CN116254061A - Preparation method of water-soluble powdery carbon-aluminum binding agent - Google Patents

Preparation method of water-soluble powdery carbon-aluminum binding agent Download PDF

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CN116254061A
CN116254061A CN202310284890.2A CN202310284890A CN116254061A CN 116254061 A CN116254061 A CN 116254061A CN 202310284890 A CN202310284890 A CN 202310284890A CN 116254061 A CN116254061 A CN 116254061A
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water
aluminum
carbon black
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carbon
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CN116254061B (en
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曾宪新
曾庆洋
李志强
侯高林
范学森
曹克源
张雨航
王大军
张新迎
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Xinxiang City Torlon Refractory Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J1/00Adhesives based on inorganic constituents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
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    • C09J11/04Non-macromolecular additives inorganic
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Abstract

The present invention relates to an inorganic binder. A preparation method of a water-soluble powdery carbon aluminum binding agent comprises the following steps of S1, dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine: dissolving sodium tripolyphosphate in water; adding carbon black, and stirring to enable the carbon black to be wetted and dispersed rapidly; then adding phosphoric acid, and carrying out effective acidification and activation on the carbon black through the phosphoric acid to uniformly disperse and anchor the carbon black in the phosphoric acid; s2, introducing the prepared carbon black phosphoric acid solution into a reaction kettle, adding oxalic acid as a catalyst, heating and keeping the temperature of the reaction kettle at 88-95 ℃, and slowly adding water-diluted aluminum hydroxide to generate a water-soluble carbon aluminum liquid binder; and S3, carrying out spray drying on the prepared water-soluble carbon aluminum liquid binder to prepare the water-soluble solid powdery carbon aluminum binder. The invention successfully applies the carbon black to the bonding agent industry for the first time, solves the problem of dispersion and dissolution of the carbon black in aluminum dihydrogen phosphate, and solves the problems of low initial adhesion strength and poor high-temperature performance of the water-based bonding agent.

Description

Preparation method of water-soluble powdery carbon-aluminum binding agent
Technical Field
The invention relates to an inorganic bonding agent, in particular to a water-soluble solid powdery carbon aluminum bonding agent with high initial adhesion strength and excellent high-temperature performance.
Background
The aqueous resin binder is a novel resin system which uses water to replace an organic solvent as a dispersion medium, and has the characteristics of environment friendliness, easiness in cleaning, convenience in use and the like. However, the primary adhesive strength is low, the high-temperature performance is poor, the development and the application of the composite material are limited, and the composite material is only limited in the fields of coating, paint and oilfield supporting sand at present, so that the composite material is severely limited in the fields of refractory materials, friction materials, casting molding materials and the like. For example, on unshaped refractory materials, the primary adhesive strength of the aqueous phenolic resin binder is only 8-12MPa, the high-temperature strength is 40-50 MP, and the primary adhesive strength of the traditional alcohol-soluble phenolic resin can reach 25-40MP, and the high-temperature strength is 80-120MP.
Aluminum dihydrogen phosphate is an inorganic water-soluble binding agent, has strong chemical binding force, normal temperature hardening, high strength in 250-1000 ℃, and good thermal shock resistance, but has the defects of low refractoriness and low strength above 1000 ℃.
Carbon has a high thermal stability and a sublimation temperature of about 4000 ℃. At pressures of 110-140 bar, the triple point (solid/liquid/gas) of carbon in the phase diagram is near 4020 ℃, and therefore, below 110bar pressure, carbon sublimates without melting. Carbon black is an amorphous carbon, is more reactive than graphite, has a very large surface area, and is a good reinforcing agent for rubber. Has the characteristics of light weight, high temperature resistance, corrosion resistance, fatigue resistance, creep resistance, high strength, high modulus and the like. The smaller the particle size of the carbon black, the larger the specific surface area, the better the reinforcing property, the more easy the agglomeration and the larger the dispersion difficulty, so that the carbon black is difficult to be applied to the production of the binding agent.
If the dispersion and the solubility of the carbon black can be solved, the dispersion and the dissolution of the carbon black in the aluminum dihydrogen phosphate are mainly solved, the defect of low refractoriness and high-temperature strength of the aluminum dihydrogen phosphate binding agent can be overcome, the erosion resistance and the high-temperature performance of the aluminum dihydrogen phosphate binding agent are further enhanced, and the aluminum dihydrogen phosphate binding agent is colorless, odorless and water-soluble, so that the aluminum dihydrogen phosphate binding agent can replace the water-based resin binding agent and is dominant in the development of the water-based binding agent.
There is no report of successful application of carbon black to inorganic binders at home and abroad.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a water-soluble powdery carbon aluminum binding agent, which successfully applies carbon black to the binding agent industry for the first time, solves the dispersion and dissolution problems of carbon black in aluminum dihydrogen phosphate, solves the problems of low initial adhesion strength and poor high-temperature performance of a water-based binding agent, ensures that the water-based binding agent can be better applied to the fields of refractory materials, friction materials, casting molding materials and the like, and can solve the environmental pollution caused by alcohol-soluble resin binding agents.
The invention adopts the technical scheme that:
the invention relates to a preparation method of a water-soluble powdery carbon aluminum binding agent, which comprises the steps of reducing cohesive force among carbon black particles by adding water into sodium tripolyphosphate, realizing wetting and dispersing of carbon black, adopting ultrasonic dispersion to lighten and prevent agglomeration of carbon black, adding phosphoric acid to be mixed with the carbon black, carrying out effective acidification and activation on the carbon black, uniformly dispersing and anchoring the carbon black in the phosphoric acid to prepare a carbon black phosphoric acid solution, adding oxalic acid to be used as a catalyst, slowly adding an aluminum hydroxide aqueous solution to react with the phosphoric acid to generate a liquid carbon aluminum binding agent, and finally controlling the specific gravity of the carbon aluminum binding agent, coating aluminum dihydrogen phosphate on the surfaces of carbon black fine particles to form a stable carbon aluminum structure by spray drying.
The preparation method comprises the following steps:
s1, dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine:
s1-1, adding sodium tripolyphosphate into an ultrasonic dispersion stirrer, and adding water for dissolution;
s1-2, adding carbon black, and stirring to enable the carbon black to be rapidly wetted and dispersed;
s1-3, adding phosphoric acid, and carrying out effective acidification and activation on the carbon black through the phosphoric acid to uniformly disperse and anchor the carbon black in the phosphoric acid;
s2, introducing the carbon black phosphoric acid solution prepared in the step S1 into a reaction kettle, adding oxalic acid as a catalyst, heating and keeping the temperature of the reaction kettle at 88-95 ℃, and slowly adding water-diluted aluminum hydroxide to generate a water-soluble carbon aluminum liquid binder;
s3, carrying out spray drying on the water-soluble carbon aluminum liquid binder prepared in the step S2 to obtain the water-soluble solid powdery carbon aluminum binder.
In step S1, the raw materials used are: sodium tripolyphosphate Na 5 P 3 O 10 The content is more than or equal to 96.0 percent; the content of carbon black C is more than or equal to 98.5 percent, and the grain diameter is 20-500nm; phosphoric acid H 3 PO 4 The content is more than or equal to 85 percent; diluting sodium tripolyphosphate with water in an amount which is 60-70 times the mass ratio, and then adding carbon black and phosphoric acid, wherein the mass ratio of the sodium tripolyphosphate to the carbon black to the phosphoric acid is 1: (60-70): (550-580).
In step S2, the starting material used, aluminum hydroxide Al (OH) 3 The content is more than or equal to 99.6 percent, and the catalyst is oxalic acid C 2 H 2 O 4 ·2H 2 The O content is more than or equal to 95.5 percent, and the mass and the dosage ratio of the sodium tripolyphosphate to the catalyst to the aluminum hydroxide are 1: (11-12): (130-140); the mass ratio of aluminum hydroxide to water is 1: (1.2-1.3).
In the step S3, water is added to adjust the specific gravity of the water-soluble carbon aluminum liquid binder to be 1.30-1.35, and then the water-soluble solid powdery carbon aluminum binder is prepared through spray drying, and the spray drying temperature is controlled at 103-108 ℃.
In the step S1-1, dissolving and stirring sodium tripolyphosphate for 10-25 minutes; in the step S1-2, after adding carbon black, ultrasonic dispersion and stirring are carried out for 20-30min; in the step S1-3, phosphoric acid is added to acidify and stir the carbon black for 30-40min.
In the step S2, the oxalic acid serving as a catalyst is added at one time, steam is introduced into the interlayer of the reaction kettle while stirring for heating to 88 ℃, then the aqueous solution of aluminum hydroxide is slowly added into the reaction kettle to make the liquid level boil, and the temperature of the reaction kettle is controlled at 88-95 ℃ until the reaction of the aqueous solution of aluminum hydroxide is completed.
According to the preparation method of the water-soluble powdery carbon aluminum binding agent, firstly, sodium tripolyphosphate is used as a dispersing agent, so that electrostatic repulsive force among carbon black particles is obviously increased, further crushing and dispersion stability of the particles are facilitated under the action of external force of ultrasonic waves, then through phosphoric acid activation, acidic functional groups on the surface of the carbon black are increased, the polarity is enhanced, and the electric repulsive force generated by dissociation of the acidic functional groups is more beneficial to dispersion and anchoring of the carbon black. After phosphoric acid completes the acidification and activation functions of carbon black, phosphoric acid reacts with aluminum hydroxide to generate aluminum dihydrogen phosphate and Al + The carbon contained in the material forms an Al-C covalent bond by reacting with aluminum reduced by the potential difference. Finally, the carbon black is coated by aluminum dihydrogen phosphate through spray drying, and a water-soluble solid powdery carbon aluminum binding agent is generated in situ.
The invention has the beneficial effects that:
the preparation method of the water-soluble powdery carbon aluminum binding agent prepares the inorganic water-soluble solid powdery carbon aluminum binding agent with strong overall structural performance, instant water and convenient use by a brand new thought. The adhesive has excellent initial adhesion, high temperature resistance and erosion resistance, can react with refractory material in use to produce polymerization to produce adhesive, is suitable for use in acid, alkali and neutral refractory material as adhesive, has fast hardening speed, high initial adhesion strength, excellent middle and high temperature performance, and is erosion and erosion resistance, suitable for use in fireproof material, friction material, paint, heat insulating material, casting molding material, etc. and is one ideal product to replace water resin adhesive and alcohol soluble resin adhesive, and thus has no phenol and aldehyde odor. Compared with the prior art, the method has the following characteristics:
1. the invention successfully applies the carbon black to the bonding agent industry for the first time and creatively, and provides a preparation method of the carbon-aluminum bonding agent with a brand new thought, which solves the dispersion problem of the carbon black in the bonding agent production, has excellent high-temperature strength and high-temperature erosion resistance compared with the existing aluminum dihydrogen phosphate bonding agent, and solves the problem of low initial adhesion strength compared with the water-based resin bonding agent. The method comprises the steps of dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine, adding phosphoric acid for acidizing, adding oxalic acid as a catalyst, sequentially adding aluminum hydroxide diluted by water to generate a water-soluble carbon aluminum liquid bonding agent, and performing spray drying to generate the water-soluble solid powdery carbon aluminum bonding agent.
2. The inorganic bonding agent product prepared by the preparation method of the water-soluble powdery carbon aluminum bonding agent has excellent initial viscosity, has excellent high-temperature resistance and corrosion resistance, can be widely applied to the fields of refractory materials, friction materials, coatings, heat insulation materials, casting molding materials and the like, is an ideal product for replacing resin bonding agents, can better solve the problems of low high-temperature strength of aluminum dihydrogen phosphate, low initial viscosity of water-based resin bonding agents and odor of phenol and aldehyde discharged during heating of alcohol-soluble resin bonding agents, and is particularly beneficial to the environmental protection development of manufacturing industries.
3. According to the preparation method of the water-soluble powdery carbon aluminum binding agent, the carbon black is wrapped by the aluminum dihydrogen phosphate through spray drying, so that the water-soluble solid powdery carbon aluminum binding agent product is generated in situ, and the preparation method is simple in process and environment-friendly. The sodium tripolyphosphate is adopted as the dispersing agent, so that electrostatic repulsive force among carbon black particles is obviously increased, further crushing and dispersion stability of the particles are facilitated under the action of external force of ultrasonic waves, then acidic functional groups on the surface of the carbon black are increased through phosphoric acid activation, the polarity is enhanced, and the electric repulsive force generated by dissociation of the acidic functional groups is more beneficial to dispersion and anchoring of the carbon black; after phosphoric acid completes the acidification and activation functions of carbon black, phosphoric acid reacts with aluminum hydroxide to generate aluminum dihydrogen phosphate, al + In separate partsThe intermolecular van der Waals forces and strong planar pi-pi bonds are stably anchored to the surface of C, and carbon contained in the material forms Al-C covalent bonds by reacting with aluminum reduced by the potential difference.
Drawings
FIG. 1 is a SEM topography of a water-soluble solid powdered carbon aluminum binder prepared in example 4;
FIG. 2 is a graph showing the comparison of the initial tack strength, medium temperature strength and high temperature strength of a sample block of an aluminum carbon product prepared from the water-soluble solid powdered aluminum carbon bond prepared in example 4 and other water-soluble bonds;
FIG. 3 shows XRD patterns of the water-soluble solid powdery carbon aluminum binder prepared in example 4;
fig. 4 is a graph showing the comparison of the initial tack strength, medium temperature strength and high temperature strength of aluminum carbon product samples prepared from the water-soluble solid powdery aluminum carbon binders prepared in example 4 and examples 5, 6 and 7.
Description of the embodiments
Examples
The preparation method of the water-soluble powdery carbon aluminum binding agent comprises the following steps:
s1, dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine:
s1-1, adding sodium tripolyphosphate into an ultrasonic dispersion stirrer, and adding water for dissolution;
s1-2, adding carbon black, and stirring to enable the carbon black to be rapidly wetted and dispersed;
s1-3, adding phosphoric acid, and carrying out effective acidification and activation on the carbon black through the phosphoric acid to uniformly disperse and anchor the carbon black in the phosphoric acid;
s2, introducing the carbon black phosphoric acid solution prepared in the step S1 into a reaction kettle, adding oxalic acid as a catalyst, heating and keeping the temperature of the reaction kettle at 88-95 ℃, slowly adding aluminum hydroxide diluted by water, keeping the liquid level boiling, and stirring until the reaction of the aluminum hydroxide aqueous solution is finished, so that a water-soluble carbon aluminum liquid binder is generated;
s3, carrying out spray drying on the water-soluble carbon aluminum liquid binder prepared in the step S2 to obtain the water-soluble solid powdery carbon aluminum binder.
Example 1
The preparation method of the water-soluble powdery carbon aluminum binder of this example is different from that of example 1 in that: the specification and the consumption of the used raw materials are further limited: sodium tripolyphosphate Na 5 P 3 O 10 The content is more than or equal to 96.0 percent, the content of carbon black C is more than or equal to 98.5 percent, and the grain diameter is 20-500nm; oxalic acid C 2 H 2 O 4 ·2H 2 O content is more than or equal to 95.5%, phosphoric acid H 3 PO 4 The content is more than or equal to 85 percent, aluminum hydroxide Al (OH) 3 The content is more than or equal to 99.6 percent. The raw materials are all commercial industrial chemical raw materials. The ratio of carbon black to water was tested at 1:0.85-1.15, and the dissolution and dispersion are best. Therefore, in the preparation process, firstly, adding dispersant sodium tripolyphosphate into an ultrasonic dispersion stirrer, adding water for dissolution, and diluting to 60-70 times; then adding the carbon black with the same quantity as water, and stirring to enable the carbon black to be quickly wetted and dispersed. The mass ratio of the dispersant sodium tripolyphosphate to the dosage of the carbon black, the phosphoric acid, the oxalic acid and the aluminum hydroxide is 1: (60-70): (550-580): (11-12): (130-140).
Examples
The preparation method of the water-soluble powdery carbon aluminum binder of this example is different from example 1 or example 2 in that: in the step S3, water is added to adjust the specific gravity of the water-soluble carbon aluminum liquid binder to be 1.30-1.35, and then the water-soluble solid powdery carbon aluminum binder is prepared through spray drying. The spray drying temperature is controlled at 103-108 deg.C to ensure excellent water solubility.
Examples
The preparation method of the water-soluble powdery carbon aluminum binding agent comprises the following production process steps:
step S1, dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine:
s1-1, 1kg Na 5 P 3 O 10 Adding industrial sodium tripolyphosphate with the content of more than or equal to 96.0% into an ultrasonic dispersion stirrer, and adding 65kg of water for dissolution; stirring for 10-25 min, preferably to dissolve sodium tripolyphosphate fully;
s1-2, adding 65kg of carbon black with C content more than or equal to 98.5% and particle size of 20-500nm, and stirring for 30min to enable the carbon black to be wetted and dispersed rapidly;
S1-3, then 560kg H are added 3 PO 4 Stirring for 40min the industrial phosphoric acid with the content of more than or equal to 85 percent, and carrying out effective acidification and activation on the carbon black by the phosphoric acid to uniformly disperse and anchor the carbon black in the phosphoric acid;
step S2, introducing the carbon black phosphoric acid solution prepared in the step S1 into a reaction kettle, and adding 11.5kg of C at one time 2 H 2 O 4 ·2H 2 Industrial oxalic acid with O content more than or equal to 95.5% is used as a catalyst, the temperature is raised, and 135kg of Al (OH) is taken 3 Adding 168kg of water into industrial grade aluminum hydroxide with the content of more than or equal to 99.6%, diluting, heating and controlling the temperature of a reaction kettle to 88-95 ℃, sequentially and slowly adding an aluminum hydroxide aqueous solution, keeping the liquid level boiling until the aluminum hydroxide aqueous solution is reacted, and generating a liquid water-soluble carbon aluminum liquid binder;
and S3, adding 58kg of water, measuring the specific gravity to be 1.34 by using a specific gravity meter, regulating the temperature of a spray tower to be 103-108 ℃, and spray-drying the liquid water-soluble carbon aluminum liquid bonding agent prepared in the step S2 to prepare the water-soluble solid powdery carbon aluminum bonding agent.
Examples
The preparation method of the water-soluble powdery carbon aluminum binding agent comprises the following preparation processes:
s1, dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine:
s1-1, 1kg Na 5 P 3 O 10 Adding industrial sodium tripolyphosphate with the content of more than or equal to 96.0% into an ultrasonic dispersion stirrer, and adding 70kg of water for dissolution;
s1-2, adding 70kg of carbon black with the C content of more than or equal to 98.5 percent and the granularity of 20-500nm, and cracking the carbon black by N990, and stirring for 40 minutes to enable the carbon black to be wetted and dispersed rapidly;
s1-3, then 580kg of H are added 3 PO 4 Stirring for 30min the industrial phosphoric acid with the content of more than or equal to 85 percent, and carrying out effective acidification and activation on the carbon black by the phosphoric acid to uniformly disperse and anchor the carbon black in the phosphoric acid;
s2, introducing the carbon black phosphoric acid solution prepared in the step S1 into a reaction kettle, and adding 12kg of C at one time 2 H 2 O 4 ·2H 2 Industrial oxalic acid with O content more than or equal to 95.5% is used as catalyst, 140kg Al (OH) is taken 3 Industrial grade aluminium hydroxide with content more than or equal to 99.6%Adding 182kg of water for dilution, heating to 88 ℃, starting to slowly add into a reaction kettle, controlling the temperature of the reaction kettle to 88-95 ℃ to generate a liquid water-soluble carbon aluminum liquid bonding agent, adding 69kg of water, and measuring the specific gravity to be 1.30 by using specific gravity.
S3, adjusting and controlling the temperature of the spray tower to be 103-108 ℃, and carrying out spray drying on the liquid water-soluble carbon aluminum liquid bonding agent prepared in the step S2 to prepare the water-soluble solid powdery carbon aluminum bonding agent.
Examples
The preparation method of the water-soluble powdery carbon aluminum binding agent comprises the following production process steps:
s1, dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine:
s1-1, 1kg Na 5 P 3 O 10 Adding sodium tripolyphosphate with the content of more than or equal to 96.0% into an ultrasonic dispersion stirrer, and adding 60kg of water for dissolution;
s1-2, adding 60kg of carbon black with the C content of more than or equal to 98.5 percent and the granularity of 20-200nm, and cracking the carbon black by N220, and stirring for 20 minutes to enable the carbon black to be wetted and dispersed rapidly;
s1-3, then 550kg H was added 3 PO 4 Stirring for 30min the industrial phosphoric acid with the content of more than or equal to 85 percent, and carrying out effective acidification and activation on the carbon black by the phosphoric acid to uniformly disperse and anchor the carbon black in the phosphoric acid;
s2, introducing the carbon black phosphoric acid solution prepared in the step S1 into a reaction kettle, and adding 11kg of C at one time 2 H 2 O 4 ·2H 2 Industrial oxalic acid with O content more than or equal to 95.5% is used as catalyst, 130kg Al (OH) is taken 3 Adding 156kg of water into industrial grade aluminum hydroxide with the content of more than or equal to 99.6%, diluting, heating to 88 ℃, starting to slowly add into a reaction kettle, controlling the temperature of the reaction kettle to 88-95 ℃ to generate a liquid water-soluble carbon aluminum liquid binder, adding 53kg of water, and measuring the specific gravity to be 1.35 by using specific gravity.
S3, adjusting and controlling the temperature of the spray tower to be 103-108 ℃, and carrying out spray drying on the liquid water-soluble carbon aluminum liquid bonding agent prepared in the step S2 to prepare the water-soluble solid powdery carbon aluminum bonding agent.
Examples
The preparation method of the water-soluble powdery carbon aluminum binding agent comprises the following production process steps:
s1, dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine:
s1-1, 1kg Na 5 P 3 O 10 Adding sodium tripolyphosphate with the content of more than or equal to 96.0% into an ultrasonic dispersion stirrer, and adding 63kg of water for dissolution;
s1-2, adding 70kg of carbon black with the C content of more than or equal to 98.5 percent and the granularity of 20-300nm, cracking the carbon black by N550, and stirring for 25 minutes to enable the carbon black to be wetted and dispersed rapidly;
s1-3, then 570kg H was added 3 PO 4 Stirring for 35min the industrial phosphoric acid with the content of more than or equal to 85 percent, and carrying out effective acidification and activation on the carbon black by the phosphoric acid to uniformly disperse and anchor the carbon black in the phosphoric acid;
s2, introducing the carbon black phosphoric acid solution prepared in the step S1 into a reaction kettle, and adding 11.2kg of C at one time 2 H 2 O 4 ·2H 2 Industrial oxalic acid with O content more than or equal to 95.5% is used as catalyst, 136kg Al (OH) is taken 3 Adding 166kg of water into industrial grade aluminum hydroxide with the content of more than or equal to 99.6%, diluting, heating to 88 ℃, starting to slowly add into a reaction kettle, controlling the temperature of the reaction kettle to 88-95 ℃ to generate a liquid water-soluble carbon aluminum liquid binder, adding 60kg of water, and measuring the specific gravity to be 1.34 by using specific gravity.
S3, adjusting and controlling the temperature of the spray tower to be 103-108 ℃, and carrying out spray drying on the liquid water-soluble carbon aluminum liquid bonding agent prepared in the step S2 to prepare the water-soluble solid powdery carbon aluminum bonding agent.
Fig. 1 is an SEM morphology diagram of the water-soluble solid powdery carbon aluminum binder prepared by the preparation method of example 4. The figure shows that the carbon particles are uniformly distributed, agglomeration and superposition phenomena do not occur, the aluminum dihydrogen phosphate forming film is uniformly coated on the surfaces of the carbon particles, in theory, the aluminum dihydrogen phosphate forming film can form a C-Al network structure with materials in use, so that the oxidation of carbon is prevented, the high temperature resistance, corrosion resistance and oxidation resistance of the aluminum dihydrogen phosphate are improved, the advantage of high initial adhesion strength of the aluminum dihydrogen phosphate can be effectively exerted, and the problem of the initial adhesion strength of the water-based resin binder is solved.
FIG. 2 is a graph showing the comparison of the initial tack strength, medium temperature strength and high temperature strength of the sample block of the prepared aluminum-carbon product according to the material ratios listed in Table 1, wherein the initial tack strength of the water-soluble solid powdery carbon-aluminum binder prepared in example 4 is substantially equal to the initial tack strength of aluminum dihydrogen phosphate and is higher than the initial tack strength of the alcohol-soluble phenolic resin, and is greatly higher than the initial tack strength of other water-soluble resin binders; the medium-temperature strength and the high-temperature strength are equal to those of the alcohol-soluble phenolic resin, but are superior to aluminum dihydrogen phosphate and other water-soluble resin binders. It is therefore necessary to dominate the development of aqueous resin binders.
Table 1: sample block proportioning table of prepared aluminum-carbon product
Figure 3 shows the XRD pattern of the water-soluble solid powdered carbon aluminium binder prepared in example 4. From the XRD pattern of the water-soluble solid powdered carbon aluminum binder shown in FIG. 3, a plurality of mutually independent narrow "peaks" can be seen, indicating that C has a perfect "crystalline state", and from the "peak" width, it can be determined that the crystal particle size in the sample is less than 400nm, C and Al (H) 2 PO 4 ) 3 And (5) uniformly fusing.
FIG. 4 is a graph showing the comparison of the initial tack strength, the medium temperature strength and the high temperature strength of aluminum carbon product samples prepared from the water-soluble solid powdery aluminum carbon binders prepared in example 4 and the preparation methods of examples 5, 6 and 7. The water-soluble solid powdery carbon aluminum binders prepared in examples 5, 6, and 7, were monitored as aluminum carbon product samples still prepared in the proportions shown in table 1. Compared with the sample block in example 4, the initial adhesion strength, the medium temperature strength and the high temperature strength have fluctuation and little change, and all have good high temperature performance and initial strength. The invention can be widely applied to the fields of refractory materials, friction materials, casting molding materials and the like, and is an ideal product for replacing resin binders.
Compared with the prior art, the invention adopts a dispersing technology combining chemistry and physics to uniformly disperse and anchor carbon black in water, then adds phosphoric acid and stirs to acidify and activate, then adds oxalic acid as a catalyst, adds aluminum hydroxide aqueous solution, generates a carbon-aluminum binding agent in situ through reaction, and can effectively solve the problem that the carbon black is in Al (H) 2 PO4) 3 The novel high-temperature-resistant corrosion-resistant water-soluble solid powdery carbon aluminum binding agent is prepared, has the advantages of water solubility, good cohesiveness, high initial adhesion strength, high green body strength after forming, and capability of effectively preventing oxidation of carbon in use, and can generate a carbon-coated aluminum polyphosphate glass body after medium-high temperature treatment in use, so that a strong chemical binding force is formed, and the material can form a unique C-Al network structure, and has high cohesiveness and thermal stability. So the carbon aluminum bonding agent has the characteristics of high temperature resistance, corrosion resistance and oxidation resistance. And can obviously improve the high-temperature mechanical properties such as thermal shock resistance, erosion resistance, thermal shock resistance, strength retention rate and the like of refractory materials, friction materials, coatings, heat-insulating materials and casting molding materials, reduce harmful volatile matters and contribute to improvement of the operation environment.

Claims (9)

1. A preparation method of a water-soluble powdery carbon aluminum binding agent is characterized by comprising the following steps of: the method comprises the following steps:
s1, dispersing and anchoring carbon black by adopting an inorganic dispersant sodium tripolyphosphate and an ultrasonic dispersing machine:
s1-1, adding sodium tripolyphosphate into an ultrasonic dispersion stirrer, and adding water for dissolution;
s1-2, adding carbon black, and stirring to enable the carbon black to be rapidly wetted and dispersed;
s1-3, adding phosphoric acid, and carrying out effective acidification and activation on the carbon black through the phosphoric acid to uniformly disperse and anchor the carbon black in the phosphoric acid;
s2, introducing the carbon black phosphoric acid solution prepared in the step S1 into a reaction kettle, adding oxalic acid as a catalyst, heating and keeping the temperature of the reaction kettle at 88-95 ℃, and slowly adding water-diluted aluminum hydroxide to generate a water-soluble carbon aluminum liquid binder;
s3, carrying out spray drying on the water-soluble carbon aluminum liquid binder prepared in the step S2 to obtain the water-soluble solid powdery carbon aluminum binder.
2. The method for preparing the water-soluble powdery carbon aluminum binder according to claim 1, wherein: in step S1, the raw materials used are: sodium tripolyphosphateNa 5 P 3 O 10 The content is more than or equal to 96.0 percent; the content of carbon black C is more than or equal to 98.5 percent, and the grain diameter is 20-500nm; phosphoric acid H 3 PO 4 The content is more than or equal to 85 percent; diluting sodium tripolyphosphate with water in an amount which is 60-70 times the mass ratio, and then adding carbon black and phosphoric acid, wherein the mass ratio of the sodium tripolyphosphate to the carbon black to the phosphoric acid is 1: (60-70): (550-580).
3. The method for preparing the water-soluble powdery carbon aluminum binder according to claim 1 or 2, wherein: in step S2, the starting material used, aluminum hydroxide Al (OH) 3 The content is more than or equal to 99.6 percent, and the catalyst is oxalic acid C 2 H 2 O 4 ·2H 2 The O content is more than or equal to 95.5 percent, and the mass and the dosage ratio of the sodium tripolyphosphate to the catalyst to the aluminum hydroxide are 1: (11-12): (130-140); the mass ratio of aluminum hydroxide to water is 1: (1.2-1.3).
4. A method of preparing a water-soluble powdered carbon aluminum binder as claimed in claim 3, wherein: in the step S1-1, dissolving and stirring sodium tripolyphosphate for 10-25 minutes; in the step S1-2, after adding carbon black, ultrasonic dispersion and stirring are carried out for 20-30min; in the step S1-3, phosphoric acid is added to acidify and stir the carbon black for 30-40min.
5. The method for preparing the water-soluble powdery carbon aluminum binder according to claim 1, 2 or 4, wherein: in the step S2, the oxalic acid serving as a catalyst is added at one time, steam is introduced into the interlayer of the reaction kettle while stirring for heating to 88 ℃, then the aqueous solution of aluminum hydroxide is slowly added into the reaction kettle to make the liquid level boil, and the temperature of the reaction kettle is controlled at 88-95 ℃ until the reaction of the aqueous solution of aluminum hydroxide is completed.
6. A method of preparing a water-soluble powdered carbon aluminum binder as claimed in claim 3, wherein: in the step S2, the oxalic acid serving as a catalyst is added at one time, steam is introduced into the interlayer of the reaction kettle while stirring for heating to 88 ℃, then the aqueous solution of aluminum hydroxide is slowly added into the reaction kettle to make the liquid level boil, and the temperature of the reaction kettle is controlled at 88-95 ℃ until the reaction of the aqueous solution of aluminum hydroxide is completed.
7. The method for preparing the water-soluble powdery carbon aluminum binder according to claim 1, 2, 4 or 6, wherein: in the step S3, water is added to adjust the specific gravity of the water-soluble carbon aluminum liquid binder to be 1.30-1.35, and then the water-soluble solid powdery carbon aluminum binder is prepared through spray drying, and the spray drying temperature is controlled at 103-108 ℃.
8. A method of preparing a water-soluble powdered carbon aluminum binder as claimed in claim 3, wherein: in the step S3, water is added to adjust the specific gravity of the water-soluble carbon aluminum liquid binder to be 1.30-1.35, and then the water-soluble solid powdery carbon aluminum binder is prepared through spray drying, and the spray drying temperature is controlled at 103-108 ℃.
9. The method for preparing the water-soluble powdery carbon aluminum binder according to claim 5, wherein: in the step S3, water is added to adjust the specific gravity of the water-soluble carbon aluminum liquid binder to be 1.30-1.35, and then the water-soluble solid powdery carbon aluminum binder is prepared through spray drying, and the spray drying temperature is controlled at 103-108 ℃.
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US4358500A (en) * 1981-08-20 1982-11-09 Subtex, Inc. Flame resistant insulating fabric compositions containing inorganic bonding agent
CN1120059A (en) * 1994-09-16 1996-04-10 淄博市新材料研究所 Inorganic binder and its preparation method and usage
KR20110050851A (en) * 2009-11-09 2011-05-17 조용호 Friendly environment inorganic adhesive composition and manufacturing method thereof
US20120174828A1 (en) * 2007-02-15 2012-07-12 Dalian Rino Environment Engineering Science And Technology Co., Ltd. Inorganic composite binders with high-temperature resistance

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4358500A (en) * 1981-08-20 1982-11-09 Subtex, Inc. Flame resistant insulating fabric compositions containing inorganic bonding agent
CN1120059A (en) * 1994-09-16 1996-04-10 淄博市新材料研究所 Inorganic binder and its preparation method and usage
US20120174828A1 (en) * 2007-02-15 2012-07-12 Dalian Rino Environment Engineering Science And Technology Co., Ltd. Inorganic composite binders with high-temperature resistance
KR20110050851A (en) * 2009-11-09 2011-05-17 조용호 Friendly environment inorganic adhesive composition and manufacturing method thereof

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