CN113000026A - Modified composite molecular sieve and preparation and application thereof - Google Patents
Modified composite molecular sieve and preparation and application thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28095—Shape or type of pores, voids, channels, ducts
- B01J20/28097—Shape or type of pores, voids, channels, ducts being coated, filled or plugged with specific compounds
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Abstract
The invention relates to a modified composite molecular sieve and preparation and application thereof, comprising the following steps: (1) mixing a 4A type molecular sieve, a NaY type molecular sieve and a mordenite type molecular sieve, treating by using a calcium chloride solution, and washing to obtain a molecular sieve mixture; (2) mixing the low-carbon organic acid with the molecular sieve mixture, and performing primary modification treatment; (3) and separating the product after the primary modification, mixing the product with the long carbon chain modifier, and carrying out heat treatment to obtain the target product. Compared with the prior art, the product prepared by the invention has the characteristics of high oil phase dispersibility, low adsorption heat and lower application system viscosity.
Description
Technical Field
The invention belongs to the technical field of molecular sieves, and relates to a modified composite molecular sieve, and preparation and application thereof.
Background
The molecular sieve activated powder is a molecular sieve obtained by dehydrating raw powder synthesized by a molecular sieve, is mainly used as an additive or aggregate of polyurethane coating, paint, resin and certain adhesives due to the rapid moisture absorption speed, and has the effects of reducing moisture, eliminating bubbles and improving the uniformity and strength of materials.
The molecular sieve has high surface hydroxyl polarity, and the existence of hydroxyl is a great advantage in common dehydration application, but the situation is opposite when the molecular sieve is applied to a polyurethane system, the polyurethane raw materials are polymeric polyisocyanate, polyol containing hydroxyl and polymeric amine, and the common characteristic is that the molecular sieve rich in surface hydroxyl is extremely active and reacts with the components to promote the pre-polymerization of the raw materials and reduce the pot life. Meanwhile, the molecular sieve has high surface energy, the surface has hydrophilic and oleophobic performances, the molecular sieve is easy to agglomerate and cannot be fully mixed in an organic phase, and the molecular sieve is difficult to uniformly disperse in an organic medium, so that the application effect of the molecular sieve is influenced.
At present, the prior molecular sieve activated powder in China is mostly prepared by roasting conventional molecular sieve raw powder at high temperature, has high surface activity and easy agglomeration, is difficult to wet in organic media (castor oil and the like), is easy to cause the problems of oil slurry viscosity increase and the like, and further shortens the service life of the product.
Heretofore, the mainstream technology is that the pH value of activated powder of the 3A molecular sieve obtained by using a strong acid treatment method is 7.5-9.5, and the pH value of the activated powder of the molecular sieve is reduced to reduce the alkalinity of the surface of the molecular sieve (European patent EP0346604B1), so that the influence of the surface property of the molecular sieve on the performance of polyurethane is reduced, but the strong acid is easy to damage the structure, so that the water adsorption performance of the product is easily reduced, and the particle dispersion condition is not improved.
Disclosure of Invention
The invention aims to provide a modified composite molecular sieve and preparation and application thereof, and the prepared composite molecular sieve has the characteristics of high oil phase dispersibility, long service life, low application system viscosity and the like.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a modified composite molecular sieve, which comprises the following steps:
(1) mixing a 4A type molecular sieve, a NaY type molecular sieve and a mordenite type molecular sieve, treating by using a calcium chloride solution, and washing to obtain a molecular sieve mixture;
(2) mixing the low-carbon organic acid with the molecular sieve mixture, and performing primary modification treatment;
(3) and separating the product after the primary modification, mixing the product with the long carbon chain modifier, and carrying out heat treatment to obtain the target product.
In the invention, the composite molecular sieve is used as a molecular sieve raw material, and the micro-moisture is removed by utilizing the structural difference and the polarity difference of the pore passages of the molecular sieve. The composite molecular sieve has high acid resistance, is resistant to the treatment of low-carbon chain organic acid, and can improve the acid resistance of the polyurethane adhesive when being applied to a polyurethane system. Further, the weight ratio of the 4A type molecular sieve, the NaY type molecular sieve and the mordenite molecular sieve is (50-70): (20-30): (10-20).
Further, the silicon-aluminum ratio in the mordenite molecular sieve is 10-15.
According to the invention, the internal structure of the molecular sieve is stabilized through calcium ion treatment, the molecular sieve structure is prevented from being damaged through modification and other treatments, and the influence of the molecular sieve on the water absorption performance is reduced. Further, the mass concentration of the calcium chloride solution is 2-5%, and when the calcium chloride solution is treated, the ratio of the total amount of the three molecular sieves to the mass of the calcium chloride solution is 1: (3-8).
Further, the temperature of the calcium chloride solution is 25-50 ℃ and the time is 1-3 h.
In the invention, the low-carbon organic acid is used for primary modification, so that the pore channel distribution of the molecular sieve is improved, amorphous substances in the pore channel are reduced, and the heat of adsorption is reduced. And meanwhile, water and organic acid are used for filling the molecular sieve pore channel, so that the long carbon chain modifier is prevented from entering the molecular sieve pore channel. Further, in the step (2), the low-carbon organic acid is at least one of oxalic acid, acetic acid or citric acid, and the mass ratio of the low-carbon organic acid to the molecular sieve mixture is (1-5): 100.
Preferably, the preliminarily modified product is subjected to suction filtration to obtain a filter cake, and then is mixed with the long carbon chain modifier in a mechanical grinding mode, wherein the grinding time is preferably 5-20 min.
In the invention, the long carbon chain modifier is used for only organically modifying the surface of the molecular sieve, so that the obtained molecular sieve particles can be uniformly distributed in a polyol system. Further, in the step (3), the long carbon chain modifier is at least one of pentadecanoic acid, hexadecanoic acid, heptadecanoic acid or octadecanoic acid, and the mass ratio of the long carbon chain modifier to the molecular sieve mixture is (0.5-3): 100.
in the invention, the modification of long carbon chain is combined with the activation of molecular sieve by vacuum heat treatment, and further, in the step (3), the heat treatment specifically comprises the following steps: under vacuum, firstly heating to 120-150 ℃, treating for 2-5 h, and continuously heating to 250-300 ℃ for treating for 2-5 h.
The second technical scheme of the invention provides a modified composite molecular sieve which is prepared by the preparation method.
The third technical scheme of the invention provides application of the modified composite molecular sieve, and the modified composite molecular sieve is used for removing moisture in a polyurethane binder system.
Compared with the prior art, the invention has the following advantages:
1) the modified molecular sieve is a composite of three molecular sieves with different silicon-aluminum ratios, and the micro-moisture is removed by utilizing the structural difference and the polarity difference of pore channels of the molecular sieves, so that the service life of the system is prolonged. The composite molecular sieve has high acid resistance, and can improve the acid resistance of the polyurethane adhesive when being applied to a polyurethane system.
2) The calcium ions are utilized to stabilize the composite molecular sieve pore channel structure, so that the damage to the molecular sieve structure after organic acid treatment is effectively avoided, and the water adsorption performance of the molecular sieve is stabilized.
3) The low-carbon organic acid is used for removing partial aluminum and amorphous substances in the molecular sieve, so that the pore channel distribution of the molecular sieve is improved, and the heat of adsorption is reduced. The low-carbon organic acid fills the pores of the molecular sieve, so that the long-carbon-chain organic acid is prevented from entering the inside of the pores of the molecular sieve, the low-carbon organic acid is removed in the subsequent vacuum activation process, and the water absorption performance of the molecular sieve is maintained.
4) The long carbon chain modifier is utilized to only carry out organic modification on the surface of the molecular sieve, so that the activated molecular sieve particles can be uniformly distributed in the polyol, the agglomeration is avoided, the product has the advantages of high dispersibility and low system viscosity, the initial viscosity of an application system can be reduced, and the working life is prolonged.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the long carbon chain modifier of octadecanoic acid was a product of national chemical group, Inc., and the polymethylene polyphenyl isocyanate (PAPI-27) was a product of Dow chemical company. Otherwise, unless otherwise specified, all the conventional commercial raw materials or conventional processing techniques are used in the art.
Example 1
Mixing the 4A type molecular sieve, the NaY type molecular sieve and the mordenite type molecular sieve according to the proportion of 50:30:20, wherein the silicon-aluminum ratio of the mordenite type molecular sieve is about 10. Calcium chloride solution with the mass concentration of 2% is used for processing for 3h at the temperature of 25 ℃ and the solid-to-liquid ratio of 1: 8. After washing, the mixture is treated by using a low-carbon organic acid solution, wherein the mass ratio of the low-carbon organic acid (oxalic acid in the embodiment) to the molecular sieve mixed powder is 1:100, and the treatment time is 3 hours. And performing filter pressing to obtain a filter cake after treatment, adding octadecanoic acid, wherein the mass ratio of the octadecanoic acid to the molecular sieve filter cake is 0.5:100, mixing, grinding for 5min, performing vacuum heat treatment at 120 ℃, treating for 2h, heating to 250 ℃, and treating for 2h to obtain the modified composite molecular sieve.
Example 2
Mixing a 4A type molecular sieve, a NaY type molecular sieve and a mordenite type molecular sieve according to the weight ratio of 70: 20: 10, wherein the silicon-aluminum ratio of the mordenite molecular sieve is 15. Calcium chloride solution with the mass concentration of 5% is used for processing for 2h at the temperature of 25 ℃ and the solid-to-liquid ratio of 1: 3. After washing, the mixture is treated by using a low-carbon organic acid solution, wherein the mass ratio of the low-carbon organic acid (acetic acid in the embodiment) to the molecular sieve mixed powder is 5:100, and the treatment time is 3 hours. And performing filter pressing to obtain a filter cake after treatment, adding pentadecanoic acid, mixing and grinding for 10min after the pentadecanoic acid and the molecular sieve are in a ratio of 1:100, performing vacuum heat treatment at 130 ℃ for 5h, heating to 300 ℃, and performing treatment for 2h to obtain the modified composite molecular sieve.
Example 3
Mixing a 4A type molecular sieve, a NaY type molecular sieve and a mordenite type molecular sieve according to the weight ratio of 60: 20: 20, wherein the silicon-aluminum ratio of the mordenite molecular sieve is 12. Calcium chloride solution with the mass concentration of 5% is used for processing for 1h at the temperature of 50 ℃ and the solid-to-liquid ratio of 1: 8. After washing, the powder is treated by using a low-carbon organic acid solution, wherein the mass ratio of the low-carbon organic acid (citric acid in the embodiment) to the powder is 2:100, and the treatment time is 1 h. And performing filter pressing to obtain a filter cake after treatment, adding hexadecanoic acid, wherein the ratio of the hexadecanoic acid to the molecular sieve is 3:100, mixing, grinding for 20min, performing vacuum heat treatment at 150 ℃ for 3h, heating to 250 ℃ for 5h to obtain the modified composite molecular sieve.
Example 4
Mixing a 4A type molecular sieve, a NaY type molecular sieve and a mordenite type molecular sieve according to the weight ratio of 60: 30: 10, wherein the silicon-aluminum ratio of the mordenite molecular sieve is 15. Calcium chloride solution with the mass concentration of 3% is used for processing for 2h at the temperature of 30 ℃ and the solid-to-liquid ratio of 1: 5. After washing, the powder is treated by using a low-carbon organic acid solution, wherein the mass ratio of the low-carbon organic acid (acetic acid in the embodiment) to the powder is 3:100, and the treatment time is 2 hours. And performing filter pressing to obtain a filter cake after treatment, adding heptadecanoic acid, wherein the ratio of the heptadecanoic acid to the molecular sieve is 2:100, mixing, grinding for 15min, performing vacuum heat treatment at 150 ℃ for 1h, heating to 280 ℃ for 5h to obtain the modified composite molecular sieve.
Example 5
Mixing a 4A type molecular sieve, a NaY type molecular sieve and a mordenite type molecular sieve according to the weight ratio of 70: 20: 10, wherein the silicon-aluminum ratio of the mordenite molecular sieve is 10. Calcium chloride solution with the mass concentration of 5% is used for processing for 3h at the temperature of 25 ℃ and the solid-to-liquid ratio of 1: 3. After washing, the powder is treated by using a low-carbon organic acid solution, wherein the mass ratio of the low-carbon organic acid (oxalic acid in the embodiment) to the powder is 5:100, and the treatment time is 3 hours. And performing filter pressing to obtain a filter cake after treatment, adding pentadecanoic acid, mixing the pentadecanoic acid and the molecular sieve according to the ratio of 1:100, grinding for 10min, performing vacuum heat treatment at 130 ℃ for 5h, heating to 300 ℃, and treating for 2h to obtain the modified composite molecular sieve.
Comparative example 1
Compared with the example 1, the method is basically the same, except that the molecular sieve in the example is pure 4A molecular sieve with equal mass.
Comparative example 2
Compared with the example 1, the method is basically the same, except that the molecular sieve in the example is a pure NaY molecular sieve with equal mass.
Comparative example 3
Compared with the example 1, the method is basically the same, except that the molecular sieve in the example is the pure mordenite molecular sieve with equal mass.
Comparative example 4
Essentially the same as in example 1, except that the calcium chloride treatment step was eliminated in this example.
Comparative example 5
The process is essentially the same as example 1, except that the lower organic acid treatment step is eliminated.
Comparative example 6
Essentially the same as in example 1, except that the long chain modifier treatment step was eliminated.
After the obtained composite molecular sieve and castor oil are uniformly mixed according to the proportion of 1:1, a DV-2T RV type viscometer is used for testing the viscosity, the testing condition is 25 ℃, a number six rotor is used, and the rotating speed is 30 rpm. The viscosity of the resulting sample was tested.
Weighing 5g of the obtained composite molecular sieve, placing the weighed composite molecular sieve on a marble flat plate, dropwise adding refined linseed oil by using a burette, wherein the oil adding amount is not more than 10 drops each time, pressing and grinding by using a regulating knife after adding the refined linseed oil, so that oil is infiltrated into a sample to be tested, and continuously dropwise adding the refined linseed oil at the speed until the oil and the sample form a block. And (3) from the moment, adding one drop of the linseed oil, fully grinding by using a knife, recording the volume of the consumed refined linseed oil to obtain the oil absorption value of the sample by calculating when a paste with uniform consistency is formed, is not cracked and broken right and can be adhered to a flat plate as an end point.
And testing the static water adsorption performance of the obtained composite molecular sieve.
And (3) uniformly mixing 10g of molecular sieve powder with 10mL of water, and recording the temperature change in the mixing process to obtain the water adsorption temperature rise.
The composite molecular sieve and the castor oil are uniformly mixed according to the ratio of 1:1, a high-shear stirring rod is adopted for stirring for 3 minutes during mixing, about 50g of paste is prepared and stored for 12 hours at a moisture-proof constant temperature, 9.85g of PAPI27 is added into the paste, then the paste is stirred for 2 minutes at the stirring speed of 240r/min to obtain the paste to be tested, the working life of a sample is reflected by intermittently testing the viscosity change of the paste, and the time consumed when the viscosity of the paste reaches 56 Pa.s is the working life of the sample.
The results of the tests of example 1 and comparative examples 1-6 are shown in Table 1:
TABLE 1
Comparing the data in table 1, example 1 has a low application viscosity and a high pot life. Compared with the difference between single raw powder and composite powder, the single raw powder has the problems of low static water or high viscosity, high oil absorption value and the like, the product has short working life, the composite molecular sieve can avoid the problems of low static water or high viscosity and the like of the single molecular sieve, and the working life of the product is also obviously prolonged. Comparative example 4, no calcium ion pretreatment was introduced, the water adsorption of the molecular sieve was significantly reduced, which indicates that the internal structure of the molecular sieve could be stabilized by calcium ion treatment to avoid the damage of modification to the molecular sieve structure. Comparative example 5, the temperature rise of water adsorption was significantly increased without treating the sample with an organic acid, and the pot life was somewhat shortened as compared with example 1. Comparative example 6, the long-chain modifier is not used for modification, the oil absorption value and the viscosity are both obviously increased, which shows that the sample has obviously poor oleophylic property and is difficult to be uniformly dispersed in a polyol system.
Example 6
The same as in example 2, except that the calcium chloride treatment temperature was 45 ℃.
Example 7
Compared with the example 2, the calcium chloride solid-liquid ratio is basically the same, except that the calcium chloride solid-liquid ratio is 1: 8.
Example 8
Compared with the embodiment 2, the method is basically the same, except that the mass ratio of the low-carbon organic acid to the powder is 2: 100.
Example 9
Compared with the embodiment 2, the method is basically the same, except that the mass ratio of the long-chain modifier to the powder is 3: 100.
Example 10
Compared with the embodiment 2, the method is basically the same, except that the long-chain modifier is a mixed modifier of pentadecanoic acid and octadecanoic acid, and the mass ratio of the pentadecanoic acid to the octadecanoic acid is 1: 1.
Example 11
Compared with example 2, the same, except that the weight ratio of the type 4A molecular sieve, NaY molecular sieve and mordenite molecular sieve is 60: 25: 15.
example 12
Compared with example 2, the same is true, except that the mordenite molecular sieve has a silica to alumina ratio of 12.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The preparation method of the modified composite molecular sieve is characterized by comprising the following steps:
(1) mixing a 4A type molecular sieve, a NaY type molecular sieve and a mordenite type molecular sieve, treating by using a calcium chloride solution, and washing to obtain a molecular sieve mixture;
(2) mixing the low-carbon organic acid with the molecular sieve mixture, and performing primary modification treatment;
(3) and separating the product after the primary modification, mixing the product with the long carbon chain modifier, and carrying out heat treatment to obtain the target product.
2. The preparation method of the modified composite molecular sieve of claim 1, wherein the weight ratio of the 4A type molecular sieve, the NaY type molecular sieve and the mordenite molecular sieve is (50-70): (20-30): (10-20).
3. The preparation method of the modified composite molecular sieve of claim 1, wherein the ratio of silicon to aluminum in the mordenite molecular sieve is 10-15.
4. The preparation method of the modified composite molecular sieve of claim 1, wherein the mass concentration of the calcium chloride solution is 2-5%, and when the calcium chloride solution is treated, the mass ratio of the total amount of the three molecular sieves, namely the 4A type molecular sieve, the NaY type molecular sieve and the mordenite type molecular sieve to the calcium chloride solution is 1: (3-8).
5. The method for preparing the modified composite molecular sieve of claim 1, wherein the temperature of the calcium chloride solution is 25-50 ℃ and the time is 1-3 h.
6. The preparation method of the modified composite molecular sieve of claim 1, wherein in the step (2), the low-carbon organic acid is at least one of oxalic acid, acetic acid or citric acid, and the mass ratio of the low-carbon organic acid to the molecular sieve mixture is (1-5): 100.
7. The method for preparing the modified composite molecular sieve of claim 1, wherein in the step (3), the long carbon chain modifier is at least one of pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, or octadecanoic acid, and the mass ratio of the long carbon chain modifier to the molecular sieve mixture is (0.5-3): 100.
8. the method for preparing the modified composite molecular sieve of claim 1, wherein in the step (3), the heat treatment specifically comprises: under vacuum, firstly heating to 120-150 ℃, treating for 2-5 h, and continuously heating to 250-300 ℃ for treating for 2-5 h.
9. A modified composite molecular sieve prepared by the method of any one of claims 1 to 8.
10. The use of a modified composite molecular sieve as claimed in claim 9, wherein the modified composite molecular sieve is used for moisture removal in a system comprising a polyurethane binder.
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