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WO2022233034A1 - 利用煤气化渣制备涂料用复合颜填料的方法 - Google Patents

利用煤气化渣制备涂料用复合颜填料的方法 Download PDF

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WO2022233034A1
WO2022233034A1 PCT/CN2021/092158 CN2021092158W WO2022233034A1 WO 2022233034 A1 WO2022233034 A1 WO 2022233034A1 CN 2021092158 W CN2021092158 W CN 2021092158W WO 2022233034 A1 WO2022233034 A1 WO 2022233034A1
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coal gasification
gasification slag
ultrafine
modification
physical
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PCT/CN2021/092158
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English (en)
French (fr)
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任冬寅
张梅
郭昊
王晨宁
马洪才
尚志新
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德州学院
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Priority to PCT/CN2021/092158 priority Critical patent/WO2022233034A1/zh
Priority to CN202180013784.XA priority patent/CN115066469A/zh
Publication of WO2022233034A1 publication Critical patent/WO2022233034A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C09C1/44—Carbon
    • 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
    • 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
    • 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
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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 gasification slag.
  • 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 gasification slag is the residue produced in the coal gasification process, the color is dark black, and its chemical composition includes Al 2 O 3 , CaO, Fe 2 O 3 , SiO 2 and carbon residue.
  • the amount of gasification slag accounts for about 15-20% of the total gasification coal. According to statistics, China produced about 60 million tons of gasification slag in 2019. It is expected that the annual output of gasification slag will reach 100 million tons by 2022, while The comprehensive utilization of gasification slag is less than 50%. A large amount of coal gasification slag can only be stored and disposed of, which will cause serious environmental pollution and ecological damage while occupying a large amount of arable land.
  • the present invention provides a method for preparing composite pigments and fillers for coatings by utilizing coal gasification slag.
  • a method for preparing composite pigments and fillers for coatings by using coal gasification slag comprising four treatments of pretreatment, ultrafine pulverization, physical modification and chemical modification of coal gasification slag step:
  • the pretreatment step includes any one of the three steps of drying, magnetic separation and gravity separation for coal gasification slag or any combination thereof;
  • Chemical modification of the physically modified composite pigments and fillers is carried out by modifying equipment using modifiers to obtain modified composite pigments and fillers.
  • 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, strong alkali, high pressure, etc.
  • the production process is safe, green, and environmentally friendly, and there is no three waste discharge.
  • 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 paint industry, but also truly realizes the green and high value-added utilization of coal gasification slag.
  • FIG. 1 is a flow chart of a method for preparing composite pigments and fillers for coatings by using coal gasification slag according to an embodiment of the present invention.
  • a method for preparing composite pigments and fillers for coatings by using coal gasification slag includes four treatments: pretreatment, ultrafine pulverization, physical modification and chemical modification. step:
  • the pretreatment step includes any one of the three steps of drying, magnetic separation and gravity separation or any combination thereof.
  • the drying step is to use drying equipment to dry the water content of the coal gasification slag to less than 1%.
  • the magnetic separation step is to use a magnetic separator to select a part of the iron-rich material in the dried material.
  • the magnetically selected iron-rich materials can be used as cement raw materials for the production of cement.
  • the gravity separation step is to use wind separation equipment to remove high-density impurity particles in the raw material of the gasification slag, so as to achieve the purpose of purification.
  • the 0-3 stages of drying, magnetic separation and gravity separation can be reasonably selected according to the actual conditions of the raw materials.
  • Ultrafine pulverization use ultrafine pulverization and classification equipment to pulverize the initially processed materials to a certain fineness to obtain ultrafine coal gasification slag powder, which can be used in powder coatings, water-based Paints and Paints.
  • coal gasification slag itself is derived from natural minerals, and is calcined at high temperature during the formation process, and has the characteristics of stable physical and chemical properties, high temperature resistance, acid and alkali corrosion resistance, etc.
  • the high temperature in the coal gasification process melts the inorganic minerals in the coal and forms a tight package for a large amount of residual carbon, so the coal gasification slag 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) through a suitable production process, which not only solves the problems in the coating industry, but also realizes the improvement of coal gasification. Green high-value utilization of slag.
  • the pretreatment includes at least one process of drying, magnetic separation and gravity separation of the coal gasification slag, so as to achieve the goal of reducing moisture, harmful metals and high-density impurities in the coal gasification slag.
  • the step of drying the coal gasification slag raw material is performed by a drying device, including any one of a fluidized bed dryer, a rotary dryer and a drum dryer, so that the moisture content of the coal gasification slag raw material is less than 1%.
  • the temperature range of the drying step is 80-300°C, preferably 150°C.
  • the dried coal gasification slag is subjected to magnetic separation, wherein the magnetically separated iron-rich material is used as a cement raw material, and the magnetically separated coal gasification slag is used for subsequent ultra-fine pulverization.
  • the step of magnetically separating the dried coal gasification slag is performed by a dry magnetic separator, and the range of the magnetic field strength of the dry magnetic separator is 0.02-2.0T.
  • the gravity sorting is performed by a wind sorting device, and the sorting times are 1-5 times.
  • the steps of ultra-fine pulverization, pretreated coal gasification slag are performed by ultra-fine pulverization equipment.
  • the ultrafine pulverizing equipment includes any one or any combination of ring roll mills, mechanical mills, ball mills, jet mills, steam mills, hot air jet mills, stirring mills and sand mills; Rotor or single-rotor centrifugal classifier; the particle size of coal gasification slag particles after ultrafine pulverization is between 800-12500 mesh, preferably 8000 mesh or 10000 mesh.
  • the method further includes physically modifying the ultrafine coal gasification slag powder, so as to obtain a composite pigment and filler with controllable color, excellent reinforcement effect, and excellent anticorrosion performance.
  • the physical modification is done in the grinding chamber of the ultrafine pulverizing equipment.
  • the physical modification is to feed the physical modifier, the adhesion assistant and the ultrafinely pulverized coal gasification slag powder into the mill together for pulverization and mixing (for example, mixing uniformly);
  • the physical modifier includes red dan, 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, any one or a mixture of multiple;
  • the physical modifier is 0%-60% of the amount of coal gasification slag;
  • the adhesion auxiliary includes any one of sodium silicate, potassium silicate, bissilane coupling
  • the coal gasification slag is chemically modified to obtain the modified composite pigment and filler. Furthermore, the step of chemical modification is performed by a modification apparatus.
  • 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 Any of coupling agents, titanate coupling agents, rare earth coupling agents, fatty acids and their salts, polyalcohols, higher alcohols, ammonium polyacrylate, sodium polyacrylate, sodium hexametaphosphate and sodium tripolyphosphate.
  • the dosage of the modifier is 0.01-25% (for example, 10% or 15%) of the mass of the coal gasification slag powder after ultrafine pulverization;
  • 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 water content of the coal gasification slag raw material of a factory in Xiangyuan County, Shanxi province is 0.5%, and its main chemical composition is shown in Table 1.
  • the adopted processing techniques are magnetic separation, gravity separation, ultrafine pulverization, physical modification and chemical modification.
  • the specific preparation process parameters are as follows: First, the coal gasification slag is subjected to three magnetic separations with a dry magnetic separator under a magnetic field intensity of 1.5T. The chemical composition of the coal gasification slag after magnetic separation is shown in Table 1. Then, the magnetically-separated materials are separated twice by air separation equipment to remove high-density impurity particles.
  • the water content of coal gasification slag from a factory in Ningxia is 1.4%, and its main chemical composition is shown in Table 3.
  • the adopted processing techniques are drying, magnetic separation, gravity separation, ultrafine pulverization, physical modification and chemical modification.
  • the specific preparation process parameters are as follows: first, the water content of the coal gasification slag is dried to 0.3% by using a drum dryer at an inlet temperature of 170 °C and an outlet temperature of 69 °C, and then a dry magnetic separator is used at a magnetic field strength of 1.5T. Next, the dried coal gasification slag was subjected to three magnetic separations, and the chemical composition of the material after the magnetic separation was shown in Table 3.
  • the materials are separated twice by air separation equipment to remove high-density impurity particles. Then, using 1.2% strontium chrome yellow as physical modifier and 0.1% water glass binder, through fluidized bed jet mill at 0.9Mpa pressure and 1720rpm classifier speed, the magnetic The selected coal gasification slag is ultrafinely pulverized and physically modified to obtain a composite pigment and filler B1 (the particle size distribution is shown in Table 4).
  • a high-speed mixer for the material after physical modification using 1.5% silane coupling agent (KH560) as modifier, and stirring continuously at 110 ° C for 15 minutes, the modified composite pigment and filler B2 was obtained. Its particle size distribution is shown in Table 4. shown.
  • the composite pigment and filler prepared by the method of the present invention can play the dual role of pigment and filler, and can significantly improve the affinity and dispersibility with organic resins.
  • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

一种利用煤气化渣制备涂料用复合颜填料的方法，所述方法包括对煤气化渣进行预处理、超细粉碎、物理改性和化学改性四个处理步骤。所述预处理步骤包括对煤气化渣进行干燥、磁选和重力分选三个步骤中的任一步骤或它们的任意组合。在超细粉碎中，选用超细粉碎和分级设备将预处理加工后的煤气化渣粉碎，得到超细煤气化渣粉。在物理改性中，将物理改性剂、粘合助剂在机械力化学的作用下与超细煤气化渣粉混合，得到复合颜填料。在化学改性中，通过改性设备利用改性剂对物理改性后的复合颜填料进行化学改性，制得改性复合颜填料。

Description

利用煤气化渣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气化渣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。
煤气化渣是煤气化过程中产生的残渣，颜色为深黑色，其化学成分包括Al 2O 3、CaO、Fe 2O 3、SiO 2和残炭。气化渣量大约占气化煤总量的15-20％，据统计，2019年中国约产生6000万吨气化渣，预计到2022年气化渣的年产量将达到1亿吨，而气化渣的综合利用不足50％。大量的煤气化渣只能被堆存处理，占用大量耕地的同时，也会造成严重的环境污染和生态破坏。
当前，气化渣规模化处理利用主要聚焦在建工建材、生态治理和燃料领域，但是由于其自身特点导致经济效益较低，因此煤气化渣规模化安全处置技术亟待解决。
发明内容
鉴于上述的现有涂料中黑色颜料和煤气化渣综合利用方面存在的问题，本发明提供了一种利用煤气化渣制备涂料用复合颜填料的方法。
根据本发明的一个方面，提供了一种利用煤气化渣制备涂料用复合颜填料的方法，所述方法包括对煤气化渣进行预处理、超细粉碎、物理改性和化学改性四个处理步骤：
(1)预处理步骤：所述预处理步骤包括对煤气化渣进行干燥、磁选和重力分选三个步骤中的任一步骤或它们的任意组合；
(2)超细粉碎：选用超细粉碎和分级设备将预处理加工后的煤气化渣粉碎，得到超细 煤气化渣粉；
(3)物理改性：将物理改性剂、粘合助剂在机械力化学的作用下与超细煤气化渣粉混合，得到复合颜填料；
(4)化学改性：通过改性设备利用改性剂对物理改性后的复合颜填料进行化学改性，制得改性复合颜填料。
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，对不同类型的煤气化渣适应性较高。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，真正实现对煤气化渣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气化渣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，根据本发明的一个实施例，提供了一种利用煤气化渣制备涂料用复合颜填料的方法，所述方法包括预处理、超细粉碎、物理改性和化学改性四个处理步骤：
(1)预处理步骤：所述预处理步骤包括干燥、磁选和重力分选三个步骤中的任一个或它们的任意组合。所述干燥步骤是选用干燥设备将煤气化渣水量干燥至1％以下。所述磁选步骤是利用磁选机将干燥后的物料中一部分富铁物料选出。磁选出的富铁物料可作为水泥原料，用于生产水泥。所述重力分选步骤是利用风力分选设备，将气化渣原料中高密度杂质颗粒选除，达到提纯目的。所述预处理步骤可以根据原料的实际情况合理选择干燥、磁选和重力分选中的0-3段工艺。
(2)超细粉碎：选用超细粉碎和分级设备将初加工后的物料粉碎至一定细度，得到超细煤气化渣粉，此时所述超细煤气化渣粉可用于粉末涂料、水性涂料和油漆。
(3)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，与超细煤气化渣粉混合(例如混合均匀并紧密结合)得到复合颜填料，此时得到的所述复合颜填料可用于粉末涂料、水性涂料和油漆。
(4)化学改性：利用改性设备，选择合适的改性剂及用量，对物理改性后的样品进行化学改性，制得改性复合颜填料，所述改性复合颜填料可用于粉末涂料、水性涂料和油漆。
具体地，煤气化渣本身来源于天然矿物，在形成过程经过高温煅烧，具有物化性质稳定、耐高温、耐酸碱腐蚀等特点。煤气化过程中的高温，使煤中无机矿物熔融，并形成对大量残炭的紧密包裹，因此煤气化渣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气化渣的特性，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，也实现对煤气化渣的绿色高值化利用。
所述预处理包括对煤气化渣进行干燥、磁选和重力分选中的至少一种工艺，以达到降低煤气化渣中水分、有害金属和高密度杂质的目标。由干燥设备执行所述干燥煤气化渣原料的步骤以使得煤气化渣原料的含水量低于1％，所述干燥设备包括流化床式干燥机、回转干燥机和滚筒式干燥机中的任一种或它们的任意组合，所述干燥步骤的温度范围为80-300℃，优选地150℃。
另外地，将干燥后的煤气化渣进行磁选，其中磁选出的富铁物料用作水泥原料，磁选后的煤气化渣用于后续的超细粉碎。由干法磁选机执行对干燥后的煤气化渣进行磁选的步骤，所述干法磁选机的磁场强度的范围为0.02-2.0T。
另外地，所述重力分选由风力分选设备执行，分选次数为1-5次。
在一个示例中，由超细粉碎设备执行超细粉碎，预处理后煤气化渣的步骤。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；所述分级设备为多转子或单转子离心式分级机；超细粉碎后煤气化渣颗粒的粒度在800-12500目之间，优选地8000目或10000目。
在一个示例中在超细粉碎步骤之后，所述方法还包括对超细煤气化渣粉进行物理改性，从而得到颜色可控、增强效果优异、防腐性能优越的复合颜填料。
此外，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气化渣粉一起喂入磨内粉碎并混合(例如混合均匀)；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到多种的混合物；所述物理改性剂为煤气化渣量的0％-60％；所述粘合助剂包括硅酸钠、硅酸钾、双硅烷偶联剂等中的任一种或它们的任意组合；所述粘合助剂为煤气化渣量的0％-10％。
在一个示例中，在物理改性煤气化渣步骤之后，对煤气化渣进行化学改性以得到改性复合颜填料。此外，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、聚丙烯酸铵、聚丙烯酸钠、六偏磷酸钠和三聚磷酸钠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气化渣粉体质量的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℃)。
在本发明中，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
山西省襄垣县某厂煤气化渣原料含水量为0.5％其主要化学组成如表1所示。在本实施例中，采用的加工工艺为磁选、重力分选、超细粉碎、物理改性和化学改性。具体制备工艺参数如下：首先用干法磁选机在1.5T的磁场强度下对煤气化渣进行三次磁选，磁选后的煤气化渣物料化学组成如表1所示。然后对磁选后物料用风力分选设备分选两次，选除高密度杂质颗粒。然后对预处理后物料，以质量分数为0.7％的锶铬黄和质量分数为0.4％的磷酸铁为物理改性剂，用蒸汽动能磨，在1.5Mpa蒸汽压力、1700rpm的分级机转速和211℃的磨内温度下，完成超细粉碎和物理改性，制得复合颜填料A1(粒度分布如表2所示)。最后，对物理改性后的物料，通过三辊改性机，在100℃下，以质量分数为0.7％的硅烷偶联剂(KH560)和质量分数为0.3％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A2，其粒度分布如表2所示。
表1物料化学组成
Figure PCTCN2021092158-appb-000001
Figure PCTCN2021092158-appb-000002
表2不同填料粒度分布
Figure PCTCN2021092158-appb-000003
实施例2
宁夏某厂煤气化渣原料含水量为1.4％其主要化学组成如表3所示。在本实施例中，采用的加工工艺为干燥、磁选、重力分选、超细粉碎、物理改性和化学改性。具体制备工艺参数如下：首先利用滚筒式干燥机在入口温度170℃，出口温度69℃的条件下，将煤气化渣含水量干燥至0.3％，然后用干法磁选机在1.5T的磁场强度下对干燥后的煤气化渣进行三次磁选，磁选后的物料化学组成如表3所示。对磁选后物料用风力分选设备分选两次，选除高密度杂质颗粒。然后以质量分数为1.2％锶铬黄为物理改性剂，以质量分数0.1％的水玻璃粘合剂，通过用流化床式气流磨在0.9Mpa压力和1720rpm的分级机转速下，对磁选后的煤气化渣进行超细粉碎和物理改性，得到复合颜填料B1(粒度分布如表4所示)。对物理改性后的物料利用高速搅拌机，以1.5％的硅烷偶联剂(KH560)为改性剂，在110℃下连续搅拌15min，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 PCTCN2021092158-appb-000004
表4不同填料粒度分布
Figure PCTCN2021092158-appb-000005
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 PCTCN2021092158-appb-000006
Figure PCTCN2021092158-appb-000007
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 PCTCN2021092158-appb-000008
Figure PCTCN2021092158-appb-000009
实施例5
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 PCTCN2021092158-appb-000010
Figure PCTCN2021092158-appb-000011
通过上述对比分析可知，通过本发明所述的方法制备的复合颜填料，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. 一种利用煤气化渣制备涂料用复合颜填料的方法，所述方法包括对煤气化渣进行预处理、超细粉碎、物理改性和化学改性四个处理步骤：
    (1)预处理步骤：所述预处理步骤包括对煤气化渣进行干燥、磁选和重力分选三个步骤中的任一步骤或它们的任意组合；
    (2)超细粉碎：选用超细粉碎和分级设备将预处理加工后的煤气化渣粉碎，得到超细煤气化渣粉；
    (3)物理改性：将物理改性剂、粘合助剂在机械力化学的作用下与超细煤气化渣粉混合，得到复合颜填料；
    (4)化学改性：通过改性设备利用改性剂对物理改性后的复合颜填料进行化学改性，制得改性复合颜填料。
  2. 根据权利要求1所述的方法，其中，
    由干燥设备执行所述干燥煤气化渣原料的步骤以使得煤气化渣原料的含水量低于1％，所述干燥设备包括流化床式干燥机、回转干燥机和滚筒式干燥机中的任一种或它们的任意组合，所述干燥步骤的温度范围为80-300℃。
  3. 根据权利要求2所述的方法，其中，
    所述磁选步骤是利用磁选机将干燥后的煤气化渣中一部分富铁物料选出；
    所述重力分选是利用风力分选设备，将气化渣原料中高密度杂质颗粒选除。
  4. 根据权利要求1所述的方法，其中，
    由超细粉碎设备执行超细粉碎预处理后煤气化渣的步骤。
  5. 根据权利要求4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；
    所述分级设备为多转子或单转子离心式分级机；超细粉碎后煤气化渣颗粒的粒度在800-12500目之间。
  6. 根据权利要求1-5中任一项所述的方法，其中，
    所述物理改性在超细粉碎设备的磨腔内执行。
  7. 根据权利要求6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物料一起喂入磨内粉碎并混合均匀。
  8. 根据权利要求7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、硫酸钡中的任一种或更多种的混合物；
    所述物理改性剂为煤气化渣量的0％-60％。
  9. 根据权利要求8所述的方法，其中，
    所述粘合助剂包括硅酸钠、硅酸钾、双硅烷偶联剂中任一种或它们的任意组合；
    所述粘合助剂的质量分数为煤气化渣量的0％-10％。
  10. 根据权利要求1-9中任一项所述的方法，其中，
    由改性设备执行所述化学改性的步骤。
  11. 根据权利要求10所述的方法，其中，
    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、聚丙烯酸铵、聚丙烯酸钠、六偏磷酸钠和三聚磷酸钠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，
    所述改性剂用量为超细粉碎后的煤气化渣粉体质量的0.01-25％；
    所述表面改性的温度范围为50-300℃。
  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。
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