CN114276698B - Preparation method of nano calcium carbonate for nail-free glue - Google Patents
Preparation method of nano calcium carbonate for nail-free glue Download PDFInfo
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Abstract
The invention discloses a method for preparing nano calcium carbonate for nail-free glue, which comprises the steps of adding polylol into calcined lime in a water system for digestion reaction under the conditions of high temperature and high pressure, then carrying out carbonation reaction on lime milk at low temperature in the whole process, adding a dispersing agent in the early stage of the reaction, adding a titanate coupling agent into a prepared calcium carbonate suspension for surface modification at normal temperature, heating, adding sodium stearate for wet high-temperature modification, and finally dehydrating, drying and crushing through a filter press to obtain the nano calcium carbonate for nail-free glue. The nano calcium carbonate prepared by the method through a simple process and low cost has a large specific surface area and a good reinforcing effect, endows the MS nail-free glue with excellent thixotropy and reinforcing performance, can effectively replace fumed silica, and reduces the production cost of the MS nail-free glue.
Description
Technical Field
The invention relates to the technical field of calcium carbonate, in particular to a preparation method of nano calcium carbonate for nail-free glue.
Background
With the improvement of personalized requirements in the field of home decoration, people have paid more and more attention to construction convenience and decoration attractiveness. The nail-free glue is a novel multifunctional decorative structural glue capable of replacing fastening equipment such as nails, bolts, welding and the like. Because the nail-free glue is simple and convenient to construct, high in bonding strength and high in bonding speed, most materials can be adhered without punching, and people prefer the nail-free glue more and more. The nail-free glue is mainly divided into a solvent volatile type and a moisture curing type. The solvent type nail-free glue is gradually eliminated by the market because the solvent type nail-free glue contains toxic volatile solvent, can pollute the environment and is harmful to human bodies. The moisture-curing nail-free glue does not contain organic solvents, is environment-friendly and non-toxic, and is slowly accepted by people. At present, the moisture-curing nail-free glue on the market is mainly a silane-terminated modified polyether product.
The terminal silane modified polyether nail-free glue (MS nail-free glue) mainly comprises terminal silane modified polyether resin (MS resin), a filler, a coupling agent, a water removing agent, a catalyst and the like. Wherein, the filler is an indispensable raw material and has great influence on the mechanical property of the nail-free glue. Fumed silica, nano calcium carbonate and ground calcium carbonate are the most commonly used fillers for MS nail free glues. Fumed silica has excellent reinforcing and thixotropy improving effects due to its high specific surface area, but the product price is high and the filling amount is low. The heavy calcium carbonate generally only plays a role in increasing and reducing the cost, and has no obvious reinforcing effect. At present, most of nano calcium carbonate in the market has the specific surface area of about 20m < 2 >/g and the reinforcing effect is poorer than that of fumed silica, but has the remarkable characteristics of low product price and high filling amount, and is always favored by the market.
For nano calcium carbonate, increasing the specific surface area is one of the most effective methods to enhance its reinforcement. At present, the direct improvement of the specific surface area of the nano calcium carbonate is not difficult to realize, but the problem that the nano calcium carbonate is easy to agglomerate when the specific surface area is larger exists, which greatly discounts the reinforcing effect. Meanwhile, different surface treatment agents have different reinforcing effects on different application systems, and the reinforcing effect of the powder can be improved by selecting the proper surface treatment agent.
Patent CN 1689974A discloses a process for the production of calcium carbonate having a high specific surface area. The method adopts a conventional carbonization method, controls the crystal growth of calcium carbonate by adding humic acid or sodium humate or a copolymer of maleic anhydride and acrylamide, and finally obtains the calcium carbonate powder with serious agglomeration and developed pore channels and high specific surface area. The powder of the invention is well suitable for flue gas desulfurization, but the calcium carbonate is seriously agglomerated and has poor reinforcing performance, so the powder is not suitable for most application systems.
Patent CN 104059390A discloses a modified calcium carbonate with high specific surface area and a preparation method thereof. The method is characterized in that calcium carbonate, various reagents and modified titanium dioxide are mixed and ground to finally obtain 1200-1400 mesh powder. The invention improves the specific surface area of the calcium carbonate by a physical grinding method, and has the advantages of unobvious improvement effect, high cost and poor economic benefit.
Patent CN 108083312A discloses a carbonization reactor and a method for preparing nano calcium carbonate with small particle size, high dispersibility and low oil absorption value. The method adopts a secondary carbonization method, strictly separates two steps of calcium carbonate nucleation and crystal growth, and finally obtains the nano calcium carbonate with good dispersibility and small particle size through wet grinding and surface modification. The method has complex process flow, high production cost due to the use of high-purity carbon dioxide for production, is not beneficial to large-scale production and has low economic benefit.
Patent CN 112811456A discloses a nano calcium carbonate with high specific surface area and a preparation method thereof. The method adopts a slurry-supplementing carbonization method, firstly carries out calcium carbonate nucleation carbonization, then supplements slurry to carry out calcium carbonate crystal growth carbonization, and then carries out surface treatment to finally obtain the high-specific surface nano calcium carbonate with good dispersibility. The invention adopts high-purity carbon dioxide for production, not only has high production cost, but also has high carbon dioxide content of carbonized tail gas to aggravate greenhouse effect, and simultaneously has over-high dosage of surface treating agent and general reinforcing effect.
Patent CN 107337225A discloses a method for preparing nano ellipsoidal calcium carbonate particles, which comprises dissolving calcium oxide in a non-aqueous solvent (methanol or absolute ethanol respectively combined with acetonitrile, glycerol, ethylene glycol, butanol) to prepare Ca (OH) 2 Suspending liquid, and cooling the suspending liquid to 5-15 ℃ by an ice bath; cooling the Ca (OH) 2 The suspension is transferred to a carbonization reactor, without heating, carbon dioxide is bubbled from the bottom of the carbonization reactor at a large flow rate of 200-400mL/min, and the CO feed is stopped when the pH =7-7.5 2 Then transferring the mixture to a distiller, and continuously stirring the mixture under normal pressure or distilling the mixture under reduced pressure to recover the solvent to obtain nano calcium carbonate solid particles; and crushing the calcium carbonate solid particles by a conventional method to obtain the nano ellipsoidal calcium carbonate product. Although the nano calcium carbonate with high specific surface area can be prepared, the reaction system is in a non-aqueous solvent, and compared with a mature water system, the nano calcium carbonate has the advantages of extremely high cost, extremely low industrial benefit and low industrialization value.
In summary, the problems of calcium carbonate agglomeration and excessive production cost mainly exist in the current preparation of the nano calcium carbonate with high specific surface area, which limits the development of the nano calcium carbonate towards higher reinforcement.
Disclosure of Invention
The invention provides a preparation method of active precipitated calcium carbonate for MS nail-free glue, aiming at the defect that the existing produced active precipitated calcium carbonate is filled with MS nail-free glue. The nano calcium carbonate prepared by the method through simple process and low cost has large specific surface area and good reinforcing effect, endows the MS nail-free glue with excellent thixotropy and reinforcing performance, can effectively replace fumed silica, and reduces the production cost of the MS nail-free glue.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of nano calcium carbonate for nail-free glue comprises the following steps:
(1) Calcining limestone to obtain raw burnt lime, placing the raw burnt lime into a high-temperature high-pressure digesting kettle, adding water which is 3-5 times of the mass of the raw burnt lime and 1.0-2.0% of polyol, digesting at high temperature and high pressure to prepare lime milk, removing waste residues from the lime milk by a 100-mesh screen, and adjusting the solid content of the lime milk to 4-6% for later use;
(2) Transferring the lime milk obtained in the step (1) into a carbonation reaction tower, cooling the temperature of the lime milk to 15-18 ℃ through cooling circulation, adding a crystal form control agent accounting for 0.05-0.1% of the mass of the lime milk, introducing lime kiln gas for carbonation reaction, adding a dispersing agent accounting for 0.5-1.0% of the mass of a dry calcium carbonate base after gelation, and stopping reaction until the pH value of a reaction system is 7.5 to obtain a calcium carbonate suspension;
(3) Transferring the calcium carbonate suspension liquid obtained in the step (2) to a treatment tank, firstly adding a titanate coupling agent accounting for 1.5-2.5% of the dry mass of calcium carbonate, stirring for 10-20 min, then heating the suspension liquid to 55-65 ℃, adding sodium stearate accounting for 1.5-2.0% of the dry mass of calcium carbonate, carrying out wet modification, and continuously stirring for 30-40 min to complete wet surface treatment to obtain calcium carbonate slurry;
(4) And dehydrating the calcium carbonate slurry by a filter press, drying and crushing to obtain the nano calcium carbonate for the nail-free glue.
Further, the polyhydric alcohol comprises one or two of ethylene glycol, glycerol, triethanolamine and diethanolamine.
Further, the high temperature and high pressure in the step (1) are reacted at the temperature of 130-140 ℃ and the pressure of 0.3-0.4 MPa.
Further, the crystal form control agent in the step (2) comprises one or more of sucrose, fructose, glucose and maltose.
Further, the dispersing agent comprises one or more of sodium polyacrylate, ammonium polyacrylate, polyacrylamide, polymaleic anhydride and maleic acid-acrylic acid copolymer.
Further, the titanate coupling agent includes one of isopropoxy tris (dioctyl pyrophosphate) titanate, isopropoxy tris (dioctyl phosphate) titanate, and isopropoxy tris (isostearoyl) titanate.
Further, the temperature in the early stage of carbonation is controlled not to exceed 20 ℃ and the temperature in the later stage is controlled not to exceed 30 ℃ in the step (2); the concentration of carbon dioxide in the lime kiln gas is 30-35%.
Further, the calcination in the step (1) is carried out at the temperature of 1000-1100 ℃ for 300-400 min.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. the invention adopts the digestion reaction of the high-reactivity calcined lime in the high-temperature high-pressure digestion kettle, and can obtain the calcium hydroxide suspension with small particle size and high specific surface area by the action of the polyalcohol, and the smaller the particle size of the calcium hydroxide and the lower the carbonization temperature, the higher the solubility of the calcium hydroxide, and the easier the nucleation of the calcium carbonate to form the nano calcium carbonate with high specific surface area.
2. Under the coordination of small-particle-size calcium hydroxide and low-temperature carbonization, the nano calcium carbonate with high specific surface area can be prepared more easily, and meanwhile, the low temperature is kept in the carbonization process, and the dispersing agent is added, so that the agglomeration of the nano calcium carbonate is prevented, and the good reinforcing performance is ensured.
3. The invention selects titanate coupling agent as surface treatment agent, is suitable for MS nail-free glue system, not only can further improve the reinforcement performance of nail-free glue, but also can carry out surface modification at normal temperature, and prevent the specific surface area of nano calcium carbonate from being reduced at high temperature of surface treatment.
4. The nanometer of the inventionThe specific surface area of the calcium carbonate is more than 50m 2 The filling amount of the filler is 2 to 3 times higher than that of the fumed silica, and the filler can completely replace the fumed silica under higher filling amount, and has the advantages of high reinforcement, excellent thixotropy and high filling amount.
5. The method has the advantages of simple process, low production cost and low energy consumption, and the prepared nano calcium carbonate can provide a filler with excellent performance and low cost for the MS nail-free glue and has good economic and social benefits.
Drawings
FIG. 1 is an SEM (magnification of 50000) electron micrograph of the nano calcium carbonate prepared in example 1;
FIG. 2 is SEM electron micrograph (50000 times) of nano calcium carbonate prepared in comparative example 2.
FIG. 3 is SEM electron micrograph (5000 times) of nano calcium carbonate prepared in comparative example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of nano calcium carbonate for nail-free glue comprises the following steps:
(1) Calcining limestone with the block size of 2-3 cm at the temperature of 1000 ℃ for 400min to obtain raw burnt lime, then putting the raw burnt lime into a high-temperature high-pressure digesting kettle, closing an ash inlet of the digesting kettle, then adding water with the mass of 3 times of that of the raw burnt lime and 1.5% of glycerol, starting stirring in the digesting kettle, controlling the pressure in the digesting kettle to be 0.4MPa and the temperature to be 130 ℃, after stirring and reacting for 20min, decompressing, pouring out lime milk, removing waste residues through a 100-mesh screen, and finally adding water to adjust the solid content of the lime milk to 5%;
(2) Putting 15kg of lime milk into a carbonation reaction tower, adjusting the temperature of the lime milk to 15 ℃ through cooling circulation, adding cane sugar with the mass of 0.1% of that of the lime milk, adjusting the stirring speed of the carbonation tower to be 1000r/min, starting to introduce mixed gas with the concentration of 33% of carbon dioxide, controlling the flow rate of the mixed gas to be 4m & lt 3 & gt/h, then adding sodium polyacrylate with the mass of 1.0% of the dry basis of calcium carbonate after gelation, simultaneously ensuring that the temperature is less than 20 ℃ in 10min before carbonation through cooling circulation, and stopping introducing gas immediately when the temperature is less than 30 ℃ after 10min of carbonation and the pH of a suspension is 7.5 after carbonation, terminating carbonation reaction, and finally obtaining calcium carbonate suspension;
(3) Transferring the calcium carbonate suspension liquid obtained in the step (2) to a treatment tank, adding isopropoxy tri (dioctyl pyrophosphate) titanate with the dry mass of calcium carbonate being 2.5 percent, stirring for 10min, heating the suspension liquid at 60 ℃, continuously adding sodium stearate with the dry mass of calcium carbonate being 1.5 percent, and stirring for 40min to complete surface treatment;
(4) Dewatering the surface treated slurry by a plate-and-frame filter press, drying the pressed material at 120 ℃, and finally crushing to obtain the slurry with the specific surface area of 55.12m 2 Per gram of nano calcium carbonate.
Example 2
A preparation method of nano calcium carbonate for nail-free glue comprises the following steps:
(1) Calcining limestone with the lumpiness of 2-3 cm at the temperature of 1100 ℃ for 300min to obtain raw burnt lime, then putting the raw burnt lime into a high-temperature high-pressure digesting kettle, closing an ash inlet of the digesting kettle, then adding ethylene glycol with the mass of 3 times of that of the raw burnt lime and 2.0 percent of the raw burnt lime, starting stirring in the digesting kettle, controlling the pressure in the digesting kettle to be 0.3MPa and the temperature to be 135 ℃, after stirring reaction for 20min, decompressing, pouring out lime milk, removing waste residues through a 100-mesh screen, and finally adding water to adjust the solid content of the lime milk to be 5 percent;
(2) Adding 15kg of lime milk into a carbonation reaction tower, adjusting the temperature of the lime milk to 15 ℃ through cooling circulation, adding cane sugar with the mass of 0.1% of the lime milk, adjusting the stirring speed of the carbonation tower to 1000r/min, starting introducing mixed gas with the concentration of 33% carbon dioxide, and controlling the flow of the mixed gas to be 4m 3 H, then adding ammonium polyacrylate 0.5% of calcium carbonate dry basis weight after gelation, and cooling for 10min to ensure temperature below 20 deg.C before carbonationAcidifying for 10min, cooling to below 30 deg.C, carbonating to pH of 7.5, stopping introducing gas, and terminating carbonation reaction to obtain calcium carbonate suspension;
(3) Transferring the calcium carbonate suspension liquid obtained in the step (2) to a treatment tank, firstly adding isopropoxy tri (dioctyl phosphate) titanate with the mass of 2.0 percent of the dry mass of calcium carbonate, then heating the suspension liquid at 60 ℃, and continuously adding sodium stearate with the dry mass of calcium carbonate of 2.0 percent, and stirring for 40min to complete surface treatment;
(4) Dewatering the surface treated slurry by a plate-and-frame filter press, drying the pressed material at 120 ℃, and finally crushing to obtain the slurry with the specific surface area of 50.33m 2 Per gram of nano calcium carbonate.
Example 3
A preparation method of nano calcium carbonate for nail-free glue comprises the following steps:
(1) Calcining limestone with the block size of 2-3 cm at 1050 ℃ for 350min to obtain raw calcined lime, then putting the raw calcined lime into a high-temperature high-pressure digesting kettle, closing an ash inlet of the digesting kettle, then adding water with the mass of 3 times of that of the raw calcined lime and 1.0% of triethanolamine, starting stirring in the digesting kettle, controlling the pressure in the digesting kettle to be 0.4MPa and the temperature to be 130 ℃, after stirring and reacting for 20min, decompressing, pouring out lime milk, removing waste residues through a 100-mesh screen, and finally adding water to adjust the solid content of the lime milk to 6%;
(2) Putting 15kg of lime milk into a carbonation reaction tower, adjusting the temperature of the lime milk to 16 ℃ through cooling circulation, adding 0.05% of fructose, adjusting the stirring speed of the carbonation tower to be 1000r/min, starting introducing mixed gas with 33% of carbon dioxide concentration, controlling the flow rate of the mixed gas to be 4m & lt 3 & gt/h, adding 0.5% of polyacrylamide after gelation, simultaneously ensuring that the temperature is less than 20 ℃ in 10min before carbonation through cooling circulation, the temperature is less than 30 ℃ after 10min carbonation, stopping introducing gas immediately when the pH of the suspension is 7.5 after carbonation, and terminating carbonation reaction to finally obtain calcium carbonate suspension;
(3) Transferring the calcium carbonate suspension liquid obtained in the step (2) to a treatment tank, adding isopropoxy tri (isostearyl) titanate with the mass of the dry basis of calcium carbonate being 1.5%, stirring for 10min, heating the suspension liquid at 60 ℃, continuously adding sodium stearate with the dry basis of calcium carbonate being 2.0%, stirring for 40min, and finishing surface treatment;
(4) Dewatering the surface treated slurry by a plate-and-frame filter press, drying the pressed material at 120 ℃, and finally crushing to obtain the slurry with the specific surface area of 52.78m 2 Per gram of activated calcium carbonate.
Example 4
A preparation method of nano calcium carbonate for nail-free glue comprises the following steps:
(1) Calcining limestone with the block size of 2-3 cm at the temperature of 1100 ℃ for 300min to obtain raw calcined lime, then putting the raw calcined lime into a high-temperature high-pressure digesting kettle, closing an ash inlet of the digesting kettle, then adding 3 times of water by mass of the raw calcined lime, 1.5% of diethanolamine and 0.5% of glycerol, starting stirring in the digesting kettle, controlling the pressure in the digesting kettle to be 0.4MPa and the temperature to be 140 ℃, after stirring and reacting for 20min, decompressing, pouring out lime milk, removing waste residues through a 100-mesh screen, and finally adding water to adjust the solid content of the lime milk to 4%;
(2) Adding 15kg lime milk into carbonation reaction tower, cooling to 16 deg.C, adding 0.08% maltose, adjusting the stirring speed of the carbonation tower to 1000r/min, introducing 33% carbon dioxide gas mixture, and controlling the flow of the gas mixture to 4m 3 Then, 0.3% of polymaleic anhydride is added after gelation to compound maleic acid-acrylic acid copolymer (1) and 0.4% of sodium polyacrylate, meanwhile, cooling circulation is carried out to ensure that the temperature is less than 20 ℃ 10min before carbonation, the temperature is less than 30 ℃ after 10min carbonation, gas introduction is stopped immediately when the pH of the suspension is 7.5 after carbonation, and the carbonation reaction is stopped, so that calcium carbonate suspension is finally obtained;
(3) Transferring the calcium carbonate suspension liquid obtained in the step (2) to a treatment tank, adding 2.5% of isopropoxy tri (dioctyl pyrophosphate) titanate, stirring for 10min, heating the suspension liquid to 60 ℃, continuously adding sodium stearate with the calcium carbonate dry basis mass of 1.5%, and stirring for 40min to complete surface treatment;
(4) Dewatering the surface treated slurry by a plate-and-frame filter press, drying the pressed material at 120 ℃, and finally crushing to obtain the slurry with the specific surface area of 53.73m 2 Activated carbon per gramCalcium carbonate.
Comparative example 1
(1) Calcining 2-3 cm of limestone at the temperature of 1000 ℃ for 400min to obtain raw burnt lime, then putting the raw burnt lime into a high-temperature high-pressure digesting kettle, closing an ash inlet of the digesting kettle, then adding 3 times of water by mass of the raw burnt lime, starting stirring in the digesting kettle, stirring and reacting for 20min at normal temperature and normal pressure (28 ℃), decompressing, pouring out lime milk, removing waste residues through a 100-mesh screen, and finally adding water to adjust the solid content of the lime milk to 5%;
(2) Adding 15kg of lime milk into a carbonation reaction tower, adjusting the temperature of the lime milk to 15 ℃ through cooling circulation, adding cane sugar with the mass of 0.1% of the lime milk, adjusting the stirring speed of the carbonation tower to 1000r/min, starting introducing mixed gas with the concentration of 33% carbon dioxide, and controlling the flow of the mixed gas to be 4m 3 Adding sodium polyacrylate with calcium carbonate dry basis weight of 1.0% after gelation, simultaneously, cooling for 10min before carbonation at a temperature of less than 20 deg.C and 10min after carbonation at a temperature of less than 30 deg.C, and stopping gas introduction when pH of the suspension is 7.5 after carbonation to terminate carbonation reaction to obtain calcium carbonate suspension;
(3) Transferring the calcium carbonate suspension obtained in the step (2) to a treatment tank, adding isopropoxy tri (dioctyl pyrophosphate) titanate with the dry mass of 2.5% of calcium carbonate, stirring for 10min, heating the suspension at 60 ℃, continuously adding sodium stearate with the dry mass of 1.5% of calcium carbonate, and stirring for 40min to complete surface treatment;
(4) Dewatering the surface treated slurry by a plate-and-frame filter press, drying the pressed material at 120 ℃, and finally crushing to obtain the slurry with the specific surface area of 47.54m 2 /gm 2 Per gram of nano calcium carbonate.
Comparative example 2
(1) Calcining limestone with the block size of 2-3 cm at the temperature of 1000 ℃ for 400min to obtain raw burnt lime, then putting the raw burnt lime into a high-temperature high-pressure digesting kettle, closing an ash inlet of the digesting kettle, then adding water with the mass of 3 times of that of the raw burnt lime and 1.5% of glycerol, starting stirring in the digesting kettle, controlling the pressure in the digesting kettle to be 0.4MPa and the temperature to be 130 ℃, after stirring and reacting for 20min, decompressing, pouring out lime milk, removing waste residues through a 100-mesh screen, and finally adding water to adjust the solid content of the lime milk to 5%;
(2) Adding 15kg of lime milk into a carbonation reaction tower, adjusting the temperature of the lime milk to 15 ℃ through cooling circulation, adding cane sugar with the mass of 0.1% of the lime milk, adjusting the stirring speed of the carbonation tower to 1000r/min, starting introducing mixed gas with the concentration of 33% carbon dioxide, and controlling the flow of the mixed gas to be 4m 3 Stopping introducing gas immediately when the pH of the suspension is 7.5 after carbonation, and terminating the carbonation reaction to obtain a calcium carbonate suspension finally;
(3) Transferring the calcium carbonate suspension obtained in the step (2) to a treatment tank, adding isopropoxy tri (dioctyl pyrophosphate) titanate with the dry mass of 2.5% of calcium carbonate, stirring for 10min, heating the suspension at 60 ℃, continuously adding sodium stearate with the dry mass of 1.5% of calcium carbonate, and stirring for 40min to complete surface treatment;
(4) Dewatering the surface treated slurry by a plate-and-frame filter press, drying the pressed material at 120 ℃, and finally crushing to obtain the slurry with the specific surface area of 46.16m 2 Per gram of nano calcium carbonate.
Comparative example 3
(1) Calcining limestone with the block size of 2-3 cm at the temperature of 1000 ℃ for 400min to obtain raw burnt lime, then putting the raw burnt lime into a high-temperature high-pressure digesting kettle, closing an ash inlet of the digesting kettle, then adding 3 times of water and 1.5% glycerol by mass of the raw burnt lime, starting stirring in the digesting kettle, controlling the pressure in the digesting kettle to be 0.4MPa and the temperature to be 130 ℃, after stirring and reacting for 20min, decompressing, pouring out lime milk, removing waste residues through a 100-mesh screen, and finally adding water to adjust the solid content of the lime milk to 5%;
(2) Adding 15kg of lime milk into a carbonation reaction tower, adjusting the temperature of the lime milk to 15 ℃ through cooling circulation, adding cane sugar with the mass of 0.1% of the lime milk, adjusting the stirring speed of the carbonation tower to 1000r/min, starting introducing mixed gas with the concentration of 33% carbon dioxide, and controlling the flow of the mixed gas to be 4m 3 Then adding sodium polyacrylate with calcium carbonate dry basis mass of 1.0% after gelation, and simultaneously cooling and circulating to ensure that the temperature is less than 20 deg.C 10min before carbonation and less than 30 deg.C 10min after carbonationStopping introducing gas immediately when the pH of the solution is 7.5, and terminating the carbonation reaction to obtain a calcium carbonate suspension finally;
(3) Transferring the calcium carbonate suspension liquid obtained in the step (2) to a treatment tank, heating the suspension liquid to 60 ℃, continuously adding sodium stearate with the calcium carbonate dry basis weight being 4.0%, and stirring for 40min to finish surface treatment;
(4) Dewatering the surface treated slurry by a plate-and-frame filter press, drying the pressed material at 120 ℃, and finally crushing to obtain the slurry with the specific surface area of 47.83m 2 Per gram of nano calcium carbonate.
Comparative example 4
A preparation method of nano calcium carbonate for nail-free glue comprises the following steps:
(1) Calcining limestone with the block size of 2-3 cm at the temperature of 1000 ℃ for 400min to obtain raw burnt lime, then putting the raw burnt lime into a high-temperature high-pressure digesting kettle, closing an ash inlet of the digesting kettle, then adding water with the mass of 3 times of that of the raw burnt lime and 1.5% of glycerol, starting stirring in the digesting kettle, controlling the pressure in the digesting kettle to be 0.4MPa and the temperature to be 130 ℃, after stirring and reacting for 20min, decompressing, pouring out lime milk, removing waste residues through a 100-mesh screen, and finally adding water to adjust the solid content of the lime milk to 5%;
(2) Adding 15kg of lime milk into a carbonation reaction tower, adjusting the temperature of the lime milk to 30 ℃ through cooling circulation, adding cane sugar with the mass of 0.1% of the lime milk, adjusting the stirring speed of the carbonation tower to 1000r/min, starting introducing mixed gas with the concentration of 33% carbon dioxide, and controlling the flow of the mixed gas to be 4m 3 Adding sodium polyacrylate with calcium carbonate dry basis weight of 1.0% after gelation, stopping introducing gas immediately when the pH of the suspension is 7.5 after carbonation, and stopping carbonation reaction to obtain calcium carbonate suspension finally;
(3) Transferring the calcium carbonate suspension liquid obtained in the step (2) to a treatment tank, adding isopropoxy tri (dioctyl pyrophosphate) titanate with the dry mass of calcium carbonate being 2.5 percent, stirring for 10min, heating the suspension liquid at 60 ℃, continuously adding sodium stearate with the dry mass of calcium carbonate being 1.5 percent, and stirring for 40min to complete surface treatment;
(4) Dewatering the slurry after surface treatment by plate-and-frame filter press, and pressingDrying at 120 ℃, and finally crushing to obtain the product with the specific surface area of 48.37m 2 Per gram of nano calcium carbonate.
The nano calcium carbonate prepared in the example 1 and the nano calcium carbonate prepared in the comparative example 2 are detected by a scanning electron microscope, and as can be seen from SEM images of figures 1 and 2, although the particle sizes of the example 1 and the comparative example 2 are close, the nano calcium carbonate of the comparative example 2 is seriously agglomerated, so that the specific surface area and the reinforcing property are reduced.
The nano calcium carbonate prepared in the above examples 1 to 4 and comparative examples 1 to 4 is applied to filling MS nail-free glue respectively. Weighing MS polymer according to the formula, adding the filler and the plasticizer into a kneader, heating at 120 ℃, vacuumizing, kneading for 90min, and discharging to be used as a base material. And (3) after the temperature of the base material is cooled to 45 ℃, transferring the base material to a power mixer for stirring, sequentially adding a water removing agent, a coupling agent and a catalyst, uniformly stirring in vacuum to obtain a product, subpackaging and discharging. Table l is the MS nail free glue formulation, and table 2 is the MS nail free glue comparative formulation.
Table 1: MS nail-free glue formula
Table 2: MS nail-free glue comparison formula
The MS nail-free glue prepared by the method is subjected to application test, the measurement standards of the nail-free glue for the light decorative plate in the indoor wall JC/T2186-2013 are adopted in the sag and tensile shear strength test, and the test results are shown in the following table.
In the above test results, as can be seen from comparative example 1, the specific surface area of the nano calcium carbonate can be further increased by the synergistic effect of the low-temperature carbonization technology and the high-temperature high-pressure digestion technology; as can be seen from comparative example 2, the low temperature insulation and the dispersing agent in the carbonation process contribute to preventing the agglomeration of calcium carbonate and increasing the specific surface area, thereby improving the reinforcing property; as can be seen from comparative example 3, the normal temperature surface treatment of titanate not only prevents the specific surface area of the nano calcium carbonate from decreasing before the surface treatment, but also is beneficial to improving the reinforcing performance of the MS nail-free adhesive. The nano calcium carbonate prepared by the method can further increase the specific surface area to more than 50 square meters per gram, can effectively replace fumed silica under proper filling amount, can endow MS nail-free glue with excellent reinforcing performance and thixotropy, and has unexpected effect.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments and it is not intended to limit the invention to the specific embodiments described. It will be apparent to those skilled in the art that numerous alterations and modifications can be made to the described embodiments without departing from the inventive concepts herein, and such alterations and modifications are to be considered as within the scope of the invention.
Claims (2)
1. The preparation method of the nano calcium carbonate for the nail-free glue is characterized by comprising the following steps:
(1) Calcining limestone to obtain raw burnt lime, placing the raw burnt lime into a high-temperature high-pressure digesting kettle, adding water which is 3 to 5 times of the mass of the raw burnt lime and 1.0 to 2.0 percent of polyol, digesting the mixture at high temperature and high pressure to prepare lime milk, removing waste residues from the lime milk by a 100-mesh screen, and adjusting the solid content of the lime milk to 4 to 6 percent for later use;
(2) Transferring the lime milk obtained in the step (1) into a carbonation reaction tower, cooling the lime milk to 15-18 ℃ through cooling circulation, adding a crystal form control agent with the mass of 0.05-0.1% of that of the lime milk, introducing lime kiln gas to carry out carbonation reaction, adding a dispersing agent with the mass of 0.5-1.0% of that of a dry calcium carbonate base after gelation, and stopping the reaction until the pH value of a reaction system is 7.5 to obtain a calcium carbonate suspension;
(3) Transferring the calcium carbonate suspension liquid obtained in the step (2) to a processing tank, adding a titanate coupling agent accounting for 1.5 to 2.5 percent of the dry mass of the calcium carbonate, stirring for 10 to 20min, heating the suspension liquid to 55 to 65 ℃, adding sodium stearate accounting for 1.5 to 2.0 percent of the dry mass of the calcium carbonate, carrying out wet modification, and continuously stirring for 30 to 40min to complete wet surface processing to obtain calcium carbonate slurry;
(4) Dehydrating, drying and crushing the calcium carbonate slurry by a filter press to obtain nano calcium carbonate for the nail-free glue;
the polyalcohol comprises one or two of ethylene glycol, glycerol, triethanolamine and diethanolamine;
the crystal form control agent in the step (2) comprises one or more of sucrose, fructose, glucose and maltose;
the high temperature and high pressure in the step (1) are carried out at the temperature of 130 to 140 ℃ and the pressure of 0.3 to 0.4 MPa;
the dispersant comprises one or more of sodium polyacrylate, ammonium polyacrylate, polyacrylamide, polymaleic anhydride and maleic acid-acrylic acid copolymer;
the titanate coupling agent comprises one of isopropoxy tri (dioctyl pyrophosphate) titanate, isopropoxy tri (dioctyl phosphate) titanate and isopropoxy tri (isostearoyl) titanate;
controlling the temperature at the early stage of carbonation not to exceed 20 ℃ and the temperature at the later stage not to exceed 30 ℃; the concentration of carbon dioxide in the lime kiln gas is 30 to 35 percent.
2. The preparation method of the nano calcium carbonate for the nail-free glue according to claim 1 is characterized in that: the calcination in the step (1) is carried out at the temperature of 1000 to 1100 ℃ for 300 to 400min.
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