阅读说明：本技术 含垃圾焚烧飞灰和钢渣矿渣的胶凝材料及制备方法和应用 (Cementing material containing waste incineration fly ash and steel slag and slag, preparation method and application ) 是由 倪文 张思奇 王珂 王莹 李佳 王一杰 史腾宇 于 2019-10-28 设计创作，主要内容包括：本发明涉及一种含垃圾焚烧飞灰和钢渣矿渣的胶凝材料及制备方法和应用。一种含垃圾焚烧飞灰和钢渣矿渣的胶凝材料,主要由以下成分组成：按重量份计,S95矿渣0-60份,高铝钢渣0-60份,垃圾焚烧飞灰20～40份,脱硫石膏7～13份。混凝土或充填料中胶凝材料与骨料之比为1:4-1:8,浓度77％。本发明掺杂了大量的垃圾焚烧飞灰,并且无需添加激发剂、早强剂等外加剂即可显示出良好的可工业应用的抗压强度,既可用作混凝土的胶结料,又可用于采矿充填料,是水泥的良好替代品。(The invention relates to a cementing material containing waste incineration fly ash and steel slag and slag, a preparation method and application thereof. A cementing material containing waste incineration fly ash and steel slag and slag mainly comprises the following components: 0-60 parts of S95 slag, 0-60 parts of high-aluminum steel slag, 20-40 parts of waste incineration fly ash and 7-13 parts of desulfurized gypsum. The ratio of the cementing material to the aggregate in the concrete or the filling material is 1:4-1:8, and the concentration is 77%. The invention is doped with a large amount of waste incineration fly ash, and can show good compression strength capable of being industrially applied without adding additives such as excitant, early strength agent and the like, thereby being used as cementing material of concrete, mining filling material and good substitute of cement.)

1. The cementing material containing waste incineration fly ash and steel slag and slag is characterized by mainly comprising the following components:

0-60 parts of S95 slag, 5-60 parts of high-aluminum steel slag, 20-40 parts of waste incineration fly ash and 7-13 parts of desulfurized gypsum.

2. The cementing material of claim 1, wherein the cementing material comprises, by weight, 20-60 parts of S95 slag, 20-60 parts of high-alumina steel slag, 20-40 parts of waste incineration fly ash, and 9-11 parts of desulfurized gypsum.

3. The cementitious material of claim 1, wherein the waste incineration fly ash consists essentially of: 32-42 parts of CaO, 15-28 parts of Cl and SiO by weight₂2-6 parts of Al₂O₃1-4 parts, K₂3-7 parts of O, 3-7 parts of MgO and Na₂O3-7 parts, Fe₂O₃1-3 parts.

4. The cementitious material according to claim 1, characterised in that the high-aluminium steel slag consists essentially of: 50-55 parts of CaO and SiO by weight₂1-2 parts of Al₂O₃35-40 parts of MgO 4-6 parts of SO₃1-2 parts.

5. Cement according to claim 1, characterised in that the S95 slag consists essentially of: 45-50 parts of CaO and SiO by weight₂28-32 parts of Al₂O₃10-14 parts of MgO5-7 parts of Fe₂O₃1-2 parts of SO₃0-1 part.

6. Cement according to claim 1, characterised in that the desulfurized gypsum consists essentially of: 45-50 parts of CaO and SiO by weight₂2-3 parts of Al₂O₃0-1 part of MgO, 1-2 parts of SO₃40-46 parts of Cl and 0-1 part of Cl.

7. Cement according to claim 1, characterised in that said S95The specific surface area of the slag was 500m²More than kg;

preferably, the specific surface area of the desulfurized gypsum is 400m²More than kg;

preferably, the specific surface area of the high-aluminum steel slag is 400m²More than kg.

8. A method for preparing a cementitious material as claimed in any one of claims 1 to 7, characterised in that it comprises the following steps:

uniformly mixing all the raw materials with water according to the water-to-glue ratio of 0.4-0.5: 1;

preferably, the waste incineration fly ash is prepared by adopting a grate furnace incineration technology.

9. Use of the cementitious material according to any one of claims 1 to 7 for making concrete or cementitious fillers.

10. A concrete or cementitious filler comprising aggregate and a cementitious material according to any one of claims 1 to 7; the mass ratio of the cementing material to the aggregate is 1:4-1:8, the concentration of the concrete or the cementing filler is 77 wt%, and the water-cement ratio of the cementing material is 0.35-0.45: 1;

preferably, the aggregate consists essentially of:

10-15 parts of CaO and SiO by weight₂50-60 parts of Al₂O₃6-12 parts of MgO 2-7 parts of Fe₂O₃6-12 parts of SO₃1-3 parts of Na₂O1-3 parts, K₂1-3 parts of O;

preferably, the particle size of the aggregate is mainly distributed between 4 and 120 mu m, wherein D10 is 4.0 to 7.0 mu m, D50 is 32 to 36 mu m, D90 is 110-115 mu m, and the content of less than 20 mu m accounts for more than 30 weight percent.

Technical Field

The invention relates to the field of building materials, in particular to a cementing material containing waste incineration fly ash and steel slag and slag, a preparation method and application thereof.

Background

According to statistics of research institute of E20, 257 operating waste incineration power plants are built nationwide in 2015, the total quantity of waste incineration in China is 6811 ten thousand tons, and according to national records of hazardous wastes, fly ash (hereinafter, fly ash) generated in the waste incineration process belongs to hazardous wastes and is about 3% -5% of the quantity of incineration waste, the generation quantity of the fly ash reaches 395 ten thousand tons, nearly 300 waste incineration power plants are built in 2016, and the fly ash reaches over 1000 ten thousand tons per year to the end of 2020. In the face of such huge annual output of waste incineration fly ash, the search for a reasonable green disposal method is urgent, and how to maximize the utilization of the hazardous waste such as fly ash becomes a hot content of the research in the hazardous waste disposal field of the present time. The slag, the steel slag and the desulfurized gypsum are utilized to prepare the full-solid waste cementing material by utilizing the waste incineration fly ash in a synergistic manner, so that the problems of reduction, harmlessness and resource utilization of industrial solid waste (steel slag) and urban hazardous waste (waste incineration fly ash) can be solved, the synergistic utilization of the solid waste and the hazardous waste and environmental protection are promoted, the cementing material is provided for large-scale replacement of cement solidification stabilization safety landfill or preliminary combination of a cementing filling mining technology, and the engineering application foundation is laid. However, the existing cementing material containing waste incineration fly ash has the following problems: the strength with practical value can be achieved only by adding excessive additives such as excitant, early strength agent and the like.

Disclosure of Invention

The invention aims to provide a cementing material containing waste incineration fly ash and steel slag, which is doped with a large amount of waste incineration fly ash, can show good compression strength capable of being industrially applied without adding additives such as an excitant, an early strength agent and the like, can be used as a cementing material of concrete and a mining filling material by matching with a proper aggregate, and is a good substitute of cement.

In order to achieve the above purpose, the invention provides the following technical scheme:

a cementing material containing waste incineration fly ash and steel slag and slag mainly comprises the following components:

0-60 parts of S95 slag, 5-60 parts of high-aluminum steel slag, 20-40 parts of waste incineration fly ash and 7-13 parts of desulfurized gypsum.

The cementing material has at least the following characteristics:

firstly, compared with the existing cementing material containing waste incineration fly ash and steel slag, the cementing material disclosed by the invention is simpler in composition, does not need to add additives such as an exciting agent and an early strength agent, and consists of S95 slag, high-aluminum steel slag, waste incineration fly ash and desulfurized gypsum, so that the raw material cost is greatly reduced, and the utilization rate of the waste incineration fly ash is higher.

Secondly, the composition is simplified, and simultaneously, good cementing performance can be displayed due to the synergistic effect, including compressive strength and effective solidification to various heavy metals in the fly ash. The cement paste is prepared into a neat paste test block according to GB17671-1999 cement mortar strength test method with the water-cement ratio of 0.3:1, the test block has the size of 30mm multiplied by 50mm, and the curing is carried out at the temperature of 35 ℃ and the humidity of more than 99.5 percent, thus showing good compression strength and leaching safety performance.

Thirdly, the safety is high: the adopted waste incineration fly ash has good safety, and the leaching concentration of heavy metal ions (Cr, Cu, Zn, Cd, Sb, Hg, Pb and the like) is all lower than the drinking water standard for a long time (360 d); in addition, the slag and the desulfurized gypsum have certain solidification effect on chloride ions in the fly ash, and the corrosion to other building materials such as reinforcing steel bars is avoided.

In conclusion, the cementing material of the invention utilizes slag to replace the traditional cementing agent cement, utilizes high-aluminum steel slag to fully stimulate the slag activity, and utilizes the waste incineration fly ash to prepare the all-solid-waste cementing material, so that the waste incineration fly ash is utilized as resources to the maximum extent, the better doping amount of the waste incineration fly ash in the all-solid-waste cementing system is provided, the leaching concentration of heavy metal ions in the system is still lower than the drinking water standard in short-term and long-term leaching toxicity (horizontal oscillation method), thereby solving the problems of reduction, harmlessness and resource utilization of industrial solid wastes (steel slag and slag) and urban hazardous wastes (waste incineration fly ash), promoting the synergistic utilization of the solid wastes and the hazardous wastes and environmental protection, and providing the cementing material for replacing cement solidification stabilization safety landfill in a large scale, preliminarily combining with a cementing and filling mining technology or preparing concrete for buildings, and laying the foundation of engineering application.

The S95 slag according to the present invention refers to any slag having a 28d reactivity index of not less than 95%.

The main component of the high-aluminum steel slag is mayenite (12CaO 7 Al)₂O₃) The active component content is higher, and the slag activity can be fully stimulated.

The waste incineration fly ash of the invention refers to bottom ash generated in the incineration disposal process of domestic waste or industrial waste, and does not limit the source or type of waste.

The main component of the desulfurized gypsum of the invention is similar to natural gypsum and is calcium sulfate dihydrate CaSO₄·2H₂O。

The invention also optimizes the proportion and the chemical composition of each component on the basis of the formula, so as to improve the gelling property to a greater extent or reduce the industrial cost.

Preferably, the cement containing waste incineration fly ash and steel slag consists of only the four components of S95 slag, high alumina steel slag, waste incineration fly ash and desulfurized gypsum, and each of the components may take any value within the above range, as described above. For example, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, etc. of waste incineration fly ash can be taken. The S95 slag may be taken as 10 parts, 20 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, etc. The desulfurized gypsum can be taken by 7 parts, 9 parts, 10 parts, 11 parts, 12 parts and the like. The high-aluminum steel slag can be 10 parts, 20 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts and the like.

Preferably, the cementitious material containing waste incineration fly ash and steel slag consists essentially of:

0-60% of S95 slag, 5-60% of high-aluminum steel slag, 20-40% of waste incineration fly ash and 7-13% of desulfurized gypsum by weight percentage.

Preferably, the cementitious material containing waste incineration fly ash and steel slag consists essentially of:

the composite material comprises, by weight, 20-60 parts of S95 slag, 20-60 parts of high-aluminum steel slag, 20-40 parts of waste incineration fly ash and 9-11 parts of desulfurized gypsum.

Preferably, the cementitious material containing waste incineration fly ash and steel slag consists essentially of:

the composite material comprises, by weight, 20-60% of S95 slag, 20-60% of high-aluminum steel slag, 20-40% of waste incineration fly ash and 9-11% of desulfurized gypsum.

Preferably, the waste incineration fly ash mainly consists of the following components: 32-42 parts of CaO, 15-28 parts of Cl and SiO by weight₂2-6 parts of Al₂O₃1-4 parts, K₂3-7 parts of O, 3-7 parts of MgO and Na₂O3-7 parts, Fe₂O₃1-3 parts.

Preferably, the high-aluminum steel slag mainly comprises the following components: 50-55 parts of CaO and SiO by weight₂1-2 parts of Al₂O₃35-40 parts of MgO 4-6 parts of SO₃1-2 parts.

Preferably, the S95 slag consists essentially of: 45-50 parts of CaO and SiO by weight₂28-32 parts of Al₂O₃10-14 parts of MgO5-7 parts of Fe₂O₃1-2 parts of SO₃0-1 part.

Preferably, the desulfurized gypsum consists essentially of: according to the weight portion, the CaO45-50 portions and the SiO₂2-3 parts of Al₂O₃0-1 part of MgO, 1-2 parts of SO₃40-46 parts of Cl and 0-1 part of Cl.

The chemical compositions of the refuse incineration fly, the high-alumina steel slag, the S95 slag, and the desulfurized gypsum according to the present invention refer to the contents of various metal or mineral elements in terms of oxides, and do not refer to the contents of compounds present in the refuse incineration fly, the S95 slag, or the desulfurized gypsum slag in terms of oxides. In addition, the above chemical composition results can be obtained by conventional detection methods known in the art, such as typical fluorescence detection after or without loss of ignition.

Preferably, the ratio of S95 slagArea of 500m²More than kg;

preferably, the specific surface area of the desulfurized gypsum is 400m²More than kg;

preferably, the specific surface area of the high-aluminum steel slag is 400m²More than kg.

The specific surface area of the raw materials is improved through grinding, so that the activity of the slag is stimulated, the hydration difficulty is reduced, and the uniformity of the materials is improved.

The S95 slag, waste incineration fly ash and desulfurized gypsum used in the invention can be purchased from the market or prepared by self, as long as the requirements of chemical compositions are met.

At present, the incineration treatment technology in China is mainly divided into three types: grate furnace technology, fluidized bed technology, and other incineration technologies. The waste incineration fly ash generated by the incineration technology comprises two parts, wherein one part is ash obtained by a heat recovery utilization system in front of a flue gas purification system, and comprises (boiler ash, economizer ash and superheater ash), and the other part is flue gas purification system (APC) ash, comprising wet process or semi-dry process dust remover ash, cyclone dust remover ash and bag-type dust remover ash. The fly ash used by the invention adopts a grate furnace incineration technology, and the fly ash produced by incineration through the grate furnace incineration technology contains much higher heavy metal, dioxin and chloride than the fly ash produced by other incineration technologies. However, the fly ash with such great harm still shows lower metal leaching rate after being used for preparing the cementing material, which shows that the fly ash has good synergistic effect with slag, high-aluminum steel slag and gypsum, and the synergistic effect can efficiently solidify heavy metal in the fly ash, thereby reducing the leaching rate and improving the safety of the cementing material.

When the cementing material is used, the cementing material is mixed with water according to the water-cement ratio of 0.35-0.45: 1, and concrete can be prepared by utilizing the water-cement ratio.

The cementitious material according to the invention can be used for making concrete or cementitious fillers, for example using the following formulation.

A concrete or cementitious filler comprising aggregate (whole tailings) and a cementitious material as hereinbefore described; the mass ratio of the cementing material to the aggregate is 1:4-1:8, the concentration of the concrete or the cementing filler is 77 wt%, and the water-cement ratio of the cementing material is 0.35-0.45: 1.

Preferably, the aggregate consists essentially of:

10-15 parts of CaO and SiO by weight₂50-60 parts of Al₂O₃6-12 parts of MgO 2-7 parts of Fe₂O₃6-12 parts of SO₃1-3 parts of Na₂O1-3 parts, K₂1-3 parts of O;

preferably, the particle size of the aggregate is mainly distributed between 4 and 120 mu m, wherein D10 is 4.0 to 7.0 mu m, D50 is 32 to 36 mu m, D90 is 110-115 mu m, and the content of less than 20 mu m accounts for more than 30 weight percent.

In summary, compared with the prior art, the invention achieves the following technical effects:

(1) the recovery rate of the waste incineration fly ash is improved;

(2) the raw material composition of the cementing material containing waste incineration fly ash and steel slag and slag is simplified;

(3) the high-aluminum steel slag which is difficult to be comprehensively utilized is recycled;

(4) the waste incineration fly ash, slag, high-aluminum steel slag and desulfurized gypsum have synergistic effect and show higher compressive strength and leaching safety.

(5) The cementing material has high safety and no heavy metal leaching risk;

(6) the preparation method is simple.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

Comparative example 1

The high-aluminum steel slag-fly ash-desulfurized gypsum solidified heavy metal gelled material mainly comprises the following components in percentage by mass: 60% of S95 slag powder, 30% of waste incineration fly ash and 10% of desulfurized gypsum.

The chemical compositions of the waste incineration fly ash, the S95 slag powder and the desulfurized gypsum are shown in Table 1, and the detection method comprises the following steps: x-ray fluorescence Spectroscopy (XRF), and substance composition analysis was performed by measuring secondary X-rays with an XRF-1800 type X-ray fluorescence spectrometer.

After pouring and forming, curing to different ages for leaching toxicity test, wherein the test method comprises the following steps:

the raw materials are respectively weighed according to the proportion, and the desulfurized gypsum needs to be ground to 400m²The powder of/kg, S95 needs to be ground to a specific surface of 500m²Kg, water-to-glue ratio of 0.4: 1, preparing a filling material sample according to GB17671-1999 method for testing cement mortar strength, wherein the sample has a size of 30mm multiplied by 50mm, and curing is carried out at a temperature of 35 ℃ and a humidity of more than 99.5%.

The test results are shown in Table 2.