WO2022226863A1

WO2022226863A1 - Method for preparing, by using oil sand tailing, composite pigment and filler for coating

Info

Publication number: WO2022226863A1
Application number: PCT/CN2021/090847
Authority: WO
Inventors: 任冬寅; 尚志新; 张梅; 马洪才; 曲铭海; 王培玉; 孔云
Original assignee: 德州学院
Priority date: 2021-04-29
Filing date: 2021-04-29
Publication date: 2022-11-03
Also published as: CN115443314A

Abstract

The embodiments of the present invention provide a method for preparing, by using an oil sand tailing raw material, a composite pigment and filler for a coating. The method comprises: subjecting an oil sand tailing raw material to a heat treatment, wherein the heat treatment comprises drying the oil sand tailing raw material and calcining the oil sand tailing raw material, such that on the surface of the oil sand tailing raw material, asphalt wraps particles of an oil sand tailing and is carbonized; performing coarse crushing on the heat-treated oil sand tailing; and performing superfine processing on a mixture of the coarse-crushed oil sand tailing and a toner, such that the superfine-processed oil sand tailing is used as the composite pigment and filler.

Description

Method for preparing composite pigments and fillers for coatings by using oil sand tailings

technical field

The invention belongs to the field of green resource utilization of industrial solid waste, and in particular relates to a method for preparing composite pigments and fillers for coatings by utilizing oil sand tailings.

Background technique

Currently, carbon black is the most widely used colorant (pigment) in the coatings field and is often used to produce black or gray coatings. However, 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. At present, although 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.

Oil sand tailings are the black solids remaining after oil extraction from oil sands. The main components are slightly different depending on the place of origin, but they are all dominated by natural minerals, such as calcium carbonate, quartz sand and clay minerals. The surface of natural minerals in oil sand tailings is coated with a small amount of organic matter such as bitumen and heavy oil, which makes it difficult for them to be directly utilized and stored in large quantities. However, every ton of oil extracted will produce 3-15 tons of oil sand tailings. The accumulation of a large amount of tailings not only occupies a large amount of land and pollutes the environment, but also a waste of resources.

SUMMARY OF THE INVENTION

In view of the problems existing in the comprehensive utilization of black pigments and oil sand tailings in the above-mentioned existing coatings, the present invention provides a method for preparing composite pigments and fillers for coatings by utilizing oil sand tailings.

Specifically, the inventors of the present invention realized that the oil sand tailings themselves are natural minerals, and after undergoing high temperature, alkali treatment or organic solution extraction and other processes in the process of oil extraction, they are loose and porous, easy to pulverize, Physical and chemical properties are stable and so on. In addition, the oil sand tailings are black and contain a small amount of heavy oil such as asphalt. If the particle surface of the oil sand tailings can be uniformly coated with a layer of asphalt organic matter, then the oil sand tailings will have the ability to produce composite pigments for coatings. filler potential.

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 the oil sand tailings through a suitable production process, which not only solves the problems in the coating industry, but also realizes the The green high-value utilization of oil sand tailings has good technical applicability and can comprehensively utilize various oil sand tailings.

According to one aspect of the present invention, there is provided a method for preparing composite pigments and fillers for coatings using oil sand tailings, the method comprising some of the five steps of heat treatment, coarse crushing, magnetic separation, ultra-fine processing and surface modification step:

(1) Heat treatment: The heat treatment includes two steps of drying and calcination. The drying is to use drying equipment to dry the oil sand tailings with a water content of more than 1% at a predetermined temperature, and to dry the water content to less than 1%. In the calcination, calcining equipment is used to calcine the oil sand tailings twice under a predetermined atmosphere and temperature, so that the surface asphalt of the oil sand tailings can be uniformly wrapped and carbonized respectively. The heat treatment can reasonably select the 0-2 stage process in drying and calcination according to the actual situation of the raw materials.

(2) Coarse crushing: use coarse crushing equipment to crush the heat-treated oil sand tailings to less than 0.2mm for magnetic separation.

(3) Magnetic separation: Part of the iron-rich material in the coarsely pulverized material is selected by a magnetic separator. The magnetically selected iron-rich materials can be used as cement raw materials for the production of cement. When the iron content in the material after heat treatment is low, the magnetic separation step can be omitted.

(4) Ultra-fine processing: use ultra-fine processing equipment to mix the coarsely pulverized or magnetically separated materials and toners to evenly pulverize to a certain fineness, and the ultra-finely processed materials can be used as composite pigments and fillers for Water-based paint, paint or powder coating.

(5) Surface modification: use modification equipment, select the appropriate modifier and dosage, and perform surface treatment on the ultra-finely processed materials under certain conditions to obtain modified composite pigments and fillers for water-based coatings and paints or powder coating.

It can be seen from the above that 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, and no three wastes are discharged. Sand adaptability is high. 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 oil sand tailings.

Description of drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and detailed embodiments. As far as technical personnel are concerned, other drawings can also be obtained based on these drawings without any creative effort. in:

FIG. 1 is a flow chart of a method for preparing composite pigments and fillers for coatings by utilizing oil sand tailings according to an embodiment of the present invention.

Detailed ways

In order to make the above objects, features and advantages of the present invention more clearly understood, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

Referring to Fig. 1, an embodiment of the present invention provides a method for preparing a composite pigment and filler for coatings by utilizing oil sand tailings raw materials, the method comprising:

heat treatment of the oil sand tailings raw material, wherein the heat treatment includes drying the oil sand tailings raw material and calcining the oil sand tailings raw material, so that the particles of the oil sand tailings are coated on the surface of the oil sand tailings raw material by bitumen and carbonized;

Coarsely pulverize the heat-treated oil sand tailings;

The coarsely pulverized oil sand tailings are ultra-finely processed, so that the ultra-finely processed oil sand tailings are used as the composite pigment and filler.

Specifically, the step of drying the oil sand tailings raw material is performed by a drying device so that the water content of the oil sand tailings raw material is lower than 1%, and the drying device includes a centrifugal dehydrator, a filter press, and a flash dryer , a spray dryer, a fluidized bed dryer, a rotary kiln dryer and a drum dryer, or any combination thereof, the temperature of the drying step is in the range of 100-200°C, preferably 150°C.

In addition, the calcining of the oil sand tailings raw material is performed by a calcining device under a calcining atmosphere, and the calcining device includes any one of a tunnel kiln, an internal heating rotary kiln, an external heating rotary kiln and a pusher kiln or any of them. In combination, the calcining atmosphere includes an inert gas protective atmosphere, a reducing atmosphere or a weakly oxidizing atmosphere.

In one example, the calcining includes a first calcining and a second calcining of the oil sand tailings feedstock, the first calcining at a temperature ranging from 200-350°C (eg, 250°C or 300°C) and calcining The time range for calcination is 10-480 minutes (eg 200 minutes or 300 minutes); the temperature range for the second calcination is 350-1300°C (eg 800°C or 1000°C) and the time range for calcination is 10-480 minutes (eg 300 minutes or 400 minutes).

In one example, the step of coarsely pulverizing the heat-treated oil sand tailings is performed by a coarse crushing device including a hammer crusher, a cone crusher, an impact crusher, a roller press, a vertical mill and any of the Raymond mills or any combination of them.

In one example, the step of ultra-finely processing the mixture of coarsely pulverized oil sand tailings and toner is performed by ultra-fine processing equipment including ring roll mills, mechanical mills, ball mills, jet mills, Any one or any combination of steam mill, hot air jet mill, agitated mill and sand mill; the toners include red red, 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, zinc oxide, graphite, ultramarine blue, phthalocyanine blue, barium sulfate, iron red, barium sulfate Any one or any combination thereof; the dosage of the toner is 0-90% of the powder mass of the coarsely pulverized oil sand tailings; the toner can play the role of fine-tuning and improving paint resistance. The effect of rust performance; the particle size of the ultra-fine processed oil sand tailings is between 800-12500 mesh, preferably 8000 mesh or 10000 mesh.

In addition, after the step of coarsely pulverizing the heat-treated oil sand tailings, the method further includes performing magnetic separation on the coarsely pulverized oil sand tailings, wherein the magnetically selected iron-rich material is used as a cement raw material, and after the magnetic separation The oil sand tailings are used for subsequent ultrafine processing.

Preferably, the step of magnetically separating the coarsely pulverized oil sand tailings 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.

In one example, after the step of ultra-finely processing the coarsely crushed oil sand tailings, the method further includes surface modification of the ultra-finely processed oil sand tailings to obtain modified composite pigments and fillers.

Furthermore, the step of surface modification is performed by a modification device or in a cavity of an ultrafine machining device. The surface modification can be selected according to the type of modifier and the type of ultra-fine processing equipment to be completed in the grinding chamber of the ultra-fine processing equipment, or completed by the modification equipment after the pulverization is completed.

Preferably, 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, Aluminate 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 Any one or any combination of them; the amount of the modifier is 0.01-25% (for example, 10% or 15%) of the powder mass of the ultra-finely processed oil sand tailings; the surface modifier is The typical temperature range is 50-300°C (eg 200°C).

Specifically, the coating is powder coating, water-based coating or paint.

Several specific examples are provided below to describe in detail each step of the method of the present invention. Obviously, the technical solution of the present invention is not limited to the limitations of the examples provided below.

Example 1

The raw material particle size of Indonesian oil sand tailings is greater than 0.2mm and the water content is greater than 1%. Its main chemical composition is shown in Table 1. In this embodiment, the adopted processing techniques are drying, calcination, coarse pulverization, magnetic separation, ultra-fine processing and surface modification. The specific preparation process parameters are as follows: First, the raw material of Indonesian oil sand tailings is dried with hot air through a drum dryer. The temperature of the air inlet of the drum dryer is 190 °C and the outlet temperature is 80 °C. The dried oil sand tailings The water content is 0.3%. Then, the dried oil sand tailings are calcined in two stages under the protection of nitrogen by using a tunnel kiln. The time is 120min; then use Raymond mill to grind the oil sand tailings to a particle size of less than 0.2mm, and then use a dry magnetic separator to magnetically separate the dried oil sand tailings under a magnetic field strength of 1.5T. The chemical composition of the final material is shown in Table 1. After the material after magnetic separation is mixed with 1% strontium chrome yellow uniformly, ultrafine processing is carried out with a fluidized bed jet mill at a pressure of 0.8Mpa and a classifier speed of 1700rpm to obtain a composite pigment and filler A; finally, the ultrafine processing is carried out. Part of the material after using a high-speed mixer, with 1% silane coupling agent (KH560) as the modifier, was continuously stirred at 100 ° C for 15 minutes to obtain the modified composite pigment and filler A, and its particle size distribution is shown in Table 2. .

Table 1 Chemical composition of materials

Table 2 Particle size distribution of different fillers

Example 2

The particle size of Canadian oil sand tailings is greater than 0.2 mm and the water content is greater than 1%. The main chemical composition is shown in Table 3. The processing techniques adopted in this embodiment are drying, calcination, coarse crushing, magnetic separation, ultra-fine processing and surface modification. The specific preparation process parameters are as follows: First, use a fluidized bed dryer to dry the Canadian oil sand tailings raw material with hot air. The air inlet temperature of the dryer is 183°C and the outlet temperature is 75°C. The water content of the tailings is 0.3%. Then, using an internal combustion rotary kiln, the dried oil sand tailings are calcined in two stages in a reducing atmosphere. The temperature at the kiln head is 200 °C, and the temperature at the kiln tail is 1000 °C. The calcination time of the first stage is 5min, and the second stage calcination The time is 20min; then the oil sand tailings are ground with a vertical mill to a particle size of less than 0.2mm, and then the dried oil sand tailings are subjected to magnetic separation with a dry magnetic separator under a magnetic field strength of 1.5T. The chemical composition of the material is shown in Table 3. After the magnetically separated material is mixed evenly with 1% zinc chrome yellow, the filler B is subjected to ultra-fine processing with a steam kinetic energy mill under the conditions of a steam pressure of 1.2Mpa and a temperature of 180°C in the grinding chamber. At 1500 rpm, respectively, composite pigments and fillers B were prepared (the particle size distribution is shown in Table 4). Finally, for a part of the ultra-finely processed material, 0.5% silane coupling agent (KH560) and 0.5% silane coupling agent (KH540) are sprayed directly into steam through the atomizing nozzle In the mill, in-situ modification was carried out to obtain the modified composite pigment and filler B, and its particle size distribution is shown in Table 4.

Table 3 Chemical composition of materials

Table 4 Particle size distribution of different fillers

Example 3

Using the composite pigments and fillers A and B prepared in Example 1 and Example 2, a comparison experiment was carried out with the commonly used pigment and filler systems (carbon black + titanium dioxide + calcium carbonate) in gray anti-corrosion paint. Table 5 shows:

Table 5 Gray anti-corrosion paint formulation, paint preparation process and performance comparison

Example 4

Using the modified composite pigments and fillers A and B prepared in Example 1 and Example 2, a comparison experiment was carried out with the commonly used pigment and filler systems (carbon black + titanium dioxide + calcium carbonate) in gray anti-corrosion waterborne coatings. Coating formulations and performance comparisons are shown in Table 6:

Table 6 Gray anti-corrosion water-based paint formulation, paint preparation process and performance comparison

Example 5

Using the composite pigments and fillers A and B prepared in Example 1 and Example 2, a comparison experiment was carried out with the commonly used pigment and filler systems (carbon black + titanium dioxide + calcium carbonate) in gray powder coatings. Table 7 shows:

Table 7 Powder coating formulation, coating preparation process and performance comparison

It can be clearly seen from the above comparative analysis that the surface of the composite pigment and filler prepared by the method of the present invention is tightly coated with a layer of carbon-based organic matter, which can play the dual role of pigment and filler, and can significantly improve the compatibility with organic resins. Affinity and Dispersion. Compared with the commonly used pigment and filler systems, 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.

Although some embodiments of the present general inventive concept have been shown and described, those of ordinary skill in the art will understand that The scope is defined by the claims and their equivalents.

Claims

A method for preparing composite pigments and fillers for coatings by utilizing oil sand tailings raw materials, the method comprising:

heat treatment of the oil sand tailings raw material, wherein the heat treatment includes drying the oil sand tailings raw material and calcining the oil sand tailings raw material, so that the particles of the oil sand tailings are coated on the surface of the oil sand tailings raw material by bitumen and carbonized;

Coarsely pulverize the heat-treated oil sand tailings;

The mixture of the coarsely pulverized oil sand tailings and the toner is ultra-finely processed, so that the ultra-finely processed oil sand tailings are used as the composite pigment and filler.
The method according to claim 1, wherein the step of drying the oil sand tailings raw material is performed by drying equipment, the drying equipment comprises a centrifugal dehydrator, Any one or any combination of filter presses, flash dryers, spray dryers, fluidized bed dryers, rotary kiln dryers, and drum dryers, the drying step having a temperature range of 100- 200°C.
The method according to claim 1, wherein the step of calcining the oil sand tailings raw material is performed by a calcining device comprising a tunnel kiln, an internal heat rotary kiln, an external heat rotary kiln and a pusher in a calcining atmosphere. Any one of the slab kilns or any combination thereof, the calcining atmosphere includes an inert gas protective atmosphere, a reducing atmosphere or a weakly oxidizing atmosphere.
The method of claim 3, wherein the calcining comprises a first calcining and a second calcining of the oil sand tailings raw material, the temperature of the first calcining is in the range of 200-350°C and the calcining time The range was 10-480 minutes; the temperature of the second calcination was in the range of 350-1300°C and the time of the calcination was in the range of 10-480 minutes.
The method according to claim 1, wherein the step of coarsely pulverizing the heat-treated oil sand tailings is performed by a coarse crushing device, wherein the coarse crushing equipment comprises a hammer crusher, a cone crusher, an impact crusher, Any or any combination of roller presses, vertical mills and Raymond mills.
The method according to claim 1, wherein the step of ultra-finely processing the coarsely pulverized oil sand tailings is performed by ultra-fine processing equipment, the ultra-fine processing equipment comprises a ring roller mill, a mechanical mill, a ball mill, a jet mill, Any one of steam mill, hot air jet mill, stirring mill and sand mill or any combination thereof; the particle size of oil sand tailings after ultra-fine processing is between 800-12500 mesh.
The method according to claim 1, wherein, after the step of coarsely pulverizing the heat-treated oil sand tailings, the method further comprises performing magnetic separation on the coarsely pulverized oil sand tailings, wherein the magnetically separated iron-rich material It is used as cement raw material, and the oil sand tailings after magnetic separation are used for subsequent ultra-fine processing.
The method according to claim 7, wherein the step of magnetically separating the coarsely pulverized oil sand tailings 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 method according to any one of claims 1-8, wherein, after the step of ultra-finely processing the coarsely crushed oil sand tailings, the method further comprises surface modification of the ultra-finely processed oil sand tailings properties to obtain modified composite pigments and fillers.
10. The method of claim 9, wherein the step of surface modification is performed by a modification apparatus or in a cavity of an ultrafine machining apparatus.
The method according to claim 10, wherein the modification equipment comprises any one of a three-roll reformer, a high-speed mixer and a tower reformer or any combination thereof, and the modification used in the surface modification The agents are silane coupling agents, aluminate coupling agents, titanate coupling agents, rare earth coupling agents, fatty acids and their salts, polyalcohols, higher alcohols, ammonium polyacrylate, sodium polyacrylate, hexahydrate Any one of sodium metaphosphate and sodium tripolyphosphate or any combination thereof; the dosage of the modifier is 0.01-25% of the powder mass of the oil sand tailings after ultrafine processing; the surface modification is The temperature range is 50-300℃.
The method according to any one of claims 1-11, wherein the coating is powder coating, water-based coating or paint.
The method according to claim 1, wherein the toner comprises red red, strontium chrome yellow, zinc chrome yellow, barium chrome yellow, calcium chrome yellow, phosphate, phosphomolybdate, aluminum dihydrogen tripolyphosphate, Any one or any combination of zinc molybdate, zinc borate, mica iron oxide, titanium dioxide, zinc oxide, graphite, ultramarine blue, phthalocyanine blue, barium sulfate, iron red and barium sulfate; The dosage is 0-90% of the powder mass of the coarsely pulverized oil sand tailings.