CN110467199B - Method for rapidly synthesizing P-type molecular sieve with high calcium and magnesium ion exchange performance by solid-like phase method - Google Patents
Method for rapidly synthesizing P-type molecular sieve with high calcium and magnesium ion exchange performance by solid-like phase method Download PDFInfo
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Abstract
The invention relates to a method for quickly synthesizing a P-type molecular sieve with high calcium and magnesium ion exchange performance by a solid-like phase method. The method firstly uses Na 2 SiO 3 ·9H 2 O、Al 2 (SO 4 ) 3 ·18H 2 O and a suitable amount of H 2 O mixing, and preparing silicon-aluminum xerogel by a one-step method; then NaOH and H are added 2 And O, obtaining a high-concentration synthesis system, and statically crystallizing to obtain the P-type molecular sieve with uniform appearance and good crystallization. The method combines the dual advantages of the solid-liquid bidirectional conversion process, successfully realizes the process of quickly synthesizing the P-type molecular sieve with high calcium-magnesium ion exchange performance, shortens the synthesis period by 2~8 times, reduces the dosage of the system solvent by about 11.9-77.7 percent, and effectively solves the problems of low utilization rate of raw materials, difficult treatment of mother liquor and the like compared with the traditional hydrothermal method.
Description
Technical Field
The invention relates to a method for quickly synthesizing a P-type molecular sieve with high calcium and magnesium ion exchange performance by a solid phase method.
Background
P type molecular sieve (Na) 6 A1 6 Si 10 O 32 ·12H 2 O) has the framework structure of the clinoptilolite and is mainly composed of silicon (aluminum) oxideThe tetrahedron forms a basic structural unit, namely an eight-membered silicon (aluminum) ring through sharing a vertex oxygen bridge, and is connected into straight pore channels or sinusoidal pore channels with the pore diameter of 0.31nm multiplied by 0.44nm and 0.26nm multiplied by 0.49nm, which are mutually staggered in the eight-membered ring. Due to the special structural characteristics, the catalyst is widely applied to the aspects of wastewater treatment, gas separation, ion exchange and the like, and has higher application value and market value.
At present, scholars at home and abroad mainly use fly ash, coal gangue, bentonite and the like as raw materials, a hydrothermal method is usually adopted to synthesize the P-type molecular sieve, and the method has the advantages of simple process, wide raw material source and high product crystallinity, but has a series of defects of long crystallization time, low resource utilization rate, difficult mother liquor circulation, harsh reaction conditions and the like. Such as CaoJilin, the subject group (Cao Jilin, tan Chaoyang, li Chunxu, etc.. Bentonite deep processing for preparing P-type zeolite [ J]Chemical minerals and processing, 2007,36 (1): 6-8.) bentonite is used as raw material, high-pressure activation is carried out for 3h at 150 ℃ to obtain precursor, and Al is formed according to system mol composition 2 O 3 : 2.3SiO 2 :3Na 2 O:190H 2 And (3) mixing the materials, aging for 8h at 90 ℃, adding a small amount of 4A zeolite seed crystals, and then sealing and crystallizing for 6h at 85 ℃ to obtain a solid-phase product, namely the P-type molecular sieve. Liu Zhenlu et al (Liu Zhenlu, caojilin, liu Xiuwu, et al. Synthesis and use of Fe-doped P-type molecular sieves [ J ]]Artificial crystallography, 2016, 38 (05).) using a hydrothermal synthesis method, with a molar composition of 5Na 2 O:Al 2 O 3 :8SiO 2 :xFe 3+ :(116～156)H 2 And O is mixed, stirred into a colloid at room temperature, and crystallized for 20 hours at 100 ℃ to synthesize three P-type molecular sieves with different doped iron contents. Du Yuche et al (Du Y, shi S, dai H. Water-bathing synthesis of high-surface-area zeolite P from kinetic [ J]Particuology, 2011, 9 (2): 174-178.) with diatomaceous earth, sodium hydroxide and aluminum hydroxide as precursors, al is present in molar composition 2 O 3 :7.4SiO 2 : 1.94Na 2 O:155.38H 2 And O, mixing the materials, and reacting in a constant-temperature water bath at 90 ℃ for 6 to 24h to synthesize the P-type molecular sieve.
In order to overcome the defects of the traditional hydrothermal method for synthesizing the P-type molecular sieve, the development of a green synthesis process of the P-type molecular sieve becomes a focus of research of the majority of researchers.Tang Qi et al (Tang Q, ge Y, wang K T, et al, preparation of a porous P-type zeolite with a Suspension solid method [ J ]]Materials Letters, 2015, 161, 558-560.) porous P-type molecular sieve spheres were prepared from kaolin as a starting material by crystallization at 140 ℃ for 10h using a suspension solidification method and an in-situ hydrothermal method. Lenivaldo V. Sousa et al (Sousa L V D, silva A O S, silva B J B, et al, preparation of zeolite P by purification and recovery of zeolites ZSM-22 and ZSM-35[ J ], []Materials Letters, 2018, 217) proposes a new method for obtaining a P-type molecular sieve by dissolving and recrystallizing ZSM-22 zeolite and ZSM-35 zeolite, wherein the initially synthesized molecular sieve is H-shaped, is placed in NaOH solution at 100 ℃, is further desilicated and is then recrystallized for 20H to obtain the P-type molecular sieve. Chen Yiqin et al (Chen Yiqin, calumniate chang yu, peng Zhaoxia, et al research on microwave-assisted synthesis of zeolite molecular sieves from coal gangue [ J]Coal chemical industry, 2019, 47 (01): 59-63) coal gangue is used as a main raw material, two different heating modes of traditional water bath heating and microwave-assisted heating are selected to synthesize the P-type molecular sieve, the crystallization time in the process is only 30 to 40min, but the product purity is low. Liu Yi et al (Liu Yi, yan Chunjie, zhao Jinjie, et al. Synthesis of Zeolite P1 from flash unit solution-free conditions for ammonium removal from water [ J]Journal of Cleaner Production,2018,202) a solventless process was used to mix fly ash with Na 2 SiO 3 ·9H 2 O is prepared according to a molar composition of 1.5Na. The calcium ion exchange capacity of the P-type molecular sieve product prepared by the conventional hydrothermal method is generally between 300 and 355 mg CaCO 3 ·g -1 Dry zeolite with a magnesium ion exchange capacity of about 100mg MgCO 3 ·g -1 Research on preparation of P-type molecular sieve by activating dry zeolite (Li Chunxu. Bentonite with alkaline process [ D)]The university of north river industry, 2004; kong Deshun, jiang Rongli, chen Wenlong, etc. coal series kaolin twice calcined hydrothermal synthesis of P type molecular sieve [ J]Chemical minerals and processing, 2007,36 (6): 23-25.; paramicrantha, zhang Suiying, ma Gongchao, et al, synthesis of P-type molecular sieve from rice hull ash [ J]University of Dalian Industrial science 2011,30 (2): 133-136.; yang Jun hydrothermal synthesis of P-type from rice hull and silicon sourceStudy of molecular sieves [ J]Environmental pollution and control, 2011,33 (6): 23-25.; kong Deshun, li Lin, fan Jiaxin, etc. preparation of P-type molecular sieve from high-iron high-silicon coal gangue]Silicate report, 2013 (6). At present, various improved and optimized schemes are provided for the process for synthesizing the P-type molecular sieve by the traditional hydrothermal method, but the defects of long synthesis time, high liquid-solid ratio, low raw material utilization rate, low product exchange performance and the like still exist, so the invention aims to provide a method for quickly synthesizing the P-type molecular sieve with high calcium and magnesium ion exchange performance, which has certain innovation.
Disclosure of Invention
The invention aims at the problem of large water consumption (n (H) in the traditional process for synthesizing the P-type molecular sieve by a hydrothermal method 2 O)/n(SiO 2 ) The method has the advantages of =21 to 83), long synthesis period (6 to 24h), low raw material utilization rate and difficult mother liquor treatment, and provides a method for rapidly synthesizing the P-type molecular sieve with high calcium and magnesium ion exchange performance by a solid-phase-like method. The method firstly uses Na 2 SiO 3 ·9H 2 O、Al 2 (SO 4 ) 3 ·18H 2 O and a suitable amount of H 2 Preparing silicon-aluminum xerogel by an O mixing one-step method; then NaOH and H are added 2 And O, obtaining a high-concentration synthesis system, and statically crystallizing to obtain the P-type molecular sieve with uniform appearance and good crystallization. The process combines the double advantages of the solid-liquid bidirectional conversion process to successfully realize the rapid synthesis of the P-type molecular sieve with high calcium-magnesium ion exchange performance, compared with the traditional hydrothermal method, the synthesis period is shortened by about 2~8 times, the system solvent consumption is reduced by about 11.9-77.7%, the problems of low raw material utilization rate, difficult mother liquor treatment and the like are effectively solved, and a new idea is provided for the rapid synthesis of the P-type molecular sieve.
The technical scheme of the invention is as follows:
a method for rapidly synthesizing a P-type molecular sieve with high calcium and magnesium ion exchange performance by a solid-like phase method comprises the following steps:
(1) Mixing Na 2 SiO 3 ·9H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Mixing the solid O, adding water to dissolve the solid O, heating to 60-80 ℃, and uniformly stirring to obtain a gel solution;
wherein the molar ratio is n (Na) 2 SiO 3 ·9H 2 O):n(Al 2 (SO 4 ) 3 ·18H 2 O):n(H 2 O)=5:1:(46.3~185)；
(2) Filtering the gel solution obtained in the step (1), and washing a filter cake by deionized water until no SO is generated 4 2- Drying to obtain silicon-aluminum xerogel; the filtrate is evaporated and crystallized to obtain Na 2 SO 4 A crystal;
(3) Mixing water, silicon-aluminum xerogel and NaOH to prepare reaction slurry, placing the reaction slurry in a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and statically crystallizing the reaction slurry for 1 to 5h at a constant temperature of 120-160 ℃;
wherein the mass ratio of m (xerogel), m (NaOH) and m (H) 2 O) =8:(0.96~2.06):(17.1~42.9)。
(4) And (4) filtering and drying the product obtained in the step (3) to obtain the P-type molecular sieve.
And (3) drying in the step (2) or (4) for 2 to 3.5 hours at the temperature of 100 to 110 ℃.
The invention has the beneficial effects that:
the invention adopts a solid-like phase method, takes silica-alumina xerogel as a silica-alumina source and sodium hydroxide as an alkali source, and quickly and efficiently synthesizes the P-type molecular sieve with high calcium-magnesium ion exchange performance. The method greatly reduces the consumption of water in a synthesis system, shortens the crystallization time, improves the utilization rate of raw materials, optimizes the mother liquor treatment process, and has the characteristics of simple process, easy realization of industrialization and remarkable economic advantages. In addition, the invention applies a solid-liquid bidirectional conversion mechanism and provides a new idea for rapidly synthesizing the P-type molecular sieve.
The beneficial effects are embodied in that:
(1) For a long time, the synthesis method of the P-type molecular sieve is mainly a hydrothermal method, and the synthesis system generally uses a large amount of water (n (H) 2 O)/n(SiO 2 ) 21 to 83), which undoubtedly causes the problems of low utilization rate of raw materials, difficult mother liquor circulation and the like. If can reduce the system water consumption, not only can solve water waste and the difficult processing scheduling problem of mother liquor, can also effectively reduce the autogenous pressure of reaction system and reation kettle's material requirement. Class of the inventionThe solid phase method quickly and efficiently synthesizes the P-type molecular sieve with high calcium and magnesium ion exchange performance, the solvent consumption in the synthesis system is reduced by about 11.9-77.7% compared with the traditional hydrothermal method, the defect of excessive water consumption in the traditional hydrothermal method is greatly improved, and an effective solution is provided for efficiently synthesizing the P-type molecular sieve.
(2) In the existing molecular sieve synthesis method, a hydrothermal method generally has a short induction period and a long growth period, while a solid phase synthesis method generally has a long induction period and a short growth period, and the crystallization periods of the two methods are both long comprehensively, and the synthesis period of the current traditional hydrothermal method is generally 6 to 24h. The method combines the double advantages of short induction period of the hydrothermal method and short growth period of the solid phase method, shortens the synthesis period by about 2~8 times compared with the traditional hydrothermal method, greatly reduces the water content of a synthesis system, improves the crystallization rate and the utilization rate of raw materials, and effectively solves the problems of difficult mother liquor treatment and the like.
(3) The calcium and magnesium ion exchange capacities of the product obtained by the invention can reach respectively 410mgCaCO 3 ·g -1 Dried Zeolite above and 160mg MgCO 3 ·g -1 The calcium ion exchange capacity of the P-type molecular sieve product prepared by the traditional hydrothermal synthesis is generally between 300 and 355 mg CaCO 3 ·g -1 Dry zeolite having a magnesium ion exchange capacity of about 100mg MgCO 3 ·g -1 A dry zeolite. The P-type molecular sieve synthesized by the solid-like phase method can effectively optimize the calcium and magnesium ion exchange performance of the P-type molecular sieve product and improve the calcium and magnesium ion exchange capacity of the P-type molecular sieve product.
Drawings
FIG. 1 is an XRD spectrum and SEM of a silica-alumina xerogel of example 1~6; wherein, fig. 1a is an XRD spectrogram of the silica-alumina xerogel; fig. 1b is an SEM image of a silica-alumina xerogel.
FIG. 2 is an XRD spectrum of the product P-type molecular sieve of example 1~6.
FIG. 3 is an SEM picture of a P-type molecular sieve product of example 1.
FIG. 4 is an SEM picture of a P-type molecular sieve product of example 2.
FIG. 5 is an SEM picture of a P-type molecular sieve product of example 3.
FIG. 6 is an SEM picture of a P-type molecular sieve product of example 4.
FIG. 7 is an SEM picture of a P-type molecular sieve product of example 5.
FIG. 8 is an SEM picture of a P-type molecular sieve product of example 6.
Detailed Description
Specific examples of the present invention will now be described.
Example 1: the specific operation is as follows
(1) Mixing Na 2 SiO 3 ·9H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Mixing the O solid, adding a proper amount of water for dissolving, heating to 65 ℃, and stirring for 3min to obtain a gel solution;
wherein, the molar composition n (Na) 2 SiO 3 ·9H 2 O):n(Al 2 (SO 4 ) 3 ·18H 2 O):n(H 2 O)=5:1:92.54。
(2) Filtering the gel liquid obtained in the step (1), and washing the gel liquid by using deionized water until no SO exists 4 2- (a small amount of the final washing solution was taken in a test tube and 1ml of 0.2 mol/L BaCl was added dropwise 2 The solution can be washed if no white precipitate appears), and the solid phase product is dried for 3 hours at 100 ℃ to obtain the silica-alumina xerogel (the XRD spectrogram and the SEM image are shown in figure 1);
(3) Mixing water, silicon-aluminum xerogel and NaOH to prepare reaction slurry, transferring the reaction slurry into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and statically crystallizing the reaction slurry for 3 hours in a constant-temperature drying box at 140 ℃;
wherein the mass ratio m (xerogel), m (NaOH) and m (H) 2 O)=8:1.78:28.6。
(4) And (4) filtering the product obtained in the step (3), and drying at 100 ℃ for 3 hours to obtain the P-type molecular sieve with uniform appearance and good crystallization.
(5) And (4) carrying out calcium and magnesium ion exchange capacity test on the P-type molecular sieve product obtained in the step (4):
50ml of 0.05mol/L calcium chloride solution is diluted by 10 times and transferred into a 1000ml three-neck flask, and 0.5g P type molecular sieve product is accurately weighed and added. Mechanically stirring at room temperature for 30min to reach adsorption balance, centrifuging the solid phase and the liquid phase, measuring the calcium ion concentration in the liquid phase, and calculating the calcium ion exchange capacity of the P-type molecular sieve product. (the method for measuring the magnesium ion exchange capacity is the same as the method for measuring the calcium ion exchange capacity described above)
The XRD spectrum of the product is shown as P-1 in figure 2. The morphology is shown in fig. 3, and at this time, the product has a single crystal grain structure and a large surface roughness of the crystal grain. The exchange capacities of calcium and magnesium ions of the product under the condition are 413.04mgCaCO 3 ·g -1 Dry zeolite and 163.27mg MgCO 3 ·g -1 A dry zeolite.
Example 2: the specific operation is as follows
(1) Mixing Na 2 SiO 3 ·9H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Mixing the O solid, adding a proper amount of water for dissolving, heating to 65 ℃, and stirring for 3min to obtain a gel solution;
wherein, the molar composition n (Na) 2 SiO 3 ·9H 2 O):n(Al 2 (SO 4 ) 3 ·18H 2 O):n(H 2 O)=5:1:92.54。
(2) Filtering the gel liquid obtained in the step (1), and washing the gel liquid by using deionized water until no SO exists 4 2- (a small amount of the final washing solution was taken in a test tube and 1ml of 0.2 mol/L BaCl was added dropwise 2 The solution can be washed if no white precipitate appears), and the solid phase product is dried for 3 hours at 100 ℃ to obtain silicon-aluminum xerogel;
(3) Mixing water, silicon-aluminum xerogel and NaOH to prepare reaction slurry, transferring the reaction slurry into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and statically crystallizing the reaction slurry for 3 hours in a constant-temperature drying box at 140 ℃;
wherein the mass ratio m (xerogel), m (NaOH) and m (H) 2 O)=8:1.51:28.6。
(4) And (4) filtering the product obtained in the step (3), and drying at 100 ℃ for 3 hours to obtain the P-type molecular sieve with uniform appearance and good crystallization.
(5) Same as in example 1.
The XRD spectrum of the product is shown as P-2 in figure 2. The morphology is as shown in FIG. 4The product is shown to be coarse and small but non-uniform in particle size. The exchange capacity of calcium and magnesium ions of the product is 361.54mgCaCO 3 ·g -1 Dry zeolite and 141.31mg MgCO 3 ·g -1 A dry zeolite.
Example 3: the specific operation is as follows
(1) Mixing Na 2 SiO 3 ·9H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Mixing the O solid, adding a proper amount of water for dissolving, heating to 65 ℃, and stirring for 3min to obtain a gel solution;
wherein, the molar composition n (Na) 2 SiO 3 ·9H 2 O):n(Al 2 (SO 4 ) 3 ·18H 2 O):n(H 2 O)=5:1:92.54。
(2) Filtering the gel liquid obtained in the step (1), and washing the gel liquid by using deionized water until no SO exists 4 2- (a small amount of the final washing solution was taken in a test tube and 1ml of 0.2 mol/L BaCl was added dropwise 2 The solution can be washed if no white precipitate appears), and the solid phase product is dried for 3 hours at 100 ℃ to obtain silicon-aluminum xerogel;
(3) Mixing water, silicon-aluminum xerogel and NaOH to prepare reaction slurry, transferring the reaction slurry into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and statically crystallizing the reaction slurry for 3 hours in a constant-temperature drying box at 130 ℃;
wherein the mass ratio m (xerogel), m (NaOH) and m (H) 2 O)=8:1.78:28.6。
(4) And (4) filtering the product obtained in the step (3), and drying at 100 ℃ for 3 hours to obtain the P-type molecular sieve with uniform appearance and good crystallization.
(5) Same as in example 1.
The XRD spectrum of the product is shown as P-3 in figure 2. The morphology is shown in FIG. 5, the product has uniform particle size, and part of the product has crystal grains adhered to each other to form polymer. The exchange capacities of calcium and magnesium ions in this case were 307.45mgCaCO, respectively 3 ·g -1 Dry zeolite and 122.61mg MgCO 3 ·g -1 A dry zeolite.
Example 4: the specific operation is as follows
(1) Mixing Na 2 SiO 3 ·9H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Mixing the O solid, adding a proper amount of water for dissolving, heating to 65 ℃, and stirring for 3min to obtain a gel solution;
wherein, the molar composition n (Na) 2 SiO 3 ·9H 2 O):n(Al 2 (SO 4 ) 3 ·18H 2 O):n(H 2 O)=5:1:92.54。
(2) Filtering the gel liquid obtained in the step (1), and washing the gel liquid by using deionized water until no SO exists 4 2- (a small amount of the final washing solution was taken in a test tube and 1ml of 0.2 mol/L BaCl was added dropwise 2 The solution can be washed if no white precipitate appears), and the solid phase product is dried for 3 hours at 100 ℃ to obtain silicon-aluminum xerogel;
(3) Mixing water, silicon-aluminum xerogel and NaOH to prepare reaction slurry, transferring the reaction slurry into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and statically crystallizing the reaction slurry for 3 hours in a constant-temperature drying box at 150 ℃;
wherein the mass ratio m (xerogel), m (NaOH) and m (H) 2 O)=8:1.78:28.6。
(4) And (4) filtering the product obtained in the step (3), and drying at 100 ℃ for 3 hours to obtain the P-type molecular sieve with uniform appearance and good crystallization.
(5) Same as in example 1.
The XRD spectrum of the product is shown as P-4 in figure 2. The appearance of the product is shown in figure 6, the product is of an irregular spherical structure, and certain adhesion phenomenon exists among crystal grains. The exchange capacity of calcium and magnesium ions of the product is 326.42mgCaCO 3 ·g -1 Dry zeolite and 127.08mg MgCO 3 ·g -1 A dry zeolite.
Example 5: the specific operation is as follows
(1) Mixing Na 2 SiO 3 ·9H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Mixing the O solid, adding a proper amount of water for dissolving, heating to 65 ℃, and stirring for 3min to obtain a gel solution;
wherein, the molar composition n (Na) 2 SiO 3 ·9H 2 O):n(Al 2 (SO 4 ) 3 ·18H 2 O):n(H 2 O)=5:1:92.54。
(2) Filtering the gel liquid obtained in the step (1), and washing the gel liquid by using deionized water until no SO exists 4 2- (a small amount of the final washing solution was taken in a test tube and 1ml of 0.2 mol/L BaCl was added dropwise 2 The solution can be washed if no white precipitate appears), and the solid phase product is dried for 3 hours at 100 ℃ to obtain silicon-aluminum xerogel;
(3) Mixing water, silicon-aluminum xerogel and NaOH to prepare reaction slurry, transferring the reaction slurry into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and statically crystallizing the reaction slurry for 2 hours in a constant-temperature drying box at 140 ℃;
wherein the mass ratio m (xerogel), m (NaOH) and m (H) 2 O)=8:1.78:28.6。
(4) And (4) filtering the product obtained in the step (3), and drying at 100 ℃ for 2 hours to obtain the P-type molecular sieve with uniform appearance and good crystallization.
(5) Same as in example 1.
The XRD spectrum of the product is shown as P-5 in figure 2. The morphology is shown in FIG. 7, the product has smaller grain diameter, and the surface of the crystal grain is more compact, and has more obvious adhesion phenomenon. The exchange capacity of calcium and magnesium ions of the product is 326.42mgCaCO 3 ·g -1 Dry zeolite and 127.08mg MgCO 3 ·g -1 A dry zeolite.
Example 6: the specific operation is as follows
(1) Mixing Na 2 SiO 3 ·9H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Mixing the O solid, adding a proper amount of water for dissolving, heating to 65 ℃, and stirring for 3min to obtain a gel solution;
wherein, the molar composition n (Na) 2 SiO 3 ·9H 2 O):n(Al 2 (SO 4 ) 3 ·18H 2 O):n(H 2 O)=5:1:92.54。
(2) Filtering the gel liquid obtained in the step (1), and washing the gel liquid by using deionized water until no SO exists 4 2- (A small amount of the final wash was taken in a test tube and 1ml of 0.2 mol/L B was added dropwiseaCl 2 The solution can be washed if no white precipitate appears), and the solid phase product is dried for 3 hours at 100 ℃ to obtain silicon-aluminum xerogel;
(3) Mixing water, silicon-aluminum xerogel and NaOH to prepare reaction slurry, transferring the reaction slurry into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and statically crystallizing for 4 hours in a constant-temperature drying box at 140 ℃;
wherein the mass ratio m (xerogel), m (NaOH) and m (H) 2 O)=8:1.78:28.6。
(4) And (4) filtering the product obtained in the step (3), and drying at 100 ℃ for 3 hours to obtain the P-type molecular sieve with uniform appearance and good crystallization.
(5) Same as in example 1.
The XRD spectrum of the product is shown as P-6 in figure 2. The morphology is shown in fig. 8, and the product morphology is typical coarse pellets, and the grains are single but the grain size is slightly larger. The exchange capacity of calcium and magnesium ions of the product is 417.35mgCaCO 3 ·g -1 Dry zeolite and 164.17mg MgCO 3 ·g -1 A dry zeolite.
The above examples are merely preferred embodiments of the present invention, and are not intended to limit the present invention in any way and in any way, and are within the skill of those in the art.
Claims (1)
1. A method for rapidly synthesizing a P-type molecular sieve with high calcium and magnesium ion exchange performance by a solid-like phase method is characterized by comprising the following steps:
(1) Mixing Na 2 SiO 3 ·9H 2 O and Al 2 (SO 4 ) 3 ·18H 2 Mixing the O solid, adding water to dissolve the O solid, heating the mixture to 60-80 ℃, and uniformly stirring the mixture to obtain a gel solution;
wherein the molar ratio is n (Na) 2 SiO 3 ·9H 2 O):n(Al 2 (SO 4 ) 3 ·18H 2 O):n(H 2 O)＝5:1:(46.3～185)；
(2) Filtering the gel solution obtained in the step (1), and washing a filter cake by deionized water until no SO is generated 4 2- Drying to obtain silicon-aluminum xerogel; the filtrate is evaporated and crystallized to obtain Na 2 SO 4 A crystal;
(3) Mixing water, silicon-aluminum xerogel and NaOH to prepare reaction slurry, placing the reaction slurry in a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and statically crystallizing the reaction slurry for 1 to 5 hours at a constant temperature of between 120 and 160 ℃;
wherein the mass ratio of m (xerogel), m (NaOH) and m (H) 2 O)＝8:(0.96～2.06):(17.1～42.9)；
(4) Filtering and drying the product obtained in the step (3) to obtain the P-type molecular sieve;
the drying conditions in the step (2) or (4) are all drying for 2 to 3.5 hours at the temperature of between 100 and 110 ℃.
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| CN109553114A (en) * | 2019-01-16 | 2019-04-02 | 河北工业大学 | A kind of method of the full potassium W molecular sieve of gel-like solid phase method rapid synthesis |
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| CN109553114A (en) * | 2019-01-16 | 2019-04-02 | 河北工业大学 | A kind of method of the full potassium W molecular sieve of gel-like solid phase method rapid synthesis |
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| 洗涤助剂用硅铝酸盐制备;郑爱玲等;《离子交换与吸附》;20100620(第03期);全文 * |
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