CN1167642C - Cement high-activity fine steel slag powder mixed material and method for preparing high-grade cement - Google Patents
Cement high-activity fine steel slag powder mixed material and method for preparing high-grade cement Download PDFInfo
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- CN1167642C CN1167642C CNB001248219A CN00124821A CN1167642C CN 1167642 C CN1167642 C CN 1167642C CN B001248219 A CNB001248219 A CN B001248219A CN 00124821 A CN00124821 A CN 00124821A CN 1167642 C CN1167642 C CN 1167642C
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- 239000002893 slag Substances 0.000 title claims abstract description 89
- 239000004568 cement Substances 0.000 title claims abstract description 82
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 60
- 239000010959 steel Substances 0.000 title claims abstract description 60
- 239000000843 powder Substances 0.000 title claims abstract description 37
- 230000000694 effects Effects 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000002440 industrial waste Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000010881 fly ash Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- -1 pozzolan Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000011398 Portland cement Substances 0.000 description 13
- 239000004567 concrete Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 6
- 239000012190 activator Substances 0.000 description 5
- 239000010440 gypsum Substances 0.000 description 5
- 229910052602 gypsum Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 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
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明为一种用磨细钢渣粉制造的水泥高活性混合材料及其制造方法和用其制备高标号通用水泥的方法。这种高活性细钢渣粉比表面积≥300m2/kg，粒径小于40μm的颗粒含量大于65%(重量)，7天和28天活性指数分别≥75%和80%，安定性合格。配制水泥时掺入占总重量10-50%钢渣粉和0-35%其它混合材料，可将各组分预先磨细再混合，也可将磨细的钢渣粉与粗水泥熟料及其它组分共同粉磨。该钢渣粉的制造方法为：将小于60mm的钢渣投入粉碎机中粉碎后经分级机分选。The invention relates to a high-activity cement mixed material made from finely ground steel slag powder, a manufacturing method thereof, and a method for preparing high-grade general-purpose cement using the same. The specific surface area of this high-activity fine steel slag powder is ≥300m 2 /kg, the content of particles with a particle size of less than 40μm is greater than 65% (weight), the activity index of 7 days and 28 days is ≥75% and 80%, respectively, and the stability is qualified. When preparing cement, mix 10-50% steel slag powder and 0-35% other mixed materials in the total weight. The components can be ground and mixed in advance, or the ground steel slag powder can be mixed with coarse cement clinker and other components. Grinding together. The manufacturing method of the steel slag powder is as follows: the steel slag smaller than 60 mm is put into a pulverizer for pulverization and then sorted by a classifier.
Description
本发明为一种用磨细钢渣粉制造的水泥高活性混合材料及用其配制水泥的方法，涉及建筑材料工业的水泥材料领域。The invention relates to a high-activity cement mixed material produced by grinding fine steel slag powder and a method for preparing cement by using the same, and relates to the field of cement materials in the building material industry.
与本发明相关的技术有以下几个：Technologies relevant to the present invention have the following:
(1)采用钢渣作为水泥混合材料制备钢渣矿渣水泥。其主要技术和比较先进的工艺为：将钢渣预先水闷，使之粉碎成为数厘米至数毫米的颗粒，将这些钢渣颗粒与水泥熟料、矿渣及石膏共同粉磨，达到比表面积350m2/kg，制成水泥。其中各个组分的重量比例为：钢渣≥30％，钢渣+矿渣≥60％，石膏5％左右，其余为硅酸盐水泥熟料。制成的水泥强度分为325和425两个标号。有相应的钢渣矿渣水泥国家标准。(1) Steel slag slag cement is prepared by using steel slag as cement mixture material. Its main technology and relatively advanced process are: pre-fill the steel slag with water to crush it into particles of several centimeters to several millimeters, and grind these steel slag particles together with cement clinker, slag and gypsum to reach a specific surface area of 350m 2 / kg, made into cement. The weight ratio of each component is: steel slag ≥ 30%, steel slag + slag ≥ 60%, gypsum about 5%, and the rest is Portland cement clinker. The strength of the cement made is divided into two grades of 325 and 425. There are corresponding national standards for steel slag slag cement.
(2)利用钢渣粉作为水泥混合材料，添加激发剂，制备含钢渣的水泥。其特点是：在水泥生产时加入特殊的激发剂，提高水泥强度。激发剂的种类有多种，多数为化工原料，也有一些为煅烧过的石膏。颗粒状的钢渣与水泥熟料、石膏及激发剂共同粉磨。水泥强度标号大部分为325#和425#，有少量可以达到525#。(2) Using steel slag powder as cement mixing material, adding activator to prepare steel slag-containing cement. Its characteristics are: adding a special activator during cement production to increase the strength of cement. There are many types of activators, most of which are chemical raw materials, and some are calcined gypsum. Granular steel slag is ground together with cement clinker, gypsum and activator. Most of the cement strength labels are 325# and 425#, and a small amount can reach 525#.
以上技术代表了近年来钢渣在水泥中应用技术方面的现有成果，但是对于钢渣的细度未加以控制，钢渣在水泥中的实际颗粒过粗，钢渣的活性未得到发挥，活性较低，造成钢渣水泥强度低。工厂实际生产的钢渣矿渣水泥标号主要为325#和425#。如果按照国际标准(ISO标准)来衡量，强度标号更低。如果采用掺加激发剂的方法，虽然可以将水泥强度标号提高到525#，但是国家水泥标准不允许掺加对水泥性能有影响的助剂，否则对混凝土的性能的影响难以控制。这导致了含钢渣的水泥在市场上的竞争力较弱，这使钢渣在水泥中的利用总量受到限制。The above technologies represent the existing achievements in the application of steel slag in cement in recent years, but the fineness of steel slag is not controlled, the actual particle size of steel slag in cement is too thick, the activity of steel slag is not brought into play, and the activity is low, resulting in Steel slag cement has low strength. The grades of steel slag and slag cement actually produced by the factory are mainly 325# and 425#. If measured according to international standards (ISO standards), the strength label is lower. If the method of adding activator is adopted, although the cement strength label can be increased to 525#, the national cement standard does not allow the addition of additives that affect the performance of the cement, otherwise the impact on the performance of the concrete is difficult to control. This has caused the cement containing steel slag to be less competitive in the market, which limits the total utilization of steel slag in cement.
本发明的目的是制造一种具有高活性的钢渣磨细粉，作为水泥的高活性混合材料，在水泥中掺加10-35％(重量)时，可以配制强度标号为525的水泥；在水泥中掺加35-50％(重量)时，可以配制强度标号为425的水泥。这种水泥高活性混合材料比表面积大，活性高，适用于制造525#普通硅酸盐水泥、矿渣普通硅酸盐水泥、复合普通硅酸盐水泥、钢渣矿渣水泥。磨细钢渣粉可以在水泥中单独掺加，也可以与粉煤灰、矿渣、火山灰、炉渣、沸石、煤矸石、磷渣及其它工业废渣复合掺加。制成的水泥适用于制备普通混凝土、大体积混凝土(如大型建筑的基础混凝土、大坝混凝土)、高强混凝土、预应力混凝土、混凝土预制构件等。The purpose of the present invention is to manufacture a kind of steel slag ground fine powder with high activity, as the high activity mixed material of cement, when adding 10-35% (weight) in cement, can prepare the cement that strength label is 525; When 35-50% (weight) is added in the medium, the cement whose strength number is 425 can be prepared. This cement high-activity mixed material has a large specific surface area and high activity, and is suitable for manufacturing 525# ordinary Portland cement, slag ordinary Portland cement, composite ordinary Portland cement, and steel slag slag cement. Finely ground steel slag powder can be added alone in cement, or compounded with fly ash, slag, pozzolan, slag, zeolite, coal gangue, phosphorus slag and other industrial waste. The prepared cement is suitable for preparing ordinary concrete, mass concrete (such as foundation concrete of large buildings, dam concrete), high-strength concrete, prestressed concrete, concrete prefabricated components, etc.
本发明的具体内容如下：Concrete content of the present invention is as follows:
1.钢渣采用预先磨细和分选，使其比表面积≥300m2/kg，粒径小于40μm的颗粒含量大于65％(重量)，主要性能达到：7天和28天的活性指数分别大于或等于75％和80％，均远高于国家关于用作水泥混合材料的工业废渣的活性标准规定70％的要求；密度＝2.90-3.30g/cm3，压蒸安定性合格。其中各个指标的测试评价方法均采用现有的通用方法：1. The steel slag is ground and sorted in advance, so that its specific surface area is ≥300m 2 /kg, the particle size is less than 40μm, and the particle content is greater than 65% (by weight). The main performance is: the activity index of 7 days and 28 days is greater than or It is equal to 75% and 80%, both of which are far higher than the 70% requirement of the national activity standard for industrial waste residue used as cement mixing material; density = 2.90-3.30g/cm 3 , and the pressure steaming stability is qualified. The test and evaluation methods of each indicator adopt the existing general method:
活性指数：按照“GB 12957-1991用作水泥混合材料的工业废渣活性试验方法”进行检验，以30％(重量)磨细钢渣粉与70％(重量)525#硅酸盐水泥的混合物28天的抗压强度和纯525#硅酸盐水泥28天的抗压强度之比值来表示。即：Activity index: According to "GB 12957-1991 Test method for the activity of industrial waste slag used as cement admixture", the mixture of 30% (weight) finely ground steel slag powder and 70% (weight) 525# Portland cement is used for 28 days It is expressed by the ratio of the compressive strength of pure 525# Portland cement for 28 days. Right now:
压蒸安定性：在525硅酸盐水泥中掺加30％高活性钢渣粉后，经国家水泥标准规定的压蒸法检验合格。Autoclaving stability: After adding 30% high-activity steel slag powder to 525 Portland cement, it is qualified by the autoclaving method stipulated in the national cement standard.
碱度系数：以氧化物含量(重量)之比表示：CaO/(SiO2+P2O5)Alkalinity coefficient: expressed as the ratio of oxide content (weight): CaO/(SiO 2 +P 2 O 5 )
成分要求：金属铁含量≤0.8％(重量)，游离氧化钙含量≤3％(重量)，碱度系数≥2。Ingredient requirements: metal iron content ≤ 0.8% (weight), free calcium oxide content ≤ 3% (weight), alkalinity coefficient ≥ 2.
2.掺加高活性钢渣粉混合材料生产高标号水泥的方法是：配制强度标号为525的水泥时，掺入占总重量10-35％的磨细高活性钢渣粉和占总重量0-30％的其它工业废渣，作为混合材料；配制强度标号为425的水泥时，掺入占总重量30-50％的磨细高活性钢渣粉和占总重量0-35％的其它工业废渣，作为混合材料。其中高活性钢渣粉的比表面积≥300m2/kg，其它工业废渣包括矿渣、粉煤灰、火山灰、炉渣、沸石、煤矸石、磷渣等。水泥的品种包括普通硅酸盐水泥、矿渣普通硅酸盐水泥、复合普通硅酸盐水泥、粉煤灰硅酸盐水泥、钢渣矿渣水泥。采用下列三种工艺之一制造水泥：2. The method of mixing high-activity steel slag powder mixed materials to produce high-grade cement is: when preparing cement with a strength label of 525, add finely ground high-activity steel slag powder accounting for 10-35% of the total weight and 0-30% of the total weight % other industrial waste slag, as a mixed material; when preparing cement with a strength label of 425, mix 30-50% of the total weight of finely ground high-activity steel slag powder and 0-35% of the total weight of other industrial waste slag, as a mixed Material. Among them, the specific surface area of highly active steel slag powder is ≥300m 2 /kg, and other industrial wastes include slag, fly ash, volcanic ash, furnace slag, zeolite, coal gangue, phosphorus slag, etc. The varieties of cement include ordinary Portland cement, slag ordinary Portland cement, composite ordinary Portland cement, fly ash Portland cement, and steel slag slag cement. Cement is manufactured using one of the following three processes:
(1)除钢渣粉之外，将水泥的其它各个组分也预先分别粉磨至比表面积300m2/kg以上，然后再与已经磨细的钢渣粉按照规定的比例混合均匀，制成水泥。(1) In addition to the steel slag powder, the other components of the cement are also ground in advance to a specific surface area of 300m 2 /kg or more, and then mixed with the ground steel slag powder according to the specified ratio to make cement.
(2)将水泥的其它各个组分预先分别粉磨至比表面积200m2/kg以上，然后再与已经磨细的钢渣粉按照规定的比例混合均匀，同时加以进一步粉磨，制成水泥。(2) Grind the other components of the cement separately in advance until the specific surface area exceeds 200m 2 /kg, and then mix them with the finely ground steel slag powder according to the specified ratio, and further grind them at the same time to make cement.
(3)将磨细的钢渣粉与未经预先磨细的水泥熟料及其它各个组分按照规定比例同时加入到磨机内，共同粉磨，达到总的比表面积300m2/kg以上制成水泥。(3) Add the finely ground steel slag powder, cement clinker and other components without pre-grinding into the mill at the same time according to the specified ratio, and grind together to achieve a total specific surface area of 300m 2 /kg or more. cement.
3.高活性钢渣粉水泥混合材料的制造流程如下：3. The manufacturing process of high activity steel slag powder cement mixture is as follows:
小于60mm的块状钢渣→投入粉碎机中粉碎→进入分级机分选→得到比表面积大于300m2/kg的粉状产品。其中当金属铁含量大于0.8％(重量)时，在生产过程的一个环节中插入磁选机，选除金属铁，使之含量小于0.8％(重量)。粉状产品的比表面积可以根据需要而通过调整分级机的参数进行调整，范围为300-500m2/kg。Blocky steel slag less than 60mm→put into the pulverizer for crushing→enter the classifier for sorting→obtain a powdery product with a specific surface area greater than 300m 2 /kg. Wherein when the content of metallic iron is greater than 0.8% (weight), a magnetic separator is inserted in a link of the production process to select and remove metallic iron so that the content is less than 0.8% (weight). The specific surface area of the powdery product can be adjusted by adjusting the parameters of the classifier as required, and the range is 300-500m 2 /kg.
本发明的优点和效果：Advantages and effects of the present invention:
本发明所提出的磨细钢渣粉具有水化反应活性高、水泥生产成本低、水泥强度高和综合性能好等优点。掺加部分高活性的磨细钢渣粉作为混合材料制成的水泥用于混凝土工程，可以降低混凝土的水化热温升，保证混凝土早期强度，提高后期强度，增加混凝土的抗磨损性能和抗腐蚀性能，提高混凝土耐久性。The finely ground steel slag powder proposed by the invention has the advantages of high hydration reaction activity, low cement production cost, high cement strength and good comprehensive performance. The cement made by adding part of highly active finely ground steel slag powder as a mixed material is used in concrete engineering, which can reduce the temperature rise of the heat of hydration of concrete, ensure the early strength of concrete, improve the later strength, and increase the wear resistance and corrosion resistance of concrete. properties and improve the durability of concrete.
以下为本发明的实施例：The following are embodiments of the present invention:
例1：水泥熟料预先粉磨至比表面积330m2/kg，磨细钢渣粉比表面积303m2/kg，磨细细矿渣粉比表面积383m2/kg，按照下表配料、混合均匀，制成水泥，测得水泥的压蒸安定性全部合格，凝结时间正常，符合国家标准，水泥强度如下表：
例2：磨细钢渣粉比表面积409m2/kg，然后和水泥熟料、矿渣、石膏混合后共同粉磨，制成水泥。预先粉磨至比表面积310m2/kg，磨细细矿渣粉比表面积202m2/kg，按照下表配料、混合均匀，制成水泥，测得水泥的压蒸安定性全部合格，凝结时间正常，符合国家标准，水泥强度如下表：
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| CN103553512A (en) * | 2013-07-22 | 2014-02-05 | 南京工业大学 | Method for preparing concrete by using primarily ground steel slag active micro powder |
| CN108590023B (en) * | 2016-06-27 | 2020-11-20 | 优美墅房屋工程(海南)有限责任公司 | A kind of preparation process of thermal insulation wallboard |
| CN106746809A (en) * | 2016-12-31 | 2017-05-31 | 贵州贵鑫科技环保建材有限公司 | A kind of complex slag and preparation method thereof |
| JP6323601B1 (en) * | 2017-02-02 | 2018-05-16 | 住友大阪セメント株式会社 | Concrete composition and method for producing concrete composition |
| CN109180030A (en) * | 2018-08-29 | 2019-01-11 | 北海诚德镍业有限公司 | A kind of building cementing material and construction material |
| CN109250936A (en) * | 2018-11-20 | 2019-01-22 | 黄庆周 | A kind of construction material and application by stainless steel slag preparation |
| CN110092596A (en) * | 2019-04-23 | 2019-08-06 | 山西大学 | A kind of method and production system preparing the unburned eco-cement of solid waste base |
| CN111574075B (en) * | 2020-06-05 | 2021-12-28 | 中国建筑材料科学研究总院有限公司 | High-activity mixed material prepared from waste concrete and steel slag, and preparation method and application thereof |
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2000
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