Coal gangue powder and fly ash composite master batch and preparation method thereof

Abstract

The invention relates to a coal gangue powder and fly ash composite master batch and a preparation method thereof. The coal gangue powder and fly ash composite master batch comprises the following components in parts by weight: 30-60 parts of coal gangue powder; 20 to 40 parts of fly ash; 15 to 30 parts of biodegradable resin; 5 to 10 parts of a compatilizer; 4-8 parts of a sintering aid; 4-7 parts of a surface modifier; and 2-6 parts of other auxiliary agents. The coal gangue powder and the fly ash are used, the biodegradable resin, the compatilizer, the sintering aid, the surface modifier and other aids are added, and the surface modification technology and the compatilizer are selected, so that the compatibility problem of inorganic powder and organic resin is effectively solved; the obtained composite master batch has the characteristics of high compressive strength, long weather-proof period, excellent product size stability and the like, is easy to degrade after being used, and does not cause greater pressure to the environment.

Description

Technical Field

[0001] This invention relates to the field of solid waste resource utilization technology, specifically to a composite masterbatch of coal gangue powder and fly ash and its preparation method. Background Technology

[0002] Coal dominates my country's energy structure, and the resulting large quantities of industrial solid waste, such as coal gangue and fly ash, place severe pressure on the environment. Coal gangue is a solid waste discharged during coal mining and washing; it has a low carbon content and high hardness. Fly ash is the fine ash collected from flue gas after coal combustion. Current statistics show that my country produces over 100 million tons of fly ash annually, with a utilization rate of only about 25%. Most of it is disposed of through ash storage yards, which not only occupy large amounts of land but also pollute the soil, water, and air.

[0003] In existing technologies, the main methods for disposing of fly ash and coal gangue include: landfill (which wastes land resources and causes potential environmental pollution), low-grade building material applications (such as the production of bricks and cement, which have low added value), and adsorbent preparation (which involves complicated procedures and requires sophisticated equipment). Although some studies have attempted to use fly ash as a plastic filler, problems such as poor dispersibility, poor compatibility, and impact on the mechanical properties of the products exist.

[0004] For example, patent publication number CN106064048A discloses a fly ash / coal gangue composite material and its preparation process, which mixes fly ash and coal gangue in a certain proportion and adds an adsorption aid for use in the field of adsorbents, but the application scope of this product is limited.

[0005] For example, patent publication number CN105949565A discloses an LDPE plastic masterbatch containing fly ash and its preparation method. It uses fly ash and waste LDPE plastic to prepare masterbatch for drip irrigation tape, but it mainly focuses on specific application areas and fails to make full use of coal gangue resources.

[0006] Existing technologies for the high-value utilization of coal gangue and fly ash include the preparation of building materials, ceramics, and composite materials, but they suffer from the following shortcomings: Single raw material: Most utilize single solid waste as raw material, failing to fully utilize the synergistic effect of the two; Complex process: Requires high-temperature calcination (e.g., above 1200℃) or complex modification, resulting in high energy consumption and cost; Performance limitations: Products have insufficient mechanical properties or degradability, making it difficult to meet the demands of high-end materials. Therefore, there is an urgent need to design a composite masterbatch of coal gangue powder and fly ash and its preparation method to solve these problems. Summary of the Invention

[0007] The purpose of this invention is to provide a composite masterbatch of coal gangue powder and fly ash and its preparation method, so as to solve the above-mentioned shortcomings in the prior art.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] A composite masterbatch of coal gangue powder and fly ash, comprising the following components in parts by weight:

[0010] Coal gangue powder: 30-60 parts;

[0011] Fly ash: 20-40 parts;

[0012] Biodegradable resin: 15-30 parts;

[0013] Compatibilizer: 5-10 parts;

[0014] Sintering aid: 4-8 parts;

[0015] Surface modifier: 4-7 parts;

[0016] Other adjuvants: 2-6 parts.

[0017] In a preferred embodiment of the present invention, the coal gangue powder is activated by calcination at 800-900℃ and has a particle size ≤0.15mm;

[0018] Fly ash is activated by microwave. The power of the microwave equipment is 800-1000W, the time is 5-10min, and the particle size is ≤0.075mm.

[0019] In a preferred embodiment of the present invention, the biodegradable resin includes one or more of polylactic acid, poly(3-hydroxyalkanoate), poly(ε-caprolactone), polyesters, aliphatic aromatic copolyesters, and polyvinyl alcohol.

[0020] In a preferred embodiment of the present invention, the compatibilizer is at least one of maleic anhydride-grafted polyolefin, aluminate coupling agent, or silane coupling agent.

[0021] In a preferred embodiment of the present invention, the surface modifier is a mixture of 1-2 parts coupling agent, 1-2 parts compatibilizer, and 1 part lubricant in a specified ratio. The coupling agent, compatibilizer, and lubricant are respectively silane coupling agent KH550, maleic anhydride grafting compatibilizer, and calcium stearate.

[0022] In a preferred embodiment of the present invention, the other additives include one or more of heat stabilizers, plasticizers, and colorants; the sintering aid is borax or feldspar powder.

[0023] A method for preparing the composite masterbatch of coal gangue powder and fly ash as described above includes the following steps:

[0024] S1. Raw material pretreatment: After crushing, coal gangue is ball-milled for 30-60 minutes, passed through a 100-mesh sieve, sintering aid is added, and calcined at 800-900℃ for 2-3 hours to remove organic matter and activate silicon-aluminum activity; fly ash is activated by microwave with a power of 800-1000W to improve surface activity. The particle size of coal gangue powder is ≤0.15mm, and the particle size of fly ash is ≤0.075mm, ready for use.

[0025] S2. Mixed Modification: The treated fly ash and coal gangue powder are added to a high-speed mixer, and biodegradable resin, compatibilizer, surface modifier, and other additives are added to the interior of the high-speed mixer.

[0026] S3, Melt Extrusion: The mixed and modified raw materials are added to a twin-screw extruder and melt extruded;

[0027] S4. Granulation: The extrudate is cooled with water and granulated to obtain a composite masterbatch with a particle size of 2-5 mm.

[0028] In a preferred embodiment of the present invention, the high-speed mixer is used to add materials at 70% of the total capacity, the temperature is 100-120℃, the stirring time is 10-15 min, and the rotation speed is 4200-4600 r / min.

[0029] In a preferred embodiment of the present invention, the screw length-to-diameter ratio of the twin-screw extruder is 40:1-48:1, and the main machine speed is 300-500 r / min.

[0030] In a preferred embodiment of the present invention, the twin-screw extruder has at least three temperature zones: the zone temperatures from the feeding end to the extrusion end are: feeding zone temperature 100-140℃, melting zone temperature 170-190℃, and extrusion zone temperature 150-170℃.

[0031] In the above technical solution, the present invention provides a composite masterbatch of coal gangue powder and fly ash and its preparation method, which has the following beneficial effects:

[0032] By utilizing coal gangue powder and fly ash, along with the addition of biodegradable resins, compatibilizers, sintering aids, surface modifiers, and other additives, a large amount of industrial solid waste such as coal gangue and fly ash is utilized. This solves the pollution problems of these wastes on personnel, land, and the environment, prevents pollution caused by industrial waste, and conforms to the concepts of circular economy and sustainable development. Through the selection of surface modification technology and compatibilizers, the compatibility problem between inorganic powders and organic resins is effectively solved. The resulting composite masterbatch has the characteristics of high compressive strength, long weather resistance, and excellent product dimensional stability.

[0033] This composite masterbatch can be used to produce a variety of plastic products, such as drip irrigation tape, packaging materials, and engineering plastic parts, providing a new way for the comprehensive utilization of fly ash and coal gangue. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this invention. For those skilled in the art, other drawings can be obtained based on these drawings.

[0035] Figure 1 This is a flowchart illustrating an embodiment of the present invention: a composite masterbatch of coal gangue powder and fly ash and its preparation method.

[0036] Figure 2 Performance test table provided for an embodiment of the present invention of a composite masterbatch of coal gangue powder and fly ash and its preparation method. Detailed Implementation

[0037] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with the accompanying drawings and preferred embodiments, is provided below.

[0038] like Figure 1 As shown in the embodiment of the present invention, a composite masterbatch of coal gangue powder and fly ash is composed of the following components in parts by weight:

[0039] Coal gangue powder: 30-60 parts;

[0040] Fly ash: 20-40 parts;

[0041] Biodegradable resin: 15-30 parts;

[0042] Compatibilizer: 5-10 parts;

[0043] Sintering aid: 4-8 parts;

[0044] Surface modifier: 4-7 parts;

[0045] Other adjuvants: 2-6 parts.

[0046] Among them, the coal gangue powder is activated by calcination at 800-900℃ and has a particle size ≤0.15mm;

[0047] Fly ash is activated by microwave, with a power of 800-1000W and a activation time of 5-10 minutes, resulting in a particle size ≤0.075mm. The biodegradable resin includes one or more of polylactic acid, poly(3-hydroxyalkanoate), poly(ε-caprolactone), polyesters, aliphatic aromatic copolyesters, and polyvinyl alcohol. The compatibilizer is at least one of maleic anhydride-grafted polyolefin, aluminate coupling agent, or silane coupling agent. The surface modifier is a mixture of 1-2 parts coupling agent, 1-2 parts compatibilizer, and 1 part lubricant in a specified ratio; the coupling agent, compatibilizer, and lubricant correspond to silane coupling agent KH550, maleic anhydride-grafted compatibilizer, and calcium stearate, respectively. Other additives include one or more of heat stabilizers, plasticizers, and colorants; the sintering aid is borax or feldspar powder.

[0048] A method for preparing composite masterbatch such as coal gangue powder and fly ash includes the following steps:

[0049] S1. Raw material pretreatment: After crushing, coal gangue is ball-milled for 30-60 minutes, passed through a 100-mesh sieve, sintering aid is added, and calcined at 800-900℃ for 2-3 hours to remove organic matter and activate silicon-aluminum activity; fly ash is activated by microwave with a power of 800-1000W to improve surface activity. The particle size of coal gangue powder is ≤0.15mm, and the particle size of fly ash is ≤0.075mm, ready for use.

[0050] S2. Mixing and Modification: The treated fly ash and coal gangue powder are added to a high-speed mixer, and biodegradable resin, compatibilizer, surface modifier, and other additives are added to the interior of the high-speed mixer. The high-speed mixer is fed at 70% of its total capacity, the temperature is 100-120℃, the stirring time is 10-15 min, and the speed is 4200-4600 r / min.

[0051] S3. Melt Extrusion: The mixed and modified raw materials are added to a twin-screw extruder for melt extrusion. The screw length-to-diameter ratio of the twin-screw extruder is 40:1-48:1, and the main extruder speed is 300-500 r / min. The twin-screw extruder has at least three temperature zones: from the feeding end to the extrusion end, the zone temperatures are: feeding zone temperature 100-140℃, melting zone temperature 170-190℃, and extrusion zone temperature 150-170℃.

[0052] S4. Granulation: The extrudate is cooled with water and granulated to obtain a composite masterbatch with a particle size of 2-5 mm.

[0053] Example 1

[0054] A composite masterbatch of coal gangue powder and fly ash is composed of the following components in parts by weight: coal gangue powder: 30 parts; fly ash: 40 parts; biodegradable resin: 15 parts; compatibilizer: 5 parts; sintering aid: 4 parts; surface modifier: 4 parts; other additives: 2 parts.

[0055] Among them, the coal gangue powder is activated by calcination at 850℃ and has a particle size ≤0.15mm;

[0056] Fly ash was activated using microwave equipment with a power of 900W for 10 minutes, resulting in a particle size ≤0.075mm. The biodegradable resin was polylactic acid. The compatibilizer was a silane coupling agent. The surface modifier was a mixture of 2 parts coupling agent, 2 parts compatibilizer, and 1 part lubricant, respectively. Other additives included plasticizers and colorants; the sintering aid was feldspar powder.

[0057] A method for preparing composite masterbatch such as coal gangue powder and fly ash includes the following steps:

[0058] S1. Raw material pretreatment: After crushing, coal gangue is ball-milled for 50 minutes, passed through a 100-mesh sieve, and sintering aids are added. The mixture is then calcined at 850℃ for 2-3 hours to remove organic matter and activate silicon-aluminum activity. Fly ash is activated by microwave (900W) to enhance surface activity. The particle size of coal gangue powder is ≤0.15mm, and the particle size of fly ash is ≤0.075mm. This is then set aside. S2. Mixing and modification: The treated fly ash and coal gangue powder are added to a high-speed mixer. Biodegradable resin, compatibilizer, surface modifier, and other additives are added to the high-speed mixer. The high-speed mixer is filled to 70% of its total capacity, at a temperature of 110℃, a stirring time of 15 minutes, and a rotation speed of 4500 r / min. S3. Melt Extrusion: The mixed and modified raw materials are added to a twin-screw extruder for melt extrusion. The twin-screw extruder has a screw length-to-diameter ratio of 40:35:1 and a main extruder speed of 400 r / min. The twin-screw extruder has at least three temperature zones: from the feeding end to the extrusion end, the zone temperatures are: feeding zone temperature 110℃, melting zone temperature 170℃, and extrusion zone temperature 150℃. S4. Granulation: The extrudate is water-cooled and pelletized to obtain composite masterbatch with a particle size of 2-5 mm.

[0059] Example 2

[0060] A composite masterbatch of coal gangue powder and fly ash is composed of the following components in parts by weight: coal gangue powder: 35 parts; fly ash: 28 parts; biodegradable resin: 22 parts; compatibilizer: 5 parts; sintering aid: 4 parts; surface modifier: 4 parts; other additives: 2 parts.

[0061] Among them, the coal gangue powder is activated by calcination at 850℃ and has a particle size ≤0.15mm;

[0062] Fly ash was activated using microwave equipment with a power of 900W for 10 minutes, resulting in a particle size ≤0.075mm. The biodegradable resin was polylactic acid. The compatibilizer was a silane coupling agent. The surface modifier was a mixture of 2 parts coupling agent, 2 parts compatibilizer, and 1 part lubricant, respectively. Other additives included plasticizers and colorants; the sintering aid was feldspar powder.

[0063] A method for preparing composite masterbatch such as coal gangue powder and fly ash includes the following steps:

[0064] S1. Raw material pretreatment: After crushing, coal gangue is ball-milled for 50 minutes, passed through a 100-mesh sieve, and sintering aids are added. The mixture is then calcined at 850℃ for 2-3 hours to remove organic matter and activate silicon-aluminum activity. Fly ash is activated by microwave (900W) to enhance surface activity. The particle size of coal gangue powder is ≤0.15mm, and the particle size of fly ash is ≤0.075mm. This is then set aside. S2. Mixing and modification: The treated fly ash and coal gangue powder are added to a high-speed mixer. Biodegradable resin, compatibilizer, surface modifier, and other additives are added to the high-speed mixer. The high-speed mixer is filled to 70% of its total capacity, at a temperature of 110℃, a stirring time of 15 minutes, and a rotation speed of 4500 r / min. S3. Melt Extrusion: The mixed and modified raw materials are added to a twin-screw extruder for melt extrusion. The twin-screw extruder has a screw length-to-diameter ratio of 40:35:1 and a main extruder speed of 400 r / min. The twin-screw extruder has at least three temperature zones: from the feeding end to the extrusion end, the zone temperatures are: feeding zone temperature 110℃, melting zone temperature 170℃, and extrusion zone temperature 150℃. S4. Granulation: The extrudate is water-cooled and pelletized to obtain composite masterbatch with a particle size of 2-5 mm.

[0065] Example 3

[0066] A composite masterbatch of coal gangue powder and fly ash is composed of the following components in parts by weight: coal gangue powder: 37 parts; fly ash: 22 parts; biodegradable resin: 26 parts; compatibilizer: 5 parts; sintering aid: 4 parts; surface modifier: 4 parts; other additives: 2 parts.

[0067] Among them, the coal gangue powder is activated by calcination at 850℃ and has a particle size ≤0.15mm;

[0068] Fly ash was activated using microwave equipment with a power of 900W for 10 minutes, resulting in a particle size ≤0.075mm. The biodegradable resin was polylactic acid. The compatibilizer was a silane coupling agent. The surface modifier was a mixture of 2 parts coupling agent, 2 parts compatibilizer, and 1 part lubricant, respectively. Other additives included plasticizers and colorants; the sintering aid was feldspar powder.

[0069] A method for preparing composite masterbatch such as coal gangue powder and fly ash includes the following steps:

[0070] S1. Raw material pretreatment: After crushing, coal gangue is ball-milled for 50 minutes, passed through a 100-mesh sieve, and sintering aids are added. The mixture is then calcined at 850℃ for 2-3 hours to remove organic matter and activate silicon-aluminum activity. Fly ash is activated by microwave (900W) to enhance surface activity. The particle size of coal gangue powder is ≤0.15mm, and the particle size of fly ash is ≤0.075mm. This is then set aside. S2. Mixing and modification: The treated fly ash and coal gangue powder are added to a high-speed mixer. Biodegradable resin, compatibilizer, surface modifier, and other additives are added to the high-speed mixer. The high-speed mixer is filled to 70% of its total capacity, at a temperature of 110℃, a stirring time of 15 minutes, and a rotation speed of 4500 r / min. S3. Melt Extrusion: The mixed and modified raw materials are added to a twin-screw extruder for melt extrusion. The twin-screw extruder has a screw length-to-diameter ratio of 40:35:1 and a main extruder speed of 400 r / min. The twin-screw extruder has at least three temperature zones: from the feeding end to the extrusion end, the zone temperatures are: feeding zone temperature 110℃, melting zone temperature 170℃, and extrusion zone temperature 150℃. S4. Granulation: The extrudate is water-cooled and pelletized to obtain composite masterbatch with a particle size of 2-5 mm.

[0071] The masterbatches obtained in Examples 1, 2, and 3 above were subjected to performance tests, such as... Figure 2 It can be seen that the masterbatch prepared in the example has the best performance.

[0072] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A composite masterbatch of coal gangue powder and fly ash, characterized in that, It consists of the following components in parts by weight: Coal gangue powder: 30-60 parts; Fly ash: 20-40 parts; Biodegradable resin: 15-30 parts; Compatibilizer: 5-10 parts; Sintering aid: 4-8 parts; Surface modifier: 4-7 parts; Other adjuvants: 2-6 parts.

2. The composite masterbatch of coal gangue powder and fly ash according to claim 1, characterized in that, The coal gangue powder is activated by calcination at 800-900℃, and the particle size is ≤0.15mm; Fly ash is activated by microwave. The power of the microwave equipment is 800-1000W, the time is 5-10min, and the particle size is ≤0.075mm.

3. The composite masterbatch of coal gangue powder and fly ash according to claim 1, characterized in that, Biodegradable resins include one or more of polylactic acid, poly(3-hydroxyalkanoate), poly(ε-caprolactone), polyesters, aliphatic aromatic copolyesters, and polyvinyl alcohol.

4. The composite masterbatch of coal gangue powder and fly ash according to claim 1, characterized in that, The compatibilizer is at least one of maleic anhydride-grafted polyolefin, aluminate coupling agent, or silane coupling agent.

5. The composite masterbatch of coal gangue powder and fly ash according to claim 1, characterized in that, The surface modifier is a mixture of 1-2 parts coupling agent, 1-2 parts compatibilizer, and 1 part lubricant in a certain proportion. The coupling agent, compatibilizer, and lubricant correspond to silane coupling agent KH550, maleic anhydride grafting compatibilizer, and calcium stearate, respectively.

6. The composite masterbatch of coal gangue powder and fly ash according to claim 1, characterized in that, The other additives include one or more of heat stabilizers, plasticizers, and colorants; the sintering aid is borax or feldspar powder.

7. A method for preparing composite masterbatch of coal gangue powder and fly ash as described in any one of claims 1-6, characterized in that, Includes the following steps: S1. Raw material pretreatment: After crushing, coal gangue is ball-milled for 30-60 minutes, passed through a 100-mesh sieve, sintering aid is added, and calcined at 800-900℃ for 2-3 hours to remove organic matter and activate silicon-aluminum activity; fly ash is activated by microwave with a power of 800-1000W to improve surface activity. The particle size of coal gangue powder is ≤0.15mm, and the particle size of fly ash is ≤0.075mm, ready for use. S2. Mixed Modification: The treated fly ash and coal gangue powder are added to a high-speed mixer, and biodegradable resin, compatibilizer, surface modifier, and other additives are added to the interior of the high-speed mixer. S3, Melt Extrusion: The mixed and modified raw materials are added to a twin-screw extruder and melt extruded; S4. Granulation: The extrudate is cooled with water and granulated to obtain a composite masterbatch with a particle size of 2-5 mm.

8. The method for producing composite masterbatch of coal gangue powder and fly ash according to claim 7, characterized in that, The high-speed mixer is used to add materials at 70% of the total capacity, with a temperature of 100-120℃, a mixing time of 10-15 minutes, and a rotation speed of 4200-4600 r / min.

9. The method for producing composite masterbatch of coal gangue powder and fly ash according to claim 7, characterized in that, The screw length-to-diameter ratio of the twin-screw extruder is 40:1-48:1, and the main machine speed is 300-500 r / min.

10. The method for producing composite masterbatch of coal gangue powder and fly ash according to claim 9, characterized in that, The temperature zones of a twin-screw extruder should be at least three: from the feeding end to the extrusion end, the zone temperatures should be: feeding zone temperature 100-140℃, melting zone temperature 170-190℃, and extrusion zone temperature 150-170℃.

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