CN113956012A

CN113956012A - Preparation method of all-solid waste steel tube concrete containing waste incineration fly ash

Info

Publication number: CN113956012A
Application number: CN202111584177.7A
Authority: CN
Inventors: 翟玉新; 王长龙; 王飞; 张凯帆; 田小平; 李鑫; 陈敬亮; 马锦涛; 荆牮霖; 平浩岩; 张鸿泽; 曲俞; 董磊; 史乐贤
Original assignee: Tianjin Tianxing Fuda Technology Co ltd; China Railway Construction Group Co Ltd; Hebei University of Engineering
Current assignee: Tianjin Tianxing Fuda Technology Co ltd; China Railway Construction Group Co Ltd; Hebei University of Engineering
Priority date: 2021-12-23
Filing date: 2021-12-23
Publication date: 2022-01-21
Anticipated expiration: 2041-12-23
Also published as: CN113956012B

Abstract

The invention discloses a preparation method of full-solid waste steel tube concrete containing waste incineration fly ash, which comprises the following steps: s1, preparing coarse aggregate and steel slag particles smaller than 5 mm; s2, preparing fine aggregate and molybdenum tailing particles of 0.038 mm-0.074 mm; s3, grinding waste incineration fly ash, steel slag particles smaller than 5mm and molybdenum tailing particles of 0.038-0.074 mm; s4, grinding the refining slag and the vanadium-titanium slag; s5 grinding the phosphogypsum; s6, mixing the powder materials in the S3, the S4 and the S5 to obtain a composite gelled material; s7, mixing the composite cementing material, the fine aggregate, the coarse aggregate, the bean curd wastewater and the water reducing agent, stirring, molding and curing to obtain the concrete product. The preparation method can solve the problems of harmlessness, reduction and difficult resource utilization of waste incineration fly ash and bulk industrial solid wastes, thereby achieving the purposes of changing waste into valuable, generating higher economic value of the solid wastes, realizing green sustainable development of the solid wastes, saving energy and protecting environment.

Description

Preparation method of all-solid waste steel tube concrete containing waste incineration fly ash

Technical Field

The invention relates to the technical field of concrete filled steel tubes, in particular to a preparation method of full-solid waste concrete filled steel tubes containing waste incineration fly ash.

Background

The Steel pipe Concrete (CFST for short) is a composite material with excellent performance, and the core Concrete is in a three-dimensional compression state by means of the hoop constraint action of the Steel pipe on the core Concrete in the compression process, so that the core Concrete has higher compressive strength and compressive deformation capacity, and meanwhile, the Steel pipe strengthens the geometric stability of the Steel pipe wall by means of the supporting action of the Filled Concrete, and changes the instability mode of the hollow Steel pipe. However, the void causes problems in the aspects of bearing capacity, stress and strain, rigidity, stability and the like of the steel pipe concrete structure, and seriously restricts the service performance and the service life of the steel pipe concrete structure. The steel slag is used as a cementing material and fine aggregate to be applied to the concrete filled steel tube, the expansion component in the steel slag can compensate the shrinkage of the concrete, and the steel tube has the closed moisture-proof environment and the hoop constraint effect, so that the concrete structure damage caused by the later hydration expansion of the steel slag can be avoided.

The steel slag is the waste slag generated in the steel-making process, the annual output of steel in China leaps the first in the world at the end of the last century, and the annual generated steel slag is about 10-12% of the steel yield. The steel slag has weak gelation, poor grindability and poor volume stability, so that the application of the steel slag in large scale and high added value is greatly limited, and the utilization rate of the steel slag in China is less than 40 percent at present. A large amount of steel slag which is piled up occupies a large area of land and has certain harm to the environment.

In recent years, the garbage incineration project in China is increased rapidly. The statistical data of the research institute of E20 show that the nearly 257 seats garbage incineration power plants are put into operation in 2015, and the annual garbage incineration amount reaches 6811 million tons. According to the national records of dangerous wastes, the fly ash generated in the waste incineration belongs to dangerous wastes, the generation amount of the fly ash accounts for about 3% -5% of the amount of the incinerated wastes, and the generation amount of the fly ash reaches 395 million tons in 2015. By the end of 2020, the annual output of the waste incineration fly ash can reach more than 1000 ten thousand tons. In the face of high content of harmful substances in the waste incineration fly ash, how to maximize and greenly dispose the waste incineration fly ash becomes a hotspot of research in the field of hazardous wastes.

How to effectively utilize solid wastes such as steel slag, waste incineration fly ash and the like to prepare the steel tube concrete can solve the problems of harmlessness, reduction and recycling of the waste incineration fly ash and the large amount of industrial solid wastes, promote the cooperative utilization and environmental protection of dangerous wastes and industrial solid wastes, and provide raw materials for replacing cement-based steel tube concrete on a large scale, and the technical problem needs to be solved urgently by people.

Disclosure of Invention

Aiming at the technical problems in the prior art, the invention provides a preparation method of full-solid waste steel tube concrete containing waste incineration fly ash, which can overcome the defects in the prior art.

In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:

a preparation method of full-solid waste steel tube concrete containing waste incineration fly ash is characterized by comprising the following steps:

s1 preparing coarse aggregate and steel slag particles smaller than 5 mm: after the steel slag is crushed to 5-20mm by a jaw crusher, putting the steel slag into a carbonization box for carbonization for 60-72 hours, wherein the carbonization conditions are as follows: CO 2₂The concentration is 15%, the temperature is 20 +/-1 ℃, the humidity is 85 +/-1%, the carbonized steel slag is dried for 12 hours at the temperature of 105 ℃, then the steel slag is placed into an empty ball mill for crushing and shaping, the steel slag is crushed for 30-60 minutes at the rotating speed of 48r/min, steel slag particles with the size of 5-10 mm are screened as coarse aggregate for later use, and steel slag particles with the size of less than 5mm are screened for later use;

s2, preparing fine aggregate and molybdenum tailing particles of 0.038 mm-0.074 mm: screening the molybdenum tailings by using a hydrocyclone to obtain particles larger than 0.074mm and particles of 0.038 mm-0.074 mm, respectively drying at 105 ℃ for 12h, taking the dried molybdenum tailings particles larger than 0.074mm as fine aggregates, and keeping the dried molybdenum tailings particles of 0.038 mm-0.074 mm for later use;

s3, grinding waste incineration fly ash, steel slag particles smaller than 5mm and molybdenum tailing particles of 0.038-0.074 mm: drying the waste incineration fly ash at 105 ℃ for 12h, putting the waste incineration fly ash, steel slag particles which are sieved in S1 and are smaller than 5mm, and molybdenum tailing particles which are dried in S2 and are 0.038 mm-0.074 mm into a ball mill to be ground to 350-500 m²/kg；

S4 grinding refining slag and vanadium-titanium slag: respectively drying the refining slag and the vanadium-titanium slag at 105 ℃ for 12h, and respectively grinding the dried materials to 500-650 m²/kg；

S5 grinding phosphogypsum: drying phosphogypsum at 105 deg.C for 12hGrinding the dried material to 400-500 m²/kg；

S6, mixing the powder materials obtained by grinding in S3, S4 and S5 in proportion to obtain a composite gelled material;

s7, mixing the composite cementing material, the fine aggregate, the coarse aggregate, the bean curd wastewater and the water reducing agent, stirring, molding and curing to obtain the concrete product: uniformly mixing the composite cementing material, the fine aggregate and the coarse aggregate to obtain a mixture, adding the bean curd wastewater and the water reducing agent which are refrigerated and filtered at 4-6 ℃, uniformly stirring by using a stirrer to obtain mixed slurry, and finally pouring, demoulding and maintaining the mixed slurry to obtain the concrete product.

Further, the steel slag in the S1 contains 20-50% of CaO and SiO by mass₂ 10~30%，Al₂O₃1~10%，Fe₂O₃ 5~30%，MgO 1~15%，FeO 1~12%，Na₂O 0.01~2%，K₂O 0.01~2%，SO₃0~0.3%，P₂O₅1-6% and 0.01-5% of ignition loss.

Further, the mass percentage of each component in the molybdenum tailings in the S2 is SiO₂ 35~70%，Al₂O₃ 5~20%，MgO 1~7%，CaO 1~8%，Fe₂O₃ 1~12%，Na₂O 0.01~3%，K₂O 0.01~3%，P₂O₅0.01-3% and 0.01-8% of loss on ignition.

Further, the waste incineration fly ash in the S3 comprises 25-45% of CaO and SiO by mass₂1~10%，Al₂O₃ 1~5%，Fe₂O₃ 0.1~5%，MgO 1~8%，FeO 0.01~2%，Na₂O 1~7%，K₂1-7% of O, 10-30% of Cl and 0.01-5% of loss on ignition.

Further, in the S4 refining slag, the mass percentage of each component is CaO 45-60%, and Al₂O₃ 20~30%，SiO₂5~10%，MgO 2~8%，Fe₂O₃ 1~5%，SO₃ 1~4%。

Further, the vanadium-titanium slag in S4 contains SiO as each component in percentage by mass₂ 10~35%，Al₂O₃ 10~20%，MgO 5~10%，CaO 15~30%，Fe₂O₃ 0.1~3%，Na₂O 0.01~2%，K₂O 0.01~2%，MnO 0.1~1.5%，TiO₂ 10~25%，SO₃0.1-2 percent and 0.01-8 percent of loss on ignition.

Further, in the S5, the mass percentage of each component in the phosphogypsum is CaO 35-50%, and SiO₂ 1~4%，Al₂O₃ 0~1.5%，MgO 1~4%，SO₃ 30~45%，P₂O₅1-6% and 0.01-3% of ignition loss.

Further, the composite cementing material in the S6 comprises, by weight, 20-40 parts of steel slag particles smaller than 5mm, 10-40 parts of refining slag, 20-50 parts of vanadium-titanium slag, 10-20 parts of waste incineration fly ash, 10-20 parts of molybdenum tailing particles of 0.038 mm-0.074 mm, and 5-11 parts of phosphogypsum.

Further, the water reducing agent in S7 is one or more of polycarboxylic acid type, naphthalene type, aminobenzene sulfonic acid type and melamine type high-efficiency water reducing agents.

Further, the mass ratio of the composite cementing material, the coarse aggregate and the fine aggregate in the S7 is as follows: 350-620: 830-1200: 730-1070, wherein the addition amount of the bean curd waste water is 35-50% of the weight of the composite cementing material, and the addition amount of the water reducing agent is 3-5 per mill of the weight of the composite cementing material.

The invention has the beneficial effects that: the preparation method of the all-solid waste steel tube concrete containing the waste incineration fly ash can solve the problems of harmlessness, reduction and difficult resource utilization of the waste incineration fly ash and the large amount of industrial solid wastes, thereby changing waste into valuable, promoting the cooperative utilization of the hazardous wastes and the solid wastes and protecting the environment, and the product has good compressive strength and leaching safety performance, provides raw materials for replacing cement-based steel tube concrete in a large scale, lays an engineering foundation, generates higher economic value of the solid wastes, and realizes the purposes of green sustainable development of the solid wastes, energy conservation and environmental protection.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.

FIG. 1 is a flow chart of a method for preparing all-solid waste steel pipe concrete containing fly ash from incineration of garbage according to an embodiment of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.

In order to facilitate understanding of the above-described technical aspects of the present invention, the above-described technical aspects of the present invention will be described in detail below in terms of specific usage.

Example 1

A preparation method of full-solid waste steel tube concrete containing waste incineration fly ash is shown in figure 1 and comprises the following steps:

crushing the S1 steel slag to 5-20mm by a jaw crusher, and then putting the crushed steel slag into a carbonization box for carbonization for 60 hours, wherein the carbonization conditions are as follows: CO 2₂The concentration is 15%, the temperature is 20 +/-1 ℃, and the humidity is 85% +/-1; drying the carbonized steel slag at 105 ℃ for 12h, then putting the steel slag into an empty ball mill for crushing and shaping, crushing for 60min at the rotating speed of 48r/min, screening, wherein 5-10 mm particles are used as coarse aggregate for later use, and screening steel slag particles smaller than 5mm for later use;

s2, screening the molybdenum tailings by a hydrocyclone (slurry concentration is 25%), drying particles larger than 0.074mm at 105 ℃ for 12 hours to serve as fine aggregates, and keeping the molybdenum tailings particles of 0.038 mm-0.074 mm for later use;

s3, drying 57.85kg of waste incineration fly ash at 105 ℃ for 12h, putting the dried waste incineration fly ash, 57.85kg of steel slag particles with the particle size of less than 5mm after being sieved in S1 and 28.93kg of molybdenum tailing particles with the particle size of 0.038-0.074 mm in S2 into a ball mill to be ground to 350-500 m²/kg；

S4, respectively drying 115.70kg of refining slag and 57.85kg of vanadium-titanium slag at 105 ℃ for 12 hours, and respectively grinding the dried materials to 500-650 m²/kg；

S5, drying 31.82kg of phosphogypsum at 105 ℃ for 12h, and grinding the dried material to 400-500 m²/kg；

S6, mixing the powder materials in the S3, the S4 and the S5 in proportion to obtain 350kg of composite gelled material;

s7, uniformly mixing 350kg of composite cementing material, 1200kg of steel slag coarse aggregate and 730kg of molybdenum tailings with the particle size larger than 0.074mm to obtain a mixture, adding 175kg of bean curd wastewater which is refrigerated at 4-6 ℃ and filtered and 1.05kg of water reducing agent, and uniformly stirring by using a stirrer to obtain mixed slurry; finally, pouring, demolding and maintaining the mixed slurry to obtain 1cm³A concrete article.

In this embodiment, in the step S1, the steel slag includes, by mass, 20 to 50% of CaO and SiO₂ 10~30%，Al₂O₃1~10%，Fe₂O₃ 5~30%，MgO 1~15%，FeO 1~12%，Na₂O 0.01~2%，K₂O 0.01~2%，SO₃0~0.3%，P₂O₅1-6% and 0.01-5% of ignition loss.

The mass percentage of each component in the molybdenum tailings in the S2 is SiO₂ 35~70%，Al₂O₃ 5~20%，MgO 1~7%，CaO 1~8%，Fe₂O₃ 1~12%，Na₂O 0.01~3%，K₂O 0.01~3%，P₂O₅0.01-3% and 0.01-8% of loss on ignition.

The S3 waste incineration fly ash comprises 25-45% of CaO and SiO by mass₂ 1~10%，Al₂O₃ 1~5%，Fe₂O₃ 0.1~5%，MgO 1~8%，FeO 0.01~2%，Na₂O 1~7%，K₂1-7% of O, 10-30% of Cl and 0.01-5% of loss on ignition.

The refining slag in the S4 comprises, by mass, 45-60% of CaO and Al₂O₃ 20~30%，SiO₂5~10%，MgO 2~8%，Fe₂O₃ 1~5%，SO₃ 1~4%。

The mass percentage of each component in the vanadium-titanium slag in the S4 is SiO₂ 10~35%，Al₂O₃ 10~20%，MgO 5~10%，CaO 15~30%，Fe₂O₃ 0.1~3%，Na₂O 0.01~2%，K₂O 0.01~2%，MnO 0.1~1.5%，TiO₂ 10~25%，SO₃0.1-2 percent and 0.01-8 percent of loss on ignition.

In the S5, the mass percentage of each component in the phosphogypsum is CaO 35-50%, and SiO₂ 1~4%，Al₂O₃ 0~1.5%，MgO 1~4%，SO₃ 30~45%，P₂O₅1-6% and 0.01-3% of ignition loss.

The composite cementing material in the S6 comprises, by weight, 20 parts of steel slag particles smaller than 5mm, 40 parts of refining slag, 20 parts of vanadium-titanium slag, 20 parts of waste incineration fly ash, 10 parts of molybdenum tailing particles of 0.038 mm-0.074 mm, and 11 parts of phosphogypsum.

And the water reducing agent in the S7 is a polycarboxylic acid water reducing agent.

Example 2

crushing the S1 steel slag to 5-20mm by a jaw crusher, and then putting the crushed steel slag into a carbonization box for carbonization for 72 hours, wherein the carbonization conditions are as follows: CO 2₂The concentration is 15%, the temperature is 20 +/-1 ℃, and the humidity is 85% +/-1; drying the carbonized steel slag at 105 ℃ for 12h, then putting the steel slag into an empty ball mill for crushing and shaping, crushing for 30min at the rotating speed of 48r/min, screening 5-10 mm particles as coarse aggregate for later use, and screening steel slag particles smaller than 5mm for later use;

s2, screening the molybdenum tailings by a hydrocyclone (slurry concentration is 40%), drying particles larger than 0.074mm at 105 ℃ for 12 hours to serve as fine aggregates, and keeping the molybdenum tailings particles of 0.038 mm-0.074 mm for later use;

s3, drying 28.15kg of waste incineration fly ash at 105 ℃ for 12h, putting 112.59kg of particle steel slag with the particle size smaller than 5mm after being sieved in S1 and 26.30kg of molybdenum tailing particles with the particle size of 0.038-0.074 mm in S2 into a ball mill to be ground to 350-500 m²/kg；

S4, respectively drying 28.15kg of refining slag and 140.74kg of vanadium-titanium slag at 105 ℃ for 12 hours, and respectively grinding the dried materials to 500-650 m²/kg；

S5, drying 14.07kg of phosphogypsum at 105 ℃ for 12h, and grinding the dried material to 400-500 m²/kg；

S6, mixing the powder materials in the S3, the S4 and the S5 in proportion to obtain 380kg of composite gelled material;

s7, uniformly mixing 380kg of composite cementing material, 1130kg of coarse aggregate and 750kg of molybdenum tailings with the particle size larger than 0.074mm to obtain a mixture, adding 152kg of bean curd wastewater and 1.90kg of water reducing agent which are refrigerated at 4-6 ℃ and filtered, and uniformly stirring by using a stirrer to obtain mixed slurry; finally, pouring, demolding and maintaining the mixed slurry to obtain 1cm³A concrete article.

The mass percentage of each component in the vanadium-titanium slag in the S4 is SiO₂ 10~35%，Al₂O₃ 10~20%，MgO 5~10%，CaO 15~30%，Fe₂O₃ 0.1~3%，Na₂O 0.01~2%，K₂O 0.01~2%，MnO 0.1~1.5%，TiO₂ 10~25%，SO₃0.1 to 2, loss on ignition0.01~8%。

The composite cementing material in the S6 comprises 40 parts of steel slag particles smaller than 5mm, 10 parts of refining slag, 50 parts of vanadium-titanium slag, 10 parts of waste incineration fly ash, 20 parts of molybdenum tailing particles of 0.038 mm-0.074 mm and 5 parts of phosphogypsum by weight.

And the water reducing agent in the S7 is a naphthalene water reducing agent.

Example 3

crushing the S1 steel slag to 5-20mm by a jaw crusher, and then putting the crushed steel slag into a carbonization box for carbonization for 65 hours, wherein the carbonization conditions are as follows: CO 2₂The concentration is 15%, the temperature is 20 +/-1 ℃, and the humidity is 85% +/-1; drying the carbonized steel slag at 105 ℃ for 12h, then putting the steel slag into an empty ball mill for crushing and shaping, crushing for 50min at the rotating speed of 48r/min, screening 5-10 mm particles as coarse aggregate for later use, and screening steel slag particles smaller than 5mm for later use;

s2, screening the molybdenum tailings by a hydrocyclone (the slurry concentration is 30%), drying particles larger than 0.074mm at 105 ℃ for 12 hours to serve as fine aggregates, and keeping the molybdenum tailings particles of 0.038 mm-0.074 mm for later use;

s3, drying 48.87kg of waste incineration fly ash at 105 ℃ for 12h, putting 97.73kg of steel slag particles with the particle size less than 5mm after being sieved in S1 and 48.87kg of molybdenum tailing particles with the particle size of 0.038-0.074 mm in S2 into a ball mill to be ground to 350-500 m²/kg；

S4, respectively drying 81.45kg of refining slag and 114.02kg of vanadium-titanium slag at 105 ℃ for 12h, and respectively grinding the dried materials to 500-650 m²/kg；

S5, drying 26.06kg of phosphogypsum at 105 ℃ for 12h, and grinding the dried material to 400-500 m²/kg；

S6, mixing the powder materials in the S3, the S4 and the S5 in proportion to obtain 417kg of composite gelled material;

s7 gelling 417kg of compositeUniformly mixing 900kg of steel slag coarse aggregate, 1070kg of molybdenum tailings with the particle size of more than 0.074mm to obtain a mixture, adding 194kg of bean curd wastewater and 1.67kg of water reducing agent which are refrigerated at 4-6 ℃ and filtered, and uniformly stirring by using a stirrer to obtain mixed slurry; finally, pouring, demolding and maintaining the mixed slurry to obtain 1cm³A concrete article.

The composite cementing material in the S6 comprises, by weight, 30 parts of steel slag particles smaller than 5mm, 25 parts of refining slag, 35 parts of vanadium-titanium slag, 15 parts of waste incineration fly ash, 15 parts of molybdenum tailing particles of 0.038 mm-0.074 mm, and 8 parts of phosphogypsum.

And the water reducing agent in the S7 is an aminobenzene sulfonic acid water reducing agent.

Example 4

crushing the S1 steel slag to 5-20mm by a jaw crusher, and then putting the crushed steel slag into a carbonization box for carbonization for 70 hours, wherein the carbonization conditions are as follows: CO 2₂The concentration is 15%, the temperature is 20 +/-1 ℃, and the humidity is 85% +/-1; drying the carbonized steel slag at 105 ℃ for 12h, then putting the steel slag into an empty ball mill for crushing and shaping, crushing for 40min at the rotating speed of 48r/min, screening 5-10 mm particles as coarse aggregate for later use, and screening steel slag particles smaller than 5mm for later use;

s2, screening the molybdenum tailings by a hydrocyclone (the slurry concentration is 35%), drying particles larger than 0.074mm at 105 ℃ for 12 hours to serve as fine aggregates, and keeping the molybdenum tailings particles of 0.038 mm-0.074 mm for later use;

s3, drying 49.41kg of waste incineration fly ash at 105 ℃ for 12h, putting the dried waste incineration fly ash, 102.94kg of steel slag particles with the particle size of less than 5mm after being sieved in S1 and 74.12kg of molybdenum tailing particles with the particle size of 0.038-0.074 mm in S2 into a ball mill to be ground to 350-500 m²/kg；

S4, respectively drying 144.12kg of refining slag and 164.71kg of vanadium-titanium slag at 105 ℃ for 12 hours, and respectively grinding the dried materials to 500-650 m²/kg；

S5, drying 24.70kg of phosphogypsum at 105 ℃ for 12h, and grinding the dried material to 400-500 m²/kg；

S6, mixing the powder materials in the S3, the S4 and the S5 in proportion to obtain 560kg of composite gelled material;

s7, uniformly mixing 560kg of composite cementing material, 1000kg of steel slag coarse aggregate and 772kg of molybdenum tailings with the particle size larger than 0.074mm to obtain a mixture, adding the mixture, refrigerating at 4-6 ℃, and adding196kg of the filtered bean curd wastewater and 1.68kg of a water reducing agent are uniformly stirred by a stirrer to obtain mixed slurry; finally, pouring, demolding and maintaining the mixed slurry to obtain 1cm³A concrete article.

In this embodiment, in the step S1, the steel slag includes, by mass, 20 to 50% CaO and SiO₂ 10~30%，Al₂O₃1~10%，Fe₂O₃ 5~30%，MgO 1~15%，FeO 1~12%，Na₂O 0.01~2%，K₂O 0.01~2%，SO₃0~0.3%，P₂O₅1-6% and 0.01-5% of ignition loss.

The mass percentage of each component in the molybdenum tailing slag in the S2 is SiO₂ 35~70%，Al₂O₃ 5~20%，MgO 1~7%，CaO 1~8%，Fe₂O₃ 1~12%，Na₂O 0.01~3%，K₂O 0.01~3%，P₂O₅0.01-3% and 0.01-8% of loss on ignition.

The mass percentage of each component in the S3 waste incineration fly ash slag is CaO 25-45%, SiO₂ 1~10%，Al₂O₃ 1~5%，Fe₂O₃ 0.1~5%，MgO 1~8%，FeO 0.01~2%，Na₂O 1~7%，K₂1-7% of O, 10-30% of Cl and 0.01-5% of loss on ignition.

The refining slag in the S4 contains CaO 45-60 wt% and Al₂O₃ 20~30%，SiO₂5~10%，MgO 2~8%，Fe₂O₃ 1~5%，SO₃ 1~4%。

The mass percentage of each component in the vanadium-titanium slag refining slag in the S4 is SiO₂ 10~35%，Al₂O₃ 10~20%，MgO 5~10%，CaO 15~30%，Fe₂O₃ 0.1~3%，Na₂O 0.01~2%，K₂O 0.01~2%，MnO 0.1~1.5%，TiO₂ 10~25%，SO₃0.1-2 percent and 0.01-8 percent of loss on ignition.

The mass percentage of each component in the phosphogypsum slag in the S5 is CaO 35-50%, and SiO₂ 1~4%，Al₂O₃ 0~1.5%，MgO 1~4%，SO₃ 30~45%，P₂O₅ 1~6%，The loss on ignition is 0.01-3%.

The composite cementing material in the S6 comprises 25 parts of steel slag particles smaller than 5mm, 35 parts of refining slag, 40 parts of vanadium-titanium slag, 12 parts of waste incineration fly ash, 18 parts of molybdenum tailing particles of 0.038 mm-0.074 mm and 6 parts of phosphogypsum by weight.

And the water reducing agent in the S7 is a melamine high-efficiency water reducing agent.

Example 5

crushing the S1 steel slag to 5-20mm by a jaw crusher, and then putting the crushed steel slag into a carbonization box for carbonization for 72 hours, wherein the carbonization conditions are as follows: CO 2₂The concentration is 15%, the temperature is 20 +/-1 ℃, and the humidity is 85% +/-1; drying the carbonized steel slag at 105 ℃ for 12h, then putting the steel slag into an empty ball mill for crushing and shaping, crushing for 40min at the rotating speed of 48r/min, screening 5-10 mm particles as coarse aggregate for later use, and screening steel slag particles smaller than 5mm for later use;

s3, drying 75.79kg of waste incineration fly ash at 105 ℃ for 12h, putting the dried waste incineration fly ash, 147.37kg of steel slag particles with the particle size of less than 5mm after being sieved in S1 and 50.53kg of molybdenum tailing particles with the particle size of 0.038-0.074 mm in S2 into a ball mill to be ground to 350-500 m²/kg；

S4, respectively drying 63.16kg of refining slag and 105.26kg of vanadium-titanium slag at 105 ℃ for 12 hours, and respectively grinding the dried materials to 500-650 m²/kg；

S5, drying 37.89kg of phosphogypsum at 105 ℃ for 12h, and grinding the dried material to 400-500 m²/kg；

S6, mixing the powder materials in S3, S4 and S5 in proportion to obtain 480kg of composite gelled material;

s7, uniformly mixing 480kg of composite cementing material, 1080kg of steel slag coarse aggregate and 750kg of molybdenum tailings with the particle size larger than 0.12mm to obtain a mixture, adding 177kg of bean curd wastewater and 1.56kg of water reducing agent which are refrigerated at 4-6 ℃ and filtered, and uniformly stirring by using a stirrer to obtain mixed slurry;finally, pouring, demolding and maintaining the mixed slurry to obtain 1cm³A concrete article.

The composite cementing material in the S6 comprises, by weight, 35 parts of steel slag particles smaller than 5mm, 15 parts of refining slag, 25 parts of vanadium-titanium slag, 18 parts of waste incineration fly ash, 12 parts of molybdenum tailing particles of 0.038 mm-0.074 mm, and 9 parts of phosphogypsum.

Example 6

crushing the S1 steel slag to 5-20mm by a jaw crusher, and then putting the crushed steel slag into a carbonization box for carbonization for 60 hours, wherein the carbonization conditions are as follows: CO 2₂The concentration is 15%, the temperature is 20 +/-1 ℃, and the humidity is 85% +/-1; drying the carbonized steel slag at 105 ℃ for 12h, then putting the steel slag into an empty ball mill for crushing and shaping, crushing for 50min at the rotating speed of 48r/min, screening 5-10 mm particles as coarse aggregate for later use, and screening steel slag particles smaller than 5mm for later use;

s2, screening the molybdenum tailings by a hydrocyclone (slurry concentration is 28%), drying particles larger than 0.074mm at 105 ℃ for 12 hours to serve as fine aggregate, and keeping the molybdenum tailings particles of 0.038 mm-0.074 mm for later use;

s3, drying 60.14kg of waste incineration fly ash at 105 ℃ for 12h, putting the dried waste incineration fly ash, 161.94kg of steel slag particles with the particle size of less than 5mm after being sieved in S1 and 74.03kg of molybdenum tailing particles with the particle size of 0.038-0.074 mm in S2 into a ball mill to be ground to 350-500 m²/kg；

S4, respectively drying 138.81kg of refining slag and 138.81kg of vanadium-titanium slag at 105 ℃ for 12 hours, and respectively grinding the dried materials to 500-650 m²/kg；

S5, drying 46.27kg of phosphogypsum at 105 ℃ for 12h, and grinding the dried material to 400-500 m²/kg；

S6, mixing the powder materials in S3, S4 and S5 in proportion to obtain 620kg of composite gelled material;

s7, uniformly mixing 620kg of composite cementing material, 830kg of steel slag coarse aggregate and 872kg of molybdenum tailings with the particle size of more than 0.074mm to obtain a mixture, adding 248kg of bean curd wastewater and 1.86kg of water reducing agent which are refrigerated at 4-6 ℃ and filtered, and uniformly stirring by using a stirrer to obtain mixed slurry; finally, pouring, demolding and maintaining the mixed slurry to obtain 1cm³A concrete article.

In this exampleIn the step S1, the steel slag contains 20-50% of CaO and SiO by mass₂ 10~30%，Al₂O₃1~10%，Fe₂O₃ 5~30%，MgO 1~15%，FeO 1~12%，Na₂O 0.01~2%，K₂O 0.01~2%，SO₃0~0.3%，P₂O₅1-6% and 0.01-5% of ignition loss.

The composite cementing material in the S6 comprises, by weight, 35 parts of steel slag particles smaller than 5mm, 30 parts of refining slag, 30 parts of vanadium-titanium slag, 13 parts of waste incineration fly ash, 16 parts of molybdenum tailing particles of 0.038 mm-0.074 mm and 10 parts of phosphogypsum.

After the steel slag powder is carbonized, the average value of the grinding work index is improved by 20-30 MJ/T, and the grinding energy consumption of the steel slag is reduced; the f-CaO in the steel slag is reduced by 30-60%, and the f-MgO is reduced by 20-55%.

The vanadium-titanium slag meets the requirement of S75 of GB/T18046-2017 granulated blast furnace slag powder used in cement, mortar and concrete, and the density is more than or equal to 2.8g/cm³Activity index 7d is more than or equal to 55 percent, 28d is more than or equal to 75 percent, and radioactivity I_RaLess than or equal to 1.0 and I_rLess than or equal to 1.0. The test of the refined vanadium-titanium slag according to HJ 557-.

The waste incineration fly ash is bottom ash generated in the process of incinerating industrial waste or household waste by a mechanical grate incineration process. The test of the refined waste incineration fly ash according to HJ 557-.

The main component of the phosphogypsum is CaSO₄·2H₂O, similar to natural gypsum or desulfurized gypsum. Meets the requirement of industrial byproduct gypsum specified in GB/T21371-2019 'industrial byproduct gypsum for cement'. CaSO in phosphogypsum₄·2H₂O and CaSO₄The total amount is more than or equal to 90 percent, the chloride ion is less than or equal to 0.4 percent, and the pH value is more than or equal to 5.

The bean curd wastewater is refrigerated at 4-6 ℃ and filtered, and the application of the bean curd wastewater in concrete has the effect of a water reducing agent.

And (3) detection results: the leaching concentration of heavy metal of each raw material is shown in table 1; the concrete strength values are given in table 2; the mortar samples are prepared according to GB17671-1999 cement mortar strength test method, the sizes of the mortar samples are 40mm multiplied by 160mm, the mortar samples are maintained under the standard conditions that the temperature is 35 ℃ and the humidity is more than 95%, the leaching concentrations of heavy metals at different ages are tested, and the test results are shown in Table 3.

After the proportion of the raw materials is optimized, the cementing material provided by the invention has excellent leaching safety, the leaching concentration of heavy metal ions is lower than the sanitary standard of drinking water, and meanwhile, the cementing material meets the III-class standard of underground water.

The concrete filled steel tube prepared by the preparation method has the following characteristics:

firstly, compared with the existing composite cementing material cement for steel pipe concrete, the composite cementing material is more green, low-carbon and environment-friendly in composition and free of additives, is composed of six components of steel metallurgical slag (steel slag, refining slag and vanadium-titanium slag), molybdenum tailings, waste incineration fly ash and phosphogypsum, greatly reduces the cost of the cementing material for the steel pipe concrete, and has higher utilization rate of the waste incineration fly ash.

Second, the steel pipe concrete exhibits good cementitious properties, including compressive strength and effective curing of various heavy metals in the waste incineration fly ash. The water-to-gel ratio is 0.31-0.48, and according to GB/T50081 plus 2019 'test method standards for physical and mechanical properties of concrete', the composite cementing material, the molybdenum tailings and the steel slag coarse aggregate are used for preparing a concrete test block, the size of the test block is 100mm multiplied by 100mm, and the test block is maintained under standard maintenance conditions, so that good compressive strength and leaching safety performance are displayed.

Thirdly, the safety is high. The safety performance of the used waste incineration fly ash is good, and the long-term leaching concentration of heavy metal ions such as Pb, Zn, Cu, Cr, Hg, Cd and the like in the waste incineration fly ash is lower than the drinking water standard; in addition, the synergistic effect of the steel slag, the refining slag, the molybdenum tailings, the vanadium-titanium slag and the phosphogypsum in the cementing material can effectively solidify chloride ions in the waste incineration fly ash, and avoid corrosion to steel pipes.

In conclusion, by means of the technical scheme, the composite cementing material utilizes the ferrous metallurgy slag (steel slag, refining slag, vanadium-titanium slag), the molybdenum tailings, the waste incineration fly ash and the phosphogypsum to replace the traditional cementing agent cement, and synergistically utilizes the waste incineration fly ash, the molybdenum tailings are used as fine aggregate, and the shaped steel slag is used as coarse aggregate to prepare the all-solid waste steel pipe concrete, so that the problems of harmlessness, reduction and resource difficulty of the waste incineration fly ash and the large amount of industrial solid wastes can be solved, the waste is changed into valuable, the hazardous waste and the solid waste are cooperatively utilized, the environment is protected, the product has good compressive strength and leaching safety performance, the raw materials are provided for replacing the cement-based steel pipe concrete in a large scale, the engineering foundation is made, the solid wastes generate higher economic value, and the aims of green sustainable development of the solid wastes, energy conservation and environmental protection are fulfilled.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A preparation method of full-solid waste steel tube concrete containing waste incineration fly ash is characterized by comprising the following steps:

S5 grinding phosphogypsum: drying the phosphogypsum at 105 ℃ for 12 hours, and grinding the dried material to 400-500 m²/kg；

2. The preparation method of claim 1, wherein the steel slag in the S1 contains 20-50% by mass of CaO and SiO₂ 10~30%，Al₂O₃1~10%，Fe₂O₃ 5~30%，MgO 1~15%，FeO 1~12%，Na₂O 0.01~2%，K₂O 0.01~2%，SO₃0~0.3%，P₂O₅1-6% and 0.01-5% of ignition loss.

3. The preparation method of claim 1, wherein the molybdenum tailings in the S2 comprise SiO in percentage by mass₂ 35~70%，Al₂O₃ 5~20%，MgO 1~7%，CaO 1~8%，Fe₂O₃ 1~12%，Na₂O 0.01~3%，K₂O 0.01~3%，P₂O₅0.01-3% and 0.01-8% of loss on ignition.

4. The preparation method according to claim 1, wherein the fly ash from waste incineration in S3 contains CaO 25-45 wt% and SiO₂ 1~10%，Al₂O₃ 1~5%，Fe₂O₃ 0.1~5%，MgO 1~8%，FeO 0.01~2%，Na₂O 1~7%，K₂1-7% of O, 10-30% of Cl and 0.01-5% of loss on ignition.

5. The preparation method of claim 1, wherein the refining slag in S4 contains CaO 45-60 wt% and Al₂O₃ 20~30%，SiO₂5~10%，MgO 2~8%，Fe₂O₃ 1~5%，SO₃ 1~4%。

6. The preparation method according to claim 1, wherein the mass percentage of each component in the vanadium-titanium slag in S4 is SiO₂ 10~35%，Al₂O₃ 10~20%，MgO 5~10%，CaO 15~30%，Fe₂O₃ 0.1~3%，Na₂O 0.01~2%，K₂O 0.01~2%，MnO 0.1~1.5%，TiO₂ 10~25%，SO₃0.1-2 percent and 0.01-8 percent of loss on ignition.

7. The preparation method of claim 1, wherein the content of each component in the phosphogypsum in S5 is 35-50% by mass of CaO and SiO₂ 1~4%，Al₂O₃ 0~1.5%，MgO 1~4%，SO₃ 30~45%，P₂O₅1-6% and 0.01-3% of ignition loss.

8. The preparation method of the S6 steel slag-containing composite cementing material is characterized in that the composite cementing material in S6 comprises, by weight, 20-40 parts of steel slag particles with a particle size of less than 5mm, 10-40 parts of refined slag, 20-50 parts of vanadium-titanium slag, 10-20 parts of waste incineration fly ash, 10-20 parts of molybdenum tailing particles with a particle size of 0.038 mm-0.074 mm, and 5-11 parts of phosphogypsum.

9. The preparation method of claim 1, wherein the water reducing agent in S7 is one or more of polycarboxylic acid type, naphthalene type, aminobenzene sulfonic acid type and melamine type high-efficiency water reducing agents.

10. The preparation method according to claim 1, wherein the mass ratio of the composite cementing material, the coarse aggregate and the fine aggregate in S7 is as follows: 350-620: 830-1200: 730-1070, wherein the addition amount of the bean curd waste water is 35-50% of the weight of the composite cementing material, and the addition amount of the water reducing agent is 3-5 per mill of the weight of the composite cementing material.