CN112939508B - A kind of carbide slag-based micro-expansion agent and preparation method thereof - Google Patents
A kind of carbide slag-based micro-expansion agent and preparation method thereof Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 77
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 33
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 29
- 229930006000 Sucrose Natural products 0.000 claims abstract description 29
- 239000005720 sucrose Substances 0.000 claims abstract description 27
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 22
- 239000004626 polylactic acid Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008961 swelling Effects 0.000 claims abstract description 5
- 239000003245 coal Substances 0.000 claims description 37
- 239000010881 fly ash Substances 0.000 claims description 22
- 239000010440 gypsum Substances 0.000 claims description 21
- 229910052602 gypsum Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 229960004793 sucrose Drugs 0.000 claims 8
- 238000007789 sealing Methods 0.000 claims 4
- 238000005507 spraying Methods 0.000 claims 3
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 238000007873 sieving Methods 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- 238000007605 air drying Methods 0.000 claims 1
- 238000000498 ball milling Methods 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000005997 Calcium carbide Substances 0.000 abstract description 29
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 abstract description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 17
- 238000006703 hydration reaction Methods 0.000 abstract description 16
- 230000036571 hydration Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 abstract description 8
- 239000004568 cement Substances 0.000 abstract description 8
- 229910001653 ettringite Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract 4
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002910 solid waste Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
-
- 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
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明的一种电石渣基微膨胀剂及其制备方法，该微膨胀剂含有CaO、活性Al2O3、硫酸钙，当掺加到水泥基胶凝材料中时，首先是Al2O3、硫酸钙与CaOH发生反应生成具有微膨胀性的钙矾石，使胶凝材料在前期具有微膨胀性；之后是CaO外部包裹的聚乳酸在碱性环境下降解，CaO与水发生反应生成具有微膨胀性的CaOH，使得胶凝材料体系具有更持续的膨胀性；聚乳酸是一种高分子聚合物，它在碱性环境下降解，它在膨胀剂中起到了延迟CaO发生水化的作用，蔗糖具有调节水化的作用，在聚乳酸和蔗糖的复合调节作用下使得胶凝材料体系具有较好的微膨胀性。The invention provides a calcium carbide slag-based micro-expansion agent and a preparation method thereof. The micro-expansion agent contains CaO, active Al 2 O 3 and calcium sulfate. When mixed into the cement-based cementitious material, the micro expansion agent is Al 2 O 3 first. , Calcium sulfate reacts with CaOH to form ettringite with slight expansion, which makes the cementitious material have slight expansion in the early stage; after that, the polylactic acid wrapped by CaO is degraded in an alkaline environment, and the reaction between CaO and water generates a The slightly swellable CaOH makes the cementitious material system have more continuous swelling; PLA is a high molecular polymer, it degrades in an alkaline environment, and it plays a role in delaying the hydration of CaO in the swelling agent , sucrose has the effect of regulating hydration, and under the compound regulation of polylactic acid and sucrose, the gelling material system has better micro-expansion.
Description
技术领域technical field
本发明属于土木工程材料领域，尤其涉及一种电石渣基微膨胀剂及其制备方法。The invention belongs to the field of civil engineering materials, in particular to a calcium carbide slag-based micro-expansion agent and a preparation method thereof.
背景技术Background technique
现有膨胀剂有许多品种，大多数品种以钙矾石为膨胀源，属于硫铝酸钙类膨胀剂，不具有持续的微膨胀性，而且采用高品位的矿物原料、生产工艺技术复杂和高温煅烧难度较大等原因，生产成本普遍较高。There are many varieties of existing expansion agents, most of which use ettringite as the expansion source, belong to calcium sulfoaluminate type expansion agents, do not have continuous micro-expansion, and use high-grade mineral raw materials, complex production technology and high temperature. Due to the difficulty of calcination and other reasons, the production cost is generally high.
本发明的电石渣基微膨胀剂具有较为持续的膨胀效果，用于水泥基胶凝材料(含混凝土)，在凝结硬化过程中可产生微膨胀，补偿收缩。The calcium carbide slag-based micro-expansion agent of the present invention has a relatively continuous expansion effect, is used for cement-based cementitious materials (including concrete), and can generate micro-expansion in the process of setting and hardening to compensate for shrinkage.
发明内容SUMMARY OF THE INVENTION
本发明目的在于提供一种电石渣基微膨胀剂及其制备方法,以解决现有膨胀剂不具有较为持续的膨胀性的技术问题。The purpose of the present invention is to provide a calcium carbide slag-based micro-expansion agent and a preparation method thereof, so as to solve the technical problem that the existing expansion agent does not have relatively continuous expansion.
为解决上述技术问题，本发明的具体技术方案如下：For solving the above-mentioned technical problems, the concrete technical scheme of the present invention is as follows:
电石渣基微膨胀剂，包括如下重量份的原料：Carbide slag-based micro-expansion agent, including the following raw materials by weight:
电石渣733份，煤矸石131份，粉煤灰91份，脱硫石膏30份，蔗糖5份，聚乳酸10份。733 parts of calcium carbide slag, 131 parts of coal gangue, 91 parts of fly ash, 30 parts of desulfurized gypsum, 5 parts of sucrose, and 10 parts of polylactic acid.
进一步，所述电石渣、煤矸石、粉煤灰、脱硫石膏过200目方孔筛，筛余量小于5％。Further, the calcium carbide slag, coal gangue, fly ash, and desulfurization gypsum are passed through a 200-mesh square-hole sieve, and the sieve balance is less than 5%.
进一步，所述电石渣为乌兰察布市所产电石渣；所述煤矸石为鄂尔多斯地区所产高铝煤矸石；所述粉煤灰为鄂尔多斯地区所产固废；所述脱硫石膏为鄂尔多斯地区电厂所产固废。Further, the calcium carbide slag is calcium carbide slag produced in Ulanqab City; the coal gangue is high-alumina coal gangue produced in the Ordos region; the fly ash is solid waste produced in the Ordos region; the desulfurized gypsum is the Ordos region Solid waste produced by regional power plants.
进一步，所述电石渣中CaO含量为69％，烧失量为30％，所述煤矸石中Al2O3和SiO2含量为82％，烧失量为17％；所述粉煤灰Al2O3和SiO2含量为60％，烧失量为35％；所述脱硫石膏中SO3含量为54％；蔗糖主要成分为C12H22O11纯度为99.4％。Further, the content of CaO in the calcium carbide slag is 69%, the loss on ignition is 30%, the content of Al 2 O 3 and SiO 2 in the coal gangue is 82%, and the loss on ignition is 17%; the fly ash Al The content of 2 O 3 and SiO 2 is 60%, and the loss on ignition is 35%; the content of SO 3 in the desulfurized gypsum is 54%; the main component of sucrose is C 12 H 22 O 11 , and the purity is 99.4%.
当膨胀剂加入到水泥基材料中时，CaO、CaSO4、Al2O3、SiO2和水泥水化所产生的CaOH会发生以下化学反应：When the expansion agent is added to the cement-based material, the following chemical reactions occur between CaO, CaSO 4 , Al 2 O 3 , SiO 2 and CaOH produced by cement hydration:
[反应式1][Reaction 1]
CaO+H2O→2CaOHCaO+H 2 O→2CaOH
[反应式2][Reaction 2]
Al2O3+3Ca(OH)2+3CaSO4+29H2O→3(CaO·Al2O3·3CaSO4·32H2O)Al 2 O 3 +3Ca(OH) 2 +3CaSO 4 +29H 2 O→3(CaO·Al 2 O 3 ·3CaSO 4 ·32H 2 O)
电石渣主要提供CaO，是膨胀剂的主要成分，它与水发生反应生成具有膨胀性的CaOH；煤矸石主要提供Al2O3，煤矸石在经过高温活化后，其中所含的具有活性的Al2O3会与CaSO4以及CaOH发生反应生成具有膨胀性的钙矾石；粉煤灰主要提供Al2O3，在水化过程中它不但可以生成具有微膨胀性的钙矾石，而且它在胶凝材料中起到微集料效应，提高胶凝材料体系的密实性；脱硫石膏主要提供CaSO4，在碱激发过程中可以与Al2O3、Ca(OH)2、H2O发生反应生成具有膨胀性的钙矾石；蔗糖要作用是调控电石渣的水化速度，防止水化过快导致体系出现微裂缝而影响其强度；聚乳酸主要作用是延迟CaO水化的时间，防止CaO在水化初期就发生剧烈水化反应生成大量具有膨胀性的Ca(OH)2。Carbide slag mainly provides CaO, which is the main component of the expansion agent, which reacts with water to form CaOH with expansion; coal gangue mainly provides Al 2 O 3 . After the coal gangue is activated at high temperature, the active Al contained in it 2 O 3 will react with CaSO 4 and CaOH to form ettringite with swellability; fly ash mainly provides Al 2 O 3 , which can not only generate ettringite with slight swelling during the hydration process, but also It plays a micro-aggregate effect in the cementitious material and improves the compactness of the cementitious material system; the desulfurized gypsum mainly provides CaSO 4 , which can interact with Al 2 O 3 , Ca(OH) 2 and H 2 O during the alkali excitation process. The reaction generates ettringite with swellability; the main function of sucrose is to regulate the hydration speed of carbide slag, and prevent the system from micro-cracks and affect its strength due to excessive hydration; the main function of polylactic acid is to delay the hydration time of CaO, prevent In the early stage of hydration, CaO undergoes violent hydration reaction to generate a large amount of swellable Ca(OH) 2 .
电石渣基微膨胀剂的制备方法，包括以下步骤：The preparation method of carbide slag-based micro-expansion agent comprises the following steps:
(1)制备微膨胀剂所需材料配比为：电石渣733份、煤矸石131份、粉煤灰91份、脱硫石膏30份、蔗糖5份，聚乳酸10份。(1) The proportion of materials required for preparing the micro-expansion agent is: 733 parts of calcium carbide slag, 131 parts of coal gangue, 91 parts of fly ash, 30 parts of desulfurized gypsum, 5 parts of sucrose, and 10 parts of polylactic acid.
(2)材料预处理：利用行星球磨机对电石渣、煤矸石进行球磨，过200目方孔筛，筛余量＜5％；粉煤灰过200目方孔筛，筛余量＜5％；脱硫石膏过325目方孔筛，筛余量＜5％；将上述材料置于鼓风干燥箱中烘干24h,烘干温度为105℃，密封保存备用。(2) Material pretreatment: use a planetary ball mill to ball mill carbide slag and coal gangue, pass through a 200-mesh square-hole sieve, and the sieve balance is less than 5%; fly ash is passed through a 200-mesh square-hole sieve, and the sieve balance is less than 5%; Desulfurized gypsum was passed through a 325 mesh square-hole sieve, and the sieve balance was less than 5%; the above materials were dried in a blast drying oven for 24 hours at a drying temperature of 105°C, and sealed for later use.
(3)电石渣煅烧：将预处理的电石渣置于高温炉内，并以5℃/min的升温速率将炉温升至910℃，在910℃下煅烧60min，然后将电石渣取出，在空气中冷却至室温，密封保存防止受潮。(3) Carbide slag calcination: place the pretreated carbide slag in a high-temperature furnace, raise the furnace temperature to 910°C at a heating rate of 5°C/min, calcinate at 910°C for 60 minutes, then take out the carbide slag, Cool to room temperature in the air, and store in an airtight container to prevent moisture.
(4)煤矸石煅烧：将预处理的煤矸石置于高温炉中，以5℃/min的升温速率将炉温升至800℃并保温煅烧60min，然后将煤矸石取出，在空气中冷却至室温，密封保存。(4) Coal gangue calcination: place the pretreated coal gangue in a high-temperature furnace, raise the furnace temperature to 800°C at a heating rate of 5°C/min and keep calcined for 60 minutes, then take out the coal gangue and cool it in air to Room temperature, sealed and stored.
(5)将蔗糖与水以1:2的配比进行混合，充分搅拌将蔗糖溶解。然后将电石渣置于混合搅拌其中，混合搅拌器的参数为：容器φ120cm,旋转次数为300次/min，旋转行程为100mm，振动次数为150次/min，震动高度为40mm；电石渣置于混合搅拌器后将蔗糖溶液以喷雾的形式均匀的洒在电石渣上，使电石渣与蔗糖溶液充分混合，使蔗糖溶液充分地将电石渣包裹；将混合好的电石渣置于鼓风干燥箱中进行烘干备用。(5) Mix sucrose and water in a ratio of 1:2, and stir well to dissolve the sucrose. Then the carbide slag is placed in the mixing and stirring, and the parameters of the mixing mixer are: the container is φ120cm, the number of rotations is 300 times/min, the rotation stroke is 100mm, the number of vibrations is 150 times/min, and the vibration height is 40mm; After mixing the mixer, evenly sprinkle the sucrose solution on the calcium carbide slag in the form of spray, so that the calcium carbide slag and the sucrose solution are fully mixed, so that the sucrose solution fully wraps the calcium carbide slag; the mixed calcium carbide slag is placed in a blast drying oven Drying in reserve.
(6)将聚乳酸溶于二氯甲烷中，配比为1:4；将上述经过裹糖的电石渣置于混合搅拌器中，搅拌器参数为：容器φ120cm,旋转次数为300次/min，旋转行程为100mm，振动次数为150次/min，震动高度为40mm；然后以雾化形式将聚乳酸溶液均匀的喷洒在电石渣上，使聚乳酸对电石渣进行充分地包裹，利用旋转蒸发仪器于50℃下对二氯甲烷进行真空去除；将制备好的电石渣进行密封存放，防止受潮。(6) dissolving polylactic acid in methylene chloride, the ratio is 1:4; the above-mentioned sugar-coated carbide slag is placed in a mixing mixer, and the mixer parameters are: the container is φ120cm, and the number of rotations is 300 times/min , the rotation stroke is 100mm, the number of vibrations is 150 times/min, and the vibration height is 40mm; then the polylactic acid solution is evenly sprayed on the calcium carbide slag in the form of atomization, so that the polylactic acid can fully wrap the calcium carbide slag, using rotary evaporation The instrument removes dichloromethane under vacuum at 50 °C; the prepared carbide slag is sealed and stored to prevent moisture.
(7)膨胀剂的制备：将上述制备好的电石渣与煤矸石、粉煤灰、脱硫石膏以733∶131∶91∶30的配比进行混合，再将混合材料置于物料混合搅拌机中进行充分混合，即制得膨胀剂。(7) Preparation of expansion agent: the calcium carbide slag prepared above is mixed with coal gangue, fly ash, and desulfurized gypsum in a ratio of 733:131:91:30, and then the mixed material is placed in a material mixing mixer to carry out Mix well, that is, make the expansion agent.
本发明的一种电石渣基微膨胀剂及其制备方法，具有以下优点：A calcium carbide slag-based micro-expanding agent and a preparation method thereof of the present invention have the following advantages:
(1)具有微膨胀功能(1) with micro-expansion function
本发明用于水泥基胶凝材料(含混凝土)时具有较好的微膨胀性，在聚乳酸和蔗糖的复合调控作用下，可使微膨胀剂在水泥基胶凝材料(含混凝土)凝结硬化过程中具有较为持续的膨胀性。The present invention has better micro-expansion when used in cement-based cementitious materials (including concrete), and under the compound control action of polylactic acid and sucrose, the micro-expansion agent can be coagulated and hardened on cement-based cementitious materials (including concrete). During the process, it has a relatively continuous expansion.
(2)造价低廉(2) low cost
用于该发明的主要材料是固废，和传统膨胀剂相比，该发明具有原料易得、造价低廉等优点。The main material used in the invention is solid waste. Compared with the traditional expansion agent, the invention has the advantages of easy availability of raw materials and low cost.
(3)有效利用固废(3) Effective use of solid waste
该发明所使用的主要材料为电石渣、煤矸石、粉煤灰等工业固废，其固废使用占比可达到98％，对固废的有效利用不但可以减低产品的造价，而且还有可以效解决工业固废污染大气、土资源、水资源等一系列问题。The main materials used in the invention are industrial solid wastes such as calcium carbide slag, coal gangue, and fly ash, and the proportion of solid waste used can reach 98%. The effective use of solid waste can not only reduce the cost of products, but also can Effectively solve a series of problems such as industrial solid waste polluting the air, soil resources, and water resources.
具体实施方式Detailed ways
为了更好地了解本发明，下面对本发明一种电石渣基微膨胀剂及其制备方法做进一步详细的描述。In order to better understand the present invention, a calcium carbide slag-based micro-expansion agent of the present invention and a preparation method thereof will be described in further detail below.
制备1000g电石渣基微膨胀剂，所需的材料及配比如下：To prepare 1000g calcium carbide slag-based micro-expansion agent, the required materials and proportions are as follows:
电石渣733g，煤矸石131g，粉煤灰91g，脱硫石膏30g，蔗糖5g，聚乳酸10g。Carbide slag 733g, coal gangue 131g, fly ash 91g, desulfurization gypsum 30g, sucrose 5g, polylactic acid 10g.
电石渣、煤矸石、粉煤灰、脱硫石膏过200目方孔筛，筛余量小于5％。Carbide slag, coal gangue, fly ash, and desulfurization gypsum pass through a 200-mesh square-hole sieve, and the sieve balance is less than 5%.
电石渣为乌兰察布市所产电石渣；所述煤矸石为鄂尔多斯地区所产高铝煤矸石；所述粉煤灰为鄂尔多斯地区所产固废；所述脱硫石膏为鄂尔多斯地区电厂所产固废。Carbide slag is calcium carbide slag produced in Ulanqab City; the coal gangue is high-alumina coal gangue produced in Ordos area; the fly ash is solid waste produced in Ordos area; the desulfurization gypsum is produced by power plants in Ordos area solid waste.
电石渣中CaO含量为69％，烧失量为30％，所述煤矸石中Al2O3和SiO2含量为82％，烧失量为17％；所述粉煤灰Al2O3和SiO2含量为60％，烧失量为35％；所述脱硫石膏中SO3含量为54％；蔗糖主要成分为C12H22O11纯度为99.4％；聚乳酸摩尔质量为10000g。The CaO content in the carbide slag is 69%, and the loss on ignition is 30%; the content of Al 2 O 3 and SiO 2 in the coal gangue is 82%, and the loss on ignition is 17%; the fly ash Al 2 O 3 and The content of SiO 2 is 60%, the loss on ignition is 35%; the content of SO 3 in the desulfurized gypsum is 54%; the main component of sucrose is C 12 H 22 O 11 , the purity is 99.4%; the molar mass of polylactic acid is 10000g.
当膨胀剂加入到水泥基材料中时，CaO、CaSO4、Al2O3、SiO2和水泥水化所产生的CaOH会发生以下化学反应：When the expansion agent is added to the cement-based material, the following chemical reactions occur between CaO, CaSO 4 , Al 2 O 3 , SiO 2 and CaOH produced by cement hydration:
[反应式1][Reaction 1]
CaO+H2O→2CaOHCaO+H 2 O→2CaOH
[反应式2][Reaction 2]
Al2O3+3Ca(OH)2+3CaSO4+29H2O→3(CaO·Al2O3·3CaSO4·32H2O)Al 2 O 3 +3Ca(OH) 2 +3CaSO 4 +29H 2 O→3(CaO·Al 2 O 3 ·3CaSO 4 ·32H 2 O)
电石渣主要提供CaO，是膨胀剂的主要成分，它与水发生反应生成具有膨胀性的CaOH；煤矸石主要提供Al2O3，煤矸石在经过高温活化后，其中所含的具有活性的Al2O3会与CaSO4以及CaOH发生反应生成具有膨胀性的钙矾石；粉煤灰主要提供Al2O3，在水化过程中它不但可以生成具有微膨胀性的钙矾石，而且它在胶凝材料中起到微集料效应，提高胶凝材料体系的密实性；脱硫石膏主要提供CaSO4，在碱激发过程中可以与Al2O3、Ca(OH)2、H2O发生反应生成具有膨胀性的钙矾石；蔗糖要作用是调控电石渣的水化速度，防止水化过快导致体系出现微裂缝而影响其强度；聚乳酸主要作用是延迟CaO水化的时间，防止CaO在水化初期就发生剧烈水化反应生成大量具有膨胀性的Ca(OH)2。Carbide slag mainly provides CaO, which is the main component of the expansion agent, which reacts with water to form CaOH with expansion; coal gangue mainly provides Al 2 O 3 . After the coal gangue is activated at high temperature, the active Al contained in it 2 O 3 will react with CaSO 4 and CaOH to form ettringite with swellability; fly ash mainly provides Al 2 O 3 , which can not only generate ettringite with slight swelling during the hydration process, but also It plays a micro-aggregate effect in the cementitious material and improves the compactness of the cementitious material system; the desulfurized gypsum mainly provides CaSO 4 , which can interact with Al 2 O 3 , Ca(OH) 2 and H 2 O during the alkali excitation process. The reaction generates ettringite with swellability; the main function of sucrose is to regulate the hydration speed of carbide slag, and prevent the system from micro-cracks and affect its strength due to excessive hydration; the main function of polylactic acid is to delay the hydration time of CaO, prevent In the early stage of hydration, CaO undergoes violent hydration reaction to generate a large amount of swellable Ca(OH) 2 .
电石渣基微膨胀剂的制备方法，包括以下步骤：The preparation method of carbide slag-based micro-expansion agent comprises the following steps:
(1)制备微膨胀剂所需材料配比为：电石渣733g，煤矸石131g，粉煤灰91g，脱硫石膏30g，蔗糖5g，聚乳酸10g。(1) The ratio of materials required for preparing the micro-expansion agent is: 733g of carbide slag, 131g of coal gangue, 91g of fly ash, 30g of desulfurized gypsum, 5g of sucrose, and 10g of polylactic acid.
(2)材料预处理：利用行星球磨机对电石渣、煤矸石进行球磨，过200目方孔筛，筛余量＜5％；粉煤灰过200目方孔筛，筛余量＜5％；脱硫石膏过200目方孔筛，筛余量＜5％；将上述材料置于鼓风干燥箱中烘干24h,烘干温度为105℃，密封保存备用。(2) Material pretreatment: use a planetary ball mill to ball mill carbide slag and coal gangue, pass through a 200-mesh square-hole sieve, and the sieve balance is less than 5%; fly ash is passed through a 200-mesh square-hole sieve, and the sieve balance is less than 5%; The desulfurized gypsum was passed through a 200-mesh square-hole sieve, and the sieve balance was less than 5%; the above materials were dried in a blast drying oven for 24 hours at a drying temperature of 105°C, and sealed for future use.
(3)电石渣煅烧：将预处理的电石渣置于高温炉内，并以5℃/min的升温速率将炉温升至910℃，在910℃下煅烧60min，然后将电石渣取出，在空气中冷却至室温，密封保存防止受潮。(3) Carbide slag calcination: place the pretreated carbide slag in a high-temperature furnace, raise the furnace temperature to 910°C at a heating rate of 5°C/min, calcinate at 910°C for 60 minutes, then take out the carbide slag, Cool to room temperature in the air, and store in an airtight container to prevent moisture.
(4)煤矸石煅烧：将预处理的煤矸石置于高温炉中，以5℃/min的升温速率将炉温升至800℃并保温煅烧60min，然后将煤矸石取出，在空气中冷却至室温，密封保存。(4) Coal gangue calcination: place the pretreated coal gangue in a high-temperature furnace, raise the furnace temperature to 800°C at a heating rate of 5°C/min and keep calcined for 60 minutes, then take out the coal gangue and cool it in the air to Room temperature, sealed and stored.
(5)将蔗糖与水以1:2的配比进行混合，充分搅拌将蔗糖溶解。然后将电石渣置于混合搅拌其中，混合搅拌器的参数为：容器φ120cm,旋转次数为300次/min，旋转行程为100mm，振动次数为150次/min，震动高度为40mm；电石渣置于混合搅拌器后将蔗糖溶液以喷雾的形式均匀的洒在电石渣上，使电石渣与蔗糖溶液充分混合，使蔗糖溶液充分地将电石渣包裹；将混合好的电石渣置于鼓风干燥箱中进行烘干备用。(5) Mix sucrose and water in a ratio of 1:2, and stir well to dissolve the sucrose. Then the carbide slag is placed in the mixing and stirring, and the parameters of the mixing mixer are: the container is φ120cm, the number of rotations is 300 times/min, the rotation stroke is 100mm, the number of vibrations is 150 times/min, and the vibration height is 40mm; After mixing the mixer, evenly sprinkle the sucrose solution on the calcium carbide slag in the form of spray, so that the calcium carbide slag and the sucrose solution are fully mixed, so that the sucrose solution fully wraps the calcium carbide slag; the mixed calcium carbide slag is placed in a blast drying oven Drying in reserve.
(6)将聚乳酸溶于二氯甲烷中，配比为1:4；将上述经过裹糖的电石渣置于混合搅拌器中，搅拌器参数为：容器φ120cm,旋转次数为300次/min，旋转行程为100mm，振动次数为150次/min，震动高度为40mm；然后以雾化形式将聚乳酸溶液均匀的喷洒在电石渣上，使聚乳酸对电石渣进行充分地包裹，利用旋转蒸发仪器于50℃下对二氯甲烷进行真空去除；将制备好的电石渣进行密封存放，防止受潮。(6) dissolving polylactic acid in methylene chloride, the ratio is 1:4; the above-mentioned sugar-coated carbide slag is placed in a mixing mixer, and the mixer parameters are: the container is φ120cm, and the number of rotations is 300 times/min , the rotation stroke is 100mm, the number of vibrations is 150 times/min, and the vibration height is 40mm; then the polylactic acid solution is evenly sprayed on the calcium carbide slag in the form of atomization, so that the polylactic acid can fully wrap the calcium carbide slag, using rotary evaporation The instrument removes dichloromethane under vacuum at 50 °C; the prepared carbide slag is sealed and stored to prevent moisture.
(7)膨胀剂的制备：将上述制备好的电石渣与煤矸石、粉煤灰、脱硫石膏以733∶131∶91∶30的配比进行混合，再将混合材料置于物料混合搅拌机中进行充分混合，即制得膨胀剂。(7) Preparation of expansion agent: the calcium carbide slag prepared above is mixed with coal gangue, fly ash, and desulfurized gypsum in a ratio of 733:131:91:30, and then the mixed material is placed in a material mixing mixer to carry out Mix well, that is, make the expansion agent.
可以理解，本发明是通过一些实施例进行描述的，本领域技术人员知悉的，在不脱离本发明的精神和范围的情况下，可以对这些特征和实施例进行各种改变或等效替换。另外，在本发明的教导下，可以对这些特征和实施例进行修改以适应具体的情况及材料而不会脱离本发明的精神和范围。因此，本发明不受此处所公开的具体实施例的限制，所有落入本申请的权利要求范围内的实施例都属于本发明所保护的范围内。It can be understood that the present invention is described by some embodiments, and those skilled in the art know that various changes or equivalent substitutions can be made to these features and embodiments without departing from the spirit and scope of the present invention. In addition, in the teachings of this invention, these features and embodiments may be modified to adapt a particular situation and material without departing from the spirit and scope of the invention. Therefore, the present invention is not limited by the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of the present application fall within the protection scope of the present invention.
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