CN112876120B - Sludge incineration ash-based composite admixture and preparation method and application thereof - Google Patents
Sludge incineration ash-based composite admixture and preparation method and application thereof Download PDFInfo
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- CN112876120B CN112876120B CN202110162737.3A CN202110162737A CN112876120B CN 112876120 B CN112876120 B CN 112876120B CN 202110162737 A CN202110162737 A CN 202110162737A CN 112876120 B CN112876120 B CN 112876120B
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- 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
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- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/28—Cements from oil shales, residues or waste other than slag from combustion residues, e.g. ashes or slags from waste incineration
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use 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)
- Combustion & Propulsion (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a sludge incineration ash-based composite admixture and a preparation method and application thereof, belonging to the field of building materials. The sludge incineration ash-based composite admixture mainly comprises sludge incineration ash, fly ash and an excitant, wherein the mass ratio of the sludge incineration ash to the fly ash is (10-50): (50-90), wherein the addition amount of the exciting agent is not more than 5% of the total mass of the sludge incineration ash and the fly ash. According to the invention, the sludge incineration ash is treated by adopting the heavy metal stabilizer, so that the harm of leaching of the solidified heavy metal is stabilized, and the harmless, stabilization and resource utilization of the sludge incineration ash are realized by adopting a physical-chemical combined excitation means and controlling the ball milling time, the addition amount of the exciting agent and the like. The method of the invention has simple integral process and is convenient for wide popularization and application.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a sludge incineration ash-based composite admixture as well as a preparation method and application thereof.
Background
In recent years, due to the continuous deterioration of water environment and the attention on environmental protection in China, a large number of sewage treatment plants are built nationwide. The sludge is a by-product of sewage treatment, the components are complex, the contents of heavy metals, pathogenic microorganisms and refractory microorganisms are high, and serious secondary pollution can be caused if the sludge is not properly treated. The incineration can lead the organic matters in the sludge to be thoroughly decomposed into inorganic matters, carbon dioxide and water under the high-temperature condition, and simultaneously can realize the reduction and harmless treatment of the sludge, which is the current most main sludge heat treatment utilization mode, thereby generating a large amount of sludge incineration ash.
Chemical components of sludge incineration ash are SiO 2 、Al 2 O 3 Mainly, the chemical composition is similar to the main chemical composition of the fly ash. The sludge incineration ash is a porous material, has large water demand, and simultaneously soluble salts and heavy metals such as Zn, cr and the like in the sludge incineration ash are easy to leach, so that the risk of environmental pollution and safety exists. The incineration boiler and incineration process parameters have large difference when the sludge is incinerated, so that the sludge incineration ash has large component difference, siO 2 The content is different from 10 percent to 50 percent, the fineness difference of the collected incineration ash is obvious, the material property fluctuation of the sludge incineration ash in different batches is large, the activity is low, and the resource utilization of the sludge incineration ash is greatly limited.
Therefore, a technology for safely treating and improving the activity of the sludge incineration ash needs to be developed to realize the stabilization, harmlessness and resource utilization of the sludge incineration ash.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a sludge incineration ash-based composite admixture, a preparation method and a use thereof, which are used for solving the problems of the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
One of the purposes of the invention is to provide a sludge incineration ash-based composite admixture which mainly comprises sludge incineration ash, coal ash and an excitant, wherein the mass ratio of the sludge incineration ash to the coal ash is (10-50): (50-90), wherein the addition amount of the excitant is not more than 5% of the total mass of the sludge incineration ash and the fly ash.
Preferably, the mass ratio of the sludge incineration ash powder to the fly ash can be (10-30): (70-90), and may be (20-40): (60-80), and may be (30-50): (50-70).
Preferably, the addition amount of the exciting agent is 0.1-2% of the total mass of the sludge incineration ash powder and the fly ash.
Preferably, the sludge incineration ash is obtained by carrying out incineration treatment on sludge and then carrying out ball milling on the sludge. In the invention, the sludge comes from a municipal sewage treatment plant.
The sludge incineration ash is physically modified by mechanical ball milling, so that on one hand, the microscopic morphology of the sludge incineration ash subjected to mechanical ball milling is changed from a porous state to a small particle aggregation state, the problem of large water demand is effectively solved, meanwhile, the fineness is improved, the reaction area is increased when the sludge incineration ash is used as an admixture, and the gelling activity is improved. On the other hand, the mechanical ball milling treatment improves the quality of the sludge incineration ash and reduces the fluctuation of the quality and material property of the sludge incineration ash.
More preferably, the incineration temperature is 450 ℃ to 1000 ℃. More preferably, the rotation speed of the ball milling is 300r/min to 500r/min, and the ball milling time is 10min to 30min.
Preferably, the screen allowance of the sludge incineration ash passing through a screen with the aperture of 45 mu m is less than or equal to 30 percent.
Preferably, the total mercury, the total arsenic, the total cadmium, the total chromium and the total lead in the sludge-incinerated ash are respectively less than or equal to 5 mg/kg, 75 mg/kg, 5 mg/kg, 600 mg/kg and 300 mg/kg, respectively. The content detection method of heavy metal mercury and arsenic in the invention refers to the specification of HJ702-2014 microwave digestion/atomic fluorescence method for measuring mercury, arsenic, selenium, bismuth and antimony in solid waste, and the content detection method of heavy metal cadmium, chromium, lead and the like refers to the specification of HJ781-2016 inductively coupled plasma emission spectrometry for measuring metal elements in solid waste 22.
Preferably, the sludge incineration ash is a mixture formed by mixing a sludge incineration ash raw material and a heavy metal stabilizer, and the leaching toxicity of the heavy metal in the mixture is as follows: the total mercury is less than or equal to 0.02mg/L, the total arsenic is less than or equal to 0.6mg/L, the total cadmium is less than or equal to 0.1mg/L, the total chromium is less than or equal to 1.5mg/L, and the total lead is less than or equal to 2.0mg/L. The detection method of the technical indexes such as total mercury, total arsenic and total cadmium refers to the environmental safety detection standard CECS397 of cement-based recycled materials: heavy metal leaching toxicity as specified in 2015.
In the invention, the phosphate in the heavy metal stabilizer can form heavy metal salt with extremely low solubility with the heavy metal in the sludge incineration ash, such as zinc phosphate, chromium phosphate and the like, so that on one hand, the leaching amount of the heavy metal is greatly reduced, and on the other hand, heavy metal ions can be exchanged and adsorbed in montmorillonite lattices of the sodium modified bentonite and are more firmly and difficultly leached.
More preferably, the heavy metal stabilizer consists of bentonite, phosphate, sodium carbonate and modified mullite powder, and the mass ratio of the bentonite to the phosphate to the sodium carbonate to the modified mullite powder is (20-40): (30-45): (5-10): (15 to 25).
Further preferably, the SiO of the bentonite is calculated on a dry basis of the bentonite 2 The content is more than or equal to 60 percent, the pH value is 7 to 9, the average grain diameter is 0.9 to 11 mu m, the dispersion degree is less than or equal to 65 mu m, and the ignition loss is less than or equal to 5 percent. The SiO 2 The content of (A) is obtained by converting the mole number of Si element in bentonite into SiO 2 The quality of (2) is obtained.
Further preferably, the preparation method of the modified mullite powder comprises the following steps: immersing the mullite powder into a sulfuric acid aqueous solution, stirring, carrying out suction filtration, drying, and calcining at 400-500 ℃ for 4-5 h to obtain the modified mullite powder.
Still further preferably, the concentration of the sulfuric acid aqueous solution is (0.05-0.15) mol/L, and the mass-volume ratio of the mullite powder to the sulfuric acid is 1g: (4-6) ml.
Still more preferably, the stirring is carried out at 900r/min to 1100r/min for 30min to 40min
Further preferably, the phosphate is selected from one or both of sodium dihydrogen phosphate and potassium dihydrogen phosphate.
More preferably, the mass ratio of the heavy metal stabilizer to the sludge incineration ash is (0.01-5): 100.
More preferably, the mass ratio of the heavy metal stabilizer to the sludge incineration ash is (3-5): 100.
More preferably, the preparation method of the heavy metal stabilizer comprises the following steps: mixing bentonite, phosphate, sodium carbonate and modified mullite powder in proportion, mixing and stirring in a water bath at 50-90 ℃ for 20-40 min, and drying to obtain the heavy metal stabilizer with the water content of less than 1%.
Preferably, the screen allowance of the fly ash passing through a 45-micron sieve is less than or equal to 30 percent, the water demand ratio is less than or equal to 105 percent, the ignition loss is less than or equal to 8 percent, the water content is less than or equal to 1.0 percent, the strength activity index is more than or equal to 70 percent, the stability is qualified and less than or equal to 5.0 percent, the mass fraction of sulfur trioxide in the fly ash is less than or equal to 3.0 percent, the free calcium oxide is less than or equal to 1.0 percent, and the radioactivity ratio activity of natural radionuclides radium-226, thorium-232 and potassium-40 simultaneously meets the requirement I Ra Less than or equal to 1.0 and I γ Less than or equal to 1.0. The detection method of the technical indexes such as the water demand ratio, the ignition loss and the like of the fly ash refers to the regulations in GB/T1596-2017 fly ash for cement and concrete.
Preferably, the exciting agent is one or more selected from aluminum sulfate, sodium sulfate, calcium hydroxide, calcium oxide, magnesium sulfate and sodium hydroxide.
The addition of the excitant effectively improves the retardation of the sludge incineration ash, accelerates the hydration reaction process of the cementing material, generates hydration products such as Calcium Silicate Hydrate (CSH), calcium aluminate hydrate and the like, improves the mechanical property of the sludge incineration ash-based cementing body, simultaneously generates the CSH gel which has larger adsorbability to heavy metals, can solidify the heavy metals scattered in the cementing body, passivates the heavy metals in the sludge incineration ash, solves the problem that the sludge incineration ash is difficult to treat, and realizes the resource utilization of the sludge incineration ash. Preferably, the activator consists essentially of calcium oxide, aluminum sulfate and calcium hydroxide.
More preferably, the mass ratio of the calcium oxide to the aluminum sulfate to the calcium hydroxide is 1 (1-5) to 1. Further preferably, the mass ratio of calcium oxide, aluminum sulfate and calcium hydroxide is 1.
The second purpose of the invention is to provide a preparation method of the sludge incineration ash-based composite admixture, which comprises the following steps of mixing sludge incineration ash, fly ash and an excitant.
Preferably, the mixing is dry mixing, and the mixing time is 8-12 min.
More preferably, the mixing time is 9min to 12min.
The invention also aims to provide the sludge incineration ash-based composite admixture which is used as a substitute for fly ash in cement concrete building materials.
When the sludge incineration ash-based composite admixture provided by the invention is used in cement concrete, the microscopic morphology of the sludge incineration ash is changed from a porous state to a small particle aggregation state through ball milling modification, so that a certain water reducing effect is achieved, and the improvement of the working performance of the concrete is facilitated; the addition of the excitant effectively improves the retardation of the sludge incineration ash, and is beneficial to improving the cementation property and the mechanical property of the concrete. Therefore, the sludge incineration ash-based composite admixture provided by the invention can replace fly ash to be well used in cement concrete building materials, so that the resource utilization level of the sludge incineration ash is improved, and the production cost of cement concrete is reduced.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the sludge incineration ash is treated by adopting the heavy metal stabilizer, so that the harm of leaching of the solidified heavy metal is stabilized, and the gelation activity of the sludge incineration ash is improved by more than 20% by adopting a physical-chemical combined excitation means through controlling the ball milling time and adding the excitant, so that the harmless, stabilization and resource utilization of the sludge incineration ash are realized. The method has simple integral process and is convenient for wide popularization.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
In the embodiment of the application, the exciting agent is a mixture of calcium oxide, aluminum sulfate and calcium hydroxide, and the mass ratio of calcium oxide, aluminum sulfate and calcium hydroxide is 1.
In the embodiment of the application, the fly ash is II-grade fly ash which is specified in national standard GB/T1596-2017 fly ash for cement and concrete in a certain power plant and is used as a raw material, the chemical components of the fly ash are shown in Table 1, and the strength activity index is more than or equal to 70%.
TABLE 1 main technical indexes of fly ash
| Index (es) | 45 μm sieve fraction% | Water requirement/%) | Ignition loss/% | Water content% | Stability of | Radioactivity |
| Parameter(s) | 23.6 | 100 | 4.7 | 0.5 | Qualified | Qualified |
Example 1
In the embodiment, the sludge incineration ash is prepared by mixing a sludge incineration ash raw material and a heavy metal stabilizer, and comprises the following steps:
(1) Preparing modified mullite powder: immersing the mullite powder into a sulfuric acid aqueous solution, stirring for 40min at the rotating speed of 1000r/min, carrying out vacuum filtration, drying, and then calcining for 4.5h at the high temperature of 450 ℃ in a nitrogen atmosphere to obtain the modified mullite powder. Wherein the mass volume ratio of the mullite powder to the sulfuric acid is 1g:5ml, the concentration of the sulfuric acid aqueous solution is 0.1mol/L.
(2) And mixing the bentonite, the sodium dihydrogen phosphate, the sodium carbonate and the modified mullite powder according to the mass ratio of 25.
(3) And mixing the heavy metal stabilizer with the sludge incineration ash raw material according to the mass ratio of 1.
The mixture ratio of the heavy metal stabilizer and the mass ratio of the sludge incineration ash raw material to the heavy metal stabilizer in examples 2 to 4 are shown in table 2, and the results of the heavy metal content are shown in table 2 in the same manner as in example 1.
TABLE 2 compounding ratios and heavy metal test results of examples 1 to 4 and comparative example 1
Example 5
In this example, the sludge incineration ash-based composite admixture was prepared as follows:
and (2) dry-mixing the sludge incineration ash and the fly ash for 10min according to the mass ratio of 20. Wherein the sludge incineration ash is sludge which is incinerated, and the fineness obtained after the treatment of ball milling at the rotating speed of 300r/min and the ball milling time of 10min is 22.1 percent of the screen residue passing through a screen with the aperture of 45 mu m; based on the dry weight of the sludge, the total mercury, the total arsenic, the total cadmium, the total copper, the total chromium, the total zinc, the total lead and the total nickel in the sludge incineration ash are respectively less than or equal to 5 mg/kg, less than or equal to 75 mg/kg, less than or equal to 5 mg/kg, less than or equal to 800 mg/kg, less than or equal to 600 mg/kg, less than or equal to 2000 mg/kg, less than or equal to 300 mg/kg and less than or equal to 100 mg/kg. The obtained sludge incineration ash-based composite admixture is subjected to index measurement such as strength activity index, drying shrinkage and the like, and the detection result is detailed in table 4.
The specific parameters in examples 5 to 7 are shown in Table 3, the other steps are the same as in example 5, and the test results are shown in Table 4.
Comparative example 2
The sludge incineration ash which is not subjected to ball milling is directly used as a raw material, other parameters are detailed in a table 3 in the same way as in example 5, and the detection results are detailed in a table 4.
Comparative example 3
The concrete parameters are detailed in table 3 and the detection results are detailed in table 4, which are the same as those in example 6 except that no exciting agent is added.
Comparative example 4
The specific parameters are detailed in Table 3 and the results are detailed in Table 4, using only one activator, otherwise the same as in example 7.
TABLE 3 compounding ratios, ball milling speeds and times, screen margins of the composite admixtures of examples 5 to 7 and comparative examples 2 to 4
TABLE 4 technical Performance indexes of composite admixtures of examples 5 to 7 and comparative examples 2 to 4
As can be seen from Table 4, the strength activity index, the stability, the radioactivity and other properties of the prepared sludge incineration ash-based composite admixture 28d meet the requirements of II-grade fly ash in the national standard GB/T1596-2017 fly ash for cement and concrete, and the radioactivity meets the requirements (I) in the GB6566-2010 radionuclide limits for building materials Ra ≤1.0，I γ ≤1.0)。
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims (6)
1. The sludge incineration ash-based composite admixture for the building material is characterized by comprising sludge incineration ash, coal ash and an excitant, wherein the mass ratio of the sludge incineration ash to the coal ash is (10-50): (50 to 90), wherein the addition amount of the excitant is not more than 5% of the total mass of the sludge incineration ash and the coal ash, the excitant is a mixture of calcium oxide, aluminum sulfate and calcium hydroxide, and the mass ratio of the calcium oxide to the aluminum sulfate to the calcium hydroxide is 1;
the sludge incineration ash is a mixture formed by mixing a sludge incineration ash raw material and a heavy metal stabilizer, and the leaching toxicity of heavy metals in the mixture is as follows: total mercury is less than or equal to 0.02mg/L, total arsenic is less than or equal to 0.6mg/L, total cadmium is less than or equal to 0.1mg/L, total chromium is less than or equal to 1.5mg/L, and total lead is less than or equal to 2.0 mg/L;
the heavy metal stabilizer consists of bentonite, phosphate, sodium carbonate and modified mullite powder, wherein the mass ratio of the bentonite to the phosphate to the sodium carbonate to the modified mullite powder is (20 to 40): (30 to 45): (5 to 10): (15 to 25) of the reaction mixture,
the preparation method of the modified mullite powder comprises the following steps: immersing the mullite powder into a sulfuric acid aqueous solution, stirring, filtering, drying, and calcining at 400-500 ℃ for 4-5 hours to obtain the modified mullite powder.
2. The sludge incineration ash-based composite admixture according to claim 1, wherein the sludge incineration ash has a screen residue amount of 30% or less passing through a screen having a pore size of 45 μm.
3. The sludge incineration ash-based composite admixture according to claim 1, wherein the mass ratio of the heavy metal stabilizer to the sludge incineration ash raw material is (0.01 to 5): 100.
4. The sludge incineration ash-based composite admixture according to claim 1, wherein the SiO of bentonite is based on the dry basis of bentonite 2 The content is more than or equal to 60 percent, the pH value is 7 to 9, the average grain diameter is 0.9 to 11 mu m, the dispersion degree is less than or equal to 65 mu m, and the ignition loss is less than or equal to 5 percent;
and/or the phosphate is selected from one or two of sodium dihydrogen phosphate and potassium dihydrogen phosphate.
5. The sludge incineration ash-based composite admixture according to claim 1, wherein the amount of fly ash passing through a 45 μm sieve is 30% or less, the water demand ratio is 105% or less, the loss on ignition is 8% or less, the water content is 1.0% or less, the strength activity index is 70% or more, the stability is qualified 5.0% or less, and the radioactivity ratio of natural radionuclides radium-226, thorium-232 and potassium-40 in the fly ash simultaneously satisfies I Ra Less than or equal to 1.0 and I γ ≤1.0。
6. The method for producing the sludge incineration ash-based composite admixture according to any one of claims 1 to 5, wherein the method comprises mixing sludge incineration ash, fly ash and an activator.
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| CN113461356B (en) * | 2021-07-09 | 2023-03-21 | 上海市政工程设计研究总院（集团）有限公司 | Method for preparing active admixture by sludge and muck |
| CN114873939A (en) * | 2022-06-10 | 2022-08-09 | 上海宝宁环保科技有限公司 | Equipment and method for preparing concrete admixture by recycling sludge incineration ash |
| CN116063011A (en) * | 2022-12-23 | 2023-05-05 | 上海市建筑科学研究院有限公司 | Cementing material special for secant pile concrete and preparation method and application thereof |
| CN116553852A (en) * | 2023-04-10 | 2023-08-08 | 上海复洁环保科技股份有限公司 | Retarder and reinforcing agent, retarder cement for roads and preparation method of retarder and reinforcing agent |
| CN117486551A (en) * | 2024-01-02 | 2024-02-02 | 北京哈泰克工程技术有限公司 | Composite material based on sludge incineration ash and preparation method thereof |
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| CN112876120A (en) | 2021-06-01 |
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