将生石膏和矿渣搀合，这给磨碎工序带来了不少困难。石膏在这种搀合物中倾向于结块，使其难以达到预期的磨碎细度。因此为保证石膏均匀分布所要求的细度，如硫酸矿渣水泥所要求那样，是极难达到的。相反，选择本发明的合成矿渣不需将该矿渣磨碎到这么大的细度，并使其能与同样细度的石膏进行其后的混合，但也能得到预期均匀度的混合物。
根据本发明，最好选择合成矿渣的磨碎细度为2800-3500cm2/g，这种细度明显地不如已知矿渣水泥所要求的磨碎细度大。
为了保证其后发生预期的硫代铝酸盐反应，最好将Al2O3含量调到12-18％(重量)。
CaSO4的使用量最好为8-15％(重量)，这时矿渣碱度选为大于1.45，优选为约1.5，这可保证快速硬化。
Al2O3含量可用添加黏土或矾土的特别简单方式来加以调节，这种调节可在液态矿渣相中进行。
通常钢渣约含16％(重量)SiO2，50％(重量)CaO和1％(重量Al2O3。这种钢渣可作为石灰载体以调节其它矿渣，例如废物煅烧渣的碱度。高炉矿渣一般属于酸性矿渣，极少情况下其碱度会大于1.1或1.2。通常，高炉矿渣水泥含SiO2的量约为37％(重量)，CaO的量约为32％(重量)。但是，在这种高炉矿渣中，所含Al2O3的量一般约为13％(重量)，因此，液态钢矿渣和高炉矿渣的混合物在调节所含Al2O3的碱度和用例如金属浴还原钢矿渣中所含过量铬和铁之后，就适宜作合成矿渣，该矿渣可继续加工为硫酸盐水泥。同样可使用废物煅烧装置或废渣焚烧装置的炉渣或烟尘，因其含有金属氧化物而应在金属浴中还原纯化，使其组成适合用于制造硫酸盐水泥。废物煅烧炉渣一般亦属于酸性炉渣，这类炉渣一般含10-25％(重量)Al2O3，碱度小于0.5。因此这类炉渣所含SiO2的份额比含CaO高，因此，若不相应地调节其碱度和相应地还原其中的金属氧化物，该炉渣就不适于作原料。同样，亦应对适合作水凝活性合成矿渣的矿渣混合物在液相进行调节，以确保所需碱度值为1.35-1.6，只有这样的碱度才能保证硫代铝酸盐反应在无需添加熟石灰或波特兰水泥引发初级水合的条件下进行，否则生成的凝胶层将防碍这个反应的进行。
为了进行比较，制造了一种硫酸盐矿渣水泥与本发明制造的水泥相比较。比较其结果表明，本发明的水泥在抗压强度变化过程的特征是三天之后强度稍低一点，而最终强度较高。硫酸盐矿渣水泥在三天后抗压强度值为41N/mm2，而本发明之水泥为38N/mm2。28天之后，硫酸盐矿渣水泥的抗压强度达到76N/mm2，而本发明之水泥却达到82N/mm2。本发明水泥的抗弯强度是已知硫酸盐矿渣水泥的两倍。硫酸盐矿渣水泥的抗弯强度达7N/mm2，而本发明水泥达14N/mm2。
从这些对比试验可以看出，本发明水泥的特点是收缩趋势相当小。当矿渣水泥和普通高炉矿渣混合水泥出现裂纹时，本发明水泥由于收缩趋势相当小，基本排除了裂纹生成的可能性，而确实地未发现裂纹。
分析过程中，磨碎细度是根据ASTM标准C 204-55中的布氏比表面积测定。对比试验中所用的硫酸盐矿渣水泥需更耗费及更细的研磨，其研磨细度达5000cm2/g，与此相反，用于对比试验的本发明的水泥只需磨碎到细度为3000cm2/g。
Claims (6)
1.一种硫酸盐水泥或硫酸盐水泥集料的制造方法，其特征在于，炉渣碱度CaO/SiO2为1.35-1.6的水凝活性合成矿渣，例如废物煅烧渣和/或混有金属氧化物还原后的熔融钢渣的高炉矿渣，该合成矿渣还含有10-20％(重量)的Al2O3和低于2.5％(重量)的氧化铁，该合成矿渣与占总混合物5-20％(重量)的碱土金属硫酸盐，如磨碎状的生石膏、尾气石膏、烟气脱硫装置的石膏、石膏或无水石膏相混合。
2.权利要求1的方法，其特征在于，合成矿渣的研磨细度为2800-3500cm2/g。
3.权利要求1或2的方法，其特征在于，其Al2O3含量调到12-18％(重量)。
4.权利要求1，2或3的方法，其特征在于，CaSO4的用量为8-15％(重量)。
5.权利要求1-4中之一的方法，其特征在于，其矿渣碱度选为大于1.45，优选为约1.5。
6.权利要求1-5中之一的方法，其特征在于，其Al2O3的含量通过添加黏土或矾土进行调节。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ATA611/97 | 1997-04-09 | ||
| AT0061197A AT404723B (de) | 1997-04-09 | 1997-04-09 | Verfahren zur herstellung von sulfatzement oder sulfatzementzuschlagstoffen |
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| CN1229404A true CN1229404A (zh) | 1999-09-22 |
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| CN98800449A Pending CN1229404A (zh) | 1997-04-09 | 1998-03-12 | 硫酸盐水泥或硫酸盐水泥集料的制造方法 |
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| Country | Link |
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| US (1) | US6139621A (zh) |
| EP (1) | EP0923506A3 (zh) |
| JP (1) | JP2000505776A (zh) |
| CN (1) | CN1229404A (zh) |
| AR (1) | AR010411A1 (zh) |
| AT (1) | AT404723B (zh) |
| AU (1) | AU725892B2 (zh) |
| BG (1) | BG62883B1 (zh) |
| BR (1) | BR9804812A (zh) |
| CA (1) | CA2257643A1 (zh) |
| CZ (1) | CZ424498A3 (zh) |
| HR (1) | HRP980137B1 (zh) |
| HU (1) | HUP0302627A2 (zh) |
| ID (1) | ID21227A (zh) |
| MA (1) | MA24518A1 (zh) |
| NZ (1) | NZ333268A (zh) |
| RU (1) | RU2163574C2 (zh) |
| SK (1) | SK168098A3 (zh) |
| TR (1) | TR199802561T1 (zh) |
| WO (1) | WO1998045218A2 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360450C (zh) * | 2000-03-28 | 2008-01-09 | 杰富意钢铁株式会社 | 熔渣硬化体的制造方法 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6409819B1 (en) * | 1998-06-30 | 2002-06-25 | International Mineral Technology Ag | Alkali activated supersulphated binder |
| AT408653B (de) * | 1999-12-20 | 2002-02-25 | Tribovent Verfahrensentwicklg | Verfahren zum herstellen von mergelschlacken |
| DE50107982D1 (de) * | 2000-01-28 | 2005-12-15 | Holcim Ltd | Verfahren zum herstellen von puzzolanischen zumahlstoffen für die zementindustrie aus stahlschlacken unter verwendung eines reduzierenden metallbades |
| US6666996B1 (en) | 2000-12-11 | 2003-12-23 | Tribovent Verfahrensentwicklung, Gmbh | Process for producing marl slags |
| RU2444553C1 (ru) * | 2010-12-29 | 2012-03-10 | Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный горный институт имени Г.В. Плеханова (технический университет)" | Тампонажный состав для изоляции зон поглощения |
| FI126049B (fi) | 2013-09-12 | 2016-06-15 | Global Ecoprocess Services Oy | Menetelmä metallien käsittelemiseksi |
| CN105837152A (zh) * | 2016-06-14 | 2016-08-10 | 安徽华业建工集团有限公司 | 一种建筑水泥及其制备方法 |
| CN106587879B (zh) * | 2016-12-12 | 2019-02-05 | 武汉中理环保科技有限公司 | 一种渣炒石膏制备石膏干混砂浆的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE430629A (zh) * | ||||
| US2248032A (en) * | 1938-02-22 | 1941-07-01 | Ici Ltd | Manufacture of cements from calcium sulphate and blast furnace slag |
| JPS5144536B2 (zh) * | 1972-10-19 | 1976-11-29 | ||
| DE2611889C3 (de) * | 1976-03-20 | 1978-11-02 | Ferdinand Dr.Rer.Mont. 6374 Steinbach Fink | Verfahren zur Herstellung von Bindemitteln aus Hüttenabfallen |
| NL173980C (nl) * | 1976-11-05 | 1984-04-02 | Nederlandse Cement Ind | Werkwijze voor het winnen van ijzer uit een slak van de oxystaalbereiding en het vormen van een residuslak met nuttige eigenschappen. |
| JPS5542250A (en) * | 1978-09-21 | 1980-03-25 | Osaka Cement | Swelling solidifying material |
| JPS55102677A (en) * | 1979-01-29 | 1980-08-06 | Chiyoda Chem Eng & Constr Co Ltd | Improvement in strength of hydrous soft ground |
| JPS5817556B2 (ja) * | 1979-12-29 | 1983-04-07 | 千代田化工建設株式会社 | 悪臭を持つ含水軟弱土の脱臭強度増加方法 |
| US4443260A (en) * | 1982-06-14 | 1984-04-17 | Chiyoda Chemical Engineering & Constr., Co., Ltd. | Method for strengthening soft soil |
| SU1085949A1 (ru) * | 1982-07-09 | 1984-04-15 | Государственный Всесоюзный Научно-Исследовательский Институт Цементной Промышленности | Сырьева смесь дл получени сульфоалюминатного клинкера |
| JPS60231445A (ja) * | 1984-04-28 | 1985-11-18 | 日本磁力選鉱株式会社 | 高塩基度製鋼スラグの利用方法 |
| JPS6117452A (ja) * | 1984-07-02 | 1986-01-25 | 日本磁力選鉱株式会社 | 製鋼スラグ、石炭灰の有効利用方法 |
| SU1303575A1 (ru) * | 1985-04-19 | 1987-04-15 | Липецкий политехнический институт | В жущее |
| US4652310A (en) * | 1985-11-20 | 1987-03-24 | Nippon Magnetic Dressing Co., Ltd. | Process for making a hardening agent for weak soil or sludge from steel making slag |
| DE3609568A1 (de) * | 1986-03-21 | 1987-09-24 | Fink Gerdinand | Herstellen eines zementes aus blasstahlschlacken |
| JP2710359B2 (ja) * | 1988-10-04 | 1998-02-10 | 電気化学工業株式会社 | 低アルカリセメント組成物及び上水道ライニング管 |
| SU1708788A1 (ru) * | 1988-12-27 | 1992-01-30 | Научно-Исследовательский И Проектно-Технологический Институт По Разработке Машин, Механизмов И Оснастки Для Городского Хозяйства Г.Москвы | В жущее |
| US5273579A (en) * | 1990-06-19 | 1993-12-28 | Mitsubishi Mining And Cement Co., Ltd. | Quick setting compositions |
| NL9201266A (nl) * | 1992-07-14 | 1994-02-01 | Pelt & Hooykaas | Werkwijze voor het regelen van de samenstelling van staalslakken. |
| JPH06115998A (ja) * | 1992-10-06 | 1994-04-26 | Nippon Cement Co Ltd | 水硬性組成物の製造方法 |
| JPH10245555A (ja) * | 1997-02-28 | 1998-09-14 | Mitsubishi Materials Corp | 有機質土用セメント系固化材 |
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1997
- 1997-04-09 AT AT0061197A patent/AT404723B/de not_active IP Right Cessation
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1998
- 1998-03-12 US US09/202,063 patent/US6139621A/en not_active Expired - Fee Related
- 1998-03-12 HU HU0302627A patent/HUP0302627A2/hu unknown
- 1998-03-12 RU RU99100300/03A patent/RU2163574C2/ru active
- 1998-03-12 CA CA002257643A patent/CA2257643A1/en not_active Abandoned
- 1998-03-12 CZ CZ984244A patent/CZ424498A3/cs unknown
- 1998-03-12 CN CN98800449A patent/CN1229404A/zh active Pending
- 1998-03-12 SK SK1680-98A patent/SK168098A3/sk unknown
- 1998-03-12 EP EP98909205A patent/EP0923506A3/de not_active Withdrawn
- 1998-03-12 YU YU56198A patent/YU56198A/sh unknown
- 1998-03-12 BR BR9804812-0A patent/BR9804812A/pt active Search and Examination
- 1998-03-12 NZ NZ333268A patent/NZ333268A/xx unknown
- 1998-03-12 AU AU63846/98A patent/AU725892B2/en not_active Ceased
- 1998-03-12 JP JP10542129A patent/JP2000505776A/ja active Pending
- 1998-03-12 TR TR1998/02561T patent/TR199802561T1/xx unknown
- 1998-03-12 WO PCT/AT1998/000066 patent/WO1998045218A2/de not_active Application Discontinuation
- 1998-03-12 ID IDW990005A patent/ID21227A/id unknown
- 1998-03-16 HR HR980137A patent/HRP980137B1/xx not_active IP Right Cessation
- 1998-04-02 MA MA25025A patent/MA24518A1/fr unknown
- 1998-04-02 ZA ZA982824A patent/ZA982824B/xx unknown
- 1998-04-08 AR ARP980101645A patent/AR010411A1/es unknown
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360450C (zh) * | 2000-03-28 | 2008-01-09 | 杰富意钢铁株式会社 | 熔渣硬化体的制造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| HRP980137B1 (en) | 2000-06-30 |
| AU725892B2 (en) | 2000-10-26 |
| MA24518A1 (fr) | 1998-12-31 |
| EP0923506A2 (de) | 1999-06-23 |
| SK168098A3 (en) | 1999-06-11 |
| YU56198A (sh) | 2000-03-21 |
| BG62883B1 (bg) | 2000-10-31 |
| BG103052A (en) | 1999-09-30 |
| RU2163574C2 (ru) | 2001-02-27 |
| CA2257643A1 (en) | 1998-10-15 |
| NZ333268A (en) | 2000-07-28 |
| US6139621A (en) | 2000-10-31 |
| TR199802561T1 (xx) | 1999-10-21 |
| ID21227A (id) | 1999-05-06 |
| JP2000505776A (ja) | 2000-05-16 |
| CZ424498A3 (cs) | 1999-07-14 |
| AR010411A1 (es) | 2000-06-07 |
| WO1998045218A2 (de) | 1998-10-15 |
| EP0923506A3 (de) | 1999-12-01 |
| HUP0302627A2 (hu) | 2003-11-28 |
| BR9804812A (pt) | 1999-12-14 |
| ZA982824B (en) | 1998-10-05 |
| AT404723B (de) | 1999-02-25 |
| WO1998045218A3 (de) | 1999-04-01 |
| HRP980137A2 (en) | 1999-02-28 |
| ATA61197A (de) | 1998-06-15 |
| AU6384698A (en) | 1998-10-30 |
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