CN112588258A - Composite A-type molecular sieve raw powder containing wave absorbing material and full-zeolite molecular sieve, and preparation method and application thereof - Google Patents
Composite A-type molecular sieve raw powder containing wave absorbing material and full-zeolite molecular sieve, and preparation method and application thereof Download PDFInfo
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Abstract
A composite A-type molecular sieve raw powder containing wave absorbing materials and a full-zeolite molecular sieve, and preparation methods and applications thereof belong to the technical field of molecular sieves. The composite A-type molecular sieve raw powder containing the wave-absorbing material comprises a micro-nano wave-absorbing material and an A-type molecular sieve obtained by in-situ growth by taking the wave-absorbing material as a seed crystal; the wave-absorbing material-containing composite A-type molecular sieve raw powder can be prepared into the wave-absorbing material-containing all-zeolite molecular sieve through the working procedures of molding, crystal transformation, ion exchange and activation. The prepared full zeolite molecular sieve containing the wave-absorbing material can deeply adsorb specific molecules and is quickly regenerated by microwave heating.
Description
Technical Field
The invention relates to a technology in the field of molecular sieves, in particular to a composite A-type molecular sieve raw powder containing a wave absorbing material and a full zeolite molecular sieve, and a preparation method and application thereof.
Background
The lithium ion battery mainly comprises an anode, a cathode and electrolyte, and can be charged and discharged only by means of insertion and desorption of lithium ions between the anode and the cathode through the electrolyte; during the first charge and discharge of the lithium ion battery, a reaction also occurs between the electrolyte and the electrode material to form a Solid Electrolyte Interphase (SEI), which has an important effect on the performance of the lithium ion battery. However, the electrolyte solution is inevitably contaminated with a trace amount of impurities such as water, acid and alcohol during the production process, and even if the electrolyte solution is a commercial electrolyte solution having excellent performance, the content of these impurities is also presentAbout 0.001%, but these trace impurities still destroy and change the properties of the SEI film, thereby reducing the reversible capacity and cycle performance of the battery; in addition, the trace amount of water may decompose lithium hexafluorophosphate in the electrolyte, and may react with organic solvent in the electrolyte to produce alcohol, and at the same time, the lithium ion battery may consume lithium ion during charging and discharging to produce LiOH and Li2O, HF, all of which can degrade the performance of the lithium ion battery. The purity of the electrolyte has a significant impact on the electrochemical performance of the lithium ion battery.
The molecular sieve has strong moisture absorption capacity and excellent performance, and can be almost used for dehydrating various solvents, so the molecular sieve is widely applied to laboratories and industries. For the lithium ion nonaqueous electrolyte, a lithium type molecular sieve is theoretically prepared by taking a proper molecular sieve as a raw material, and micro water in the lithium type molecular sieve and small molecular impurities such as hydrogen fluoride, methanol and the like with the size similar to that of water molecules can be effectively removed.
Patent application CN200810050070.2 (2008) discloses a method for preparing Li-LSX molecular sieve, which obtains K by exchanging LSX for a plurality of times through potassium ion aqueous solution+LSX, and then obtaining NH through multiple exchange of ammonium ion aqueous solution4-LSX, finally Li-LSX is obtained by lithium exchange, and NH is required to be recovered in the lithium exchange process3Facilitating Li exchange; the method adopts NH4 +The transitional exchange method improves the utilization rate of Li, the treatment process is complex, and the possibility of damaging the molecular sieve framework exists in the frequent hydrothermal ion exchange process due to the poor hydrothermal stability of the low-silicon aluminum molecular sieve framework, so that the final finished product cannot be used for removing impurities from the lithium ion nonaqueous electrolyte. On the other hand, the reason that the Li-LSX prepared by the application cannot be used for removing impurities from the lithium ion nonaqueous electrolyte is that the preparation of the molecular sieve raw powder is involved, but in actual use, the molecular sieve raw powder is usually prepared into pellets through a pelletizing process and can be normally used; in the ball-making process, binder and other additives are inevitably added, so even if the Li exchange degree is high in the early stage, the content of lithium ions is inevitably reduced correspondingly after the ball-making process, and the binder and the like are caused when the lithium ion non-aqueous electrolyte deeply absorbs a little waterThe ion exchange in the material also brings secondary pollution of other ions, and particularly, the sodium ion pollution is fatal to the lithium ion nonaqueous electrolyte.
In addition to the above problems, the problem of how to efficiently desorb and regenerate the molecular sieve adsorbing impurities and the problem of controlling the manufacturing cost of the adsorbent are also faced in the impurity removal process of a large amount of lithium ion nonaqueous electrolyte.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
The A-type molecular sieve is easy to prepare and low in cost in various types of molecular sieves, and can be used for obtaining 3A, 4A and 5A molecular sieves through exchange with different ions, so that the screening, separation and adsorption effects on molecules with different sizes are realized. In view of the above, the invention provides a composite a-type molecular sieve raw powder containing a wave-absorbing material, an all-zeolite molecular sieve, and a preparation method and application thereof, aiming at the defects in the prior art, and the prepared all-zeolite molecular sieve can deeply adsorb specific molecules and can be rapidly regenerated by microwave heating, so that the activation regeneration efficiency is improved.
The invention provides a composite A-type molecular sieve raw powder containing a wave-absorbing material, which comprises a micro-nano wave-absorbing material and an A-type molecular sieve obtained by in-situ growth by taking the micro-nano wave-absorbing material as a seed crystal, wherein the A-type molecular sieve coats the wave-absorbing material.
In some technical schemes, the micro-nano wave-absorbing material comprises one or more of silicon carbide particles, silicon carbide fibers, carbon fibers, graphene, carbon nanotubes and carbon black; the Type A molecular sieve is one of LTA (Linde Type A) Type molecular sieves, typically, such as 3A molecular sieve, 4A molecular sieve, 5A molecular sieve.
Preferably, the size of the wave-absorbing material is 1nm-100 μm, more preferably 10nm-10 μm.
The invention provides a preparation method of the composite A-type molecular sieve raw powder containing the wave-absorbing material, which comprises the steps of weighing micro-nano wave-absorbing material powder, placing the micro-nano wave-absorbing material powder into a precursor reaction solution of the A-type molecular sieve, and then heating by microwave for reaction; in the microwave heating process, the wave-absorbing material is selectively heated, and is used as a seed crystal for the growth of the molecular sieve to grow and synthesize the A-type molecular sieve in situ under the action of the surface effect of particles, and the synthesized A-type molecular sieve coats the wave-absorbing material; and drying after the reaction is finished to obtain the composite A type molecular sieve raw powder containing the wave absorbing material.
In some technical schemes, the precursor reaction solution of the A-type molecular sieve is alkaline silicon-aluminum reaction solution, and the molar ratio of the materials of the reaction solution is xM2O:ySiO2:Al2O3:zH2O, wherein M is one or more of alkali metal ions and organic ammonium ions, x is 2-12, y is 1.5-6.5, and z is 30-400; the microwave heating output power is 0.1-2kW, the reaction temperature is 40-110 ℃, the reaction time is 1-48h, and the drying temperature is 80-120 ℃. Preferably, the heating temperature is 60-100 ℃, and the reaction time is 1-24 h.
The third aspect of the invention provides a preparation method of an all-zeolite molecular sieve containing wave-absorbing materials, which comprises the following steps:
s1, molding: uniformly mixing the composite A type molecular sieve raw powder containing the wave absorbing material and a binder in proportion, forming in a granulator after mixing and grinding, and drying and roasting to obtain a formed particle material;
s2, crystal transformation: drying the formed particle material prepared in the step S1, placing the dried formed particle material in an alkaline solution, heating, and carrying out crystallization reaction to convert a binder in the formed particle material into zeolite crystals to obtain the all-zeolite molecular sieve;
s3, ion exchange: soaking the whole zeolite molecular sieve prepared in the step S2 in water after absorbing moisture, conveying the whole zeolite molecular sieve into an ion exchange column through a peristaltic pump, heating the whole zeolite molecular sieve to the ion exchange temperature, introducing a target ion solution for ion exchange, washing the whole zeolite molecular sieve with deionized water after the ion exchange reaction is finished, dehydrating, and collecting the whole zeolite molecular sieve modified by the target ions;
s4, activation: pre-drying the target ion modified full zeolite molecular sieve prepared in the step S3, feeding the product after pre-drying into an activation furnace for roasting, cooling to a discharge temperature after roasting, discharging, and screening to obtain a finished product of the full zeolite molecular sieve containing the wave absorbing material; if necessary, the sieving is carried out under the protection of nitrogen or dry air.
Preferably, the binder is present in the shaped particulate material in a proportion of 5% to 20% by weight; the binder is one or more of kaolin, halloysite and allophane.
Step S1, one or more than one additive is added, and the additive is used for optimizing various performances of the formed granular material, such as strength increase, abrasion reduction, porosity improvement and the like; the additive comprises one or more of water glass, aluminum sol, silica sol, organic silicon resin emulsion, pyrophosphate, aluminum hydrogen phosphate, cellulose and derivatives thereof, tannin extract and the like. The molding state can be spherical, strip-shaped and the like, and the molding state is designed according to a specific application scene.
In step S2, the alkaline solution is at least one of a sodium hydroxide solution, a potassium hydroxide solution, and a calcium hydroxide solution, and the mass percentage concentration of the solution is 1% to 40%, preferably 1% to 15%; the heating temperature is 65-125 deg.C, preferably 75-95 deg.C.
In step S3, the target ion solution is at least one of a soluble chloride solution, a hydroxide solution, a sulfate solution, and a nitrate solution containing target ions, and the mass percentage concentration of the solution is 1% to 40%; the ion exchange temperature is 50-130 ℃, and the pH value is controlled within the range of 6-12 in the ion exchange reaction process; the temperature of deionized water used for rinsing is 60-90 ℃.
In the step S4, the drying temperature is controlled to be 80-220 ℃, and the moisture of the dried product is controlled to be 5-15%; preheating the activation furnace by adopting dry gas, and then roasting the target ion modified full zeolite molecular sieve prepared in the step S3; the preheating temperature is 400-800 ℃, the roasting temperature is 500-580 ℃, the roasting time is 3-5 hours, and the discharging temperature is 50-20 ℃. The drying gas is preferably pure nitrogen or dry compressed air with a dew point in the range of-50 ℃ to-90 ℃.
The invention provides a wave-absorbing material-containing all-zeolite molecular sieve, which is prepared by adopting the preparation method; the particle size distribution of the full zeolite molecular sieve containing the wave-absorbing material is 0.1-5.0mm, the ion exchange degree in the process is more than or equal to 95%, the static water adsorption is more than or equal to 20wt%, the water content is less than or equal to 1.5wt%, and the wear rate is less than 1.5 wt%.
In some technical schemes, the full zeolite molecular sieve containing the wave-absorbing material is activated and regenerated by microwave heating after being adsorbed. After the molecular sieve finishes adsorption, the molecular sieve is cleaned, then microwave heating and activation are carried out to realize dehydration and regeneration of the molecular sieve, and the adsorption capacity of the molecular sieve is recovered, so that the cyclic utilization of the molecular sieve is realized; the microwave heating output power is 0.5-2kW, the temperature of the whole zeolite molecular sieve containing the wave-absorbing material is raised to 100 ℃ and 250 ℃, and the treatment is carried out for 1-40min, thereby completing the activation regeneration.
The fifth aspect of the invention provides an application of a full zeolite molecular sieve containing a wave-absorbing material as an adsorbent in impurity removal, in particular an application in impurity removal of a lithium ion nonaqueous electrolyte.
The diameters of the molecules of trace impurities such as water, hydrogen fluoride and methanol in the lithium ion non-aqueous electrolyte are basically less than 0.4nm, and the molecular radius of an organic solvent in the electrolyte is large; therefore, the adoption of the wave-absorbing material-containing full-zeolite lithium type molecular sieve with the pore diameter of 4A can remove impurities, and ensure that the organic solvent cannot be removed by adsorption; if the all-zeolite lithium type molecular sieve containing the wave-absorbing material with the aperture of 3A or 5A is adopted, the impurity removal effect is slightly poor; in the application, the full-zeolite lithium type molecular sieve containing the wave-absorbing material can avoid secondary pollution caused by ion exchange in the impurity removal process.
Technical effects
Compared with the prior art, the invention has the following technical effects:
1) by adding the micro-nano material with the wave-absorbing function, the synthesis of the molecular sieve is accelerated, the synthesis efficiency of the molecular sieve is improved, the composite A-type molecular sieve raw powder containing the wave-absorbing material is synthesized, and the all-zeolite molecular sieve with the efficient microwave heating function is further prepared; after the molecular sieve adsorbs small molecular substances such as water in electrolyte, the adsorbed small molecular substances can be removed efficiently by microwave heating with low energy consumption, the heating and regenerating time can be reduced from a level of hours to about half an hour, even to a level of minutes, and the rapid cyclic utilization of the molecular sieve, even the online rapid regeneration, is realized; although the full zeolite molecular sieve containing the wave-absorbing material can also be heated and activated by high-temperature airflow similarly to desorption and regeneration of other molecular sieves, the activation and regeneration process is difficult to play the role of the wave-absorbing material and cannot realize online activation;
2) based on the surface effect of the wave-absorbing functional material in the microwave heating process, the composite A-type molecular sieve raw powder containing the wave-absorbing material is synthesized, organic or inorganic template agents are not required to be added for removal, the process is simple, and the effect of the wave-absorbing functional material is different from that of the template agents;
3) the molecular sieve powder is prepared into particles, so that the passing performance of electrolyte in the adsorption process can be improved, the adsorption treatment efficiency is improved, and compared with the traditional powdery molecular sieve, the filtering time can be reduced from the hour level to the minute level;
4) the caking agent with a non-zeolite crystal structure is converted into zeolite crystals by carrying out crystal transformation treatment on the caking agent added in the forming procedure, so that the adsorption performance of the molecular sieve is improved, and the adsorption capacity can be improved by 5-20% compared with that of the non-crystal-transformed molecular sieve; the full zeolite molecular sieve can be prepared without repeated hydrothermal exchange, and the structural stability is effectively improved;
5) the prepared full-zeolite molecular sieve containing the wave-absorbing material can fully play the deep water removal characteristic of the molecular sieve, simplify the water removal process, improve the water removal efficiency and improve the quality of electrolyte; and if the all-zeolite lithium type molecular sieve containing the wave-absorbing material is adopted, Na+、K+The content is extremely low, and the lithium ion-resistant lithium ion battery can not react with Li when absorbing molecules such as trace water, hydrogen fluoride, methanol and the like in electrolyte+Exchange to influence Li in electrolyte+The purity, especially the secondary pollution can not be generated, thereby ensuring the cycle performance of the lithium ion battery.
Detailed Description
The present invention will be described in detail with reference to specific embodiments. The experimental procedures, in which specific conditions are not specified in the examples, were carried out according to the conventional methods and conditions.
Example 1
The embodiment relates to a preparation method of an all-zeolite lithium type molecular sieve containing a wave absorbing material, which comprises the steps of S1-S5.
S1, in-situ synthesis of composite A-type molecular sieve raw powder with a wave absorbing function:
3Na according to the molar ratio of the materials2O:2SiO2:Al2O3:128H2Weighing sodium silicate and sodium aluminate, preparing the sodium silicate and the sodium aluminate into solutions respectively, adding sodium hydroxide into the two solutions respectively, and then uniformly mixing the two solutions;
weighing 1kg of silicon carbide powder, adding the alkaline silica-alumina sol reaction solution (feeding according to the theoretical yield of the A-type molecular sieve of 9 kg), putting the mixture into a microwave reactor, and reacting for 10min at 100W to obtain the composite 4A molecular sieve raw powder containing the silicon carbide wave-absorbing material.
S2, ball making:
weighing 8kg (dry basis) of prepared composite 4A molecular sieve raw powder containing the silicon carbide wave-absorbing material and 2kg of kaolin, putting the raw powder and the kaolin into a mixer with the diameter of phi 500mm, and mixing for 30 minutes to obtain a mixture;
weighing 5kg (weight converted into dry basis) of the mixture, putting the mixture into an EIRICH automatic forming machine, and injecting the mixed solution for forming, wherein the diameter of formed particles is 1.2-1.8 mm;
and (3) placing the formed particles into a vacuum muffle furnace, and roasting for 2-3 hours at the temperature of 350-550 ℃ to obtain the spherical particle material.
And (3) placing the spherical particle material in a drying dish, cooling to room temperature, sampling and measuring the static water adsorption, wherein the static water adsorption amount reaches 21.7 wt%.
S3, crystal transformation:
weighing 3kg of spherical granular materials, putting the spherical granular materials into deionized water, and weighing 4.84kg of the spherical granular materials; adding 3kg of spherical particle materials into a sodium hydroxide solution with the mass percentage concentration of 8% according to the weight ratio of the prepared crystallization reaction solution to the spherical particle materials of 3.5:1 to obtain a crystallization reaction solution;
heating to 95 deg.c, setting in solution tank and crystallizing for 3 hr.
After the crystallization reaction is finished, firstly washing with 50 liters of cold water, then washing with 10 liters of hot water at 70 ℃ twice, and then washing with cold water until the pH is =8 (measured by test paper), thereby obtaining a crystallization reaction molecular sieve ball; sampling and analyzing the pH value to reach 10.45.
And (3) performing water absorption test on the crystallized reaction molecular sieve balls:
and (3) testing conditions are as follows: absorbing water for 24 hours at 25 ℃ and RH 50; as a result: 21.7wt% before crystallization reaction and 24.5wt% after crystallization reaction.
S4, lithium exchange:
crystallizing and reacting molecular sieve balls (4A molecular sieve) to absorb moisture after crystal transformation, putting the balls into lithium exchange equipment, soaking the balls in water, and heating the materials in the equipment and maintaining the temperature at 85-90 ℃; introducing a lithium sulfate solution with the mass percentage concentration of 1-8% into the equipment, and controlling the pH value to be 6-12; detecting the ion concentration in the liquid from a sampling outlet of the equipment after a period of time, and finishing the lithium exchange reaction after the ion concentration in the liquid reaches a certain value to obtain the full-zeolite lithium molecular sieve; and (3) washing the all-zeolite lithium type molecular sieve in the equipment by using deionized water, discharging the material after the washing is qualified, and dehydrating and collecting the all-zeolite lithium type molecular sieve.
S5, activation:
slowly adding the full-zeolite lithium molecular sieve into a belt type oven for pre-drying treatment, controlling the temperature in the oven to be between 80 and 220 ℃, controlling the moisture of the dried material to be between 5 and 15 percent, and collecting the material in a container;
the dried material is put into a vertical activation furnace, and pure nitrogen or dry compressed air with dew point of-70 ℃ is heated to 600 ℃ through an electric heater; introducing hot gas into the vertical activation furnace, heating the material to the temperature of 500 ℃ and 580 ℃, roasting, and preserving heat for 3-5 hours to obtain a finished product of the silicon carbide-containing wave-absorbing material full-zeolite lithium molecular sieve;
and then cooling the finished product of the full-zeolite lithium type molecular sieve containing the wave absorbing material in the vertical furnace to 50-20 ℃ by adopting a cooler, then screening under the protection of nitrogen or qualified dry air, and filling into a packaging barrel.
The prepared all-zeolite lithium type molecular sieve finished product containing the wave absorbing material is detected, the static water adsorption is 23.6wt%, the Li exchange degree is 96.6%, the bulk density is 0.69g/ml, the abrasion rate is 0.09wt%, the average particle size is 1.38mm, the screening particle size (less than 1.00) is 0.1wt%, the screening particle size (more than 1.70) is 0.1wt%, the water content is 0.952wt%, and the performance is excellent; the finished product has better sphericity and uniform particle size, can obtain better accumulation effect, and meets the impurity removal requirement of the lithium ion battery electrolyte.
Example 2
This example relates to a method for preparing an all-zeolite lithium-type molecular sieve, comprising steps S1-S4.
S1, ball making:
8kg (dry basis) of a commercial 4A molecular sieve (chemical formula 3 Na) was weighed2O:2SiO2:Al2O3:128H2O) raw powder and 2kg of kaolin are put into a mixer with the diameter of 500mm and mixed for 30 minutes;
weighing 5kg of mixture, putting the mixture into an EIRICH automatic forming machine, and injecting the mixed solution for forming, wherein the diameter of formed particles is 1.2-1.8 mm;
and (3) placing the formed particles into a vacuum muffle furnace, and roasting for 2-3 hours at the temperature of 350-550 ℃ to obtain the spherical particle material.
And (3) placing the spherical particle material in a drying dish, cooling to room temperature, sampling and measuring the static water adsorption, wherein the static water adsorption amount reaches 20.0 wt%.
S2, crystal transformation:
adding 3kg of spherical particle materials into a sodium hydroxide solution with the mass percentage concentration of 8% according to the weight ratio of the prepared crystallization reaction solution to the spherical particle materials of 3.5:1 to obtain a crystallization reaction solution;
heating to 95 deg.c, setting in solution tank and crystallizing for 3 hr.
After the crystallization reaction is finished, firstly washing with 50 liters of cold water, then washing with 10 liters of hot water at 70 ℃ twice, and then washing with cold water until the pH is =8 (measured by test paper), thereby obtaining a crystallization reaction molecular sieve ball; sampling and analyzing the pH value to reach 10.45.
And (3) performing water absorption test on the crystallized reaction molecular sieve balls:
and (3) testing conditions are as follows: absorbing water for 24 hours at 25 ℃ and RH 50; as a result: 20.0wt% before crystallization reaction and 22.3wt% after crystallization reaction.
S3, lithium exchange:
crystallizing and reacting molecular sieve balls (4A molecular sieve) to absorb moisture after crystal transformation, putting the balls into lithium exchange equipment, soaking the balls in water, and heating the materials in the equipment and maintaining the temperature at 85-90 ℃; introducing a lithium sulfate solution with the mass percentage concentration of 1-8% into the equipment, and controlling the pH value to be 6-12; detecting the ion concentration in the liquid from a sampling outlet of the equipment after a period of time, and finishing the lithium exchange reaction after the ion concentration in the liquid reaches a certain value to obtain the full-zeolite lithium molecular sieve; and (3) washing the all-zeolite lithium type molecular sieve in the equipment by using deionized water, discharging the material after the washing is qualified, and dehydrating and collecting the all-zeolite lithium type molecular sieve.
S4, activation:
slowly adding the full-zeolite lithium molecular sieve into a belt type oven for pre-drying treatment, controlling the temperature in the oven to be between 80 and 220 ℃, controlling the moisture of the dried material to be between 5 and 15 percent, and collecting the material in a container;
the dried material is put into a vertical activation furnace, and pure nitrogen or dry compressed air with dew point of-70 ℃ is heated to 600 ℃ through an electric heater; introducing hot gas into the vertical activation furnace, heating the material to the temperature of 500-;
and then cooling the finished product of the full-zeolite lithium molecular sieve in the vertical furnace to 20-50 ℃ by adopting a cooler, then screening under the protection of nitrogen or qualified dry air, and packaging into a packaging barrel.
The prepared finished product is detected to have 22.5wt% of static water adsorption, 94.0% of Li exchange degree, 0.70g/ml of bulk density, 0.15wt% of abrasion rate, 1.34mm of average particle size, 0.5wt% of screening particle size (< 1.00), 0.5wt% of screening particle size (> 1.70), 0.952wt% of water content and excellent performance; the finished product has better sphericity and uniform particle size, can obtain better accumulation effect, and meets the impurity removal requirement of the lithium ion battery electrolyte.
Example 3
The embodiment relates to a preparation method of an all-zeolite calcium type molecular sieve containing a wave-absorbing material, which comprises the steps of S1-S5.
S1, in-situ synthesis of composite A-type molecular sieve raw powder with a wave absorbing function:
according to the material molar ratio of 12M2O:60SiO2:Al2O3:400H2Weighing sodium silicate and water, uniformly mixing to prepare a solution, weighing a tetramethylammonium hydroxide solution, and adding aluminum isopropoxide and sodium hydroxide to prepare a solution; uniformly mixing the two solutions, wherein the molar ratio of tetramethylammonium hydroxide (TMA) to sodium ions in the mixed solution is 1.675;
0.5kg of silicon carbide powder is weighed, added into alkaline silica-alumina sol reaction liquid (the materials are added according to the theoretical yield of the A-type molecular sieve of 9.5 kg), put into a microwave reactor and reacted for 60min at 100W, and the composite 4A molecular sieve raw powder containing the silicon carbide wave-absorbing material is obtained.
S2, ball making:
weighing 9kg (dry basis) of prepared composite 4A molecular sieve raw powder containing the silicon carbide wave-absorbing material and 1kg of halloysite, putting the weighed raw powder and the halloysite into a mixer with the diameter of phi 500mm, and mixing for 30 minutes;
weighing 5kg (weight converted into dry basis) of the mixture, putting the mixture into an EIRICH automatic forming machine, and injecting the mixed solution for forming, wherein the diameter of formed particles is 1.2-1.8 mm;
placing the formed granular material into a vacuum muffle furnace, and roasting at 350-550 ℃ for 2-3 hours to obtain the spherical granular material.
And (3) placing the spherical particle material in a drying dish, cooling to room temperature, sampling and measuring the static water adsorption, wherein the static water adsorption amount reaches 25.2 wt%.
S3, crystal transformation:
adding 3kg of spherical particle materials into a sodium hydroxide solution with the mass percentage concentration of 8% according to the weight ratio of the prepared crystallization reaction solution to the spherical particle materials of 3.5:2 to obtain a crystallization reaction solution;
heating to 95 ℃, placing the mixture into a solution tank, and carrying out crystallization reaction for 3 hours;
after the crystallization reaction is finished, firstly washing with 50 liters of cold water, then washing with 10 liters of hot water at 70 ℃ twice, and then washing with cold water until the pH is =8 (measured by test paper), thereby obtaining a crystallization reaction molecular sieve ball; sampling and analyzing the pH value to reach 10.45.
And (3) performing water absorption test on the crystallized reaction molecular sieve balls:
and (3) testing conditions are as follows: absorbing water for 24 hours at 25 ℃ and RH 50; as a result: 25.2wt% before crystallization reaction and 28.0wt% after crystallization reaction.
S4, calcium crossing:
crystallizing to obtain crystallized molecular sieve balls (4A molecular sieve) for absorbing moisture, placing into calcium exchange equipment, soaking in water, and heating the materials in the equipment to 85-90 deg.C; introducing a calcium chloride solution with the mass percentage concentration of 2-10% into the equipment, and controlling the pH value to be 6-9; detecting the ion concentration in the liquid from a sampling outlet of the equipment after a period of time, and finishing the calcium exchange reaction after the ion concentration in the liquid reaches a certain value to obtain the full-zeolite calcium type molecular sieve (5A molecular sieve); and (3) washing the full zeolite calcium type molecular sieve in the equipment by using deionized water, discharging the material after the washing is qualified, and dehydrating and collecting the full zeolite calcium type molecular sieve.
S5, activation:
slowly adding the full-zeolite calcium type molecular sieve into a belt type oven for pre-drying treatment, controlling the temperature in the oven to be between 80 and 220 ℃, controlling the moisture of the dried material to be between 5 and 15 percent, and collecting the material in a container;
the dried material is put into a vertical activation furnace, and pure nitrogen or dry compressed air with dew point of-70 ℃ is heated to 600 ℃ through an electric heater; introducing hot gas into the vertical activation furnace, heating the material to the temperature of 500-;
and then cooling the whole zeolite calcium type molecular sieve containing the wave absorbing material in the vertical furnace to 50-20 ℃ by adopting a cooler, screening the finished product under the protection of nitrogen or qualified dry air, and filling into a packaging barrel.
The prepared finished product is detected to have 24.1wt% of static water adsorption, 95.2% of calcium exchange degree, 0.69g/ml of bulk density, 0.07wt% of abrasion rate, 1.31mm of average particle size, 0.4wt% of screening particle size (< 1.00), 0.3wt% of screening particle size (> 1.70), 0.952wt% of water content and excellent performance; the finished product has better sphericity and uniform particle size, can obtain better accumulation effect, and meets the impurity removal requirement of the lithium ion battery electrolyte.
Example 4
The embodiment relates to a preparation method of an all-zeolite calcium type molecular sieve, which comprises the steps of S1-S4.
S1, ball making:
9kg (dry basis) of a commercial 4A molecular sieve (formula 12M) was weighed2O·60SiO2·Al2O3·400H2O, M is tetramethylammonium ion) raw powder, 1kg of halloysite, and the mixture is placed in a mixer with the diameter of phi 500mm and mixed for 30 minutes;
weighing 5kg (weight converted into dry basis) of the mixture, putting the mixture into an EIRICH automatic forming machine, and injecting the mixed solution for forming, wherein the diameter of formed particles is 1.2-1.8 mm;
and (3) placing the formed particles into a vacuum muffle furnace, and roasting for 2-3 hours at the temperature of 350-550 ℃ to obtain the spherical particle material.
And (3) placing the spherical particle material in a drying dish, cooling to room temperature, sampling and measuring the static water adsorption, wherein the static water adsorption amount reaches 22.7 wt%.
S2, crystal transformation:
adding 3kg of spherical particle materials into a sodium hydroxide solution with the mass percentage concentration of 8% according to the weight ratio of the prepared crystallization reaction solution to the spherical particle materials of 3.5:2 to obtain a crystallization reaction solution;
heating to 95 deg.c, setting in solution tank and crystallizing for 3 hr.
After the crystallization reaction is finished, firstly washing with 50 liters of cold water, then washing with 10 liters of hot water at 70 ℃ twice, and then washing with cold water until the pH is =8 (measured by test paper), thereby obtaining a crystallization reaction molecular sieve ball; sampling and analyzing the pH value to reach 10.45.
And (3) performing water absorption test on the crystallized reaction molecular sieve balls:
and (3) testing conditions are as follows: absorbing water for 24 hours at 25 ℃ and RH 50; as a result: 22.7wt% before crystallization reaction and 25.2wt% after crystallization reaction.
S3, calcium crossing:
crystallizing to obtain crystallized molecular sieve balls (4A molecular sieve) for absorbing moisture, placing into calcium exchange equipment, soaking in water, and heating the materials in the equipment to 85-90 deg.C; introducing a calcium chloride solution with the mass percentage concentration of 2-10% into the equipment, and controlling the pH value to be 6-9; detecting the ion concentration in the liquid from a sampling outlet of the equipment after a period of time, and finishing the calcium exchange reaction after the ion concentration in the liquid reaches a certain value to obtain the full-zeolite calcium type molecular sieve (5A molecular sieve); and (3) washing the full zeolite calcium type molecular sieve in the equipment by using deionized water, discharging the material after the washing is qualified, and dehydrating and collecting the full zeolite calcium type molecular sieve.
S4, activation:
slowly adding the full-zeolite calcium type molecular sieve into a belt type oven for pre-drying treatment, controlling the temperature in the oven to be between 80 and 220 ℃, controlling the moisture of the dried material to be between 5 and 15 percent, and collecting the material in a container;
the dried material is put into a vertical activation furnace, and pure nitrogen or dry compressed air with dew point of-70 ℃ is heated to 600 ℃ through an electric heater; introducing hot gas into the vertical activation furnace, heating the material to the temperature of 500-;
and then cooling the finished product of the full zeolite calcium type molecular sieve in the vertical furnace to 50-20 ℃ by adopting a cooler, then screening under the protection of nitrogen or qualified dry air, and packaging into a packaging barrel.
The prepared finished product is detected to have 22.1wt% of static water adsorption, 94.3% of calcium exchange degree, 0.69g/ml of bulk density, 0.07wt% of abrasion rate, 1.31mm of average particle size, 0.4wt% of screening particle size (< 1.00), 0.3wt% of screening particle size (> 1.70), 0.952wt% of water content and excellent performance; the finished product has better sphericity and uniform particle size, can obtain better accumulation effect, and meets the impurity removal requirement of the lithium ion battery electrolyte.
When the molecular sieve absorbs water in the electrolyte to reach saturation or the adsorption capacity is reduced to a certain value, the molecular sieve is cleaned, and then the molecular sieve absorbing water is dehydrated and regenerated by adopting the microwave high-temperature activation process, so that the adsorption capacity of the molecular sieve can be restored, and the cyclic utilization of the molecular sieve is realized.
Comparing examples 1-2 and 3-4, it can be seen that the whole zeolite molecular sieve can be prepared by using the common commercial A-type molecular sieve through the procedures of ball preparation, crystallization, crystal transformation and activation, and then the impurities of the lithium ion nonaqueous electrolyte are removed; however, the microwave heating synthesis of the composite A-type molecular sieve raw powder in the embodiment 1 and the embodiment 3 has the advantages of quick reaction and low energy consumption, and the full zeolite molecular sieve containing the wave-absorbing material is further prepared, so that the static water adsorption performance and the like are further improved.
Putting the whole zeolite molecular sieves prepared in the embodiments 2 and 4 under the conditions of 25 ℃ and RH50, absorbing water for 24 hours, and then putting the whole zeolite molecular sieves into an oven for desorption and regeneration; drying for 2h at 150 ℃, wherein the power of an oven is 2kW, the water content is reduced to be not more than 10%, and the power consumption estimation value is 4 kW.h; if the water content is reduced to 10% by microwave heating, the microwave power is 1kW, the time is consumed for 1h, and the power consumption estimation value is 1 kW.h;
putting the whole zeolite molecular sieve containing the wave-absorbing material prepared in the embodiment 1 and the embodiment 3 at the temperature of 25 ℃ and RH50 for absorbing water for 24 hours, and then putting the whole zeolite molecular sieve into a microwave heater for desorption and regeneration; the microwave is started for 30min, the power is 1kW, the water content can be reduced to below 10 percent, and the power consumption estimation value is 0.5 kW.h;
it can be found that the microwave heating activation regeneration of the all-zeolite molecular sieves containing the wave-absorbing materials prepared in the embodiments 1 and 3 can realize the rapid cyclic utilization of the molecular sieves, and the energy consumption cost is greatly reduced.
It is to be emphasized that: the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (15)
1. A preparation method of composite A type molecular sieve raw powder containing wave-absorbing material is characterized in that micro-nano wave-absorbing material powder is weighed and placed in A type molecular sieve precursor reaction solution, and then microwave heating is carried out for reaction; in the microwave heating process, the wave-absorbing material is selectively heated, and is used as a seed crystal for the growth of the molecular sieve to grow and synthesize the A-type molecular sieve in situ under the action of the surface effect of particles, and the synthesized A-type molecular sieve coats the wave-absorbing material; and drying after the reaction is finished to obtain the composite A type molecular sieve raw powder containing the wave absorbing material.
2. The preparation method of claim 1, wherein the precursor reaction solution of the type A molecular sieve is an alkaline silicon-aluminum reaction solution, and the molar ratio of the materials of the reaction solution is xM2O:ySiO2:Al2O3:zH2O, wherein M is one or more of alkali metal ions and organic ammonium ions, x is 2-12, y is 1.5-6.5, and z is 30-400; the microwave heating output power is 0.1-2kW, the reaction temperature is 40-110 ℃, the reaction time is 1-48h, and the drying temperature is 80-120 ℃.
3. The preparation method of claim 1, wherein the micro-nano-sized wave-absorbing material comprises one or more of silicon carbide particles, silicon carbide fibers, carbon fibers, graphene, carbon nanotubes and carbon black; the A-type molecular sieve is one of LTA-type molecular sieves.
4. The preparation method according to claim 1, wherein the size of the wave-absorbing material is 1nm-100 μm.
5. The preparation method according to claim 1, wherein the size of the wave-absorbing material is 10nm-10 μm.
6. A composite A type molecular sieve raw powder containing wave absorbing materials is characterized by being prepared based on the preparation method of any one of claims 1 to 5; the wave-absorbing material comprises a micro-nano wave-absorbing material and an A-type molecular sieve which is obtained by taking the micro-nano wave-absorbing material as a seed crystal and growing in situ, wherein the A-type molecular sieve coats the wave-absorbing material.
7. A preparation method of an all-zeolite molecular sieve containing wave-absorbing materials is characterized by comprising the following steps:
s1, molding: uniformly mixing the composite A type molecular sieve raw powder containing the wave absorbing material and a binder in proportion, forming in a granulator after mixing and grinding, and drying and roasting to obtain a formed particle material;
s2, crystal transformation: drying the formed particle material prepared in the step S1, placing the dried formed particle material in an alkaline solution, heating, and carrying out crystallization reaction to convert a binder in the formed particle material into zeolite crystals to obtain the all-zeolite molecular sieve;
s3, ion exchange: soaking the whole zeolite molecular sieve prepared in the step S2 in water after absorbing moisture, conveying the whole zeolite molecular sieve into an ion exchange column through a peristaltic pump, heating the whole zeolite molecular sieve to the ion exchange temperature, introducing a target ion solution for ion exchange, washing the whole zeolite molecular sieve with deionized water after the ion exchange reaction is finished, dehydrating, and collecting the whole zeolite molecular sieve modified by the target ions;
s4, activation: and (4) pre-drying the target ion modified full zeolite molecular sieve prepared in the step (S3), feeding the product after pre-drying into an activation furnace for roasting, cooling to the discharge temperature after roasting, discharging, and screening to obtain the finished product of the full zeolite molecular sieve containing the wave absorbing material.
8. The method as claimed in claim 7, wherein the binder is present in the shaped particulate material in a proportion of 5% to 20% by weight; the binder is one or more of kaolin, halloysite and allophane.
9. The method according to claim 7, wherein one or more additives selected from the group consisting of water glass, aluminum sol, silica sol, silicone resin emulsion, pyrophosphate, aluminum hydrogen phosphate, cellulose and its derivatives, tannin extract are further added in step S1.
10. The method according to claim 7, wherein in step S2, the alkaline solution is at least one of sodium hydroxide solution, potassium hydroxide solution and calcium hydroxide solution, and the concentration of the solution is 1-40% by mass; the heating temperature is 65-125 ℃.
11. The method according to claim 7, wherein in step S3, the target ion solution is at least one of a soluble chloride solution, a hydroxide solution, a sulfate solution and a nitrate solution containing target ions, and the mass percent concentration of the solution is 1% -40%; the ion exchange temperature is 50-130 ℃, and the pH value is controlled within the range of 6-12 in the ion exchange reaction process; the temperature of deionized water used for rinsing is 60-90 ℃.
12. The preparation method according to claim 7, wherein in step S4, the drying temperature is controlled to be 80-220 ℃, and the moisture content of the dried product is controlled to be 5% -15%; preheating the activation furnace by adopting dry gas, and then roasting the target ion modified full zeolite molecular sieve prepared in the step S3; the preheating temperature is 400-800 ℃, the roasting temperature is 500-580 ℃, the roasting time is 3-5 hours, and the discharging temperature is 50-20 ℃.
13. An all-zeolite molecular sieve containing wave-absorbing materials, which is characterized by being prepared by the preparation method of any one of claims 7 to 12; the particle size distribution of the full zeolite molecular sieve containing the wave-absorbing material is 0.1-5.0mm, the ion exchange degree in the process is more than or equal to 95%, the static water adsorption is more than or equal to 20wt%, the water content is less than or equal to 1.5wt%, and the wear rate is less than 1.5 wt%.
14. The all-zeolite molecular sieve containing wave-absorbing material of claim 13, wherein the all-zeolite molecular sieve containing wave-absorbing material is activated and regenerated by microwave heating after being adsorbed; the microwave heating output power is 0.5-2kW, the temperature of the whole zeolite molecular sieve containing the wave-absorbing material is raised to 100 ℃ and 250 ℃, and the treatment is carried out for 1-40min, thereby completing the activation regeneration.
15. The use of the all-zeolite molecular sieve containing a wave-absorbing material of claim 14 as an adsorbent for impurity removal.
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| CN113797709A (en) * | 2021-10-28 | 2021-12-17 | 江西省杰夫环保科技有限公司 | Microcrystalline rotating wheel zeolite molecular sieve for efficiently removing VOCs (volatile organic compounds) and preparation method thereof |
| WO2022183776A1 (en) * | 2021-03-03 | 2022-09-09 | 苏州立昂新材料有限公司 | Composite type-a molecular sieve raw powder containing wave-absorbing material, full-zeolite molecular sieve, preparation method therefor, and application thereof |
| CN116135300A (en) * | 2021-11-16 | 2023-05-19 | 香港城市大学深圳研究院 | Selective CO capture 2 Adsorbent of (2) and preparation and application thereof |
| CN116750776A (en) * | 2023-05-15 | 2023-09-15 | 洛阳新翎微纳新材料有限公司 | Li-A type molecular sieve for lithium electrolyte and preparation method and application thereof |
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| CN114433016B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | 5A molecular sieve adsorbent and preparation method thereof |
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