CN212369938U - Film-making liquid production device of NaA molecular sieve membrane and preparation device of molecular sieve membrane - Google Patents
Film-making liquid production device of NaA molecular sieve membrane and preparation device of molecular sieve membrane Download PDFInfo
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Abstract
The utility model relates to a film-forming liquid apparatus for producing of NaA molecular sieve membrane and preparation facilities of molecular sieve membrane belong to molecular sieve membrane preparation technical field. Including membrane forming liquid apparatus for producing and hydrothermal synthesis cauldron (13), membrane forming liquid apparatus for producing include: the batching kettle (6) is used for preparing membrane preparation liquid; the stirring device (9) is arranged inside the batching kettle (6) and is used for stirring the membrane preparation liquid; the variable frequency motor (1) is connected with the stirring device (9) and is used for rotating the stirring device (9); the frequency converter (2) is connected with the variable frequency motor (1) and is used for controlling the rotating speed of the variable frequency motor (1); the batching kettle jacket (7) is positioned on the outer wall of the batching kettle (6) and is used for cooling the membrane-making liquid; the delivery pump (4), the batching kettle jacket (7) and the condenser are connected in sequence to form a closed pipeline. Compared with the NaA molecular sieve inner membrane synthesized at home and abroad, the NaA molecular sieve membrane synthesized by the method has high repeatability and excellent performance.
Description
Technical Field
The utility model relates to a film-forming liquid apparatus for producing of NaA molecular sieve membrane and preparation facilities of molecular sieve membrane belong to molecular sieve membrane preparation technical field. In particular to a method for preparing NaA molecular sieve membrane preparation solution, which is also suitable for preparing other molecular sieve membranes.
Background
The pervaporation membrane separation technology is used for organic solvent dehydration, has the advantages of remarkable energy conservation and emission reduction, and is particularly suitable for separation of azeotropic and near-boiling mixtures. The effective aperture of the NaA molecular sieve membrane is 0.41 nm, is larger than the diameter of water molecules and smaller than the diameter of most organic molecules, has strong hydrophilicity, and is particularly suitable for pervaporation dehydration of organic solvents. The NaA molecular sieve membrane has attracted extensive attention due to the excellent performance in the aspect of pervaporation dehydration, and since the early 90 s of the last century, a plurality of researchers at home and abroad are dedicated to the development of the preparation and application technology of the NaA molecular sieve membrane, and the NaA molecular sieve membrane has been in the history of nearly twenty years. At present, NaA molecular sieve membrane pervaporation dehydration technology has many application examples, and a commercial membrane and a complete set thereof are sold internationally.
In 1999, Mitsui Shipbuildng corporation of Japan developed NaA molecular sieve membrane products by using the patent technology taught by Kita of university of Hill, Japan, and the NaA molecular sieve membrane pervaporation dehydration technology was first put to industrial application, and the first set of NaA molecular sieve membrane industrial dehydration device was established. The device consists of 16 membrane modules, each membrane module comprises 125 membrane tubes, the structures and the layouts of the modules are shown in fig. 1-7, when the treatment capacity is 600L/h at 120 ℃, absolute ethyl alcohol can be prepared by dehydrating 90 wt.% of waste ethyl alcohol solution, and the water content in a product is lower than 0.2 wt.%. Subsequently, Mitsui company has successively established more than 60 sets of NaA molecular sieve membrane pervaporation devices, which are widely applied to the fields of chemical industry, medicine, food, microelectronics and the like. From 2002, GFT in germany developed an ethanol dehydration process using NaA molecular sieve membrane manufactured by Mitsui in japan, and established a large pervaporation dehydration apparatus. The Inocermic company in Germany also successfully develops a four-channel NaA molecular sieve membrane product with high performance. Currently, only a few companies, such as Mitsui, Inocermic, germany, and Smart, uk, are internationally available for commercial production of NaA molecular sieve membranes.
The research and application of the NaA molecular sieve membrane in China are relatively late, and in recent years, the NaA molecular sieve membrane is widely concerned and rapidly developed by researchers. In 2009, the Nanjing industry university and the Nanjing Jiuxisi high-tech limited company collaborated to build an industrial production line for producing 12 ten thousand tubes of support bodies every year, and the large-scale production of the molecular sieve membrane in China is realized. 2011, combined with social financing, the high-tech company of nine days in Jiangsu was established to 10000 m2A NaA molecular sieve membrane large-scale production line in one year is specially used for the production, application and popularization of molecular sieve membranes, and more than 200 sets of pervaporation and steam permeation dehydration devices are successfully designed and put into use.
However, in the prior art, there is an urgent need for further improvement of the separation effect of NaA molecular sieve membranes after membrane formation.
SUMMERY OF THE UTILITY MODEL
The utility model discloses discover after the research: in the process of preparing the synthetic liquid of the molecular sieve membrane, the temperature rise caused by violent stirring can promote the reaction of the aluminum source and the silicon source, can cause the reduction of effective components in the membrane preparation liquid substantially, and leads to the reduction of the effective components in the membrane preparation process, thereby influencing the overall performance of the NaA molecular sieve membrane. The utility model discloses further discover, if stir the processing to the membrane making solution of NaA molecular sieve membrane in temperature or the time of short on the high side, because the crystal nucleus does not form in a large number to influence the growth rate of hydrothermal crystallization in-process NA molecular sieve crystal, consequently the utility model discloses the discovery is through adopting ageing treatment membrane making solution under the low temperature and the low-speed stirring, can improve the quality of membrane making effectively.
Based on the discovery above, the utility model discloses a technical scheme is:
the utility model discloses a first aspect provides:
a preparation method of a NaA molecular sieve membrane comprises the following steps:
preparing a molecular sieve membrane synthetic solution;
coating molecular sieve crystal seeds on the surface of a support body;
carrying out hydro-thermal synthesis on the NaA molecular sieve membrane in the synthetic solution by using the support body coated with the seed crystal;
wherein, the preparation process of the molecular sieve membrane synthetic fluid comprises the following steps: adding silicon source and aluminum source raw materials into a reactor, stirring at a high speed for a period of time under the action of cooling, and stirring at a low speed for a period of time under the action of cooling to obtain a synthetic liquid.
In one embodiment, high speed stirring means a rotation speed of 5000 to 100000 n/min, preferably 5000 to 10000 n/min.
In one embodiment, the low speed stirring is a rotation speed of 0 to 5000 n/min, preferably 1000 to 3000 n/min.
In one embodiment, the high-speed stirring time is 0.01-5 hours, preferably 0.5-2 hours; the low-speed stirring time is 5-48 h, preferably 12-16 h.
In one embodiment, the agitation process employs a high speed emulsifier, paddle agitator, or frame agitator.
In one embodiment, the temperature during high speed stirring is controlled at (50-100 deg.C) and the temperature during low speed stirring is controlled at (15-50 deg.C).
In one embodiment, the cooling effect is achieved by using a recirculating cooling system in which the cooling fluid is tap water, brine or an aqueous glycol solution.
In one embodiment, the material of the support is selected from alumina, zirconia, or titania or mullite, and the type of the support is one of a sheet type, a tubular type or a hollow fiber.
In one embodiment, the method for coating the molecular sieve seeds is selected from dip coating, wiping, vacuum suction or ultrasonic seed coating, the NaA molecular sieve seeds are coated on the outer surface or the inner surface of the porous support body, and the average particle size of the NaA molecular sieve seeds is 0.1-10 μm, preferably 0.2-3 μm; the concentration of the NaA type molecular sieve seed crystal suspension is 1-100 g/L, preferably 2.5-20 μm.
In one embodiment, the composition ratio in the synthetic fluid is: SiO2, Al2O3, Na2O, H2O =1, (0.2-2), (0.5-4) and (15-500).
The second aspect of the present invention provides:
a film-making liquid apparatus for producing of NaA molecular sieve membrane, includes:
the material preparation kettle is used for preparing membrane preparation liquid;
the stirring device is arranged in the batching kettle and is used for stirring the membrane preparation liquid;
the variable frequency motor is connected with the stirring device and is used for rotating the stirring device;
the frequency converter is connected with the variable frequency motor and is used for controlling the rotating speed of the variable frequency motor;
the batching kettle jacket is positioned on the outer wall of the batching kettle and used for cooling the membrane making liquid;
the delivery pump, the batching kettle jacket and the condenser are connected in sequence to form a closed pipeline.
In one embodiment, a feed valve is further provided on the batching kettle for controlling the addition of material to the batching kettle.
In one embodiment, a discharge valve is further arranged on the batching kettle and used for controlling the discharge of materials in the batching kettle.
The third aspect of the present invention provides:
a preparation device of a NaA molecular sieve membrane comprises the membrane preparation liquid production device and a hydrothermal synthesis kettle.
In one embodiment, the hydrothermal synthesis kettle is further provided with a molecular sieve membrane tube.
In one embodiment, in the membrane-forming liquid production device, the stirring device is internally provided with a hollow structure filled with a heat conduction medium, the hollow structure is also provided with an evaporation tube filled with a heat pump working medium, and two ends of the evaporation tube are respectively connected with a working medium outlet and a working medium inlet; the hydrothermal synthesis kettle is provided with a heater, the outer wall of the hydrothermal synthesis kettle is provided with a synthesis kettle jacket, a condensing pipe is arranged inside the synthesis kettle jacket, one end of the condensing pipe is connected with a working medium outlet through an expansion valve, and the other end of the condensing pipe is connected with a working medium inlet through a compressor.
The fourth aspect of the present invention provides:
the NaA molecular sieve membrane preparation device is applied to preparation of molecular sieve membranes.
In one embodiment, the NaA molecular sieve membrane is used to improve the selective separation or water permeation flux of an organic solvent dehydration process of a molecular sieve membrane.
Advantageous effects
Adopt the utility model discloses technical scheme synthesizes out the NaA molecular sieve membrane that length is 800mm, and the dehydration performance shows through pervaporation technology representation result, is 70 ℃ at operating temperature, and when the feed liquid is 10 wt.% ethanol/water solution system for water content, the separation factor of this membrane>10000, flux>2.5 kg·h–1·m–2And has high selectivity and permeation flux. Compared with the prior art, the utility model discloses creatively proposes the cooling cycle and the frequency conversion stirring that utilize the batching cauldron, has solved the temperature rise that exists and the problem of ageing in preparation NaA molecular sieve membrane solution preparation process to this method is simple, easy going. Utilize the utility model discloses a synthetic NaA molecular sieve membrane of method compares with the performance of the synthetic NaA molecular sieve inner membrance at home and abroad, and the repeatability is high, excellent performance, simultaneously because the medicine that the membrane was used is the industrial grade raw materials for the membrane cost reduces by a wide margin, is fit for large-scale industrial production.
Drawings
FIG. 1 is a device for preparing a synthetic solution for membrane production provided by the present invention;
FIG. 2 is another apparatus for preparing a film-forming composition;
FIG. 3 is a schematic diagram of a hydrothermal synthesis reactor;
FIG. 4 is an electron micrograph of a NaA molecular sieve membrane prepared in example 1;
FIG. 5 is an electron micrograph of a NaA molecular sieve membrane prepared in example 1;
FIG. 6 is an electron micrograph of a NaA molecular sieve membrane prepared in example 5;
FIG. 7 is a result of characterization of XRD, in which (a) is an XRD pattern of the NaA molecular sieve membrane prepared in comparative example 1; (b) the curve is the XRD pattern of the NaA molecular sieve membrane prepared in example 5
Wherein, 1, a variable frequency motor; 2. a frequency converter; 3. a condenser; 4. a delivery pump; 5. a discharge valve; 6. a batching kettle; 7. a material mixing kettle jacket; 8. a feed valve; 9. a stirring device; 10. an evaporation tube; 11. a working medium outlet; 12. a working medium inlet; 13. a hydro-thermal synthesis kettle; 14. a molecular sieve membrane tube; 15. a synthesis kettle jacket; 16. an expansion valve; 17. a compressor; 18. a heater; 19. a condenser tube.
Detailed Description
The utility model discloses the technical problem that will solve is: in the prior art, in the preparation process of the NaA molecular sieve membrane, the temperature rise and the aging-free process are generated in the preparation process of a membrane preparation solution. Thereby influencing the formation of crystal nuclei and causing the problem of batch difference of the performance of the prepared molecular sieve membrane after membrane formation. The crystal nucleus amount of the NaA molecular sieve is increased by controlling the processes of cooling circulation and variable-frequency stirring in the burdening process. The first step in the preparation process of the NaA molecular sieve membrane is preparation of a membrane preparation solution, in order to better uniformly mix a silicon source and an aluminum source in the preparation process of the membrane preparation solution, vigorous stirring is required in the initial stirring process, and a large amount of heat is generated in the process, so that the temperature of the membrane preparation solution is continuously increased. With the increase of the temperature, the reaction of the aluminum source and the silicon source is accelerated, so that the effective components of the aluminum source and the silicon source are reduced in the preparation process of the membrane, and the overall performance of the NaA molecular sieve membrane is influenced. Furthermore, in the prior art, the stirring time of the film preparation solution of the NaA molecular sieve film is short (less than or equal to 2 hours), and in the short stirring process, a large amount of crystal nuclei are not formed, so that the growth rate of NA molecular sieve crystals in the hydrothermal crystallization process is influenced, and therefore, the long-time aging is favorable for the large amount of formation of the NaA molecular sieve crystal nuclei, so that the separation performance of the film is improved. In industrial production, the aging is carried out at low temperature and under low-speed stirring.
Based on the above findings, the process of the preparation method of the present invention mainly comprises: preparing a molecular sieve membrane synthetic solution; coating molecular sieve crystal seeds on the surface of a support body; and carrying out hydrothermal synthesis on the NaA molecular sieve membrane in the synthetic solution by using the support body coated with the seed crystal.
The preparation process of the molecular sieve membrane synthetic fluid comprises the following steps: adding silicon source and aluminum source raw materials into a reactor, stirring at a high speed for a period of time under the action of cooling, and stirring at a low speed for a period of time under the action of cooling to obtain a synthetic liquid.
In one embodiment, high speed stirring means a rotation speed of 5000 to 100000 n/min, preferably 5000 to 10000 n/min.
In one embodiment, the low speed stirring is a rotation speed of 0 to 5000 n/min, preferably 1000 to 3000 n/min.
In one embodiment, the high-speed stirring time is 0.01-5 hours, preferably 0.5-2 hours; the low-speed stirring time is 5-48 h, preferably 12-16 h.
In one embodiment, the agitation process employs a high speed emulsifier, paddle agitator, or frame agitator.
In one embodiment, the temperature during high speed stirring is controlled to be in the range of 40 to 100 deg.C, preferably 50 to 75 deg.C, and the temperature during low speed stirring is controlled to be in the range of 15 to 50 deg.C, preferably 25 to 40 deg.C.
In one embodiment, the cooling effect is achieved by using a recirculating cooling system in which the cooling fluid is tap water, brine or an aqueous glycol solution.
In one embodiment, the material of the support is selected from alumina, zirconia, or titania or mullite, and the type of the support is one of a sheet type, a tubular type or a hollow fiber.
In one embodiment, the method for coating the molecular sieve seeds is selected from dip coating, wiping, vacuum suction or ultrasonic seed coating, the NaA molecular sieve seeds are coated on the outer surface or the inner surface of the porous support body, and the average particle size of the NaA molecular sieve seeds is 0.1-10 μm, preferably 0.2-3 μm; the concentration of the NaA type molecular sieve seed crystal suspension is 1-100 g/L, preferably 2.5-20 μm.
The synthetic liquid comprises an aluminum source and a silicon source, the aluminum source is aluminum hydroxide, aluminum foil, aluminum powder, sodium metaaluminate or aluminum isopropoxide and the like, the silicon source is silica sol, sodium silicate, tetraethyl orthosilicate and the like, and the alkali is sodium hydroxide. The dosage and the proportion of the raw materials in the film-making liquid are different according to the aluminum source and the silicon source adopted and according to A12O3、SiO2、Na2O、H2The proportion of O is calculated by calculation; in one embodiment, the composition ratio in the synthetic fluid is: SiO2, Al2O3, Na2O, H2O =1, (0.2-2), (0.5-4) and (15-500). The synthesis temperature is 100-180 ℃, the crystallization time is 6-30 h, and the hydrothermal synthesis frequency is 1 time or multiple times. The aging temperature, the aging time, the synthesis temperature and the synthesis time of the membrane can be adjusted according to needs, and the microstructure of the membrane crystal with different appearances can be obtained by controlling the conditions, so that the change of the membrane flux is caused.
Based on the above method, the utility model also provides a preparation facilities of membrane-making liquid, as shown in figure 1:
the method comprises the following steps:
the batching kettle 6 is used for preparing membrane making liquid;
the stirring device 9 is arranged inside the batching kettle 6 and is used for stirring the membrane preparation liquid;
the variable frequency motor 1 is connected with the stirring device 9 and is used for rotating the stirring device 9;
the frequency converter 2 is connected with the variable frequency motor 1 and is used for controlling the rotating speed of the variable frequency motor 1;
the batching kettle jacket 7 is positioned on the outer wall of the batching kettle 6 and used for cooling the membrane preparation liquid;
the delivery pump 4, the batching kettle jacket 7 and the condenser are sequentially connected to form a closed pipeline;
and a feed valve 8 is also arranged on the batching kettle 6 and used for controlling the feeding of the materials into the batching kettle 6.
The batching kettle 6 is also provided with a discharge valve 5 for controlling the discharge of the materials in the batching kettle 6.
The frequency modulation rotating speed of the frequency converter 2 is 0-100000 n/min, and the stirring device 9 can work under the conditions of high-speed stirring and low-speed stirring, wherein the high-speed stirring refers to the rotating speed of 5000-100000 n/min, and preferably 5000-10000 n/min; the low-speed stirring is carried out at a rotating speed of 0-5000 n/min, preferably 1000-3000 n/min.
In addition, the production device of the membrane-making solution can also be matched with a hydrothermal synthesis device to form a production device of the NaA molecular sieve membrane.
As shown in fig. 2 and fig. 3, the utility model also provides a production device of NaA molecular sieve membrane, which is composed of a preparation device of membrane-making liquid in fig. 2 and a hydrothermal synthesis kettle in fig. 3, the hydrothermal synthesis kettle 13 is further provided with a molecular sieve membrane tube 14, in the membrane-making liquid production device, the interior of the stirring device 9 is a hollow structure filled with heat-conducting medium, the hollow structure is further provided with an evaporation tube 10 filled with heat pump working medium, the evaporation tube 10 is filled with heat pump working medium, and two ends of the evaporation tube 10 are respectively connected with a working medium outlet 11 and a working medium inlet 12; the hydrothermal synthesis kettle 13 is provided with a heater 18, the outer wall of the hydrothermal synthesis kettle 13 is provided with a synthesis kettle jacket 15, a condenser pipe 19 is arranged inside the synthesis kettle jacket 15, one end of the condenser pipe 19 is connected with the working medium outlet 11 through an expansion valve 16, and the other end of the condenser pipe 16 is connected with the working medium inlet 12 through a compressor 17.
In the second stage of the synthesis of the membrane-forming solution, the aging treatment needs to be performed under the conditions of slow stirring and low temperature, so that after the rotating speed of the stirring device 9 is reduced, the material in the membrane-forming solution cannot flow to a proper degree, the rapid and uniform cooling of the internal reaction solution cannot be realized when the temperature is reduced through the jacket, and the problem of uneven crystal nucleus of the membrane-forming solution is easily caused. Therefore, when the production device of the film-forming liquid is adopted, the stirring interior is a hollow structure, meanwhile, because the evaporation tube 10, the condenser tube 19, the expansion valve 16 and the compressor 17 inside form a closed cycle through the working medium outlet 11 and the working medium inlet 12, the closed pipeline is filled with heat pump working media (R122, R130, R152 and the like can be adopted), so that the closed pipeline and the closed pipeline form a heat pump cycle mutually, and when the heat pump is started, heat near the stirring device 9 can be rapidly conducted into the heat pump system through the evaporation tube 10 by a heat conducting medium (such as metal, heat conducting oil, alcohol and the like), then the heat is transferred to a condensing pipe 19 in the synthesis kettle jacket 15 through the circulation work of a heat pump system, the hydrothermal synthesis kettle 13 is supplied with heat by heat conduction to reach a desired temperature for hydrothermal synthesis. Therefore, by adopting the mode of directly obtaining heat from the stirring device 9, on one hand, the heat can still be directly absorbed from the reaction liquid under the condition of lower stirring rotating speed, on the other hand, the direct contact with the internal reaction liquid is also ensured, the uniformity of temperature reduction is improved, the aging effect of the reaction liquid is better, and the batch uniformity of the prepared molecular sieve membrane is obviously improved.
As right the utility model discloses further improvement, the utility model discloses at the in-process of preparation seed crystal suspension, still added the small-size graphite alkene after handling in suspension, can effectively improve the surface compactness of the molecular sieve membrane that the preparation obtained, can show and improve separation effect. The preparation method of the graphene comprises the following main steps: synthesizing graphene oxide by a Hummers method, synthesizing graphene by a thermal expansion method, and performing secondary reduction by sodium borohydride to obtain small-sized graphene; in this step, graphene is synthesized by an expansion method, and specific steps can be performed according to the prior art, such as: a key process and a reaction mechanism [ J ] of graphene synthesis by a Hummers method are adopted in Rexiameng, Wangyuan L, and He, 2013, 1 and 5; for the secondary reduction treatment of sodium borohydride, the reduction treatment can be performed according to the prior art, such as the following documents: preparation of graphene and characterization of the graphene [ J ] by a thermal expansion stripping method, namely Liuxianwu, yellow snow plum, Huayanli, and the like, and 2013, 36(2):23-25 of nonmetallic ore. After graphene is obtained, the graphene can be added into a suspension of NaA molecular sieve seed crystals, the graphene and the seed crystals can be loaded on the surface of a support body together in a crystal coating mode, and finally, a NaA molecular sieve membrane is obtained through a conventional hydrothermal synthesis method. The crystal coating time of the support body in the crystal seed liquid is 5-30 s, and the crystal seed coating method is a dip coating method, a wiping method, a vacuum suction method or an ultrasonic crystal seed coating method. The molecular sieve carrier can be selected from alumina, zirconia, titanium oxide or mullite, and the carrier is one of a sheet type, a tubular type and a hollow fiber type.
The NaA molecular sieve membrane prepared by the method has more uniform and compact surface, and improves water flux and separation factors applied to the solvent dehydration process.
Based on the above method, a typical preparation process is as follows:
s1: preparation of graphene
Firstly, graphene oxide is prepared by a Hummers method, graphene is prepared by a thermal expansion method, and the graphene is subjected to secondary reduction by sodium borohydride to obtain graphene with a smaller size.
S2: preparation of seed crystal suspension containing graphene
Dispersing NaA molecular sieve seed crystals in deionized water, and treating by ultrasonic waves to uniformly disperse the NaA molecular sieve seed crystals to obtain a NaA molecular sieve seed crystal suspension. Adding graphene into the NaA molecular sieve seed crystal suspension liquid which is uniformly dispersed, strongly stirring, and then carrying out ultrasonic treatment to obtain the seed crystal suspension liquid which is uniformly dispersed and contains the graphene. The sheet diameter of the added graphene is 5-10 mu m, and the adding content is 0.2-2 wt% of the mass of the seed crystal suspension. The average particle size of the NaA molecular sieve seed crystal is 1-4 mu m. The concentration of the NaA type molecular sieve seed crystal suspension is 0.5-2 g/L.
S3: precoated seed crystal
And (3) placing the porous support body in the seed crystal suspension containing graphene of S2, taking out, and placing in an oven for drying to obtain the seeded support body.
S4: synthetic NaA molecular sieve membrane
The NaA molecular sieve membrane preparation solution is prepared by the method. And (3) putting the crystal seed support prepared in the step (S3) into a reaction kettle, pouring a film preparation solution, carrying out hydrothermal synthesis reaction, taking out the membrane tube after the reaction is finished, adjusting the pH value with deionized water, and putting the membrane tube into an oven for drying to obtain the NaA molecular sieve membrane.
The NaA molecular sieve membrane prepared by the method is suitable for the dehydration process of the solvent, and the suitable organic solvent can be one or a mixture of more of amide solvents, alcohol solvents, nitrile solvents, amine solvents, ether solvents, aldehyde solvents or sulfone solvents. The molecular sieve membrane can show the advantages of improving filtration flux, good operation stability and good separation effect in the solvent dehydration process, and is mainly and directly used for neutral organic solvent dehydration, acidic organic solvent dehydration, separation and purification among organic solvents and the like.
The pervaporation performance test method of the molecular sieve membrane comprises the following steps: pervaporation performance of a membrane is generally determined by the flux of permeate through a unit membrane area per unit timeJ (kg/m2H) and a separation factor α, a andJis defined as follows:
in the formulay i Andy j respectively represent the mass fractions of organic matter and water on the permeation side,x i andx j respectively representing the mass fractions of organic matter and water in the raw material.
In the formulaΔMRepresents the permeate mass (kg),Sdenotes the membrane surface area (m)2)，tRepresents the permeation time (h).
Example 1
The synthesis solution was prepared using the apparatus shown in FIG. 1.
The composition ratio in the synthetic liquid is as follows: SiO2, Al2O3, Na2O, H2O =1:0.8:1.5: 300.
Adding sodium metaaluminate into sodium hydroxide and deionized water into a batching system in sequence through a charging hole, starting variable frequency high-speed stirring to 5000 n/min, starting a cooling circulating water system, and stirring for 5min to form an aluminum solution. Then adding sodium silicate solution to control the temperature of the synthetic liquid at 50 +/-1 ℃, stirring for 1h, adjusting a frequency converter to stir at a low speed for 2500 n/min to control the temperature of the synthetic liquid at 30 +/-1 ℃, stirring for 15 h, and then closing the frequency converter stirrer and the cooling circulating water system.
Step 2: preparation of seeded support
Weighing 10g of NaA molecular sieve seed crystal with the average particle size of about 2 mu m, dispersing the NaA molecular sieve seed crystal into 990 g of deionized water, placing the NaA molecular sieve seed crystal into a seed crystal tank on a stirrer, stirring for 10 hours, and then carrying out ultrasonic treatment for 30 min to obtain NaA type molecular sieve seed crystal suspension liquid, wherein the concentration of the seed crystal suspension liquid is 10 g/L; and (3) immersing the support body fixed on the support body support into the seed crystal suspension for 5s, taking out the support body support, and putting the support body support into an oven for drying for later use.
And step 3: preparing a NaA molecular sieve membrane, namely preparing a NaA molecular sieve membrane,
placing the seeded support obtained in the step 2 into a membrane reactor, conveying the membrane preparation solution obtained in the step 1 into the membrane reactor by using a conveying pump, heating for hydrothermal synthesis to start crystallization reaction, reacting at 120 ℃ for 4 hours, and taking out and cooling after the reaction is finished; washing with deionized water and drying to obtain the NaA molecular sieve membrane.
Example 2
The synthesis solution was prepared using the apparatus shown in FIG. 1.
The composition ratio in the synthetic liquid is as follows: SiO2: Al2O3: Na2O: H2O =1:1.5:1.2: 200.
Adding sodium metaaluminate into sodium hydroxide and deionized water into a batching system in sequence through a charging hole, starting variable frequency high-speed stirring to 10000n/min, starting a cooling circulating water system, and stirring for 5min to form an aluminum solution. Then adding sodium silicate solution to control the temperature of the synthetic liquid at 55 +/-1 ℃, stirring for 0.5 h, adjusting a frequency converter to stir at a low speed of 1500 n/min to control the temperature of the synthetic liquid at 35 +/-1 ℃, stirring for 23.5 h, and then closing the frequency converter stirrer and a cooling circulating water system
Step 2: preparation of seeded support
Weighing 5 g of NaA molecular sieve seed crystal with the average particle size of about 1 mu m, dispersing the NaA molecular sieve seed crystal into 990 g of deionized water, placing the NaA molecular sieve seed crystal into a seed crystal tank on a stirrer, stirring for 10 hours, and then carrying out ultrasonic treatment for 30 min to obtain NaA type molecular sieve seed crystal suspension liquid, wherein the concentration of the seed crystal suspension liquid is 5 g/L; and (3) immersing the support body fixed on the support body support into the seed crystal suspension for 5s, taking out the support body support, and putting the support body support into an oven for drying for later use.
And step 3: preparing a NaA molecular sieve membrane, namely preparing a NaA molecular sieve membrane,
placing the seeded support obtained in the step 2 into a membrane reactor, conveying the membrane preparation solution obtained in the step 1 into the membrane reactor by using a conveying pump, heating for hydrothermal synthesis to start crystallization reaction, and taking out and cooling after the reaction is finished; washing with deionized water and drying to obtain the NaA molecular sieve membrane.
Example 3
The synthesis solution was prepared using the apparatus shown in FIG. 1.
The composition ratio in the synthetic liquid is as follows: SiO2: Al2O3: Na2O: H2O =1: 2: 2: 120.
Adding sodium metaaluminate into sodium hydroxide and deionized water into a batching system in sequence through a charging hole, starting variable frequency high-speed stirring to 10000n/min, starting a cooling circulating water system, and stirring for 5min to form an aluminum solution. And then adding a sodium silicate solution, controlling the temperature of the synthetic liquid at 60 +/-1 ℃, stirring for 2 hours, adjusting a frequency converter to stir at a low speed for 2000 n/min, controlling the temperature of the synthetic liquid at 27 +/-1 ℃, stirring for 22 hours, and then closing the frequency converter stirrer and the cooling circulating water system.
Step 2: preparation of seeded support
Weighing 15 g of NaA molecular sieve seed crystal with the average particle size of about 3 mu m, dispersing the NaA molecular sieve seed crystal into 990 g of deionized water, placing the NaA molecular sieve seed crystal into a seed crystal tank on a stirrer, stirring for 10 hours, and then carrying out ultrasonic treatment for 30 min to obtain NaA type molecular sieve seed crystal suspension liquid, wherein the concentration of the seed crystal suspension liquid is 15 g/L; and (3) immersing the support body fixed on the support body support into the seed crystal suspension for 5s, taking out the support body support, and putting the support body support into an oven for drying for later use.
And step 3: preparing a NaA molecular sieve membrane, namely preparing a NaA molecular sieve membrane,
placing the seeded support obtained in the step 2 into a membrane reactor, conveying the membrane preparation solution obtained in the step 1 into the membrane reactor by using a conveying pump, heating for hydrothermal synthesis to start crystallization reaction, and taking out and cooling after the reaction is finished; washing with deionized water and drying to obtain the NaA molecular sieve membrane.
Example 4
The differences from example 1 are: the apparatus shown in fig. 2 and 3 is used.
The composition ratio in the synthetic liquid is as follows: SiO2, Al2O3, Na2O, H2O =1:0.8:1.5: 300.
Adding sodium metaaluminate into sodium hydroxide and deionizing into a batching system in sequence through a charging hole, starting a frequency conversion high-speed stirring system to 5000 n/min, starting a heat pump cooling system, wherein the contact area of a stirring device 9 and synthetic liquid is 1/3 of the contact area of a batching kettle and the synthetic liquid, a heat transfer medium adopts heat conduction oil, and R152 adopted by a heat pump working medium is stirred for 5min to form an aluminum solution. And then adding a sodium silicate solution, controlling the temperature of the synthetic liquid at 51 +/-1 ℃, stirring for 1h, adjusting a frequency converter to stir at a low speed for 2500 n/min, controlling the temperature of the synthetic liquid at 30 +/-1 ℃, stirring for 15 h, and then closing the frequency converter stirrer and the heat pump system.
Step 2: preparation of seeded support
Weighing 10g of NaA molecular sieve seed crystal with the average particle size of about 2 mu m, dispersing the NaA molecular sieve seed crystal into 990 g of deionized water, placing the NaA molecular sieve seed crystal into a seed crystal tank on a stirrer, stirring for 10 hours, and then carrying out ultrasonic treatment for 30 min to obtain NaA type molecular sieve seed crystal suspension liquid, wherein the concentration of the seed crystal suspension liquid is 10 g/L; and (3) immersing the support body fixed on the support body support into the seed crystal suspension for 5s, taking out the support body support, and putting the support body support into an oven for drying for later use.
And step 3: preparing a NaA molecular sieve membrane, namely preparing a NaA molecular sieve membrane,
placing the seeded support obtained in the step 2 into a membrane reactor, conveying the membrane preparation solution obtained in the step 1 into the membrane reactor by using a conveying pump, heating for hydrothermal synthesis to start crystallization reaction, reacting at 120 ℃ for 4 hours, and taking out and cooling after the reaction is finished; washing with deionized water and drying to obtain the NaA molecular sieve membrane.
Example 5
The differences from example 1 are: in the process of preparing the seed crystal suspension, graphene is added into the suspension at the same time.
The preparation process of the small-sized graphene comprises the following steps:
preparing graphene oxide by a Hummers method: mixing 1g of natural graphite and concentrated H2SO4、H3PO4The three are placed in a three-neck flask and concentrated with H2SO4And H3PO4The volume ratio of (A) to (B) is 9: 1, 6g of potassium permanganate are added in portions, and the mixture is stirred for 1 hour in an ice-water bath. The temperature is raised to 50 ℃, and the reaction is carried out for 12 hours under the condition of heat preservation. Pouring the obtained product into ice water, adding a proper amount of hydrogen peroxide while stirring until the color of the solution turns to be golden yellow, then filtering, and washing the product with HCl (5 volume percent) and distilled water until the pH value is close to 7. And finally, dispersing the obtained graphite oxide in water, carrying out ultrasonic treatment for 8 hours, and placing the graphite oxide in a vacuum drying oven for drying for later use.
Preparing graphene by a thermal expansion method: putting 0.1 g of graphite oxide powder into a 100mL ceramic crucible, binding a cover with a thin iron wire for fixing, putting the bound crucible into a muffle furnace at 1050 ℃, taking out after 30 s to obtain strippable graphite, adding the strippable graphite into an aqueous solution according to 1 mg/mL, carrying out ultrasonic treatment for 20 min to obtain a graphene suspension, and carrying out freeze drying to obtain graphene.
Carrying out secondary reduction on graphene by using sodium borohydride: weighing 100 mg of graphene oxide, adding the graphene oxide into a 250mL flask, adding 100mL of deionized water, adjusting the pH value of a reaction solution to 9-10 by using a sodium carbonate solution with the mass fraction of 5%, performing ultrasonic treatment for 2h to completely disperse the graphene oxide, adding 1g of sodium borohydride, refluxing for 24 h, changing the yellow brown color of the solution into black color, performing suction filtration on a sample while the solution is hot, washing the sample for 3 times by using deionized water and absolute ethyl alcohol respectively, and then drying the sample in an oven at 50-60 ℃ for 12h to obtain small-sized graphene, wherein the sheet diameter is 5-10 mu m.
The synthesis solution was prepared using the apparatus shown in FIG. 1.
The composition ratio in the synthetic liquid is as follows: SiO2, Al2O3, Na2O, H2O =1:0.8:1.5: 300.
Adding sodium metaaluminate into sodium hydroxide and deionized water into a batching system in sequence through a charging hole, starting variable frequency high-speed stirring to 5000 n/min, starting a cooling circulating water system, and stirring for 5min to form an aluminum solution. And then adding a sodium silicate solution, controlling the temperature of the synthetic liquid to be 55 +/-1 ℃, stirring for 1h, adjusting a frequency converter to be at a low speed and stirring for 2500 n/min, controlling the temperature of the synthetic liquid to be 30 +/-1 ℃, stirring for 15 h, and then closing the frequency converter stirrer and the cooling circulating water system.
Step 2: preparation of seeded support
Weighing 10g of NaA molecular sieve seed crystal with the average particle size of about 2 mu m, dispersing the NaA molecular sieve seed crystal in 990 g of deionized water, placing the NaA molecular sieve seed crystal in a seed crystal tank on a stirrer, stirring for 10 hours, then carrying out ultrasonic treatment for 30 min, weighing 10g of graphene with the sheet diameter of 5 mu m, and adding the graphene into the NaA molecular sieve seed crystal suspension liquid which is uniformly dispersed to obtain NaA type molecular sieve seed crystal suspension liquid; and (3) immersing the support body fixed on the support body support into the seed crystal suspension for 5s, taking out the support body support, and putting the support body support into an oven for drying for later use.
And step 3: preparing a NaA molecular sieve membrane, namely preparing a NaA molecular sieve membrane,
placing the seeded support obtained in the step 2 into a membrane reactor, conveying the membrane preparation solution obtained in the step 1 into the membrane reactor by using a conveying pump, heating for hydrothermal synthesis to start crystallization reaction, reacting at 120 ℃ for 4 hours, and taking out and cooling after the reaction is finished; washing with deionized water and drying to obtain the NaA molecular sieve membrane.
Comparative example 1
The differences from example 1 are: in the process of preparing the synthetic liquid, the temperature is not reduced during high-speed stirring.
The synthesis solution was prepared using the apparatus shown in FIG. 1.
The composition ratio in the synthetic liquid is as follows: SiO2, Al2O3, Na2O, H2O =1:0.8:1.5: 300.
Adding sodium metaaluminate into sodium hydroxide and deionized water into a batching system in sequence through a charging hole, starting variable frequency high-speed stirring to 5000 n/min, starting a cooling circulating water system, and stirring for 5min to form an aluminum solution. Then adding sodium silicate solution, stirring for 1h, adjusting a frequency converter to stir at a low speed for 2500 n/min, controlling the temperature of the synthetic liquid at 50 +/-1 ℃, stirring for 15 h, and then closing the frequency converter stirrer and a cooling circulating water system.
Step 2: preparation of seeded support
Weighing 10g of NaA molecular sieve seed crystal with the average particle size of about 2 mu m, dispersing the NaA molecular sieve seed crystal into 990 g of deionized water, placing the NaA molecular sieve seed crystal into a seed crystal tank on a stirrer, stirring for 10 hours, and then carrying out ultrasonic treatment for 30 min to obtain NaA type molecular sieve seed crystal suspension liquid, wherein the concentration of the seed crystal suspension liquid is 10 g/L; and (3) immersing the support body fixed on the support body support into the seed crystal suspension for 5s, taking out the support body support, and putting the support body support into an oven for drying for later use.
And step 3: preparing a NaA molecular sieve membrane, namely preparing a NaA molecular sieve membrane,
placing the seeded support obtained in the step 2 into a membrane reactor, conveying the membrane preparation solution obtained in the step 1 into the membrane reactor by using a conveying pump, heating for hydrothermal synthesis to start crystallization reaction, reacting at 120 ℃ for 4 hours, and taking out and cooling after the reaction is finished; washing with deionized water and drying to obtain the NaA molecular sieve membrane.
Comparative example 2
The differences from example 1 are: in the process of preparing the synthetic liquid, the low-speed stirring time is 2 hours.
The synthesis solution was prepared using the apparatus shown in FIG. 1.
The composition ratio in the synthetic liquid is as follows: SiO2, Al2O3, Na2O, H2O =1:0.8:1.5: 300.
Adding sodium metaaluminate into sodium hydroxide and deionized water into a batching system in sequence through a charging hole, starting variable frequency high-speed stirring to 5000 n/min, starting a cooling circulating water system, and stirring for 5min to form an aluminum solution. And then adding a sodium silicate solution, controlling the temperature of the synthetic liquid at 51 +/-1 ℃, stirring for 1h, adjusting a frequency converter to stir at a low speed for 2500 n/min, controlling the temperature of the synthetic liquid at 30 +/-1 ℃, stirring for 2h, and then closing the frequency converter stirrer and the cooling circulating water system.
Step 2: preparation of seeded support
Weighing 10g of NaA molecular sieve seed crystal with the average particle size of about 2 mu m, dispersing the NaA molecular sieve seed crystal into 990 g of deionized water, placing the NaA molecular sieve seed crystal into a seed crystal tank on a stirrer, stirring for 10 hours, and then carrying out ultrasonic treatment for 30 min to obtain NaA type molecular sieve seed crystal suspension liquid, wherein the concentration of the seed crystal suspension liquid is 10 g/L; and (3) immersing the support body fixed on the support body support into the seed crystal suspension for 5s, taking out the support body support, and putting the support body support into an oven for drying for later use.
And step 3: preparing a NaA molecular sieve membrane, namely preparing a NaA molecular sieve membrane,
placing the seeded support obtained in the step 2 into a membrane reactor, conveying the membrane preparation solution obtained in the step 1 into the membrane reactor by using a conveying pump, heating for hydrothermal synthesis to start crystallization reaction, reacting at 120 ℃ for 4 hours, and taking out and cooling after the reaction is finished; washing with deionized water and drying to obtain the NaA molecular sieve membrane.
Performance testing
1. Batch repeatability test
Batch repeatability test is through using the utility model provides a membrane method carries out the performance contrast with the molecular sieve membrane that traditional method obtained.
Firstly, 5 NaA molecular sieve membranes are prepared by adopting the membrane preparation method in the embodiments 1, 4 and 5;
next, 5 NaA zeolite membranes were prepared by the membrane formation method in comparative examples 1 and 2.
TABLE 1 comparison of results of pervaporation experiments on NaA molecular sieve membranes synthesized in batch repeatability tests
TABLE 2 comparison of results of pervaporation experiments on NaA molecular sieve membranes synthesized in batch repeatability tests
Comparing two different methods, the utility model has better pervaporation performance of the synthesized membrane and 5 synthesized separation factors in the membrane>10000, flux>2.6kg·h–1·m–2. Which is difficult to achieve by the conventional methodAnd (4) obtaining. Especially the RSD of the separation factor is only 1.20 to 5.97 percent by adopting the method of the utility model, and reaches 33.46 to 48.99 percent by adopting the traditional method.
The field emission scanning electron micrographs of the NaA molecular sieve inner film prepared in example 1 and the NaA molecular sieve inner film are shown in fig. 4 and 5, and it can be seen from the pictures that the prepared molecular sieve film is complete and free of defects. As can be seen from fig. 6, in example 5, the surface layer of the molecular sieve membrane is more uniform and the separation factor is better than that in example 1.
2. Molecular sieve membrane separation performance test
The NaA molecular sieves obtained in examples 1 to 5 and comparative examples 1 to 2 were subjected to pervaporation under the following test conditions: the operating temperature was 70 ℃, and the separation system was a 10 wt.% ethanol/water solution. The results obtained are shown in table 1.
TABLE 3 results of ethanol dehydration pervaporation experiments on molecular sieve membranes synthesized
As can be seen from the table, the utility model provides a separation factor of NaA molecular sieve membrane>10000, flux>2.6 kg·h–1·m–2And has high selectivity and permeation flux. In the comparative examples, the total flux of 1 to 2 is only 2.331 to 2.64 kg.h–1·m–2The separation factor is only 5400-7730.
The NaA molecular sieves obtained in examples 2 to 6 and comparative example 1 were subjected to pervaporation under the following test conditions: the operating temperature was 90 ℃ and the separation system was a pyridine/water solution with a water content of 95 wt.%, the run was carried out for 20h, and the separation factor was determined by sampling every 5h, as follows for each example and control:
TABLE 4 results of experiments on dehydration, pervaporation of pyridine on molecular sieve membranes synthesized
As can be seen from the table, in the process of dehydrating the alkalescent organic solvent, the molecular sieve membrane prepared by the utility model adopts the graphene and the NaA crystal seed to compound, thus effectively improving the separation effect of pyridine/water; as can be seen from the examples 1 and the comparative examples 5, the NaA molecular sieve membrane added with the graphene enables membrane layers to be more compact and seed crystals to be more densely combined, and has longer running stability when being used in the process of alkaline solvent dehydration, and after the NaA molecular sieve membrane is used for running for 15-20 hours, the molecular factor is reduced, which indicates that the surface of the membrane has defects.
Claims (6)
1. A film-forming liquid production device of a NaA molecular sieve film is characterized by comprising:
the batching kettle (6) is used for preparing membrane preparation liquid;
the stirring device (9) is arranged inside the batching kettle (6) and is used for stirring the membrane preparation liquid;
the variable frequency motor (1) is connected with the stirring device (9) and is used for rotating the stirring device (9);
the frequency converter (2) is connected with the variable frequency motor (1) and is used for controlling the rotating speed of the variable frequency motor (1);
the batching kettle jacket (7) is positioned on the outer wall of the batching kettle (6) and is used for cooling the membrane-making liquid;
the delivery pump (4), the batching kettle jacket (7) and the condenser are connected in sequence to form a closed pipeline.
2. The film-forming liquid production device for the NaA molecular sieve membrane according to claim 1, wherein a feed valve (8) is further arranged on the batching kettle (6) and used for controlling the feeding of materials into the batching kettle (6).
3. The film-forming liquid production device for the NaA molecular sieve film according to claim 1, wherein a discharge valve (5) is further arranged on the batching kettle (6) and used for controlling the discharge of materials in the batching kettle (6).
4. A molecular sieve membrane production apparatus, comprising the membrane-forming liquid production apparatus according to claim 1 and a hydrothermal synthesis reactor (13).
5. The device for preparing the molecular sieve membrane according to claim 4, wherein the hydrothermal synthesis kettle (13) is further provided with a molecular sieve membrane tube (14).
6. The molecular sieve membrane preparation device according to claim 4, wherein in the membrane-forming liquid production device, the stirring device (9) is hollow and filled with a heat transfer medium, the hollow structure is further provided with an evaporation tube (10), the evaporation tube (10) is filled with a heat pump working medium, and two ends of the evaporation tube (10) are respectively connected with the working medium outlet (11) and the working medium inlet (12); the hydrothermal synthesis kettle (13) is provided with a heater (18), the outer wall of the hydrothermal synthesis kettle (13) is provided with a synthesis kettle jacket (15), the synthesis kettle jacket (15) is internally provided with a condenser pipe (19), one end of the condenser pipe (19) is connected with the working medium outlet (11) through an expansion valve (16), and the other end of the condenser pipe (19) is connected with the working medium inlet (12) through a compressor (17).
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