WO2022233038A1 - 利用煤矸石制备涂料用复合颜填料的方法 - Google Patents

利用煤矸石制备涂料用复合颜填料的方法 Download PDF

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WO2022233038A1
WO2022233038A1 PCT/CN2021/092166 CN2021092166W WO2022233038A1 WO 2022233038 A1 WO2022233038 A1 WO 2022233038A1 CN 2021092166 W CN2021092166 W CN 2021092166W WO 2022233038 A1 WO2022233038 A1 WO 2022233038A1
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coal gangue
mill
calcining
fillers
coating
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French (fr)
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尚志新
张梅
郭昊
王晨宁
马洪才
任冬寅
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德州学院
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Priority to CN202180013820.2A priority Critical patent/CN115066468B/zh
Priority to PCT/CN2021/092166 priority patent/WO2022233038A1/zh
Publication of WO2022233038A1 publication Critical patent/WO2022233038A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C—CHEMISTRY; METALLURGY
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/003—Flushing
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/043—Drying, calcination
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Definitions

  • the invention belongs to the field of green resource utilization of industrial solid waste, and particularly relates to a method for preparing composite pigments and fillers for coatings by using coal gangue.
  • carbon black is the most widely used colorant (pigment) in the coatings field and is often used to produce black or gray coatings.
  • pigment the most widely used colorant (pigment) in the coatings field and is often used to produce black or gray coatings.
  • the composition, density, particle size, hydrophilicity and other physical and chemical properties of carbon black are quite different from commonly used inorganic fillers (such as calcium carbonate, barium sulfate, calcined kaolin, talc, wollastonite, etc.) Delamination leads to floating and blooming of the paint, which in turn affects the storage stability of the paint.
  • Carbon black has a large specific surface area and high oil absorption value, and it is easy to absorb a large amount of solvents and additives, causing problems such as thickening, thickening and whitening of oil-based coatings after storage.
  • titanium dioxide-based white composite pigments and fillers are prepared by physical coating or chemical coating, due to the difference in properties of carbon black and inorganic fillers, it is difficult to obtain the corresponding composite pigments and fillers, and there is no black composite pigment yet. related reports on fillers.
  • Coal gangue is a rock with more than 50% dry basis ash produced during the mining and washing process of coal mines, accounting for about 12% of the coal mining volume. In 2020 alone, about 800 million tons of coal gangue will be produced in China. According to incomplete statistics, China's current coal gangue stockpile has reached 6 billion tons, covering an area of about 200,000 mu. A large amount of coal gangue accumulation occupies a large amount of land and will also cause surface subsidence, soil erosion, groundwater pollution and air pollution. . At present, the comprehensive utilization rate of coal gangue in China is less than 50%. It is mainly used for coal gangue power generation, production of building materials, land reclamation and backfilling and production of calcined kaolin. Generally speaking, there are problems of low added value of products or high energy consumption.
  • the present invention provides a method for preparing composite pigments and fillers for coatings by using coal gangue.
  • coal gangue contains a small amount of coal-like organic matter, and its color is dark black.
  • coal and diagenetic minerals are mixed and symbiotic, and the combination is very stable, and the diagenetic minerals kaolin, quartz and other coatings of coal gangue are commonly used fillers. Therefore, Coal gangue has the potential to produce composite pigments and fillers for coatings.
  • the method of the invention can prepare composite pigments and fillers (that is, the composite pigments and fillers have the functions of pigments and fillers at the same time) according to the mineral properties of coal gangue through a suitable production process, which not only solves the problems in the coating industry, but also realizes the improvement of coal gangue.
  • the green and high-value utilization of this method has good technical applicability and can comprehensively utilize a variety of coal gangue.
  • a method for preparing composite pigments and fillers for coatings using coal gangue comprising some of the five steps of pretreatment, heat treatment, ultrafine pulverization, physical modification and chemical modification :
  • Pretreatment mainly includes four steps: washing, screening, coarse crushing and magnetic separation.
  • the water washing is to wash off the sediment and floating dust on the surface of the coal gangue with water.
  • the screening is to manually remove the symbiotic minerals with light color and uneven distribution of coal organic matter.
  • the coarse crushing is to use coarse crushing equipment to crush the raw ore to 80-200 mesh.
  • the magnetic separation is to use a magnetic separator to remove particles with high iron content in the coarsely crushed material.
  • Heat treatment is to calcine the magnetically separated material in multiple stages to remove the volatile matter in the coal gangue, and this process can be omitted for the coal gangue with low volatile matter.
  • Ultrafine pulverization use ultrafine pulverizing equipment to pulverize the coal gangue to a certain fineness, and the ultrafine pulverized material can be used as a composite pigment and filler for water-based paints, paints or powder coatings.
  • Chemical modification Use modification equipment, select the appropriate modifier and dosage, and perform surface treatment on the material after physical modification under certain conditions to obtain modified composite pigments and fillers for water-based coatings, paints or powders coating.
  • the production processes involved in the method of the present invention are all purely physical processes, and do not involve processes such as strong acid and alkali, high pressure, etc.
  • the production process is safe, green, and environmentally friendly, without the discharge of three wastes, and is suitable for different types of coal gangue. Sex is higher.
  • the composite pigment and filler produced by the method of the invention has uniform dispersion, good affinity with resin and excellent coloring effect, and can be widely used in the fields of paint, water paint and powder coating.
  • the technical scheme of the invention not only solves the problems in the coating industry, but also truly realizes the green and high value-added utilization of coal gangue.
  • FIG. 1 is a flow chart of a method for preparing a composite pigment and filler for paint by using coal gangue according to an embodiment of the present invention.
  • an embodiment of the present invention provides a method for preparing composite pigments and fillers for coatings by utilizing coal gangue.
  • the method includes at most five steps of pretreatment, heat treatment, ultrafine pulverization, physical modification and chemical modification:
  • Pretreatment mainly includes four steps: washing, screening, coarse crushing and magnetic separation.
  • the water washing is to wash off the sediment and floating dust on the surface of the coal gangue with water.
  • the screening is to manually remove the symbiotic minerals with light color and uneven distribution of coal organic matter.
  • the coarse crushing is to use coarse crushing equipment to crush the raw ore to 80-200 mesh.
  • the magnetic separation is to use a magnetic separator to remove particles with high iron content in the coarsely crushed material.
  • Heat treatment is to calcine the magnetically separated material in multiple stages to remove the volatile matter in the coal gangue, and this process can be omitted for the coal gangue with low volatile matter.
  • Ultrafine pulverization use ultrafine pulverizing equipment to pulverize the coal gangue to a certain fineness, and the ultrafine pulverized material can be used as a composite pigment and filler for water-based paints, paints or powder coatings.
  • Chemical modification Use modification equipment, select the appropriate modifier and dosage, and perform surface treatment on the material after physical modification under certain conditions to obtain modified composite pigments and fillers for water-based coatings, paints or powders coating.
  • the coarse crushing in the pretreatment is the step of coarsely crushing the screened coal gangue by the coarse crushing equipment, and the coarse crushing equipment includes hammer crusher, cone crusher, impact crusher, roller press, vertical crusher. Mill and Raymond Mill or any combination thereof.
  • the method further includes performing magnetic separation on the coarsely pulverized coal gangue, wherein the magnetically separated iron-rich material is used as a cement raw material, and the magnetically separated coal gangue is used for subsequent ultra-fine processing .
  • the step of magnetically separating the coarsely pulverized coal gangue is performed by a dry magnetic separator, and the magnetic field strength of the dry magnetic separator is in the range of 0.02-2.0T.
  • the coal gangue is heat treated, wherein the heat treatment includes two times of calcining the coal gangue, the first calcination removes the adsorbed water and bound water in the coal gangue, so that the coal-measure organic matter and the inorganic minerals are more closely combined, and the second calcination calcines the coal gangue.
  • the low-temperature volatile matter in the gangue is removed, and the stability of the coal gangue is improved.
  • the calcining of coal gangue is carried out by a calcining device under a calcining atmosphere
  • the calcining device includes any one or any combination of a tunnel kiln, an internally heated rotary kiln, an externally heated rotary kiln and a push-plate kiln, so
  • the calcining atmosphere includes an inert gas protective atmosphere, a reducing atmosphere or a weakly oxidizing atmosphere.
  • the calcining includes a first calcination and a second calcination on the coal gangue
  • the first calcination has a temperature range of 100-200°C (eg, 150°C or 180°C) and a calcination time range for 10-480 minutes (eg 200 minutes or 300 minutes);
  • the temperature range for the second calcination is 200-1300°C (eg 250°C or 300°C) and the calcination time range is 10-480 minutes (eg 300 minutes or 400 minutes).
  • the step of ultra-finely pulverizing the coarsely pulverized coal gangue is performed by an ultra-fine pulverizing device
  • the ultra-fine pulverizing device includes a ring roll mill, a mechanical mill, a ball mill, a jet mill, a steam mill, a hot air jet mill, Any one of stirring mill and sand mill or any combination thereof;
  • the particle size of the ultrafinely pulverized coal gangue is between 800-12500 mesh, preferably 8000 mesh or 10000 mesh.
  • the ultra-finely pulverized coal gangue is physically modified to obtain a color controllable, superior anticorrosion property, and stable coloration.
  • the physical modification is completed in the grinding chamber of the ultrafine pulverizing equipment.
  • the physical modification is to feed the physical modifier, the bonding aid and the ultrafinely pulverized coal gangue together into the grinding chamber for pulverization and mixing (preferably evenly mixing);
  • the physical modifier includes Hongdan, Strontium Chrome Yellow, Zinc Chrome Yellow, Barium Chrome Yellow, Calcium Chrome Yellow, Phosphate, Phosphomolybdate, Aluminum Dihydrogen Tripolyphosphate, Zinc Molybdate, Zinc Borate, Mica Iron Oxide, Titanium Dioxide, Nano Zinc Oxide, Graphite , ultramarine blue, phthalocyanine blue, barium sulfate, iron red, iron black, barium sulfate and other substances in the mixture of any one or more;
  • the physical modifier is 0%-30% of the amount of coal gangue;
  • the adhesion assistant is sodium silicate, potassium silicate, bis-silane coupling agent, etc.; the adhesion assistant is 0%-5% of the amount of coal gangue.
  • the coal gangue powder is chemically modified to obtain the modified composite pigment and filler.
  • the step of chemical modification is performed by modification equipment.
  • the modification equipment includes any one or any combination of a three-roll modifier, a high-speed mixer and a tower modifier, and the modifier used in the surface modification is a silane coupling agent, an aluminate Coupling agents, titanate coupling agents, rare earth coupling agents, fatty acids and their salts, polyalcohols, higher alcohols, or any combination thereof; the amount of the modifier is ultrafine grinding 0.01-25% (eg 10% or 15%) of the powder mass of the gangue; the temperature range of the surface modification is 50-300°C (eg 200°C).
  • the coating is powder coating, water-based coating or paint.
  • the raw material of coal gangue from a coal mine in Zhungeer, Inner Mongolia is lump, and its main chemical composition is shown in Table 1.
  • the adopted processing techniques are water washing, screening, coarse crushing, magnetic separation, heat treatment, ultrafine crushing, physical modification and chemical modification.
  • the specific preparation process parameters are as follows: wash the dust on the surface of the coal gangue with tap water, remove the light-colored stones by hand, and after natural air drying, use a jaw crusher to pulverize the raw coal gangue ore to less than 20mm, and then use a Raymond mill to coarsely pulverize to a 200 mesh.
  • the coarse coal gangue powder is subjected to multiple magnetic separations with a dry magnetic separator under the magnetic field strength of 1.5T to reduce the iron content in the coal gangue. Then, the magnetically separated coal gangue is calcined in two stages under nitrogen protection by using a tunnel kiln, wherein the calcination temperature of the first stage is 150°C, the calcination time is 50 minutes (min), the calcination temperature of the second stage is 290°C, and the calcination time is 50 minutes (min).
  • the raw material of coal gangue from a coal mine in Yangquan, Shanxi province is lump, and its main chemical composition is shown in Table 3.
  • the adopted processing techniques are water washing, screening, coarse crushing, magnetic separation, heat treatment, ultrafine crushing, physical modification and chemical modification.
  • the specific preparation process parameters are as follows: wash the dust on the surface of the coal gangue with tap water, remove the light-colored stones by hand, and after natural air drying, use a jaw crusher to crush the raw coal gangue ore to less than 20mm, and then use a vertical mill to coarsely crush it to 200 eye.
  • the coarse coal gangue powder is subjected to multiple magnetic separations with a dry magnetic separator under the magnetic field strength of 1.4T to reduce the iron content in the coal gangue. Then, using an external combustion rotary kiln, the dried coal gangue is calcined in two stages in a reducing atmosphere.
  • the temperature of the kiln head is 100 °C
  • the temperature of the kiln tail is 400 °C.
  • the calcination time of the first stage is 10min
  • the composite pigments and fillers prepared by the method of the present invention are closely combined with a layer of stable carbon-based organic substances between layers, which can play the dual roles of pigments and fillers, and can significantly improve the compatibility with organic compounds. Resin affinity and dispersibility.
  • the method of the present invention can not only reduce the production cost of the coating, but also can significantly improve the storage, corrosion resistance, weather resistance and other properties of the coating.
  • the method of the invention has significant environmental protection significance and economic benefits, and has broad market prospects.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
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Abstract

本发明的实施例提供了一种利用煤矸石制备涂料用复合颜填料的方法。所述方法包括：预处理煤矸石，所述预处理煤矸石包括对煤矸石进行筛选和将筛选后的煤矸石进行粗粉碎；对预处理后的煤矸石进行热处理，其中所述热处理包括两次煅烧所述煤矸石；由超细粉碎设备执行热处理后的煤矸石的超细粉碎处理；对超细粉碎处理后的煤矸石进行物理改性以得到复合颜填料；对复合颜填料进行化学改性以得到改性复合颜填料。

Description

利用煤矸石制备涂料用复合颜填料的方法 技术领域
本发明属于工业固体废弃物绿色资源化利用领域，尤其涉及一种利用煤矸石制备涂料用复合颜填料的方法。
背景技术
目前，炭黑是涂料领域应用最广泛着色剂(颜料)，常被用于生产黑色或灰色涂料。然而炭黑的成分、密度、粒度、亲水性等物化性质与常用无机填料(如碳酸钙、硫酸钡、煅烧高岭土、滑石、硅灰石等)差异较大，容易引起涂料中颜料、填料的分层，导致涂料的浮色和发花，进而影响涂料的储存稳定性。炭黑比表面积较大、吸油值高，易吸附大量的溶剂和助剂，造成油性涂料储存后的返粗、变稠和泛白等问题。目前，虽然通过物理包覆或化学包覆手段，制备出钛白粉基白色复合颜填料，但是由于炭黑和无机填料性质的差异，导致得到相应的复合颜填料难度较大，尚未有黑色复合颜填料的相关报道。
煤矸石是煤矿在开采和洗选过程中产生的干基灰分大于50％的岩石，约占煤炭开采量的12％，仅2020年中国就有约8亿吨煤矸石产生。据不完全统计，中国目前煤矸石的堆存量达到60亿吨，占地约20余万亩，大量的煤矸石堆积占用大量土地的同时还会造成地表下沉、水土流失、地下水污染以及空气污染。中国目前煤矸石综合利用率不足50％，主要用于煤矸石发电、生产建材、土地复垦回填和生产煅烧高岭土，总体来看存在产品附加值较低或能耗高的问题。
发明内容
鉴于上述的现有涂料中黑色颜料和煤矸石综合利用方面存在的问题，本发明提供了一种利用煤矸石制备涂料用复合颜填料的方法。
具体地，煤矸石中含有少量的煤类有机质其颜色为深黑色，在形成过程中煤和成岩矿物夹杂共生，结合非常稳定，而且煤矸石的成岩矿物高岭土、石英等涂料常用填充料，因此，煤矸石具备生产涂料用复合颜填料的潜力。
本发明所述的方法能够针对煤矸石的矿物特性，通过合适的生产工艺制备出复合颜填料(即该复合颜填料同时具有颜料和填料的功能)，不仅解决涂料行业难题，也实现对煤矸石的绿色高值化利用，该方法技术普适性好，对多种煤矸石都能进行综合利用。
根据本发明的一个方面，提供了一种利用煤矸石制备涂料用复合颜填料的方法，所述方法包括预处理、热处理、超细粉碎、物理改性和化学改性五个步骤中的一些步骤：
(1)预处理主要包括水洗、筛选、粗碎和磁选四个步骤。所述水洗是用水洗去煤矸石表面的泥沙和浮尘。所述筛选是手工剔除出颜色较浅、煤类有机质分布不均的共生矿物。所述粗碎是利用粗碎设备将原矿粉碎至80-200目。所述磁选是利用磁选机将粗碎后物料中含铁量较高的颗粒去除。
(2)热处理：所述热处理是对磁选后的物料进行多段煅烧，去除煤矸石中的挥发分，对于挥发分较低的煤矸石可以省去此工艺。
(3)超细粉碎：选用超细粉碎设备将煤矸石粉碎至一定细度，超细粉碎后的物料可以作为复合颜填料用于水性涂料、油漆或粉末涂料。
(4)物理改性：将一定量物理改性剂，在少量粘合助剂和机械力化学的作用下，与超细煤矸石粉混合均匀，并紧密结合，得到复合颜填料，可用于水性涂料、油漆或粉末涂料。
(5)化学改性：利用改性设备，选择合适的改性剂及用量，在一定条件下对物理改性后物料进行表面处理，制得改性复合颜填料用于水性涂料、油漆或粉末涂料。
通过上述可知，本发明所述的方法所涉及的生产流程都为纯物理过程，不涉及强酸强碱、高压等过程，生产工艺安全、绿色、环保，无三废排放，对不同类型的煤矸石适应性较高。由本发明所述方法生产的复合颜填料，分散均匀、与树脂亲和性好、着色效果优异，可广泛应用于油漆、水漆和粉末涂料领域。本发明的技术方案在解决了涂料行业难题的同时，真正实现对煤矸石的绿色高附加值利用。
附图说明
为了更清楚地说明本发明实施方式的技术方案，下面将将结合附图和详细实施方式对本发明进行详细说明，显而易见地，下面描述中的附图仅仅是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。其中：
图1为根据本发明的一个实施例所述的利用煤矸石制备涂料用复合颜填料的方法的流程图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体 实施方式做详细的说明。
参见图1，本发明的实施例提供了一种利用煤矸石制备涂料用复合颜填料的方法，所述方法最多包括预处理、热处理、超细粉碎、物理改性和化学改性五个步骤：
(1)预处理主要包括水洗、筛选、粗碎和磁选四个步骤。所述水洗是用水洗去煤矸石表面的泥沙和浮尘。所述筛选是手工剔除出颜色较浅、煤类有机质分布不均的共生矿物。所述粗碎是利用粗碎设备将原矿粉碎至80-200目。所述磁选是利用磁选机将粗碎后物料中含铁量较高的颗粒去除。
(2)热处理：所述热处理是对磁选后的物料进行多段煅烧，去除煤矸石中的挥发分，对于挥发分较低的煤矸石可以省去此工艺。
(3)超细粉碎：选用超细粉碎设备将煤矸石粉碎至一定细度，超细粉碎后的物料可以作为复合颜填料用于水性涂料、油漆或粉末涂料。
(4)物理改性：将一定量物理改性剂，在少量粘合助剂和机械力化学的作用下，与超细煤矸石粉混合均匀，并紧密结合，得到复合颜填料，可用于水性涂料、油漆或粉末涂料。
(5)化学改性：利用改性设备，选择合适的改性剂及用量，在一定条件下对物理改性后物料进行表面处理，制得改性复合颜填料用于水性涂料、油漆或粉末涂料。
预处理中的粗碎是由粗碎设备执行将筛选后的煤矸石进行粗粉碎的步骤，所述粗碎设备包括锤式破碎机、圆锥式破碎机、反击式破碎机、辊压机、立磨和雷蒙磨中的任一种或它们的任意组合。在将煤矸石粗粉碎步骤之后，所述方法还包括对粗粉碎的煤矸石进行磁选，其中磁选出的富铁物料用作水泥原料，磁选后的煤矸石用于后续的超细加工。在一些实施例中，由干法磁选机执行对粗粉碎的煤矸石进行磁选的步骤，所述干法磁选机的磁场强度的范围为0.02-2.0T。
对煤矸石进行热处理，其中所述热处理包括两次煅烧煤矸石，第一次煅烧将煤矸石中的吸附水和结合水去除，使煤系有机质与无机矿物结合更加紧密，第二次煅烧将煤矸石中的低温挥发分去除，提高煤矸石的稳定性。通常，所述煅烧煤矸石由煅烧设备在煅烧气氛下执行，所述煅烧设备包括隧道窑、内热式回转窑、外热式回转窑和推板窑中的任一种或它们的任意组合，所述煅烧气氛包括惰性气体保护气氛、还原气氛或弱氧化气氛。在一个示例中，所述煅烧包括对煤矸石进行第一次煅烧和第二次煅烧，所述第一次煅烧的温度范围为100-200℃(例如150℃或180℃)并且煅烧的时间范围为10-480分钟(例如200分钟或300分钟)；第二次煅烧的温度范围为200-1300℃(例如250℃或300℃)并且煅烧的时间范围为10-480分钟(例如为300分钟或400分钟)。
在一个示例中，由超细粉碎设备执行超细粉碎粗粉碎后的煤矸石的步骤，所述超细粉碎设备包括环辊磨、机械磨、球磨机、气流磨、蒸汽磨、热空气气流磨、搅拌磨和砂磨机中的任一种或它们的任意组合；超细粉碎后的煤矸石的颗粒的粒度在800-12500目之间，优选地8000目或10000目。
在一个示例中，在超细粉碎粗碎后的煤矸石步骤之后，对超细粉碎后的煤矸石进行物理改性，进而得到颜色可控、防腐性能优越、着色稳定的。所述物理改性在超细粉碎设备的磨腔内完成。所述物理改性是将物理改性剂、粘合助剂和超细粉碎后的煤矸石一起喂入磨腔内粉碎并混合(优选地混合均匀)；所述物理改性剂包括红丹、锶铬黄、锌铬黄、钡铬黄、钙铬黄、磷酸盐、磷钼酸盐、三聚磷酸二氢铝、钼酸锌、硼酸锌、云母氧化铁、钛白粉、纳米氧化锌、石墨、群青、酞菁蓝、硫酸钡、铁红、铁黑、硫酸钡等物质中的任一种或更多种的混合物；所述物理改性剂为煤矸石量的0％-30％；所述粘合助剂为硅酸钠、硅酸钾、双硅烷偶联剂等；所述粘合助剂为煤矸石量的0％-5％。
在一个示例中，在物理改性步骤之后，对煤矸石粉进行化学改性以得到改性复合颜填料。由改性设备执行所述化学改性的步骤。所述改性设备包括三辊改性机、高速搅拌机和塔式改性机中的任一种或它们的任意组合，所述表面改性使用的改性剂为硅烷偶联剂、铝酸酯偶联剂、钛酸酯偶联剂、稀土偶联剂、脂肪酸及其盐、聚醇类物质、高级醇类中的任一种或它们的任意组合；所述改性剂用量为超细粉碎后的煤矸石的粉体质量的0.01-25％(例如10％或15％)；所述表面改性的温度范围为50-300℃(例如200℃)。
可知，所述涂料为粉末涂料、水性涂料或油漆。
以下提供了几个具体的实施例来详细说明本发明的方法的各个步骤，显然，本发明的技术方案不限于下述提供的实施例的限制。
实施例1
内蒙准格尔某煤矿的煤矸石的原料为块状，其主要化学组成如表1所示。在本实施例中，采用的加工工艺为水洗、筛选、粗粉碎、磁选、热处理、超细粉碎、物理改性和化学改性。具体制备工艺参数如下：用自来水洗去煤矸石表面灰尘，手工选除浅色的石块，自然风干后，利用颚式破碎机将煤矸石原矿粉碎至20mm以下，再用雷蒙磨粗粉碎至200目。粗碎完成后，用干法磁选机在1.5T的磁场强度下，对的煤矸石粗粉进行多次磁选，以降低煤矸石中的含铁量。然后利用隧道窑在氮气保护下对磁选后的煤矸石进行两段煅烧，其中第一段煅烧温度为150℃，煅烧时间为50分钟(min)，第二段煅烧温度为290℃，煅烧时间为60min； 将煅烧后物料加入质量分数为0.5％的锶铬黄和质量分数为0.4％的酞菁蓝后，用流化床式气流磨在0.85Mpa压力和1700rpm的分级机转速下进行超细粉碎和物理改性，得到复合颜填料A1；最后对超细粉碎后的部分物料利用高速搅拌机，以质量分数为1％的硅烷偶联剂(KH560)为改性剂，在120℃下连续搅拌15min，制得改性复合颜填料A2，其粒度分布如表2所示。
表1物料化学组成
Figure PCTCN2021092166-appb-000001
表2不同填料粒度分布
Figure PCTCN2021092166-appb-000002
实施例2
山西阳泉某煤矿的煤矸石的原料为块状，其主要化学组成如表3所示。在本实施例中，采用的加工工艺为水洗、筛选、粗粉碎、磁选、热处理、超细粉碎，物理改性和化学改性。具体制备工艺参数如下：用自来水洗去煤矸石表面灰尘，手工选除浅色的石块，自然风干后，利用颚式破碎机将煤矸石原矿粉碎至20mm以下，再用立磨粗粉碎至200目。粗碎完成后，用干法磁选机在1.4T的磁场强度下，对的煤矸石粗粉进行多次磁选，以降低煤矸石中的含铁量。然后利用外燃式回转窑，在还原气氛下对干燥后的煤矸石进行两段煅烧，窑头温度为100℃，窑尾温度为400℃，第一段煅烧时间为10min，第二段煅烧时间为20min。将煅烧后的物料加入质量分数为0.5％的磷酸锌和质量分数为0.5％的锶铬黄后，用蒸汽动能磨在1.2Mpa蒸汽压力、磨腔内温度为180℃和分级机转速为1500rpm的条件下，进行超细粉碎和物理改性，制备复合颜填料B1(粒度分布如表4所示)。最后，对物理改性后的物料，通过三辊改性机，在110℃下，以质量分数为0.5％的硅烷偶联剂(KH560)和质量分数为0.5％的硅烷偶联剂(KH540)为改性剂，完成化学改性制得改性复合颜填料B2，其粒度分布如表4所示。
表3物料化学组成
Figure PCTCN2021092166-appb-000003
表4不同填料粒度分布
Figure PCTCN2021092166-appb-000004
实施例3
利用实施例1和实施例2中制备的改性复合颜填料A2和B2，在灰色防腐油漆中与常用的颜填料体系(炭黑+钛白体+碳酸钙，对照例)进行对比实验，涂料配方和性能对比如表5所示：
表5灰色防腐油漆配方、涂料制备工艺及性能对比
Figure PCTCN2021092166-appb-000005
Figure PCTCN2021092166-appb-000006
实施例4
利用实施例1和实施例2中制备的复合颜填料A1和B1，在灰色防腐水性涂料中与常用的颜填料体系(炭黑+钛白体+碳酸钙，对照例)进行对比实验。涂料配方和性能对比如表6所示：
表6灰色防腐水性涂料配方、涂料制备工艺及性能对比
Figure PCTCN2021092166-appb-000007
Figure PCTCN2021092166-appb-000008
实施例5
利用实施例1和实施例2中制备的复合颜填料A1和B1，在灰色粉末涂料中与常用的颜填料体系(炭黑+钛白体+碳酸钙，对照例)进行对比实验，涂料配方和性能对比如表7所示：
表7粉末涂料配方、涂料制备工艺及性能对比
Figure PCTCN2021092166-appb-000009
Figure PCTCN2021092166-appb-000010
通过上述对比分析可以明显看出，通过本发明所述的方法制备的复合颜填料，层间紧密结合一层稳定的碳类有机物，能够起到颜料和填料的双重作用，而且能够显著提高与机树脂的亲和性和分散性。与常用的颜填料体系相比，本发明所述的方法不仅能够降低涂料生产成本，而且能够显著提高涂料的储存、防腐、耐候性等性能。本发明所述的方法具有显著的环保意义和经济效益，市场前景广阔。
虽然本总体发明构思的一些实施例已被显示和说明，本领域普通技术人员将理解，在不背离本总体发明构思的原则和精神的情况下，可对这些实施例做出改变，本发明的范围以权利要求和它们的等同物限定。

Claims (13)

  1. 一种利用煤矸石制备涂料用复合颜填料的方法，所述方法包括：
    预处理煤矸石，所述预处理煤矸石包括对煤矸石进行筛选和将筛选后的煤矸石进行粗粉碎；
    对预处理后的煤矸石进行热处理，其中所述热处理包括两次煅烧所述煤矸石；
    由超细粉碎设备执行热处理后的煤矸石的超细粉碎处理；
    对超细粉碎处理后的煤矸石进行物理改性以得到复合颜填料；
    对复合颜填料进行化学改性以得到改性复合颜填料。
  2. 根据权利要求1所述的方法，其中，
    由改性设备执行所述化学改性的步骤，所述改性设备包括三辊改性机、高速搅拌机和塔式改性机中的任一种或它们的任意组合，所述表面改性的温度范围为50-300℃。
  3. 根据权利要求2所述的方法，其中，
    所述化学改性使用的改性剂为硅烷偶联剂、铝酸酯偶联剂、钛酸酯偶联剂、稀土偶联剂、脂肪酸及其盐、聚醇类物质、高级醇类中的任一种或它们的任意组合；
    所述改性剂用量为超细粉碎后的煤矸石的粉体质量的0.01-25％。
  4. 根据权利要求1所述的方法，其中，
    所述物理改性在超细粉碎设备的磨腔内完成。
  5. 根据权利要求4所述的方法，其中，
    所述物理改性是将物理改性剂、粘合助剂和超细粉碎后的煤矸石一起喂入磨腔内粉碎并混合。
  6. 根据权利要求5所述的方法，其中，
    所述物理改性剂包括红丹、锶铬黄、锌铬黄、钡铬黄、钙铬黄、磷酸盐、磷钼酸盐、三聚磷酸二氢铝、钼酸锌、硼酸锌、云母氧化铁、钛白粉、纳米氧化锌、石墨、群青、酞菁蓝、硫酸钡、铁红、铁黑、硫酸钡等物质中的任一种或更多种的混合物；
    所述物理改性剂为煤矸石量的0％-30％。
  7. 根据权利要求6所述的方法，其中，
    所述粘合助剂为硅酸钠、硅酸钾、双硅烷偶联剂中的任一种或它们的任意组合；
    所述粘合助剂的质量分数为煤矸石量的0％-5％。
  8. 根据权利要求1所述的方法，其中，
    所述超细粉碎设备包括环辊磨、机械磨、球磨机、气流磨、蒸汽磨、热空气气流磨、搅拌磨和砂磨机中的任一种或它们的任意组合；
    超细粉碎后的煤矸石的颗粒的粒度在800-12500目之间。
  9. 根据权利要求1所述的方法，其中，
    所述煅烧煤矸石由煅烧设备在煅烧气氛下执行；
    所述煅烧设备包括隧道窑、内热式回转窑、外热式回转窑和推板窑中的任一种或它们的任意组合；
    所述煅烧气氛包括惰性气体保护气氛、还原气氛或弱氧化气氛。
  10. 根据权利要求9所述的方法，其中，
    所述两次煅烧煤矸石包括对煤矸石进行第一次煅烧和第二次煅烧，所述第一次煅烧的温度范围为100-200℃并且煅烧的时间范围为10-480分钟；
    第二次煅烧的温度范围为200-1300℃并且煅烧的时间范围为10-480分钟。
  11. 根据权利要求1所述的方法，其中，
    由粗碎设备将筛选后的煤矸石进行粗粉碎，所述粗碎设备包括锤式破碎机、圆锥式破碎机、反击式破碎机、辊压机、立磨和雷蒙磨中的任一种或它们的任意组合。
  12. 根据权利要求11所述的方法，其中，
    在将煤矸石粗粉碎之后，所述方法还包括对粗粉碎的煤矸石进行磁选。
  13. 根据权利要求1-12中任一项所述的方法，其中，
    所述涂料为粉末涂料、水性涂料或油漆。
PCT/CN2021/092166 2021-05-07 2021-05-07 利用煤矸石制备涂料用复合颜填料的方法 WO2022233038A1 (zh)

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