CN111847944B - Ferrochromium slag for concrete aggregate and preparation method thereof - Google Patents

Ferrochromium slag for concrete aggregate and preparation method thereof Download PDF

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Publication number
CN111847944B
CN111847944B CN202010718223.7A CN202010718223A CN111847944B CN 111847944 B CN111847944 B CN 111847944B CN 202010718223 A CN202010718223 A CN 202010718223A CN 111847944 B CN111847944 B CN 111847944B
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slag
ferrochrome slag
metakaolin
parts
ferrochrome
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CN111847944A (en
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周永祥
贺阳
夏京亮
高超
王伟
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Cabr Building Materials Co ltd
China Academy of Building Research CABR
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China Academy of Building Research CABR
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04Waste materials; Refuse
    • C04B18/14Waste materials; Refuse from metallurgical processes
    • C04B18/141Slags
    • C04B18/144Slags from the production of specific metals other than iron or of specific alloys, e.g. ferrochrome slags
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10Coating or impregnating
    • C04B20/1055Coating or impregnating with inorganic materials
    • C04B20/1074Silicates, e.g. glass
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/34Non-shrinking or non-cracking materials
    • C04B2111/343Crack resistant materials
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention belongs to the technical field of concrete modification, and particularly relates to ferrochrome slag for concrete aggregate and a preparation method thereof, wherein the ferrochrome slag comprises the following components in parts by weight: 80-95 parts of ferrochromium slag, 5-10 parts of metakaolin and 8-15 parts of zeolite powder, wherein the metakaolin and the zeolite powder form composite powder and are attached to the surface of the ferrochromium slag. The invention carries out technical innovation from the viewpoint of inhibiting chromium dissolution and solidifying dissolved chromium, so that the ferrochrome slag can be applied to concrete and has industrial value.

Description

Ferrochromium slag for concrete aggregate and preparation method thereof
Technical Field
The invention belongs to a concrete modification technology, and particularly relates to ferrochrome slag for concrete aggregate and a preparation method thereof.
Background
China is a big country for producing ferrochrome, and the yield of the ferrochrome reaches 388.6 ten thousand tons in 2014. Generally, 1.1-1.2 t of waste slag is generated when 1t of ferrochrome is produced, and about 400 million t of ferrochrome slag is generated every year in China. At present, the utilization rate of ferrochrome slag in China is only 30%, and open-air stacking of ferrochrome slag not only occupies large area of land, but also can have certain environmental risks.
In 2018, the amount of the sandstone in China exceeds 200 hundred million tons, but because the recoverable natural sandstone is less and less, and the environmental protection policy limits the sandstone recovery, sandstone resources in partial areas of China are very short, and the progress and the cost of engineering construction are directly influenced. Therefore, if the ferrochrome slag can be processed into aggregate products with the performance equivalent to that of natural sandstone, the ferrochrome slag can be used as a beneficial supplement for building sandstone undoubtedly, and is beneficial to solving the problem of shortage of sandstone resources, so that the ferrochrome slag has obvious market demand and engineering value. However, when the ferrochromium slag is used as an aggregate to prepare concrete, heavy metal chromium is easy to dissolve out, and the application of the ferrochromium slag in the concrete aggregate is restricted.
In view of the defects of the prior technical scheme of using the ferrochrome slag as the concrete aggregate, the inventor of the invention actively researches and innovates based on the practical experience and professional knowledge which are abundant for many years in the design and manufacture of the products and the application of the theory, so as to create the ferrochrome slag for the concrete aggregate and the preparation method thereof, so that the ferrochrome slag can be applied to the concrete aggregate and has higher practicability. After continuous research and design and repeated trial production and improvement, the invention with practical value is finally created.
Disclosure of Invention
The invention aims to provide ferrochrome slag for concrete aggregate, which is technically innovated from the viewpoint of inhibiting chromium dissolution and solidifying dissolved chromium, so that the ferrochrome slag can be applied to concrete, the aims of reducing heavy metal pollution and changing waste into valuable are fulfilled, and the industrial value is high.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides ferrochrome slag for concrete aggregate, which comprises the following components in parts by weight: 80-95 parts of ferrochromium slag, 5-10 parts of metakaolin and 8-15 parts of zeolite powder, wherein the metakaolin and the zeolite powder form composite powder and are attached to the surface of the ferrochromium slag. The ultrafine pores of the zeolite powder can be adsorbed on the dissolved chromium in the concrete, so that the dissolved chromium in the concrete is fixed, and the chromium pollution is further reduced; the metakaolin can produce stable compound solidified chromium with chromium in a cement hydration environment, on one hand, the metakaolin plays a role in fixing the chromium and prevents the chromium from dissolving out to pollute the environment, and on the other hand, the stable chromium compound effectively improves the rigidity of concrete and the binding force between the concrete and aggregate, namely, stable chemical bonds are formed between the cement and the aggregate, the impact resistance of the concrete cement is improved, and the cracking of the concrete is prevented.
Furthermore, the particle size of the composite powder is 5-30 nm. The metakaolin and the zeolite powder form composite particles under the catalytic action of the ferrochrome, and the synergistic effect of the metakaolin and the zeolite powder is generated, so that the chromium can be effectively fixed, the alkali silicate reaction of other aggregates in the concrete can be inhibited, and the cracking phenomenon of the concrete is prevented.
Furthermore, the particle size of the metakaolin is 5-10 nm.
Furthermore, the particle size of the zeolite powder is 2-10 nm.
Further, the zeolite powder is any one or a mixture of more of chabazite powder, erionite powder or phillipsite powder. The zeolite powder is a natural zeolite material, has an aluminosilicate structure, has a firmer silicon-aluminum framework and more active sites due to lower aluminum content and higher silicon content, and is easier to form composite particles with metakaolin.
The invention also aims to provide a preparation method of ferrochrome slag for concrete aggregate, which has the same effect.
The technical effects of the invention are realized by the following technical scheme:
the preparation method of the ferrochrome slag for the concrete aggregate comprises the following operation steps:
s1, heating ferrochromium slag to 140-180 ℃ for 2-3 hours, and heating to 400-500 ℃ for 1-2 hours;
s2, cooling the ferrochrome slag obtained in the step S1 to room temperature, adding the ferrochrome slag into a saturated calcium hydroxide aqueous solution, completely soaking for 1d, and filtering to obtain calcium hydroxide modified ferrochrome slag;
and S3, mixing the ferrochromium slag modified by the calcium hydroxide obtained in the step S2 with zeolite powder and metakaolin to ensure that the zeolite powder and the metakaolin are attached to the surface of the ferrochromium slag to obtain the ferrochromium slag for the concrete aggregate.
As a preferable method of the above technical scheme, the preparation method comprises the following operation steps:
s1, heating ferrochromium slag to 150 ℃ for 2h, and heating to 450 ℃ for 1 h; the gradient heating further oxidizes the chromium, so that the chromium is not easy to dissolve out; the heat energy of the chromium compound can be released by slow cooling to generate crystals, so that the chromium compound is more stable chemically;
s2, cooling the ferrochrome slag obtained in the step S1 to room temperature, adding the ferrochrome slag into a saturated calcium hydroxide aqueous solution, completely soaking for 1d, and filtering to obtain calcium hydroxide modified ferrochrome slag; the main purpose of soaking in saturated calcium hydroxide water for 1d is to dissolve out unstable chromium in advance and avoid the unstable chromium from being dissolved into concrete;
and S3, mixing the ferrochromium slag modified by the calcium hydroxide obtained in the step S2 with zeolite powder and metakaolin to ensure that the zeolite powder and the metakaolin are attached to the surface of the ferrochromium slag to obtain the ferrochromium slag for the concrete aggregate.
As a preferable embodiment of the above technical solution, the specific operation method of step S3 is as follows:
A1. adding the calcium hydroxide modified ferrochrome slag into an aqueous solution of potassium permanganate and ferrocene, and heating to 35-40 ℃;
A2. and D, adding the calcium hydroxide modified ferrochromium slag treated in the step A1 into a mixed aqueous solution of metakaolin and zeolite powder, heating to 50-60 ℃, continuously stirring for 30min, filtering and drying to obtain the ferrochromium slag for the concrete aggregate.
As a preferable scheme of the technical scheme, the aqueous solution mixed by metakaolin and zeolite powder comprises the following components in parts by weight: 5-10 parts of metakaolin, 8-15 parts of zeolite powder, 2-3 parts of hexadecyl trimethyl ammonium bromide, 1-2 parts of EDTA, 4-6 parts of titanate coupling agent and the balance of water. Under the catalytic action of ferrochromium, metakaolin and zeolite powder can form composite powder particles by adding cetyl trimethyl ammonium bromide and titanate coupling agent, wherein EDTA is an auxiliary dispersant.
In conclusion, the invention has the following beneficial effects:
the ferrochrome slag for the concrete aggregate provided by the invention can fix chromium, prevent the chromium from dissolving out in concrete, and enable the ferrochrome slag to be applied to the concrete aggregate.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the embodiments, features and effects of the ferrochrome slag for concrete aggregate according to the present invention will be described in detail as follows.
Wherein the particle size of the composite powder is 5-30 nm; the particle size of the metakaolin is 5-10 nm; the particle size of the zeolite powder is 2-10 nm.
Example 1: the ferrochrome slag for the concrete aggregate comprises the following components in parts by weight: 95 parts of ferrochromium slag, 10 parts of metakaolin and 15 parts of chabazite powder, wherein the metakaolin and the zeolite powder form composite powder and are attached to the surface of the ferrochromium slag.
The preparation method comprises the following steps:
s1, heating ferrochromium slag to 150 ℃ for 2h, and heating to 450 ℃ for 1 h;
s2, cooling the ferrochrome slag obtained in the step S1 to room temperature, adding the ferrochrome slag into a saturated calcium hydroxide aqueous solution, completely soaking for 1d, and filtering to obtain calcium hydroxide modified ferrochrome slag;
and S3, mixing the calcium hydroxide modified ferrochromium slag obtained in the step S2 with chabazite powder and metakaolin to enable the chabazite powder and the metakaolin to be attached to the surface of the ferrochromium slag, so as to obtain the ferrochromium slag for the concrete aggregate.
Example 2: the ferrochrome slag for the concrete aggregate comprises the following components in parts by weight: 80 parts of ferrochromium slag, 5 parts of metakaolin and 8 parts of maotaite powder, wherein the metakaolin and the zeolite powder form composite powder and are attached to the surface of the ferrochromium slag.
The preparation method comprises the following steps:
s1, heating ferrochromium slag to 150 ℃ for 2h, and heating to 450 ℃ for 1 h;
s2, cooling the ferrochrome slag obtained in the step S1 to room temperature, adding the ferrochrome slag into a saturated calcium hydroxide aqueous solution, completely soaking for 1d, and filtering to obtain calcium hydroxide modified ferrochrome slag;
and S3, mixing the ferrochromium slag modified by the calcium hydroxide obtained in the step S2 with zeolite powder and metakaolin to enable the erionite powder and the metakaolin to be attached to the surface of the ferrochromium slag to obtain the ferrochromium slag for the concrete aggregate.
Example 3: the ferrochrome slag for the concrete aggregate comprises the following components in parts by weight: 80 parts of ferrochromium slag, 5 parts of metakaolin and 8 parts of maotaite powder, wherein the metakaolin and the zeolite powder form composite powder and are attached to the surface of the ferrochromium slag.
The preparation method comprises the following steps:
s1, heating ferrochromium slag to 150 ℃ for 2h, and heating to 450 ℃ for 1 h;
s2, cooling the ferrochrome slag obtained in the step S1 to room temperature, adding the ferrochrome slag into a saturated calcium hydroxide aqueous solution, completely soaking for 1d, and filtering to obtain calcium hydroxide modified ferrochrome slag;
and S3, mixing the ferrochromium slag modified by the calcium hydroxide obtained in the step S2 with zeolite powder and metakaolin to enable the erionite powder and the metakaolin to be attached to the surface of the ferrochromium slag to obtain the ferrochromium slag for the concrete aggregate.
The specific operation method of step S3 is as follows:
A1. adding the calcium hydroxide modified ferrochrome slag into an aqueous solution of potassium permanganate and ferrocene, and heating to 35-40 ℃;
A2. and D, adding the calcium hydroxide modified ferrochromium slag treated in the step A1 into a mixed aqueous solution of metakaolin and zeolite powder, heating to 50-60 ℃, continuously stirring for 30min, filtering and drying to obtain the ferrochromium slag for the concrete aggregate.
Example 4: the ferrochrome slag for the concrete aggregate comprises the following components in parts by weight: 80 parts of ferrochromium slag, 5 parts of metakaolin and 8 parts of maotaite powder, wherein the metakaolin and the zeolite powder form composite powder and are attached to the surface of the ferrochromium slag.
The preparation method comprises the following steps:
s1, heating ferrochromium slag to 150 ℃ for 2h, and heating to 450 ℃ for 1 h;
s2, cooling the ferrochrome slag obtained in the step S1 to room temperature, adding the ferrochrome slag into a saturated calcium hydroxide aqueous solution, completely soaking for 1d, and filtering to obtain calcium hydroxide modified ferrochrome slag;
and S3, mixing the ferrochromium slag modified by the calcium hydroxide obtained in the step S2 with zeolite powder and metakaolin to enable the erionite powder and the metakaolin to be attached to the surface of the ferrochromium slag to obtain the ferrochromium slag for the concrete aggregate.
The specific operation method of step S3 is as follows:
A1. adding the calcium hydroxide modified ferrochrome slag into an aqueous solution of potassium permanganate and ferrocene, and heating to 35-40 ℃;
A2. and D, adding the calcium hydroxide modified ferrochromium slag treated in the step A1 into a mixed aqueous solution of metakaolin and zeolite powder, heating to 50-60 ℃, continuously stirring for 30min, filtering and drying to obtain the ferrochromium slag for the concrete aggregate. The aqueous solution mixed by metakaolin and zeolite powder comprises the following components in parts by weight: 5-10 parts of metakaolin, 8-15 parts of zeolite powder, 2-3 parts of hexadecyl trimethyl ammonium bromide, 1-2 parts of EDTA, 4-6 parts of titanate coupling agent and the balance of water. Under the catalytic action of ferrochromium, metakaolin and zeolite powder can form composite powder particles by adding cetyl trimethyl ammonium bromide and titanate coupling agent, wherein EDTA is an auxiliary dispersant.
The test method of the content of the dissoluble chromium and the test data of the example 4 are as follows:
the method for determining leachable heavy metals in cement mortar GB/T30810 tests the leaching condition of the heavy metals of a concrete system after a certain period of hydration reaction, and the test results of each group of 28d are shown in Table 1. The ferrochrome slag aggregate can introduce a certain amount of leachable Mn, Zn and Cr, and the content is in positive correlation with the doping amount of the ferrochrome slag aggregate. From the results, even if the ferrochrome slag aggregate is completely adopted, the leachable heavy metal content of the concrete is lower than 0.2mg/L limited by the technical Specification for cement kiln co-processing solid waste GB 30760. On one hand, under the normal smelting process, the amount of chromium existing in a water-soluble state in the ferrochrome slag is very low; in addition, the C-S-H gel can perform physical adsorption and chemical combination on heavy metal ions in the cement hydration reaction process. Therefore, the content of leachable heavy metals in ferrochrome slag aggregate concrete is very limited.
TABLE 1 concrete leachable heavy metal content (mg/L)
Figure BDA0002598998480000081
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. The ferrochrome slag for the concrete aggregate is characterized by comprising the following components in parts by weight: 80-95 parts of ferrochromium slag, 5-10 parts of metakaolin and 8-15 parts of zeolite powder, wherein the metakaolin and the zeolite powder form composite powder and are attached to the surface of the ferrochromium slag; the preparation method of the ferrochrome slag for the concrete aggregate comprises the following operation steps:
s1, heating the ferrochromium slag to 140-180 ℃ for 2-3 h, and heating to 400-500 ℃ for 1-2 h;
s2, cooling the ferrochrome slag obtained in the step S1 to room temperature, adding the ferrochrome slag into a saturated calcium hydroxide aqueous solution, completely soaking for 1d, and filtering to obtain calcium hydroxide modified ferrochrome slag;
s3, adding the ferrochrome slag modified by the calcium hydroxide obtained in the step S2 into a mixed aqueous solution of zeolite powder and metakaolin, so that the zeolite powder and the metakaolin are attached to the surface of the ferrochrome slag, and obtaining the ferrochrome slag for the concrete aggregate; the mixed aqueous solution of metakaolin and zeolite powder comprises the following components: 5-10 parts of metakaolin, 8-15 parts of zeolite powder, 2-3 parts of hexadecyl trimethyl ammonium bromide, 1-2 parts of EDTA, 4-6 parts of titanate coupling agent and the balance of water.
2. The ferrochrome slag for concrete aggregate according to claim 1, wherein the particle size of the composite powder is 5-30 nm.
3. The ferrochromium slag for concrete aggregates according to claim 1, wherein the particle size of the metakaolin is 5-10 nm.
4. The ferrochrome slag for concrete aggregates as claimed in claim 1, wherein the zeolite powder has a particle size of 2-10 nm.
5. The ferrochromium slag for concrete aggregates according to claim 1, characterized in that the zeolite powder is any one or a mixture of chabazite powder, erionite powder or phillipsite powder.
6. The method for preparing ferrochrome slag for concrete aggregate according to claim 1, comprising the following steps:
s1, heating the ferrochrome slag to 150 ℃ for 2 hours, and heating to 450 ℃ for 1 hour;
s2, cooling the ferrochrome slag obtained in the step S1 to room temperature, adding the ferrochrome slag into a saturated calcium hydroxide aqueous solution, completely soaking for 1d, and filtering to obtain calcium hydroxide modified ferrochrome slag;
s3, adding the ferrochrome slag modified by the calcium hydroxide obtained in the step S2 into a mixed aqueous solution of zeolite powder and metakaolin, and enabling the zeolite powder and the metakaolin to be attached to the surface of the ferrochrome slag to obtain the ferrochrome slag for the concrete aggregate.
7. The preparation method of ferrochrome slag for concrete aggregate according to claim 6, wherein the specific operation method of step S3 is as follows:
a1, adding the calcium hydroxide modified ferrochrome slag into a potassium permanganate and ferrocene aqueous solution, and heating to 35-40 ℃;
a2, adding the calcium hydroxide modified ferrochrome slag treated in the step A1 into a mixed aqueous solution of metakaolin and zeolite powder, heating to 50-60 ℃, continuously stirring for 30min, filtering and drying to obtain the ferrochrome slag for the concrete aggregate.
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