CN117229012B - Non-alkali excitation type steel slag cementing material and preparation method thereof - Google Patents
Non-alkali excitation type steel slag cementing material and preparation method thereof Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 122
- 239000010959 steel Substances 0.000 title claims abstract description 122
- 239000002893 slag Substances 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000003513 alkali Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000005284 excitation Effects 0.000 title abstract description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 29
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229940029036 ethylenediamine tetraethanol Drugs 0.000 claims abstract description 23
- -1 ethylenediaminetetraacetic acid diesters Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 14
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 11
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 11
- 229940120146 EDTMP Drugs 0.000 claims description 9
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- GMCBSXCBAPZBFF-UHFFFAOYSA-N 2-[2-[bis(2-ethoxy-2-oxoethyl)amino]ethyl-(carboxymethyl)amino]acetic acid Chemical group CCOC(=O)CN(CC(=O)OCC)CCN(CC(O)=O)CC(O)=O GMCBSXCBAPZBFF-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- KVJXEJFFQNSORF-UHFFFAOYSA-L disodium acetic acid diacetate Chemical compound [Na+].[Na+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O KVJXEJFFQNSORF-UHFFFAOYSA-L 0.000 claims 1
- 230000036571 hydration Effects 0.000 abstract description 14
- 238000006703 hydration reaction Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 235000011148 calcium chloride Nutrition 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VIEZPRZRGBVOCX-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]-2-ethylbutanoic acid Chemical compound C(C)C(C(=O)O)(N(CCN(CC(=O)O)CC(=O)O)CC(=O)O)CC VIEZPRZRGBVOCX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000001664 diethylamino group Chemical class [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 229940012017 ethylenediamine Drugs 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
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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
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
本发明涉及钢渣基胶凝材料技术领域，尤其是涉及一种非碱类激发型钢渣胶凝材料及其制备方法，本发明通过乙二胺衍生物在钢渣粉磨过程中形成预处理激发，并添加乙二胺四乙醇、乙二胺四乙酸二酯类、醇胺、无机盐实现水化激发，实现非碱类激发，协同提高钢渣作为胶凝材料的强度，实现100%利用钢渣制备高强度、低碱度、高稳定性的胶凝材料，提高钢渣利用率。The present invention relates to the technical field of steel slag-based cementitious materials, and in particular to a non-alkali excitation type steel slag cementitious material and a preparation method thereof. The present invention uses an ethylenediamine derivative to form pretreatment excitation during the steel slag grinding process, and Adding ethylenediaminetetraethanol, ethylenediaminetetraacetic acid diesters, alcoholamines, and inorganic salts achieves hydration excitation and non-alkali excitation, which synergistically improves the strength of steel slag as a cementitious material, achieving 100% utilization of steel slag to produce high strength , low alkalinity and high stability cementitious materials to improve steel slag utilization.
Description
技术领域Technical field
本发明涉及钢渣基胶凝材料技术领域，尤其是涉及一种非碱类激发型钢渣胶凝材料及其制备方法。The present invention relates to the technical field of steel slag-based cementitious materials, and in particular to a non-alkali excitation type steel slag cementitious material and a preparation method thereof.
背景技术Background technique
钢渣是冶炼钢铁过程中产生的固体废弃物，随每年钢铁的生产，钢渣的量也在逐年累积。Steel slag is a solid waste produced during the smelting process of steel. With the annual steel production, the amount of steel slag is also accumulating year by year.
而目前钢渣资源化利用率不足40%，且没有一种能够大规模消纳钢渣的途径，未被利用的钢渣造成了大量的土地资源浪费和污染。At present, the resource utilization rate of steel slag is less than 40%, and there is no way to consume steel slag on a large scale. Unused steel slag has caused a lot of waste of land resources and pollution.
若能将钢渣用于胶凝材料，不仅能极大促进钢渣利用，而且能减少水泥的使用，同时起到节能降碳的目的。If steel slag can be used as cementitious materials, it will not only greatly promote the utilization of steel slag, but also reduce the use of cement, while achieving the purpose of energy saving and carbon reduction.
而钢渣活性低的问题使其不能够像水泥一样完全被当作良好的胶凝材料来使用，而只能充当矿物掺合料、骨料等被掺入到水泥中。The low activity of steel slag prevents it from being used as a good cementing material like cement, but can only be used as mineral admixtures, aggregates, etc. to be incorporated into cement.
目前的研究也大多以30%的比例加入到水泥中，这极大制约了钢渣的利用。Current research also mostly adds steel slag to cement at a proportion of 30%, which greatly restricts the utilization of steel slag.
而在强度激发方面，多以碱激发为主，例如氢氧化钠、石灰、水玻璃、电石渣等，但成本大，工作性不易控制，并且制备得到的胶凝材料碱度较高，制备得到的建材制品碱性大，易产生返碱、花白等质量问题，此外，钢渣含有部分游离氧化钙，造成钢渣具有安定性不足的隐患，限制钢渣的大规模使用。In terms of strength excitation, alkali excitation is mostly used, such as sodium hydroxide, lime, water glass, carbide slag, etc., but the cost is high, the workability is difficult to control, and the prepared cementitious material has high alkalinity, and the prepared Building materials products are highly alkaline and are prone to quality problems such as alkalinization and whitening. In addition, steel slag contains some free calcium oxide, which causes the hidden danger of insufficient stability of steel slag and limits the large-scale use of steel slag.
本发明针对钢渣活性激发、强度提升有限这一问题，提供了一种非碱激发且100%利用钢渣制备高强度胶凝材料的方法，对于提高转炉钢渣在建材领域中的应用有着积极的促进作用。Aiming at the problem of active activation and limited strength improvement of steel slag, the present invention provides a method for preparing high-strength cementitious materials with non-alkali activation and 100% utilization of steel slag, which has a positive role in promoting the application of converter steel slag in the field of building materials. .
发明内容Contents of the invention
为解决现有技术中存在的钢渣活性依靠碱类激发、强度提升有限问题，本发明提供一种非碱类激发型钢渣胶凝材料及其制备方法，详细的，本发明通过乙二胺衍生物在钢渣粉磨过程中形成预处理激发，并添加乙二胺四乙醇、乙二胺四乙酸二酯类、醇胺、无机盐实现水化激发，实现非碱类激发，协同提高钢渣作为胶凝材料的强度，实现100%利用钢渣制备高强度、低碱度、高稳定性的胶凝材料，提高钢渣利用率。In order to solve the existing problems in the prior art that the activity of steel slag relies on alkali excitation and the strength is limited, the present invention provides a non-alkali excitation type steel slag gelling material and a preparation method thereof. In detail, the present invention uses ethylenediamine derivatives Pretreatment excitation is formed during the grinding process of steel slag, and ethylenediaminetetraethanol, ethylenediaminetetraacetic acid diesters, alcoholamines, and inorganic salts are added to achieve hydration excitation, non-alkali excitation, and synergistically improving the gelling effect of steel slag The strength of the material enables 100% utilization of steel slag to prepare cementitious materials with high strength, low alkalinity and high stability, thereby improving the utilization rate of steel slag.
具体的，本发明非碱类激发型钢渣胶凝材料的制备方法，由如下步骤制备而成：Specifically, the method for preparing the non-alkali excited steel slag cementitious material of the present invention is prepared by the following steps:
1）将钢渣与乙二胺衍生物溶液进行共同粉磨，过筛，得钢渣活化粉；1) Grind steel slag and ethylenediamine derivative solution together and sieve to obtain steel slag activated powder;
2）将钢渣活化粉与乙二胺四乙醇、乙二胺四乙酸二酯类、醇胺、无机盐复合溶液混合，即得；2) Mix steel slag activated powder with ethylenediaminetetraethanol, ethylenediaminetetraacetic acid diesters, alcoholamines, and inorganic salt composite solutions to obtain;
其中，所述乙二胺衍生物为乙二胺四乙酸二钠和乙二胺四亚甲基膦酸的混合物；Wherein, the ethylenediamine derivative is a mixture of disodium ethylenediaminetetraacetate and ethylenediaminetetramethylenephosphonic acid;
所述无机盐为CaCl2、KSCN中的至少一种。The inorganic salt is at least one of CaCl 2 and KSCN.
钢渣中的主要矿物包括C3S、C2S、C2F以及RO相，其中提供胶凝活性的主要是C3S和C2S，本发明首先在钢渣粉磨时加入乙二胺四亚甲基膦酸和乙二胺四乙酸二钠，整体上对钢渣结构进行酸化与络合处理，增加钢渣中的各种矿物的溶解性能，乙二胺四亚甲基膦酸更多对钢渣起酸化的作用，乙二胺四乙酸二钠更多与钢渣中的金属离子络合，促进其在溶液中溶解平衡向右移动，本发明研究表明，乙二胺四亚甲基膦酸和乙二胺四乙酸二钠两者结合可使游离氧化钙充分暴露水化位点，提高其自激发能力，加速游离氧化钙的水化，降低浆体硬化后氧化钙含量，并协同达到提高钢渣活性、促进矿物相溶解的目的。The main minerals in steel slag include C 3 S, C 2 S, C 2 F and RO phases, among which C 3 S and C 2 S mainly provide gelling activity. In the present invention, ethylene diamine tetrahydrofuran is first added during grinding of steel slag. Methylenephosphonic acid and disodium ethylenediaminetetraacetate acidify and complex the steel slag structure as a whole, increasing the solubility of various minerals in the steel slag. Ethylenediaminetetramethylenephosphonic acid has more effects on steel slag. Playing an acidifying role, disodium ethylenediaminetetraacetate is more complexed with the metal ions in the steel slag, promoting its dissolution equilibrium in the solution to shift to the right. The research of the present invention shows that ethylenediaminetetramethylenephosphonic acid and ethylenediaminetetraacetic acid The combination of disodium diamine tetraacetate can fully expose the hydration sites of free calcium oxide, improve its self-activation ability, accelerate the hydration of free calcium oxide, reduce the calcium oxide content after slurry hardening, and synergistically improve the activity of steel slag , the purpose of promoting the dissolution of mineral phases.
优选的，步骤1）钢渣为转炉钢渣。Preferably, the steel slag in step 1) is converter steel slag.
优选的，步骤1）乙二胺衍生物有效含量为钢渣质量的0.01-0.05%。Preferably, the effective content of the ethylenediamine derivative in step 1) is 0.01-0.05% of the steel slag mass.
优选的，步骤1）乙二胺四乙酸二钠和乙二胺四亚甲基膦酸的质量比为1:0.5-2。Preferably, the mass ratio of step 1) disodium ethylenediaminetetraacetate and ethylenediaminetetramethylenephosphonic acid is 1:0.5-2.
优选的，步骤1）钢渣活化粉粒径小于75μm。Preferably, the particle size of the activated steel slag powder in step 1) is less than 75 μm.
优选的，步骤2）乙二胺四乙酸二酯类为乙二胺四乙酸二乙酯。Preferably, the diester of ethylenediaminetetraacetate in step 2) is diethyl ethylenediaminetetraacetate.
优选的，步骤2）醇胺为三乙醇胺、三异丙醇胺、二乙醇单异丙醇胺的至少一种。Preferably, the alcoholamine in step 2) is at least one of triethanolamine, triisopropanolamine, and diethanolmonoisopropanolamine.
更优选的，步骤2）醇胺为二乙醇单异丙醇胺，无机盐为CaCl2。More preferably, the alcohol amine in step 2) is diethanol monoisopropanolamine, and the inorganic salt is CaCl 2 .
优选的，步骤2）乙二胺四乙醇、乙二胺四乙酸二酯类、醇胺、无机盐总有效含量为钢渣活性粉质量的0.01-0.1%，乙二胺四乙醇、乙二胺四乙酸二酯类、醇胺、无机盐质量比为1：0.5-2：0.5-2：0.5-2。Preferably, the total effective content of step 2) ethylenediaminetetraethanol, ethylenediaminetetraacetic acid diesters, alcoholamines, and inorganic salts is 0.01-0.1% of the mass of the steel slag active powder. The mass ratio of acetate diesters, alcoholamines and inorganic salts is 1:0.5-2:0.5-2:0.5-2.
并且，本发明在钢渣水化时加入乙二胺四乙醇、乙二胺四乙酸二酯类、醇胺、无机盐复合溶液可控制钢渣的水化平衡，加快钢渣水化速率，增加水化程度。Moreover, the present invention can control the hydration balance of steel slag by adding ethylenediaminetetraethanol, ethylenediaminetetraacetic acid diesters, alcoholamines, and inorganic salt composite solutions during the hydration of steel slag, speeding up the hydration rate of steel slag, and increasing the degree of hydration. .
其中，加入的醇胺能够对整体的水化，包括早期和后期的水化都起到一定的促进作用，但是效果不强，在此基础上通过加入无机盐类补充其早期强度效果，通过加入乙二胺四乙酸二酯类补充其后期强度效果，而加入的乙二胺四乙醇可以解决各类激发剂之间相容性的问题；并且，本发明加入乙二胺四乙醇、乙二胺四乙酸二酯类与醇胺相互配合可以促进钢渣中凝胶型水化产物的生成，同时无机盐类除补充早期强度的作用外，还可以补充更多金属离子参与形成水化产物，附着在钢渣活化粉上的二乙胺衍生物同时会增强醇胺和乙二胺四乙酸二酯类的激发效果，并协助乙二胺四乙醇促进各原料的相容性，提高游离氧化钙的消化程度和钢渣矿物均匀水化。Among them, the added alcoholamine can promote the overall hydration, including early and late hydration, but the effect is not strong. On this basis, the early strength effect is supplemented by adding inorganic salts. The ethylenediaminetetraacetic acid diesters supplement their later strength effects, and the added ethylenediaminetetraethanol can solve the problem of compatibility between various activators; and, the present invention adds ethylenediaminetetraethanol, ethylenediamine The interaction between tetraacetic acid diesters and alcoholamines can promote the formation of gel-type hydration products in steel slag. At the same time, inorganic salts, in addition to supplementing the early strength, can also supplement more metal ions to participate in the formation of hydration products, which are attached to the The diethylamine derivatives on the steel slag activation powder will also enhance the stimulating effect of alcoholamines and ethylenediaminetetraacetic acid diesters, and assist ethylenediaminetetraethanol to promote the compatibility of each raw material and improve the digestion of free calcium oxide. and uniform hydration of steel slag minerals.
综合而言，本发明通过在预处理增加钢渣溶解基础上进一步结合复合溶液增加钢渣水化，从而达到增加钢渣强度的目的。In summary, the present invention achieves the purpose of increasing the strength of steel slag by increasing the dissolution of steel slag through pretreatment and further combining it with a composite solution to increase the hydration of steel slag.
而目前存在的各种激发废渣强度的方式，虽然对强度提升有一定效果，但有以下缺陷：体积稳定性差，收缩大；采用碱激发，具有高碱－集料反应风险；使用过程中析碱、泛碱问题突出；激发剂成本高。Although the currently existing methods of stimulating the strength of waste residue have certain effects on improving strength, they have the following shortcomings: poor volume stability and large shrinkage; alkali stimulation is used, which has the risk of high alkali-aggregate reaction; alkali is released during use. , the problem of efflorescence is prominent; the cost of activators is high.
本发明还涉及非碱类激发型钢渣胶凝材料，具体的，由上述制备方法制备得到。The present invention also relates to a non-alkali excitation type steel slag cementing material, which is specifically prepared by the above preparation method.
本发明提供的非碱激发且100%利用钢渣制备高强度胶凝材料的方法的强度提升效果可提高纯钢渣浆体3d力学强度3.1~4.3MPa，7d力学强度可提高3.5~4.6MPa，28d力学强度可提高5.0~6.3MPa。The strength-improving effect of the non-alkali-activated and 100% utilization of steel slag method for preparing high-strength cementitious materials provided by the present invention can increase the 3d mechanical strength of pure steel slag slurry by 3.1~4.3MPa, the 7d mechanical strength by 3.5~4.6MPa, and the 28d mechanical strength. The strength can be increased by 5.0~6.3MPa.
具体实施方式Detailed ways
为表征本发明技术效果，制备钢渣胶凝材料并作为100%胶凝材料制备净浆和砂浆，采用75μm钢渣粉作为空白例，利用净浆通过雷氏夹法测试胶凝材料安定性，按照GBT17671-2021《水泥胶砂强度检验方法（ISO法）》对砂浆力学性能进行检测。In order to characterize the technical effect of the present invention, steel slag cementitious materials were prepared and used as 100% cementitious materials to prepare slurry and mortar. 75 μm steel slag powder was used as a blank example, and the slurry was used to test the stability of the cementitious materials by the Leigh clamp method, in accordance with GBT17671 -2021 "Cement Mortar Strength Test Method (ISO Method)" tests the mechanical properties of mortar.
其中，钢渣化学组成由表1所示。Among them, the chemical composition of steel slag is shown in Table 1.
表1 钢渣化学组成（%）Table 1 Chemical composition of steel slag (%)
实施例1Example 1
将钢渣与钢渣有效质量0.01%的乙二胺衍生物溶液进行共同粉磨，过75μm筛，得钢渣活化粉；将钢渣活化粉与活化钢渣粉有效质量0.02%的乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2复合溶液混合，即得；其中，所述乙二胺衍生物为乙二胺四乙酸二钠和乙二胺四亚甲基膦酸按质量比1:1的混合物，乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2质量比为1:1:1:1。Grind the steel slag and an ethylenediamine derivative solution with an effective mass of 0.01% of the steel slag together, and pass through a 75 μm sieve to obtain activated steel slag powder; grind the activated steel slag powder with an effective mass of 0.02% of the activated steel slag powder, ethylenediaminetetraethanol, ethylenediamine Mix diethyl aminetetraacetate, diethanol monoisopropanolamine, and CaCl 2 composite solutions to obtain the product; wherein, the ethylenediamine derivatives are disodium ethylenediaminetetraacetate and ethylenediaminetetramethylenephosphine The mass ratio of acids is 1:1, and the mass ratio of ethylenediaminetetraethanol, diethylethylenediaminetetraacetate, diethanolmonoisopropanolamine, and CaCl2 is 1:1:1:1.
实施例2Example 2
将钢渣与钢渣有效质量0.03%的乙二胺衍生物溶液进行共同粉磨，过75μm筛，得钢渣活化粉；将钢渣活化粉与活化钢渣粉有效质量0.06%的乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2复合溶液混合，即得；其中，所述乙二胺衍生物为乙二胺四乙酸二钠和乙二胺四亚甲基膦酸按质量比1:0.5的混合物，乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2质量比为1:2:1:1。Grind the steel slag and an ethylenediamine derivative solution with an effective mass of 0.03% of the steel slag together, and pass through a 75 μm sieve to obtain activated steel slag powder; grind the activated steel slag powder and the activated steel slag powder with an effective mass of 0.06% ethylenediaminetetraethanol, ethylenediamine Mix diethyl aminetetraacetate, diethanol monoisopropanolamine, and CaCl 2 composite solutions to obtain the product; wherein, the ethylenediamine derivatives are disodium ethylenediaminetetraacetate and ethylenediaminetetramethylenephosphine The mass ratio of acids is 1:0.5, and the mass ratio of ethylenediaminetetraethanol, diethylethylenediaminetetraacetate, diethanolmonoisopropanolamine, and CaCl2 is 1:2:1:1.
实施例3Example 3
将钢渣与钢渣有效质量0.05%的乙二胺衍生物溶液进行共同粉磨，过75μm筛，得钢渣活化粉；将钢渣活化粉与活化钢渣粉有效质量0.1%的乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2复合溶液混合，即得；其中，所述乙二胺衍生物为乙二胺四乙酸二钠和乙二胺四亚甲基膦酸按质量比1:2的混合物，乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2质量比为1:0.5:0.5:1。Grind the steel slag and an ethylenediamine derivative solution with an effective mass of 0.05% of the steel slag together, and pass through a 75 μm sieve to obtain activated steel slag powder; grind the activated steel slag powder with an effective mass of 0.1% of the activated steel slag powder, ethylenediaminetetraethanol, ethylenediamine Mix diethyl aminetetraacetate, diethanol monoisopropanolamine, and CaCl 2 composite solutions to obtain the product; wherein, the ethylenediamine derivatives are disodium ethylenediaminetetraacetate and ethylenediaminetetramethylenephosphine A mixture of acids in a mass ratio of 1:2, with a mass ratio of ethylenediaminetetraethanol, diethylethylenediaminetetraacetate, diethanolmonoisopropanolamine, and CaCl2 of 1:0.5:0.5:1.
对比例1Comparative example 1
将钢渣与钢渣有效质量0.05%的乙二胺衍生物溶液进行共同粉磨，过75μm筛，得钢渣活化粉；将钢渣活化粉与活化钢渣粉有效质量0.1%的乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2复合溶液混合，即得；其中，所述乙二胺衍生物为乙二胺四乙酸二钠，乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2质量比为1:0.5:0.5:1。Grind the steel slag and an ethylenediamine derivative solution with an effective mass of 0.05% of the steel slag together, and pass through a 75 μm sieve to obtain activated steel slag powder; grind the activated steel slag powder with an effective mass of 0.1% of the activated steel slag powder, ethylenediaminetetraethanol, ethylenediamine Diethyl aminetetraacetate, diethanol monoisopropanolamine, and CaCl 2 composite solutions are mixed to obtain; wherein, the ethylenediamine derivative is disodium ethylenediaminetetraacetate, ethylenediaminetetraethanol, ethylenediamine The mass ratio of diethyl amine tetraacetate, diethanol monoisopropanolamine, and CaCl2 is 1:0.5:0.5:1.
对比例2Comparative example 2
将钢渣与钢渣有效质量0.05%的乙二胺衍生物溶液进行共同粉磨，过75μm筛，得钢渣活化粉；将钢渣活化粉与活化钢渣粉有效质量0.1%的乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2复合溶液混合，即得；其中，所述乙二胺衍生物为乙二胺四亚甲基膦酸，乙二胺四乙醇、乙二胺四乙酸二乙酯、二乙醇单异丙醇胺、CaCl2质量比为1:0.5:0.5:1。Grind the steel slag and an ethylenediamine derivative solution with an effective mass of 0.05% of the steel slag together, and pass through a 75 μm sieve to obtain activated steel slag powder; grind the activated steel slag powder with an effective mass of 0.1% of the activated steel slag powder, ethylenediaminetetraethanol, ethylenediamine Diethyl amine tetraacetate, diethanol monoisopropanolamine, and CaCl 2 composite solutions are mixed to obtain; wherein, the ethylenediamine derivative is ethylenediamine tetramethylenephosphonic acid, ethylenediamine tetraethanol, The mass ratio of diethyl ethylenediaminetetraacetate, diethanol monoisopropanolamine, and CaCl2 is 1:0.5:0.5:1.
对比例3Comparative example 3
将钢渣与钢渣有效质量0.05%的三乙醇胺溶液进行共同粉磨，过75μm筛，得钢渣活化粉；将钢渣活化粉与活化钢渣粉有效质量0.1%的乙二胺四乙醇、二乙醇单异丙醇胺、CaCl2复合溶液混合，即得；其中乙二胺四乙醇、二乙醇单异丙醇胺、CaCl2质量比为1:0.5:1。Grind the steel slag and a triethanolamine solution with an effective mass of 0.05% of the steel slag together and pass through a 75 μm sieve to obtain activated steel slag powder; grind the activated steel slag powder with an effective mass of 0.1% ethylenediamine tetraethanol and diethyl monoisopropyl Mix the alcoholamine and CaCl 2 composite solutions to obtain; the mass ratio of ethylenediamine tetraethanol, diethanol monoisopropanolamine, and CaCl 2 is 1:0.5:1.
对比例4Comparative example 4
将钢渣与钢渣有效质量0.05%的乙二胺衍生物溶液进行共同粉磨，过75μm筛，得钢渣活化粉；将钢渣活化粉与活化钢渣粉有效质量0.1%的乙二胺四乙酸二乙酯、CaCl2复合溶液混合，即得；其中，所述乙二胺衍生物为乙二胺四乙酸二钠和乙二胺四亚甲基膦酸按质量比1:2的混合物，乙二胺四乙酸二乙酯、CaCl2质量比为1:2。Grind the steel slag and an ethylenediamine derivative solution with an effective mass of 0.05% of the steel slag together, and pass through a 75 μm sieve to obtain activated steel slag powder; grind the activated steel slag powder and diethyl ethylenediaminetetraacetate with an effective mass of 0.1% of the activated steel slag powder. , CaCl 2 composite solution is mixed to obtain; wherein, the ethylenediamine derivative is a mixture of disodium ethylenediaminetetraacetate and ethylenediaminetetramethylenephosphonic acid in a mass ratio of 1:2. The mass ratio of diethyl acetate to CaCl2 is 1:2.
对比例5Comparative example 5
将钢渣与钢渣有效质量0.05%的乙二胺衍生物溶液进行共同粉磨，过75μm筛，得钢渣活化粉；将钢渣活化粉与活化钢渣粉有效质量0.1%的乙二胺四乙醇、二乙醇单异丙醇胺复合溶液混合，即得；其中，所述乙二胺衍生物为乙二胺四乙酸二钠和乙二胺四亚甲基膦酸按质量比1:2的混合物，乙二胺四乙醇、二乙醇单异丙醇胺质量比为1:0.5。Grind the steel slag and an ethylenediamine derivative solution with an effective mass of 0.05% of the steel slag together, and pass through a 75 μm sieve to obtain activated steel slag powder; grind the activated steel slag powder with an effective mass of 0.1% ethylenediaminetetraethanol and diethanol to activate the steel slag powder. Mix the monoisopropanolamine composite solution to obtain; wherein, the ethylenediamine derivative is a mixture of disodium ethylenediaminetetraacetate and ethylenediaminetetramethylenephosphonic acid in a mass ratio of 1:2, The mass ratio of amine tetraethanol and diethanol monoisopropanolamine is 1:0.5.
经检测，结果如表2所示。After testing, the results are shown in Table 2.
表2 钢渣胶凝材料检测结果Table 2 Test results of steel slag cementitious materials
可见，本发明非碱类激发型钢渣胶凝材料制备方法对钢渣的强度提升效果明显，3d和7d最高分别提升4.3MPa和4.6Ma，28d提升效果也较好，最高提升6.3Ma，该方法表现出了良好的应用效果。It can be seen that the preparation method of the non-alkali excited steel slag cementitious material of the present invention has a significant effect on improving the strength of steel slag. The maximum improvement in 3d and 7d is 4.3MPa and 4.6Ma respectively. The improvement effect is also good in 28d, with the maximum improvement of 6.3Ma. This method shows Produced good application results.
最后应说明的是：以上各实施方式仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施方式对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施方式所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施方式技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: It is still possible to modify the technical solutions described in the foregoing embodiments, or to equivalently replace some or all of the technical features; and these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the technical solutions of the various embodiments of the present invention. scope.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5547252A (en) * | 1978-10-02 | 1980-04-03 | Chichibu Cement Kk | Manufacture of specific cement |
| SK500622012A3 (en) * | 2012-12-27 | 2014-07-02 | Považská Cementáreň, A.S. | Method for cement production and concrete mixture made by the method |
| KR20140127622A (en) * | 2013-04-25 | 2014-11-04 | 주식회사 에코마이스터 | Geopolymer using silicon manganese slag powder and the method of manufacturing the same |
| CN105776906A (en) * | 2016-03-18 | 2016-07-20 | 北京工业大学 | Additives capable of increasing slag activity |
| CN109574524A (en) * | 2018-09-28 | 2019-04-05 | 北京工业大学 | A kind of active method of raising steel slag early hydration |
| WO2020252563A1 (en) * | 2019-06-21 | 2020-12-24 | Hazelmere Research Ltd. | Admixture for cementitious mixtures |
| CN112919832A (en) * | 2021-04-01 | 2021-06-08 | 安徽马钢嘉华新型建材有限公司 | Modified grinding-aid early strength agent for steel slag and preparation method and application method thereof |
| CN113072311A (en) * | 2021-05-10 | 2021-07-06 | 南京工业大学 | Steel slag auxiliary cementing material and preparation method and application thereof |
| CN113979653A (en) * | 2021-12-01 | 2022-01-28 | 沈阳建筑大学 | Steel slag cementing material, preparation method and application |
| CN115872650A (en) * | 2022-12-31 | 2023-03-31 | 北京化工大学 | Preparation method of carbonized modified steel slag powder, carbonized modified steel slag powder and active admixture of cement-based cementitious material |
| CN115925306A (en) * | 2022-11-22 | 2023-04-07 | 河海大学 | A kind of dicalcium silicate activator and its preparation method and application |
| CN116535163A (en) * | 2023-05-09 | 2023-08-04 | 金隅冀东(唐山)混凝土环保科技集团有限公司 | Concrete blended with steel slag powder and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10131575B2 (en) * | 2017-01-10 | 2018-11-20 | Roman Cement, Llc | Use of quarry fines and/or limestone powder to reduce clinker content of cementitious compositions |
-
2023
- 2023-11-10 CN CN202311492343.XA patent/CN117229012B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5547252A (en) * | 1978-10-02 | 1980-04-03 | Chichibu Cement Kk | Manufacture of specific cement |
| SK500622012A3 (en) * | 2012-12-27 | 2014-07-02 | Považská Cementáreň, A.S. | Method for cement production and concrete mixture made by the method |
| KR20140127622A (en) * | 2013-04-25 | 2014-11-04 | 주식회사 에코마이스터 | Geopolymer using silicon manganese slag powder and the method of manufacturing the same |
| CN105776906A (en) * | 2016-03-18 | 2016-07-20 | 北京工业大学 | Additives capable of increasing slag activity |
| CN109574524A (en) * | 2018-09-28 | 2019-04-05 | 北京工业大学 | A kind of active method of raising steel slag early hydration |
| WO2020252563A1 (en) * | 2019-06-21 | 2020-12-24 | Hazelmere Research Ltd. | Admixture for cementitious mixtures |
| CN112919832A (en) * | 2021-04-01 | 2021-06-08 | 安徽马钢嘉华新型建材有限公司 | Modified grinding-aid early strength agent for steel slag and preparation method and application method thereof |
| CN113072311A (en) * | 2021-05-10 | 2021-07-06 | 南京工业大学 | Steel slag auxiliary cementing material and preparation method and application thereof |
| CN113979653A (en) * | 2021-12-01 | 2022-01-28 | 沈阳建筑大学 | Steel slag cementing material, preparation method and application |
| CN115925306A (en) * | 2022-11-22 | 2023-04-07 | 河海大学 | A kind of dicalcium silicate activator and its preparation method and application |
| CN115872650A (en) * | 2022-12-31 | 2023-03-31 | 北京化工大学 | Preparation method of carbonized modified steel slag powder, carbonized modified steel slag powder and active admixture of cement-based cementitious material |
| CN116535163A (en) * | 2023-05-09 | 2023-08-04 | 金隅冀东(唐山)混凝土环保科技集团有限公司 | Concrete blended with steel slag powder and preparation method thereof |
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