CN108786480B - Synthesizer of molecular sieve membrane for pharmaceutical chemical industry - Google Patents
Synthesizer of molecular sieve membrane for pharmaceutical chemical industry Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000126 substance Substances 0.000 title abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 112
- 239000013078 crystal Substances 0.000 claims abstract description 66
- 239000012510 hollow fiber Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000002425 crystallisation Methods 0.000 claims abstract description 31
- 230000008025 crystallization Effects 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 82
- 238000003860 storage Methods 0.000 claims description 37
- 238000007599 discharging Methods 0.000 claims description 33
- 239000002699 waste material Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000872 buffer Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000003889 chemical engineering Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 13
- 238000013461 design Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 79
- 239000003960 organic solvent Substances 0.000 description 9
- 238000005373 pervaporation Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000034655 secondary growth Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 238000003980 solgel method Methods 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis device of a molecular sieve membrane for pharmaceutical and chemical industries, which divides a traditional reaction kettle into a plurality of contact channels for single hollow fiber carrier crystallization through a separator, optimizes the inner diameter of the contact channels according to a plurality of parameters such as the viscosity of a membrane casting solution and the like so that the membrane casting solution passes through the hollow fiber carrier in a cross flow filtration-like manner, avoids the crystallization influence of molecular sieve particles in the membrane casting solution on the carrier, and ensures that the steps of seed crystal coating, carrier drying and crystallization can be carried out in sequence in the reaction kettle through reasonable process design, thereby avoiding the fracture phenomenon of the hollow fiber carrier in the moving process.
Description
Technical Field
The application relates to the technical field of pharmaceutical chemical industry, in particular to a synthesizer of a molecular sieve membrane for pharmaceutical chemical industry.
Background
In the pharmaceutical chemical field, an anhydrous grade organic solvent is indispensable, so that the anhydrous grade organic solvent is obtained by separating a small amount or a trace amount of water from the organic solvent, which is one of the most common and important unit processes in the pharmaceutical field. The pervaporation membrane technology developed in recent decades is generally accepted by people due to the inherent advantages of low energy consumption, no introduction of a third component, less pollution discharge and the like in the process of separating a small amount of water or trace water in an organic solvent. The pervaporation membrane technology is a process which takes the partial pressure difference of component steam in an organic solvent as a driving force and realizes the separation of a mixture by depending on the properties of different dissolution and diffusion rates of each component in the membrane.
Among the pervaporation membrane materials, the molecular sieve membrane is one of ceramic membranes, and has excellent competitiveness in the dehydration of the pervaporation organic solvent due to the stable crystal structure and the synthetic aperture range. The T-type molecular sieve membrane is one of the most common molecular sieve membrane types dehydrated by pervaporation organic solvent, and the common methods for synthesizing the T-type molecular sieve membrane include an in-situ synthesis method, a secondary growth method, a sol-gel method, a pore blocking method, a microwave synthesis method and the like, but the most common methods belong to the in-situ synthesis method and the secondary growth method. Compared with the two methods, the secondary growth method has the advantages of high crystallization speed, controllable crystallization speed and the like, and is more favorable for industrial production. The carriers commonly used for preparing the T-shaped molecular sieve membrane are in a sheet type, a tubular type and a hollow fiber type, but at present, only the tubular type is industrialized, wherein the sheet type is only suitable for laboratory research due to small membrane area, and the hollow fiber carrier has higher specific surface area compared with the tubular type carrier, and theoretically has better application potential.
The hollow fiber carrier for preparing the hollow fiber molecular sieve membrane is made of ceramic materials, has small outer diameter and is easy to break, but the existing preparation process of the hollow fiber molecular sieve membrane needs to go through a plurality of steps of seed crystal coating, drying, crystallization and the like, and each step is provided with a respective process device, so that the hollow fiber carrier/membrane is difficult to move on a physical position to avoid breaking, thereby reducing the qualification rate.
In addition, the existing molecular sieve membrane crystallization kettle is often an enlarged version of a laboratory small reaction kettle, and then a stirring device is added in the reaction kettle, but the complexity of the crystallization process is found to be far greater than that of the small reaction kettle adopted in the laboratory operation in the use process, wherein the molecular sieve membrane is crystallized in the large reaction kettle, molecular sieve particles are easily synthesized in situ in the solution, and the molecular sieve particles are easily adhered to the surface of a carrier due to the vortex effect generated by the stirring so as to influence the crystallization process of the surface of the carrier.
Therefore, a new synthesis device and synthesis process of the hollow fiber T-type molecular sieve membrane are needed.
Disclosure of Invention
In order to solve the problems, the invention provides a synthesis device of a molecular sieve membrane for pharmaceutical and chemical engineering of a hollow fiber T-shaped molecular sieve membrane.
The invention provides a synthesis device of a molecular sieve membrane for pharmaceutical and chemical engineering, which comprises the following steps:
a molecular sieve membrane synthesis device for pharmaceutical and chemical industries is characterized by comprising a reaction kettle, a seed crystal liquid storage tank, an air heating device and a membrane casting liquid buffer tank, wherein the upper end and the lower end of the reaction kettle are respectively connected with one end of a feeding pipeline and one end of a discharging pipeline, the other end of the feeding pipeline is connected with the seed crystal liquid feeding pipeline, the membrane casting liquid feeding pipeline and a hot air feeding pipeline through a four-way joint A, the other end of the discharging pipeline is connected with the liquid crystal liquid discharging pipeline, the membrane casting liquid discharging pipeline and a hot air emptying pipeline through a four-way joint B, the seed crystal liquid feeding pipeline and the seed crystal liquid discharging pipeline are connected with the two ends of the seed crystal liquid storage tank, the hot air feeding pipeline is connected with the air heating device, and the membrane casting liquid feeding pipeline and the membrane casting liquid; the reaction kettle is cylindrical, and has feed liquid dispersion district, feed liquid contact zone and feed liquid collecting area from the top down in proper order, wherein the feed liquid contact zone is separated into a plurality of contact passages by the separator, and single contact passage can supply single hollow fiber carrier crystallization to form membrane, wherein contact passage's internal diameter is 15-20mm, synthesizer is used for the crystallization of the hollow fiber carrier of 1.2-1.8mm external diameter to form membrane.
It should be noted that the present invention is mainly directed to hollow fiber carriers with outer diameters of 1.2-1.8mm, and carriers with different outer diameters need to be provided with contact channels with different inner diameters, but the inner diameters of the contact channels are not simply the smaller the outer diameter of the carrier is, the smaller the inner diameter of the contact channel is. But the hydrodynamics of the casting solution of the contact channel is investigated according to a plurality of known parameters such as the outer diameter of the carrier, the viscosity of the casting solution and the like, so that the parameters such as the inner diameter, the flow rate of the casting solution and the like are cooperatively adjusted to ensure the quality of the membrane to the maximum extent. When the casting solution flows through the surface of the hollow fiber carrier, the molecular sieve particles or impurities adhered to the seed crystal layer/membrane layer are washed away by the casting solution flowing through later due to reasonable inner diameter design, but the coated seed crystal is not washed away due to strong bonding force with the carrier after the drying step in the seed crystal coating process.
In addition, the inner wall of the contact channel is preferably provided with a hydrophobic coating, so that seed crystals are not remained on the inner wall after the seed crystal coating step as far as possible, the remained seed crystals can grow with the carrier, and the crystallization effect is reduced. The hydrophobic coating can be selected from polyurethane, epoxy resin, silicon resin, acrylic resin, alkyd resin and the like.
Preferably, the seed solution feed line, the hot air feed line and the membrane casting solution feed line are provided with valves V71, V73 and V75 in sequence, and the seed solution discharge line, the hot air evacuation line and the membrane casting solution discharge line are provided with valves V72, V74 and V76 in sequence.
Preferably, the membrane casting solution buffer tank is connected with a fresh membrane casting solution storage tank through a fresh membrane casting solution feeding pipe, and the fresh membrane casting solution feeding pipe is provided with a valve V79. Preferably, the fresh casting solution storage tank is provided with a stirring device which comprises a motor, a stirring shaft and a blade. When the kettle body is large, a plurality of stirring devices can be considered, and an ultrasonic device can be arranged to be matched with the stirring devices so as to keep the uniformity of each interface of the casting solution. For heating the casting solution, an electric heating device can be arranged in a fresh casting solution storage tank, or a jacket can be arranged on the outer wall of the fresh casting solution storage tank, and the fresh casting solution storage tank is heated to a proper temperature through a medium such as silicon oil. In order to ensure that the crystallization temperature meets the requirement, the buffer solution storage tank can also be provided with an electric heating device or a jacket heating device, and the pipeline between the buffer solution storage tank and the reaction kettle is shortened as much as possible so as to avoid heat loss.
Preferably, the casting solution discharging pipe line is provided with a three-way joint, and two ends of an outlet of the three-way joint are respectively connected with the casting solution buffer tank and the waste casting solution storage tank through a circulating casting solution pipeline and a waste casting solution pipeline, wherein the circulating casting solution pipeline and the waste casting solution pipeline are provided with a valve V77 and a valve V78.
Preferably, the outer wall of the reaction kettle is provided with a heat insulation layer, and the separating piece is integrally formed by stainless steel materials. The purpose of setting up the heat preservation is in order to guarantee crystallization temperature, and is the same, and it can set up extra heating device and guarantee crystallization temperature, and of course, reation kettle is inside to have temperature-measuring device.
Preferably, the feed liquid contact zone is provided with fixing members on both sides thereof to fix the hollow fiber carrier in the feed liquid contact zone.
The invention also provides a preparation method of the hollow fiber T-shaped molecular sieve membrane, which comprises the following steps:
a method for synthesizing T-shaped hollow fiber membrane is characterized in that the method comprises the processes of seed crystal coating, carrier drying and carrier crystallization; wherein,
the seed crystal coating step comprises: conveying the T-shaped seed crystal liquid into a seed crystal liquid storage tank, fixing a hollow fiber carrier in a contact channel, opening valves V71 and V72, enabling the seed crystal liquid to sequentially enter a reaction kettle through a liquid crystal liquid feeding pipeline and a feeding pipeline, returning the seed crystal liquid to the seed crystal liquid storage tank through a discharging pipeline and a seed crystal liquid discharging pipeline, closing the valve V71 after rated coating time is reached, and closing the valve V72 after the seed crystal liquid is completely returned to the seed crystal liquid storage tank to finish a seed crystal coating process;
the carrier drying process comprises the following steps: opening valves V73 and V74, allowing hot air generated in the air heating device to sequentially enter the reaction kettle through a hot air feeding pipeline and a feeding pipeline to dry the hollow fiber carrier coated with the seed crystal, allowing the dried hot air to pass through a discharging pipeline and a hot air emptying pipeline to perform emptying treatment, and closing valves V73 and V74 after rated drying time is reached;
the carrier crystallization process comprises the following steps: preparing a silicon source, an aluminum source and Na in a fresh casting solution storage tank2O、K2Inputting the casting solution of O and water into a casting solution buffer tank through a valve V79, opening a valve V75, a valve V76 and a valve V78 to enable the casting solution to sequentially enter a reaction kettle through a casting solution feeding pipeline and a feeding pipeline, and enter a waste casting solution storage tank through a discharging pipeline and a waste casting solution discharging pipeline, after the rated washing time is reached, closing the valve V78, opening a valve V77 to enable the crystallized casting solution to be recycled, after the rated crystallization time is reached, closing the valve V77 again, and opening the valve V78 to enable the casting solution to enter the waste casting solution storage tank. It should be noted that the cleaning step is provided because the liquid crystal may remain on the pipeline to some extent, the washing of the casting solution may reduce the influence of the remaining liquid crystal, the liquid crystal may be brought into the casting solution to cause contamination of the casting solution, and thus, the part of the casting solution may not be circulated into the casting solution buffer tank as much as possible. Of course, when the contaminated casting solution can satisfy the crystallization requirement, the cleaning step may not be required, thereby directly performing crystallization to minimize the production cost.
Preferably, the particle size of the T-shaped molecular sieve particles for preparing the crystal liquid is 0.7-1.5 mu m, the primary seed crystal coating time is 5-30s, the seed crystal coating step is repeated for 0-3 times, and the drying time is 6-24 h.
Preferably, the washing time is 5-100s, and the temperature of the casting film liquid is 60-120 ℃; the first crystallization reaction time is 0.5-4 h; and repeating the carrier crystallization step for 0-3 times.
The hollow fiber T-shaped molecular sieve membrane prepared according to the invention can be used for dehydrating organic solvents, and the organic solvents are selected from one of alcohol, ketone, aldehyde, ester, furan and pyridine.
Compared with the prior art, the invention has the following advantages:
1. compared with the traditional molecular sieve membrane reaction kettle, the molecular sieve membrane is divided into a plurality of contact channels for crystallization and membrane formation of each single hollow fiber carrier, and the membrane casting solution flows along the hollow fiber carrier in a cross-flow filtration-like manner by controlling the inner diameter of the contact channels and the flow rate of the feed liquid, so that molecular sieve membrane particles and impurities in the membrane casting solution are difficult to adhere to the surface of the carrier, and the crystallization degree is ensured to the maximum extent.
2. Compared with the prior art that the seed crystal coating, drying and crystallization processes of the hollow fiber molecular sieve membrane are required to be completed in different devices, the invention completes the three steps in the same device through reasonable process arrangement, avoids the breakage of the hollow fiber carrier caused by the movement of the physical position, and ensures the purity degree of the membrane casting solution through the matching of proper containers.
3. The result of the characterization of the pervaporation technology shows that when the operation temperature is 70 ℃ and the feed liquid is an ethanol/water solution system with the water content of 5wt.%, the separation factor of the membrane is more than 4000, and the flux is more than 1.5 kg.h < -1 >. m < -2 >, and the membrane has high selectivity and permeation flux.
Drawings
The invention is further illustrated with reference to the accompanying drawings and examples:
fig. 1 is a device for preparing a hollow fiber T-type molecular sieve membrane of the present invention.
FIG. 2 is a sectional top view of the contact channel of the reaction vessel shown in FIG. 1.
In the figure, 1: a reaction kettle; 1-1: a feed liquid dispersion zone; 1-2: a material liquid contact area: 1-3: a feed liquid collection zone; 1-4: a fixing member; 1-5: cutting the parts; 1-6: a contact channel; 1-7: a heat-insulating layer; 2: a seed crystal liquid storage tank; 3: an air heating device; 4: a membrane casting liquid buffer tank; 5: a fresh casting solution storage tank; 6: a waste casting solution storage tank; 7-1: valve V71; 7-2: valves V72, 7-3: valve V73; 7-4: valve V74; 7-5: valve V75; 7-6: valve V76; 7-7: valve V77; 7-8: valve V78; 7-9: valve V79; 8-1: a pump P81; 8-2: a fan; 8-3: a pump P83; 9-1: flow meter F91; 9-2: flow meter F92; 9-3: flow meter F93; 10-1: a four-way joint A; 10-2: a four-way joint B; 10-3: a three-way joint.
Detailed Description
The invention will be further described with reference to the following figures and specific examples:
the invention will now be described in further detail with reference to the figures and examples. The drawing is a simplified schematic diagram, and merely illustrates the basic configuration of the present invention in a schematic manner, and therefore it shows only the configuration related to the present invention.
Fig. 1 is a synthesis apparatus of a hollow fiber T-shaped membrane, which includes a reaction kettle 1, a seed crystal liquid storage tank 2, an air heating apparatus 3, and a casting solution buffer tank 4, wherein the upper and lower ends of the reaction kettle 1 are respectively connected to one end of a feed line and one end of a discharge line, the other end of the feed line is connected to a liquid crystal feed line, a casting solution feed line, and a hot air feed line through a four-way joint a10-1, the other end of the discharge line is connected to a liquid crystal discharge line, a casting solution discharge line, and a hot air evacuation line through a four-way joint B10-2, the seed crystal liquid feed line and the seed crystal liquid discharge line are connected to both ends of the seed crystal liquid storage tank 2, the hot air feed line is connected to the air heating apparatus, and the casting solution feed line and the casting solution; the reaction kettle 1 is cylindrical, and is sequentially provided with a feed liquid dispersion area 1-1, a feed liquid contact area 1-2 and a feed liquid collection area 1-3 from top to bottom, the feed liquid contact area 1-2 is divided into a plurality of contact channels 1-6 by a separator 1-5, a single contact channel 1-6 can be used for crystallizing and forming a film on a single hollow fiber carrier 11, fixing pieces 1-4 are arranged on two sides of the feed liquid contact area 1-2 to fix the hollow fiber carrier in the feed liquid contact area, the inner diameter of the contact channel 1-6 is 18mm, and the synthesis device is used for crystallizing and forming the film on the hollow fiber carrier with the outer diameter of 1.5 mm.
The crystal liquid feeding pipeline is provided with a valve V717-1, a pump P8-18-1 and a flow meter F9-19-1, the hot air feeding pipeline is provided with a valve V737-3, a fan 8-2 and a flow meter F929-2, the casting solution feeding pipeline is sequentially provided with a valve V757-5, a pump P8-38-3 and a flow meter F9-39-3, and the crystal liquid discharging pipeline, the hot air emptying pipeline and the casting solution discharging pipeline are sequentially provided with valves V727-2, V747-4 and V767-6. The casting solution buffer tank 4 is connected with a fresh casting solution storage tank 5 through a fresh casting solution feeding pipe, and the fresh casting solution feeding pipe is provided with a valve V797-9. The casting solution discharging pipe line is provided with a three-way joint 10-3, and two ends of an outlet of the three-way joint are respectively connected with the casting solution buffer tank 4 and the waste casting solution storage tank 6 through a circulating casting solution pipeline and a waste casting solution pipeline, wherein the circulating casting solution pipeline and the waste casting solution pipeline are provided with a valve V777-7 and a valve V787-8. The outer wall of the reaction kettle is provided with an insulating layer 1-7, and the separating pieces 1-5 are integrally formed by stainless steel materials.
The method for preparing the hollow fiber T-shaped molecular sieve membrane by adopting the steps comprises the following steps:
1. preparation of liquid crystal
Self-made T-shaped molecular sieve particles (with the average particle size of 0.8 um) are mixed with water to prepare seed crystal liquid with the concentration of the seed crystal liquid being 2wt.%, and the seed crystal liquid is input into a seed crystal liquid storage tank after being treated by ultrasonic and stirring for 10 min.
2. Seed coating
A hollow fiber carrier (made of alumina and with the outer diameter of 1.5 mm) is fixed on a fixing piece of a reaction kettle after being soaked and dried. And opening valves V71 and V72 to enable the seed crystal liquid to enter the reaction kettle through the liquid crystal liquid feeding pipeline and the feeding pipeline in sequence, returning the seed crystal liquid to the seed crystal liquid storage tank through the discharging pipeline and the seed crystal liquid discharging pipeline, closing the valve V71 after 30s, and closing the valve V72 after the seed crystal liquid completely returns to the seed crystal liquid storage tank to finish the primary seed crystal coating process.
3 drying of the support
And opening valves V73 and V74, allowing hot air generated in the air heating device to sequentially enter the reaction kettle through a hot air feeding pipeline and a feeding pipeline to dry the hollow fiber carrier coated with the seed crystals, allowing the dried hot air to pass through a discharging pipeline and a hot air emptying pipeline to perform emptying treatment, and closing valves V73 and V74 after 12 hours.
The coating step and the carrier drying step were repeated 1 time.
4. Preparation of casting solution
Dissolving NaOH and KOH in deionized water completely, adding NaAlO2Slowly dripping silica sol after the solution is clarified, aging at room temperature for 12h, and obtaining the casting solution with the component molar ratio of SiO2∶Al2O3∶Na2O∶K2O∶H2O is 24: 1: 8: 2: 600, and the heating temperature is set to 100 ℃. The mixture is input into a casting solution buffer tank 4 through a valve V797-9.
5. Crystallization of the support
And opening the valve V757-5, the valve V767-6 and the valve V787-8 to enable the casting solution to sequentially enter the reaction kettle 1 through the casting solution feeding pipeline and the feeding pipeline, and enter the waste casting solution storage tank 6 through the discharging pipeline and the waste casting solution discharging pipeline, after 20s, closing the valve V787-8, opening the valve V777-7 to enable the crystallized casting solution to be recycled, and after 4h, closing the valve V777-7 again and opening the valve V787-8 to enable the casting solution to enter the waste casting solution storage tank 6.
The carrier drying and carrier crystallization steps were repeated 1 time.
6. Post-treatment
And taking the crystallized T-shaped molecular sieve membrane out of the reaction kettle, washing with deionized water for multiple times, soaking in water for 6 hours, and then putting into an oven for drying for later use.
7. Performance characterization
The result of the representation of the pervaporation technology shows that when the operation temperature is 70 ℃, and the feed liquid is an ethanol/water solution system with the water content of 5wt.%, the separation factor of the membrane is 5000, and the flux is 1.6 kg.h < -1 >. m < -2 >.
The above description is only the best mode for carrying out the invention and is not intended to limit the invention. Any modification, equivalent replacement, or improvement made within the spirit and scope of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A synthesis device of a molecular sieve membrane for pharmaceutical and chemical engineering is characterized by comprising a reaction kettle (1), a seed crystal liquid storage tank (2), an air heating device (3) and a membrane casting liquid buffer tank (4), the upper end and the lower end of the reaction kettle (1) are respectively connected with one end of a feeding pipeline and one end of a discharging pipeline, the other end of the feeding pipeline is connected with a crystal liquid feeding pipeline, a casting solution feeding pipeline and a hot air feeding pipeline through a four-way joint A (10-1), the other end of the discharging pipeline is connected with a crystal seed liquid discharging pipeline, a casting solution discharging pipeline and a hot air emptying pipeline through a four-way joint B (10-2), the crystal seed liquid feeding pipeline and the crystal seed liquid discharging pipeline are connected with two ends of a crystal seed liquid storage tank (2), the hot air feeding pipeline is connected with an air heating device, and the casting solution feeding pipeline and the casting solution discharging pipeline are connected with two ends of a casting solution buffer tank (4); the reaction kettle (1) is cylindrical and is sequentially provided with a feed liquid dispersion area (1-1), a feed liquid contact area (1-2) and a feed liquid collection area (1-3) from top to bottom, wherein the feed liquid contact area (1-2) is divided into a plurality of contact channels (1-6) by separators (1-5), a single contact channel (1-6) can be used for crystallization film formation of a single hollow fiber carrier (11), the inner diameter of the contact channel (1-6) is 15-20mm, and the synthesis device is used for crystallization film formation of a hollow fiber carrier with the outer diameter of 1.2-1.8 mm;
the outer wall of the reaction kettle is provided with a heat insulation layer (1-7), and the separating pieces (1-5) are integrally formed by stainless steel materials; fixing pieces (1-4) are arranged on two sides of the feed liquid contact zone (1-2) to fix the hollow fiber carrier in the feed liquid contact zone;
a crystal liquid feeding pipeline is provided with a valve V71 (7-1), a pump P81 (8-1) and a flow meter F91 (9-1), a hot air feeding pipeline is provided with a valve V73 (7-3), a fan (8-2) and a flow meter F92 (9-2), a casting solution feeding pipeline is sequentially provided with a valve V75 (7-5), a pump P83 (8-3) and a flow meter F93 (9-3), and a seed crystal liquid discharging pipeline, a hot air emptying pipeline and a casting solution discharging pipeline are sequentially provided with a valve V72 (7-2), a valve V74 (7-4) and a valve V76 (7-6); the casting solution buffer tank (4) is connected with a fresh casting solution storage tank (5) through a fresh casting solution feeding pipe, and the fresh casting solution feeding pipe is provided with a valve V79 (7-9); the casting solution discharging pipeline is provided with a three-way joint (10-3), and two ends of an outlet of the three-way joint are respectively connected with the casting solution buffer tank (4) and the waste casting solution storage tank (6) through a circulating casting solution pipeline and a waste casting solution pipeline, wherein valves V77 (7-7) and V78 (7-8) are arranged on the circulating casting solution pipeline and the waste casting solution pipeline;
the method for preparing the hollow fiber T-shaped molecular sieve membrane by adopting the synthesis device comprises the following steps:
1. preparation of liquid crystal
Mixing T-type molecular sieve particles with the average particle size of 0.8um and water to prepare a liquid crystal with the liquid crystal concentration of 2wt.%, and inputting the liquid crystal into a seed crystal liquid storage tank after ultrasonic and stirring treatment for 10 min;
2. seed coating
Soaking and drying a hollow fiber carrier which is made of alumina and has the outer diameter of 1.5mm, and then fixing the hollow fiber carrier on a fixing piece of a reaction kettle; opening valves V71 and V72 to enable the seed crystal liquid to enter the reaction kettle through the liquid crystal liquid feeding pipeline and the feeding pipeline in sequence, returning the seed crystal liquid to the seed crystal liquid storage tank through the discharging pipeline and the seed crystal liquid discharging pipeline, closing the valve V71 after 30s, and closing the valve V72 after the seed crystal liquid completely returns to the seed crystal liquid storage tank to finish the primary seed crystal coating process;
3 drying of the support
Opening valves V73 and V74, allowing hot air generated in the air heating device to sequentially enter the reaction kettle through a hot air feeding pipeline and a feeding pipeline to dry the hollow fiber carrier coated with the seed crystal, allowing the dried hot air to be subjected to evacuation treatment through a discharging pipeline and a hot air evacuation pipeline, and closing valves V73 and V74 after 12 hours;
repeating the coating step and the carrier drying step 1 time;
4. preparation of casting solution
Dissolving NaOH and KOH in deionized water completely, adding NaAlO2Slowly dripping silica sol after the solution is clarified, aging at room temperature for 12h, and obtaining the casting solution with the component molar ratio of SiO2∶Al2O3∶Na2O∶K2O∶H2O is 24: 1: 8: 2: 600, and the heating temperature is set to be 100 ℃; inputting the mixture into a casting solution buffer tank (4) through a valve V79 (7-9);
5. crystallization of the support
Opening a valve V75 (7-5), a valve V76 (7-6) and a valve V78 (7-8) to enable the casting solution to sequentially enter the reaction kettle (1) through the casting solution feeding pipeline and the feeding pipeline, and enter the waste casting solution storage tank (6) through the discharging pipeline and the waste casting solution discharging pipeline, after 20s, closing the valve V78 (7-8), opening the valve V77 (7-7) to enable the crystallized casting solution to be recycled, after 4h, closing the valve V77 (7-7) again, and opening the valve V78 (7-8) to enable the casting solution to enter the waste casting solution storage tank (6);
repeating the carrier drying and carrier crystallization steps for 1 time;
6. post-treatment
And taking the crystallized T-shaped molecular sieve membrane out of the reaction kettle, washing with deionized water for multiple times, soaking in water for 6 hours, and then putting into an oven for drying for later use.
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| CN201710796493.8A CN107335342B (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer and synthetic method of doughnut type T molecular sieve film |
| CN201810541220.3A CN108786480B (en) | 2017-09-06 | 2017-09-06 | Synthesizer of molecular sieve membrane for pharmaceutical chemical industry |
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| CN201810541220.3A Active CN108786480B (en) | 2017-09-06 | 2017-09-06 | Synthesizer of molecular sieve membrane for pharmaceutical chemical industry |
| CN201810541231.1A Withdrawn CN108816060A (en) | 2017-09-06 | 2017-09-06 | A kind of synthesizer of medication chemistry molecular screen membrane |
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| CN108031299B (en) * | 2018-01-27 | 2019-12-17 | 浙江汇甬新材料有限公司 | synthesizer of economic nature molecular sieve membrane |
| CN111054222B (en) * | 2019-11-29 | 2021-11-19 | 宁波大学 | Successive transfer synthesis method of molecular sieve membrane |
| CN113457471B (en) * | 2021-08-05 | 2024-01-26 | 安徽工程大学 | Molecular sieve membrane and preparation method and application thereof |
| CN115057452A (en) * | 2022-07-10 | 2022-09-16 | 苏州科技大学 | Method for rapidly preparing molecular sieve and molecular sieve membrane by using 'clean' crystal seeds |
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| CN108816060A (en) | 2018-11-16 |
| CN108786481A (en) | 2018-11-13 |
| CN108786480A (en) | 2018-11-13 |
| CN107335342A (en) | 2017-11-10 |
| CN107335342B (en) | 2018-06-26 |
| CN108465384A (en) | 2018-08-31 |
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