CN110898799A - Amorphous composite oxide-halogen salt composite adsorbent and preparation method thereof - Google Patents
Amorphous composite oxide-halogen salt composite adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention provides an amorphous composite oxide-halogen salt composite adsorbent, which is characterized by comprising an amorphous oxide and a halogen salt. The amorphous composite oxide-halogen salt composite adsorbent replaces silica gel as an adsorbent, and the amorphous oxide and the halogen salt are compounded, so that various dehumidification modes are fully utilized by physical adsorption, chemical adsorption and solution absorption, the advantages of various dehumidification modes are brought into play, and the defects of each other are overcome. The reasonable pore structure and acid property of the amorphous composite oxide can improve the deep dehumidification capability under low humidity (RH is less than 20 percent); the halogen salt has obvious effect on increasing the adsorption capacity of high humidity (RH is more than or equal to 40%); the amorphous oxide and the halogen salt are compounded, so that the desorption energy consumption can be reduced, the desorption regeneration rate is improved, the dehumidification capacity of the rotating wheel under the working condition of medium and high humidity load is improved, and the running stability of the rotating wheel is improved.
Description
Technical Field
The invention relates to a preparation method of a dehumidifying material, in particular to a preparation method of an amorphous composite oxide-halogen salt composite adsorbent which can be used in the field of dehumidification.
Background
Humidity control has relatively strict requirements in various industries such as military industry, lithium battery, pharmacy and the like, and the dehumidification rotating wheel is widely applied by virtue of excellent drying capacity under low-temperature and low-humidity conditions. The core of the desiccant rotor is a desiccant material. The dehumidification rotating wheels are developed for decades, the dehumidification materials used by the dehumidification rotating wheels mainly comprise silica gel type and molecular sieve type, and the lithium chloride rotating wheels are gradually eliminated. A secondary dehumidification rotating wheel is needed in a low dew point scene, namely, the front rotating wheel is a silica gel type dehumidification rotating wheel and is responsible for greatly reducing the moisture content of fresh air; the rear rotating wheel is a molecular sieve type dehumidifying rotating wheel and is responsible for generating low-dew-point fresh air. The amorphous composite oxide-halogen salt composite adsorbent is used for replacing silica gel and is used for dehumidifying rotating wheels.
The conventional dehumidification rotating wheel has the advantages of small dynamic adsorption capacity, high regeneration temperature, high desorption energy consumption, poor hydrothermal stability and performance attenuation caused by high-temperature aging. The dehumidification rotating wheel with the halogen salt lithium chloride as the dehumidification agent has the advantages of low cost of the dehumidification agent, large dehumidification amount and low regeneration energy consumption, but the lithium chloride has extremely low dehumidification capacity in a low humidity range, and the lithium chloride is liquefied and escaped after absorbing water under a high humidity condition to cause equipment corrosion, so that the lithium chloride is gradually eliminated at present. The composite oxide containing amorphous silica-alumina has the defects of huge potential for dynamic dehumidification, small saturated adsorption capacity and unsatisfactory dehumidification performance under high humidity due to huge specific surface area, adjustable pore structure, reasonable micro-mesoporous distribution, more surface acid centers and consistent acidity.
At present, the process for preparing the silica gel dehumidification rotating wheel mainly comprises water glass immersion acidification. The inorganic fiber carrier containing corrugated pore channels is soaked in water glass with proper concentration, preliminarily dried, then subjected to in-situ reaction with acid, washed to remove impurity ions, and dried to complete the loading of the silica gel. The main existing problems are that the strong basicity of the water glass easily causes the corrosion of the inorganic carrier; the water glass has high viscosity, poor load uniformity and small single load capacity, and the corrugated channel is easy to block holes; the uniformity degree of the in-situ reaction is poor, and gaps of the inorganic fiber carrier are easy to block to prevent further reaction of the water glass and the acid; hydrated silica gel is dehydrated and shrunk in the drying process of silica gel generated by reaction, so that the rotating core of the rotating wheel is easy to deform, a corrugated channel is blocked, and the wind resistance is easy to cause overlarge. In addition, when the relative humidity of the processed air is low, the dehumidification amount of the dehumidification rotating wheel is seriously reduced.
Disclosure of Invention
The dehumidifying material is an amorphous composite oxide-halogen salt composite material, and has the characteristics of no liquefaction of water absorption, large dynamic adsorption capacity, low regeneration temperature and good hydrothermal stability.
The invention provides an amorphous composite oxide-halogen salt composite adsorbent, which is characterized by comprising an amorphous oxide and a halogen salt.
Wherein the halogen salt in the adsorbent accounts for 1-30% of the mass of the composite material.
The amorphous composite oxide is composed of silicon dioxide and at least one of aluminum oxide, titanium oxide, magnesium oxide, lanthanum oxide, cerium oxide, cobalt oxide, boron oxide and vanadium oxide, and the silicon dioxide accounts for 10-99% of the total mass of the amorphous composite oxide.
The halogen salt is a fluoride salt, a chloride salt and/or a bromide salt, the fluoride salt comprises at least one of sodium fluoride, calcium fluoride and lithium fluoride, the chloride salt comprises at least one of calcium chloride, sodium chloride and lithium chloride, and the bromide salt comprises at least one of sodium bromide, calcium bromide and lithium bromide.
The invention provides a preparation method of an amorphous composite oxide-halogen salt composite adsorbent, which comprises the following steps:
A) pretreating the material, namely introducing one or more metal salt solutions and an alkaline precipitator into a reaction container, and precipitating under the stirring condition to prepare a metal oxide precursor solution; adding water to dilute a silicon source to obtain a silicon source diluent;
B) fully mixing the silicon source diluent with the metal oxide precursor solution and aging to obtain a mixed solution 1;
C) adding an acid solution into the mixed solution 1 to adjust the pH, stirring and aging to obtain a mixed solution 2:
D) filtering and washing the mixed solution 2, drying and roasting to obtain a silicon-containing amorphous composite oxide material;
E) crushing the amorphous composite oxide material, adding water to prepare uniform slurry, preparing halogen salt into solution, adding the solution into the amorphous composite oxide material slurry, stirring the slurry for 1h, and adding a binder to obtain the amorphous composite oxide-halogen salt composite adsorbent.
In the step A), the metal salt solution is at least one of an aluminum source, a titanium source, a magnesium source, a lanthanum source, a cerium source, a nickel source, a cobalt source, a boron source and a vanadium source; the property-reducing precipitant is at least one of sodium hydroxide, ammonia water, potassium hydroxide, sodium carbonate and sodium bicarbonate; the silicon source is at least one of water glass, silica sol and sodium silicate.
Wherein, in the step B), the mass of the added metal oxide precursor accounts for 1-80% of the composite oxide calculated by the solid content of the oxide; the solid content of the composite oxide in the uniform slurry is 50-350 g/L; the halogen salt is at least one of lithium bromide, sodium bromide, calcium bromide, magnesium bromide, lithium chloride, sodium chloride, calcium chloride and magnesium chloride; the mass fraction of the halogen-containing salt in the halogen salt solution is 5-50 wt%.
The dehumidifying element comprises the adsorbent prepared by the method, and is used for dehumidifying a rotating wheel or a fixed bed dehumidifying module.
The preparation method of the dehumidification rotating wheel comprises the following steps: and (3) putting the runner blank into the amorphous composite oxide-halogen salt composite adsorbent for dipping/coating, and drying and roasting to obtain the dehumidification runner of the amorphous composite oxide-halogen composite adsorbent.
Wherein, the carrier used by the amorphous composite oxide-halogen of the dehumidification rotating wheel is glass fiber, ceramic fiber or inorganic fiber carrier. The binder is inorganic binder, and the inorganic binder is at least one of silica sol, water glass and aluminum sol
The technical problem to be solved by the invention is as follows:
1. the amorphous composite oxide-halogen salt composite adsorbent is used for replacing silica gel as the adsorbent, the amorphous oxide and the halogen salt are compounded, various dehumidification modes such as physical adsorption, chemical adsorption and solution absorption are fully utilized, the advantages of various dehumidification modes are brought into play, and the defects of each other are overcome. The reasonable pore structure and acid property of the amorphous composite oxide can improve the deep dehumidification capability under low humidity (RH is less than 20 percent); the halogen salt has obvious effect on increasing the adsorption capacity of high humidity (RH is more than or equal to 40%); the amorphous oxide and the halogen salt are compounded, so that the desorption energy consumption can be reduced, the desorption regeneration rate is improved, the dehumidification capacity of the rotating wheel under the working condition of medium and high humidity load is improved, and the running stability of the rotating wheel is improved.
2. The amorphous composite oxide-halogen salt composite material is used as the adsorbent, so that the loading uniformity and single loading capacity of the adsorbent are improved, the dipping/coating process is reduced, the corrosivity of the production process on a fiber carrier is reduced, and the collapse and deformation of corrugated channels are reduced.
3. Silica gel has poor heat resistance, and water loss of the silica gel particle structure is easily caused by high temperature, so irreversible damage is caused, and the adsorption capacity is reduced. The silica gel rotary core is desorbed at a high regeneration temperature (more than 120 ℃) for a long time, and the cracking phenomena such as pore canal collapse, core-rotating silica gel melting, cracking and pulverization and the like easily occur, so that the service life is influenced. The composite adsorbent containing amorphous composite oxide-halogen salt can resist high temperature of 600 ℃, has good hydrothermal stability, is used for replacing silica gel for a dehumidifying rotating wheel, and can prolong the service life of the dehumidifying rotating wheel.
In the invention, the halogen salt and the amorphous oxide are compounded, and the drying effect of the composite adsorbent is obviously better than that of silica gel due to the synergistic action of physical adsorption and chemical adsorption. The microstructure containing composite oxidation is regulated and controlled by optimizing the preparation process, and the composite oxide has hierarchical pores; an M-O-Si bond is formed on the surface of the composite oxide, so that the number and the acid strength of acid active centers of B acid and L acid on the surface of the porous dehumidifying material are improved, and the adsorption capacity of the adsorbent to water vapor molecules is enhanced. The halogen salt has far higher adsorption capacity than the inorganic porous material under high humidity condition, and has the functions of sterilization and bacteriostasis. The halogen salt is distributed in the rich gaps of the amorphous oxide, so that the contact area with water vapor is greatly increased, and the adsorption rate is increased. Meanwhile, the halogen salt after moisture absorption has the characteristic of easy desorption, so that the desorption temperature requirement on the rotary wheel is reduced, and the possibility of recycling low-quality heat sources such as industrial waste heat, solar energy and the like is created.
The dehumidifying rotating wheel adopts composite materials to replace silica gel, the production process of the rotating wheel is simpler, and the corrosion and deformation of a carrier are reduced; the hydrothermal stability and the service life of the runner can be improved; the dehumidification capacity of runner improves, and the desorption energy consumption reduces, and is strengthened to air moisture content change adaptability of air intake, and the runner operation effect is more steady.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
The invention provides an amorphous composite oxide-halogen salt composite adsorbent, which is characterized by comprising an amorphous oxide and a halogen salt.
Wherein the halogen salt in the adsorbent accounts for 1-30% of the mass of the composite material.
The amorphous composite oxide is composed of silicon dioxide and at least one of aluminum oxide, titanium oxide, magnesium oxide, lanthanum oxide, cerium oxide, cobalt oxide, boron oxide and vanadium oxide, wherein the silicon dioxide accounts for 10-99% of the weight of the amorphous composite oxide.
The halogen salt is a fluoride salt, a chloride salt and/or a bromide salt, the fluoride salt comprises at least one of sodium fluoride, calcium fluoride and lithium fluoride, the chloride salt comprises at least one of calcium chloride, sodium chloride and lithium chloride, and the bromide salt comprises at least one of sodium bromide, calcium bromide and lithium bromide.
The invention provides a preparation method of an amorphous composite oxide-halogen salt composite adsorbent, which comprises the following steps:
A) pretreating the material, namely introducing one or more metal salt solutions and an alkaline precipitator into a reaction container, and precipitating under the stirring condition to prepare a metal oxide precursor solution; adding water to dilute a silicon source to obtain a silicon source diluent;
B) fully mixing the silicon source diluent with the metal oxide precursor solution and aging to obtain a mixed solution 1;
C) adding an acid solution into the mixed solution 1 to adjust the pH, stirring and aging to obtain a mixed solution 2:
D) filtering and washing the mixed solution 2, drying and roasting to obtain a silicon-containing amorphous composite oxide material;
E) crushing the amorphous composite oxide material, adding water to prepare uniform slurry, preparing halogen salt into solution, adding the solution into the amorphous composite oxide material slurry, stirring the slurry for 1h, and adding a binder to obtain the amorphous composite oxide-halogen salt composite adsorbent.
In the step A), the metal salt solution is at least one of an aluminum source, a titanium source, a magnesium source, a lanthanum source, a cerium source, a nickel source, a cobalt source, a boron source and a vanadium source; the property-reducing precipitant is at least one of sodium hydroxide, ammonia water, potassium hydroxide, sodium carbonate and sodium bicarbonate; the silicon source is at least one of water glass, silica sol and sodium silicate.
Wherein, in the step B), the mass of the added metal oxide precursor accounts for 1-70% of the composite oxide calculated by the solid content of the oxide; the solid content of the composite oxide in the uniform slurry is 50-350 g/L; the halogen salt is at least one of lithium bromide, sodium bromide, calcium bromide, magnesium bromide, lithium chloride, sodium chloride, calcium chloride and magnesium chloride; the mass fraction of the halogen-containing salt in the halogen salt solution is 5-50 wt%; in the slurry mixture of the amorphous composite oxide and the halogen salt, the content of the halogen salt is 1-50 wt%.
The dehumidifying element comprises the adsorbent prepared by the method, and is used for dehumidifying a rotating wheel or a fixed bed dehumidifying module.
The preparation method of the dehumidification rotating wheel comprises the following steps: and (3) putting the runner blank into the amorphous composite oxide-halogen salt composite adsorbent for dipping/coating, and drying and roasting to obtain the dehumidification runner of the amorphous composite oxide-halogen composite adsorbent.
Wherein, the carrier used by the amorphous composite oxide-halogen of the dehumidification rotating wheel is glass fiber, ceramic fiber or inorganic fiber carrier. The binder is an inorganic binder, and the inorganic binder is at least one of silica sol, water glass and aluminum sol.
Example 1
The composite adsorbent and the dehumidification rotating wheel are prepared according to the following steps, and the specific steps comprise:
1) preparation of metal oxide precursor2O3Aluminum sulfate solution 50g/L and 10% ammonia water are mixed in parallel flow with a constant pH value of 8.0, and precipitation is carried out under stirring conditions, so as to prepare metal oxide precursor solutions of aluminum oxide and titanium oxide, which are marked as A. The reaction temperature is 50 ℃, and the reaction time is 2h
2) A solution containing 100g/L of SiO2 was prepared by diluting water glass having a modulus of 3.2 with water and was designated as B.
3) According to mass fraction SiO2:Al2O3Adding B into A under stirring at a ratio of 8:2, mixing well and aging for 1h, adding B into A continuously, and stirring and aging for 1 h.
4) To the mixed solution was added a 5% strength sulfuric acid solution to adjust pH 7, and the mixture was aged for 1 hour with stirring.
5) And filtering, washing, drying and roasting the aged solution to obtain the amorphous titanium-silicon composite oxide material.
6) The amorphous composite oxide material is crushed and added with water to prepare 1L of uniform slurry, and the solid content of the composite oxide is 300 g/L.
7) Preparing lithium chloride into a 20 wt% solution, and adding 200g of the lithium chloride solution into the amorphous titanium-silicon composite oxide material slurry. 100ml of slurry is taken, dried for 12h at 110 ℃, roasted for 2h at 500 ℃ and recorded as the composite adsorbent S-1. Stirring the slurry for 1h, and adding 100g of neutral silicon solvent with the solid content of 30 wt% as a binder to obtain the composite adsorbent slurry.
8) And (4) dipping/coating the runner blank by using the composite adsorbent slurry prepared in the step (7).
Drying and roasting the impregnated/coated blank to complete the amorphous composite oxide-halogen composite adsorbent dehumidifying wheel G-1.
Example 2
The composite adsorbent and the dehumidification rotating wheel are prepared according to the following steps, and the specific steps comprise: 1) preparation of metal oxide precursor2O3Aluminum sulfate solution 50g/L and 10% ammonia water are mixed in parallel flow with a constant pH value of 8.0, and precipitation is carried out under stirring conditions, so as to prepare metal oxide precursor solutions of aluminum oxide and titanium oxide, which are marked as A. The reaction temperature is 50 ℃, and the reaction time is 2h
2) A solution containing 100g/L of SiO2 was prepared by diluting water glass having a modulus of 3.2 with water and was designated as B.
3) According to mass fraction SiO2:Al2O3Adding B into A under stirring at a ratio of 6:4, mixing well and aging for 1h, adding B into A continuously, and aging for 1h under stirring.
4) To the mixed solution was added a 5% strength sulfuric acid solution to adjust pH 7, and the mixture was aged for 1 hour with stirring.
5) And filtering, washing, drying and roasting the aged solution to obtain the amorphous titanium-silicon composite oxide material.
6) The amorphous composite oxide material is crushed and added with water to prepare 1L of uniform slurry, and the solid content of the composite oxide is 300 g/L.
7) Preparing lithium chloride into a 20 wt% solution, adding 200g of the lithium chloride solution into the amorphous titanium-silicon composite oxide material slurry, taking 100ml of the slurry, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 2h, wherein the solution is recorded as a composite adsorbent S-2. Stirring the slurry for 1h, and adding 100g of neutral silicon solvent with the solid content of 30 wt% as a binder to obtain the composite adsorbent.
8) And (4) dipping/coating the runner blank by using the composite adsorbent slurry prepared in the step (7). Drying and roasting the impregnated/coated blank to complete the amorphous composite oxide-halogen composite adsorbent dehumidifying wheel G-2.
Example 3
The composite adsorbent and the dehumidification rotating wheel are prepared according to the following steps, and the specific steps comprise: 1) preparation of metal oxide precursor250g/L of titanyl sulfate solution and 10% ammonia water are mixed in parallel at a constant pH of 8.0, and precipitation is carried out under stirring to prepare metal oxide precursor solutions of alumina and titania, which are respectively designated as A. The reaction temperature is 50 ℃, and the reaction time is 2h
2) A solution containing 100g/L of SiO2 was prepared by diluting water glass having a modulus of 3.2 with water and was designated as B.
3) According to mass fraction SiO2:TiO2Adding B into A under stirring at a ratio of 8:2, mixing well and aging for 1h, adding B into A continuously, and stirring and aging for 1 h.
4) To the mixed solution was added a 5% strength sulfuric acid solution to adjust pH 7, and the mixture was aged for 1 hour with stirring.
5) And filtering, washing, drying and roasting the aged solution to obtain the amorphous titanium-silicon composite oxide material.
6) The amorphous composite oxide material is crushed and added with water to prepare 1L of uniform slurry, and the solid content of the composite oxide is 300 g/L.
7) Preparing lithium chloride into a 20 wt% solution, adding 200g of the lithium chloride solution into the amorphous titanium-silicon composite oxide material slurry, taking 100ml of the slurry, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 2h, wherein the solution is recorded as a composite adsorbent S-3. Stirring the slurry for 1h, and adding 100g of neutral silicon solvent with the solid content of 30 wt% as a binder to obtain the composite adsorbent slurry.
8) And (4) dipping/coating the runner blank by using the composite adsorbent slurry prepared in the step (7). Drying and roasting the impregnated/coated blank to complete the amorphous composite oxide-halogen composite adsorbent dehumidifying wheel G-3.
Example 4
The composite adsorbent and the dehumidifying rotary wheel are prepared according to the following stepsThe method comprises the following steps: 1) preparation of metal oxide precursor by respectively preparing TiO-containing precursor250g/L titanyl sulfate solution and Al-containing alloy2O3Aluminum sulfate solution 50g/L was mixed with 10% ammonia water at a constant pH of 8.0, and the mixture was stirred to precipitate, thereby preparing metal oxide precursor solutions of alumina and titania, respectively, and designated as A. The reaction temperature is 50 ℃, and the reaction time is 2 h.
2) A solution containing 100g/L of SiO2 was prepared by diluting water glass having a modulus of 3.2 with water and was designated as B.
3) According to mass fraction SiO2:TiO2:Al2O3Adding B into A under stirring at a ratio of 7:1:2, mixing well and aging for 1h, adding B into A continuously, and stirring and aging for 1 h.
4) To the mixed solution was added a 5% strength sulfuric acid solution to adjust pH 7, and the mixture was aged for 1 hour with stirring.
5) And filtering, washing, drying and roasting the aged solution to obtain the amorphous titanium-silicon composite oxide material.
6) The amorphous composite oxide material is crushed and added with water to prepare 1L of uniform slurry, and the solid content of the composite oxide is 300 g/L.
7) Preparing lithium chloride into a 20 wt% solution, adding 200g of the lithium chloride solution into the amorphous titanium-silicon composite oxide material slurry, taking 100ml of the slurry, drying at 110 ℃ for 12h, roasting at 500 ℃ for 2h, stirring the slurry to be the composite adsorbent S-4 slurry for 1h, and adding 100g of a neutral silicon solvent with the solid content of 30 wt% as a binder to obtain the composite adsorbent slurry.
8) And (4) dipping/coating the runner blank by using the composite adsorbent slurry prepared in the step (7). Drying and roasting the impregnated/coated blank to complete the amorphous composite oxide-halogen composite adsorbent dehumidifying wheel G-4.
Example 5
The composite adsorbent and the dehumidification rotating wheel are prepared according to the following steps, and the specific steps comprise:
1) preparation of metal oxide precursor2O350g/L of aluminum sulfate solution is mixed with 10% ammonia water with constant pH of 8.0 in parallel flow, and the mixture is stirredPrecipitation, metal oxide precursor solutions of alumina and titania are prepared, respectively, and are designated as a. The reaction temperature is 50 ℃, and the reaction time is 2h
2) A solution containing 100g/L of SiO2 was prepared by diluting water glass having a modulus of 3.2 with water and was designated as B.
3) According to mass fraction SiO2:Al2O3Adding B into A under stirring at a ratio of 8:2, mixing well and aging for 1h, adding B into A continuously, and stirring and aging for 1 h.
4) To the mixed solution was added a 5% strength sulfuric acid solution to adjust pH 7, and the mixture was aged for 1 hour with stirring.
5) And filtering, washing, drying and roasting the aged solution to obtain the amorphous titanium-silicon composite oxide material.
6) The amorphous composite oxide material is crushed and added with water to prepare 1L of uniform slurry, and the solid content of the composite oxide is 300 g/L.
7) Preparing lithium chloride into a 20 wt% solution, adding 100g of the lithium chloride solution into the amorphous titanium-silicon composite oxide material slurry, taking 100ml of the slurry, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 2h, wherein the solution is recorded as a composite adsorbent S-5. Stirring the slurry for 1h, and adding 100g of neutral silicon solvent with the solid content of 30 wt% as a binder to obtain the composite adsorbent slurry.
8) And (4) dipping/coating the runner blank by using the composite adsorbent slurry prepared in the step (7). Drying and roasting the impregnated/coated blank to complete the amorphous composite oxide-halogen composite adsorbent dehumidifying wheel G-5.
Example 6
The composite adsorbent and the dehumidification rotating wheel are prepared according to the following steps, and the specific steps comprise:
1) preparation of metal oxide precursor2O3Aluminum sulfate solution 50g/L and 10% ammonia water are mixed in parallel flow with a constant pH value of 8.0, and precipitation is carried out under stirring conditions, so as to prepare metal oxide precursor solutions of aluminum oxide and titanium oxide, which are marked as A. The reaction temperature is 50 ℃, and the reaction time is 2h
2) A solution containing 100g/L of SiO2 was prepared by diluting water glass having a modulus of 3.2 with water and was designated as B.
3) According to mass fraction SiO2:Al2O3Adding B into A under stirring at a ratio of 8:2, mixing well and aging for 1h, adding B into A continuously, and stirring and aging for 1 h.
4) To the mixed solution was added a 5% strength sulfuric acid solution to adjust pH 7, and the mixture was aged for 1 hour with stirring.
5) And filtering, washing, drying and roasting the aged solution to obtain the amorphous titanium-silicon composite oxide material.
6) The amorphous composite oxide material is crushed and added with water to prepare 1L of uniform slurry, and the solid content of the composite oxide is 300 g/L.
7) Preparing lithium chloride into a 20 wt% solution, adding 400g of the lithium chloride solution into the amorphous titanium-silicon composite oxide material slurry, taking 100ml of the slurry, drying at 110 ℃ for 12h, roasting at 500 ℃ for 2h, and recording as the synthetic adsorbent S-6. Stirring the slurry for 1h, and adding 100g of neutral silicon solvent with the solid content of 30 wt% as a binder to obtain the composite adsorbent slurry.
8) And (4) dipping/coating the runner blank by using the composite adsorbent slurry prepared in the step (7). Drying and roasting the impregnated/coated blank to complete the amorphous composite oxide-halogen composite adsorbent dehumidifying wheel G-6.
Example 7
The composite adsorbent and the dehumidification rotating wheel are prepared according to the following steps, and the specific steps comprise:
1) preparation of metal oxide precursor2O3Aluminum sulfate solution 50g/L and 10% ammonia water are mixed in parallel flow with a constant pH value of 8.0, and precipitation is carried out under stirring conditions, so as to prepare metal oxide precursor solutions of aluminum oxide and titanium oxide, which are marked as A. The reaction temperature is 50 ℃, and the reaction time is 2h
2) Taking water glass with the modulus of 3.2 to dilute the water glass into SiO-containing water glass2This is a 100g/L solution, denoted B.
3) According to mass fraction SiO2:Al2O3Adding B into A under stirring at a ratio of 8:2, mixing well and aging for 1h, adding B into A continuously, and stirring and aging for 1 h.
4) To the mixed solution was added a 5% strength sulfuric acid solution to adjust pH 7, and the mixture was aged for 1 hour with stirring.
5) And filtering, washing, drying and roasting the aged solution to obtain the amorphous titanium-silicon composite oxide material.
6) The amorphous composite oxide material is crushed and added with water to prepare 1L of uniform slurry, and the solid content of the composite oxide is 300 g/L.
7) Preparing calcium chloride into a 20 wt% solution, adding 200g of lithium chloride solution into the amorphous titanium silicon composite oxide material slurry, stirring the slurry for 1h, and adding 100g of a neutral silicon solvent with the solid content of 30 wt% as a binder. 100ml of the slurry is taken, dried for 12h at 110 ℃, roasted for 2h at 500 ℃ and recorded as synthetic adsorbent S-7. Stirring the slurry for 1h, and adding 100g of neutral silicon solvent with the solid content of 30 wt% as a binder to obtain the composite adsorbent slurry.
8) And (4) dipping/coating the runner blank by using the composite adsorbent slurry prepared in the step (7). Drying and roasting the impregnated/coated blank to complete the amorphous composite oxide-halogen composite adsorbent dehumidifying wheel G-7.
Property parameters of the composite materials S-1, S-2, S-3, S-4, S-5, S-6 and S-7 prepared in the above examples 1 to 7 were measured, respectively, and the results are shown in Table 1.
TABLE 1 Properties of the composite materials
The results of comparing the properties of the desiccant rotor G-1 prepared from the composite S-1 of example 1 of the present invention with those of a conventional silica gel SG desiccant rotor are shown in Table 2.
TABLE 2 comparison of properties of conventional molecular sieve desiccant wheels with composite S-1 desiccant wheels
Note: the thickness of the rotating wheel is 2cm, the rotating speed is 10r/h, the desorption area accounts for 25 percent, the desorption temperature is 150 ℃, and the mass of the rotating wheel is about 170 g.
In the invention, the halogen salt and the amorphous oxide are compounded, and the drying effect of the composite adsorbent is obviously better than that of silica gel due to the synergistic action of physical adsorption and chemical adsorption. The microstructure containing composite oxidation is regulated and controlled by optimizing the preparation process, and the composite oxide has hierarchical pores; an M-O-Si bond is formed on the surface of the composite oxide, so that the number and the acid strength of acid active centers of B acid and L acid on the surface of the porous dehumidifying material are improved, and the adsorption capacity of the adsorbent to water vapor molecules is enhanced. The halogen salt has far higher adsorption capacity than the inorganic porous material under high humidity condition, and has the functions of sterilization and bacteriostasis. The halogen salt is distributed in the rich gaps of the amorphous oxide, so that the contact area with water vapor is greatly increased, and the adsorption rate is increased. Meanwhile, the halogen salt after moisture absorption has the characteristic of easy desorption, so that the desorption temperature requirement on the rotary wheel is reduced, and the possibility of recycling low-quality heat sources such as industrial waste heat, solar energy and the like is created.
The dehumidifying rotating wheel adopts composite materials to replace silica gel, the production process of the rotating wheel is simpler, and the corrosion and deformation of a carrier are reduced; the hydrothermal stability and the service life of the runner can be improved; the dehumidification capacity of runner improves, and the desorption energy consumption reduces, and is strengthened to air moisture content change adaptability of air intake, and the runner operation effect is more steady.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An amorphous composite oxide-halogen salt composite adsorbent, which is characterized by comprising an amorphous oxide and a halogen salt.
2. The sorbent according to claim 1, wherein the halogen salt in the sorbent accounts for 1-30% of the mass fraction of the composite material.
3. The adsorbent according to claim 1, wherein the amorphous composite oxide is composed of silica and at least one of alumina, titania, magnesia, lanthana, ceria, cobalt oxide, boria, and vanadia, and the silica accounts for 10 to 99% of the total mass of the amorphous composite oxide.
4. The sorbent according to claim 1, wherein the halogen salt is at least one of a fluoride salt, a chloride salt, and a bromide salt.
5. A preparation method of an amorphous composite oxide-halogen salt composite adsorbent is characterized by comprising the following steps:
A) pretreating the material, namely introducing one or more metal salt solutions and an alkaline precipitator into a reaction container, and precipitating under the stirring condition to prepare a metal oxide precursor solution; adding water to dilute a silicon source to obtain a silicon source diluent;
B) fully mixing the silicon source diluent with the metal oxide precursor solution and aging to obtain a mixed solution 1;
C) adding an acid solution into the mixed solution 1 to adjust the pH, stirring and aging to obtain a mixed solution 2:
D) filtering and washing the mixed solution 2, drying and roasting to obtain a silicon-containing amorphous composite oxide material;
E) crushing the amorphous composite oxide material, adding water to prepare uniform slurry, preparing halogen salt into solution, adding the solution into the amorphous composite oxide material slurry, stirring the slurry for 1h, and adding a binder to obtain the amorphous composite oxide-halogen salt composite adsorbent.
6. The method as claimed in claim 5, wherein in the step A), the metal salt solution is at least one of aluminum source, titanium source, magnesium source, lanthanum source, cerium source, nickel source, cobalt source, boron source and vanadium source; the property-reducing precipitant is at least one of sodium hydroxide, ammonia water, potassium hydroxide, sodium carbonate and sodium bicarbonate; the silicon source is at least one of water glass, silica sol and sodium silicate.
7. The method as claimed in claim 5, wherein in the step B), the mass of the added metal oxide precursor accounts for 1-70% of the composite oxide calculated by the solid content of the oxide; the solid content of the composite oxide in the uniform slurry is 50-350 g/L; the halogen salt is at least one of lithium bromide, sodium bromide, calcium bromide, magnesium bromide, lithium chloride, sodium chloride, calcium chloride and magnesium chloride; the mass fraction of the halogen-containing salt in the halogen salt solution is 5-50 wt%.
8. A dehumidifying element comprising the adsorbent prepared by the method according to any one of claims 4 to 7, wherein the dehumidifying element is a rotary dehumidifying wheel or a fixed bed dehumidifying module.
9. The dehumidifying element of claim 8 wherein the dehumidifying rotor is prepared by: and (3) putting the runner blank into the amorphous composite oxide-halogen salt composite adsorbent for dipping/coating, and drying and roasting to obtain the dehumidification runner of the amorphous composite oxide-halogen composite adsorbent.
10. A dehumidifying element as claimed in claim 9, wherein the carrier for the amorphous composite oxide-halogen of the dehumidifying rotor is a glass fiber, ceramic fiber or inorganic fiber carrier. The binder is an inorganic binder, and the inorganic binder is at least one of silica sol, water glass and aluminum sol.
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