CN109809965B - Glycerol concentration equipment and method based on hollow fiber pervaporation membrane - Google Patents
Glycerol concentration equipment and method based on hollow fiber pervaporation membrane Download PDFInfo
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- CN109809965B CN109809965B CN201910148084.6A CN201910148084A CN109809965B CN 109809965 B CN109809965 B CN 109809965B CN 201910148084 A CN201910148084 A CN 201910148084A CN 109809965 B CN109809965 B CN 109809965B
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 277
- 239000012528 membrane Substances 0.000 title claims abstract description 262
- 238000005373 pervaporation Methods 0.000 title claims abstract description 145
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 116
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000047 product Substances 0.000 claims abstract description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 114
- 239000000243 solution Substances 0.000 claims description 85
- 238000005266 casting Methods 0.000 claims description 55
- 238000000108 ultra-filtration Methods 0.000 claims description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- 238000000926 separation method Methods 0.000 claims description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims description 20
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000012466 permeate Substances 0.000 claims description 17
- 238000005345 coagulation Methods 0.000 claims description 14
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- 239000004697 Polyetherimide Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
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- 239000011148 porous material Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims 60
- 239000011241 protective layer Substances 0.000 claims 18
- 239000012045 crude solution Substances 0.000 claims 1
- 239000012465 retentate Substances 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 abstract description 75
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- 239000012141 concentrate Substances 0.000 abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229920000223 polyglycerol Polymers 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000002309 gasification Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
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- 229920006393 polyether sulfone Polymers 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910001628 calcium chloride Inorganic materials 0.000 description 1
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- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
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- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/78—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by condensation or crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/22—Trihydroxylic alcohols, e.g. glycerol
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a glycerin concentration method and apparatus based on hollow fiber pervaporation membrane, said method uses the original hollow fiber pervaporation membrane to dehydrate and concentrate crude glycerin, the hollow fiber pervaporation membrane used has high water permeability, the flux can reach 5-10 times of cross-linked polyvinyl alcohol membrane, 2-5 times of inorganic membrane; the hollow fiber pervaporation membrane has no requirement on the water content of feed liquid, and has a wide tolerance range on pH and conductivity, so that the process can replace the traditional energy consumption processes such as reduced pressure multistage distillation and the like, is directly used for dehydrating and concentrating the feed liquid with high water content, greatly reduces the production energy consumption, reduces the equipment investment cost, further reduces the production cost of glycerin, reduces the operation cost by more than 50% compared with the traditional process, and has the concentration temperature of below 100 ℃, thereby greatly avoiding the decomposition and polymerization of glycerol, reducing byproducts and improving the product quality.
Description
Technical Field
The invention relates to the field of glycerol preparation, in particular to glycerol concentration equipment and a glycerol concentration method based on a hollow fiber pervaporation membrane.
Background
Glycerol is widely used in the industries of medicine, coating, textile, paper making, cosmetics, food, leather, electrical materials, rubber and the like.
Currently, the industrial production methods of glycerol are mainly divided into two categories: firstly, natural glycerin is prepared by taking natural oil as a raw material; the water content of the glycerol synthesized by the two methods is more than 70-80%, so that the dehydration and concentration of the glycerol are important links for obtaining high-purity glycerol, and the dehydration effect directly influences the quality of the finally obtained glycerol. In addition, the recovery of glycerol-containing waste streams produced in industrial applications is also a very important market demand. Currently, the water removal process for glycerol is mainly distillation. However, since glycerol has a high boiling point (293 ℃) and decomposes into acrolein at a temperature of 202 ℃ or higher to deteriorate or polymerize into polyglycerol, complicated multistage distillation under reduced pressure is generally required in actual practice. Although the reduced pressure multi-stage distillation method can realize dehydration and concentration of the glycerol, the defects are very obvious: first, the equipment is complex because of the instability of glycerol at high temperatures, the equipment control and operating requirements are very delicate; secondly, the occupied area of the equipment is large; thirdly, the energy consumption is very high, and the temperature of reduced pressure distillation is more than 150 ℃ due to the very high boiling point; fourthly, the product purity is low, as mentioned above, the glycerol is very sensitive to temperature, and even under the reduced pressure distillation condition of 150 ℃ and 180 ℃, a small amount of glycerol is still changed in quality; fifth, environmental impact is large.
Pervaporation, as a simple and energy-saving frontier technology, can provide an efficient concentration path in glycerol preparation and recovery. However, the inorganic pervaporation membrane materials currently on the market have a number of limitations: (1) the water content of the stock solution cannot exceed 20 percent; (2) the selective layer is very sensitive to impurities, conductivity, pH and the like, and is easily damaged by acid, alkali, salt and the like; (3) glycerol, due to its high viscosity characteristics, tends to plug the selective layer of inorganic pervaporation membranes and thus rapidly degrades membrane separation performance. Therefore, no suitable pervaporation membrane is available in the market for dehydration and concentration of glycerol, and no relevant application research is available in the industry and academia.
Disclosure of Invention
The invention aims to provide glycerol concentration equipment and a glycerol concentration method based on a hollow fiber pervaporation membrane, which are a brand new glycerol concentration process, and the glycerol concentration equipment and the glycerol concentration method adopt the original pervaporation membrane to dehydrate and concentrate a glycerol solution with high water content at the temperature lower than 100 ℃ so as to completely replace a multi-stage reduced pressure distillation technology, so that the energy consumption of the glycerol concentration process is greatly reduced, and in addition, the glycerol concentration equipment has the advantages of greatly improved product quality, simple equipment, small occupied area and small environmental influence.
In order to achieve any one of the above objects, the present invention provides a glycerol concentration method based on a hollow fiber pervaporation membrane, comprising the steps of:
s1: ultrafiltering and filtering TSS suspended impurities from the glycerol crude liquid containing 20-50% of glycerol to obtain filtered clear liquid;
s2: heating and filtering the clear liquid;
s3, adopting a hollow fiber pervaporation membrane to dewater, concentrate and filter the clear solution to obtain the recovered glycerol.
In step S1, the crude glycerol solution containing 20% to 50% of glycerol first enters an ultrafiltration unit to filter TSS suspended impurities, wherein the TSS suspended impurities include cellulose, lignin, proteins, suspended particles, and the like, the ultrafiltration unit is implemented as an ultrafiltration membrane, the ultrafiltration membrane is an inorganic ceramic membrane or an organic membrane, the ultrafiltration membrane is selected from a hollow fiber membrane, a plate-type membrane, a single-channel tubular membrane or a multi-channel tubular membrane, and the pore size of the ultrafiltration membrane is 0.01 to 0.2 microns. When the ultrafiltration membrane is a ceramic ultrafiltration membrane, the pore diameter of the ceramic ultrafiltration membrane is 0.01-0.1 micron; when the ultrafiltration membrane is an organic ultrafiltration membrane and the organic ultrafiltration membrane is a hollow fiber membrane, the aperture is 0.01-0.05 microns, the operating pressure is 0.1-3bar, and the purpose of the step is to filter TSS suspended impurities and protect the pervaporation unit;
in step S2, the filtered clear liquid obtained in step S1 is collected in a buffer tank, and the filtered clear liquid is heated to a set temperature of 60-100 ℃ by a preheater and a heater, and it is worth mentioning that in the present invention, the heating temperature of the filtered clear liquid is not more than 100 ℃, so that the glycerol solution with high water content can be dehydrated and concentrated at a temperature lower than 100 ℃, thereby preventing the glycerol from being changed into impurities such as glycerin, polyglycerol and the like in a high temperature environment, and ensuring the purity and quality of the final product.
In step S3, performing pervaporation and dehydration on the heated filtered clear solution by using an original hollow fiber pervaporation membrane, wherein an inner support layer, a selective separation layer and an outer protection layer are sequentially formed from the inside of the membrane to the outside of the membrane by using the hollow fiber pervaporation membrane, and the selective separation layer is disposed between the inner support layer and the outer protection layer, and the outer protection layer has hydrophilicity; and the outer diameter of the formed membrane is 0.8-1.5mm, the inner diameter is 0.5-1.2mm, and the wall thickness is 0.1-0.2 mm.
In addition, in step S3, the hollow fiber pervaporation membrane constitutes a pervaporation module, the permeation side of the pervaporation module is connected to a vacuum unit to maintain the vacuum degree at 5-30mbar, moisture diffuses to the permeation side in the pervaporation membrane, the moisture is condensed into liquid in a condenser, the liquid is stored in a permeate liquid tank, the concentrated glycerol enters a product tank after being cooled, the gauge pressure at the interception side of the pervaporation module is 0-3bar, the absolute pressure at the permeation side is 5-30mbar, and the purity of the obtained product is 92-95%.
Correspondingly, the invention provides glycerol concentration equipment based on a hollow fiber pervaporation membrane, which at least comprises an ultrafiltration device, a heating device, a pervaporation device, a condensation device, a conveying device and a storage device, wherein the conveying device is used for sequentially connecting the ultrafiltration device, the heating device, the pervaporation device and the condensation device so as to finish the dehydration and concentration of glycerol.
Specifically, the ultrafiltration device comprises at least one ultrafiltration unit, wherein the ultrafiltration unit consists of an ultrafiltration membrane component and accessory equipment. The ultrafiltration membrane is an inorganic ceramic membrane or an organic membrane, the ultrafiltration membrane is selected from a hollow fiber membrane, a plate-type membrane, a single-channel tubular membrane or a multi-channel tubular membrane, and the aperture of the ultrafiltration membrane is 0.01-0.2 micron. The ultrafiltration unit is used to filter TSS impurities in the crude liquid, such as lignin, proteins, suspended particles, etc., to protect the subsequent pervaporation unit.
The heating device comprises at least one preheater and a heater, waste heat is recycled under the action of the preheater, the waste heat of the product is reasonably utilized to heat the raw material liquid, and the feed liquid is heated to a specific temperature under the action of the heater so as to increase the processing capacity of the pervaporation unit.
The osmotic device comprises at least one pervaporation membrane group, the membrane used in the pervaporation membrane group is an original hollow fiber pervaporation membrane, the hollow fiber pervaporation membrane has high water permeability, the glycerol can be efficiently dehydrated at the temperature lower than 100 ℃, and the condensing device is a condenser to condense evaporated water.
As shown in fig. 1 and 2, the glycerol concentration device may be a continuous operation device or a gap operation device, and when the glycerol concentration device is a continuous operation device, the glycerol concentration device includes a first delivery pump 1, an ultrafiltration unit 2, a buffer tank 3, a preheater 5, a heater 6 and a pervaporation membrane module 7 which are connected in sequence, wherein a permeate side of the pervaporation membrane module 7 is connected with a vacuum unit 14, a second condenser 11 is arranged between the vacuum unit 14 and the pervaporation membrane module 7, the second condenser 11 is connected with a permeate liquid tank 12, one end of the permeate liquid tank 12 is connected with a third delivery pump 13, moisture is evaporated from the permeate side of the pervaporation membrane module 7 and is condensed into liquid in the second condenser 11, and then the liquid is stored in the permeate liquid tank 12; wherein the interception side of the pervaporation membrane group 7 is connected with a product tank 9, a first condenser 8 is arranged between the product tank 9 and the pervaporation membrane group 7, one end of the product tank 9 is connected with a fourth delivery pump 10, and the dehydrated glycerol flows out from the interception side of the pervaporation membrane group 7, condenses into liquid in the first condenser 8 and then is stored in the product tank 9.
In addition, a second conveying pump 4 is arranged between the buffer tank 3 and the preheater 5, and the second conveying pump 4 conveys materials into the preheater 5 and the heater 6 for heating. The working process of the whole machine is as follows: the crude liquid containing 20-50% of glycerol enters an ultrafiltration unit 2 to filter TSS suspended impurities, and the obtained filtered clear liquid is cached in a buffer tank 3; the mixture is conveyed to a preheater 5 and a heater 6 under the action of a second conveying pump 4, and enters a pervaporation membrane group 7 after being heated to a certain temperature; and (3) giving a certain vacuum degree to the permeation side of the pervaporation membrane group 7, evaporating water from the permeation side, allowing the material to flow out from the interception side, and condensing to obtain the dehydrated and concentrated glycerol.
When it is a batch operation device, it may only comprise the feed liquid tank 3, the heating device 15, the second delivery pump 4, the pervaporation membrane module 7, the second condenser 11, the permeate liquid tank 12 and the vacuum unit 14, and in this case, the ultrafiltration unit is not attached to the concentration device and is operated separately.
Specifically, at this time, one side of the feed liquid tank 3 is connected with a heating device 15, one side of the feed liquid tank 3 is connected with a pervaporation membrane group 7, wherein the permeation side of the pervaporation membrane group 7 is connected with a vacuum unit 14, a second condenser 11 is arranged between the vacuum unit 14 and the pervaporation membrane group 7, the second condenser 11 is connected with a permeate liquid tank 12, moisture is evaporated from the permeation side of the pervaporation membrane group 7 and is condensed into liquid in the second condenser 11, and then the liquid is stored in the permeate liquid tank 12; the interception side of the pervaporation membrane group 7 is connected with a feed liquid tank 3, a feed liquid delivery pump 4 is arranged between the feed liquid tank 3 and the pervaporation membrane group 7, and glycerol obtained by concentrating the pervaporation membrane group 7 is delivered back to the feed liquid tank 3.
It is worth mentioning that the hollow fiber pervaporation membrane is adopted in the invention, and the flux and the retention rate of the hollow fiber pervaporation membrane are high, and the flux can reach 5 to 10 times of that of a cross-linked polyvinyl alcohol membrane and 2 to 5 times of that of an inorganic membrane; the membrane component formed by the hollow fiber pervaporation membrane has a large filling area which can reach more than 5 times of a plate-frame membrane component and more than 20 times of a tubular membrane component under unit volume, and the specific contents of the hollow fiber pervaporation membrane are introduced as follows:
the preparation of the hollow fiber pervaporation membrane comprises the following steps:
step 1: preparing an inner layer membrane casting solution, an outer layer membrane casting solution and a core solution, wherein the inner layer membrane casting solution, the outer layer membrane casting solution and the core solution form a hollow tubular liquid membrane through a spinning nozzle;
step 2: the hollow tubular liquid film enters a coagulation bath pool after passing through an air gap to be subjected to phase change coagulation, so that hollow fiber film filaments are obtained; and
and step 3: and processing the hollow fiber membrane filaments to obtain the hollow fiber pervaporation membrane.
Wherein among said step S3, one can choose:
and step S31, soaking the hollow fiber filaments in water, a replacement solution and a micropore protection solution in sequence, and then airing in the air.
It is also possible to choose: and freeze-drying the hollow fiber membrane filaments.
In addition, in the preparation process, the flow rate of the inner layer membrane casting solution is preferably controlled to be 0.1-30ml/min, the flow rate of the outer layer membrane casting solution is 0.1-30ml/min, the flow rate of the core solution is 0.1-30ml/min, the temperature of the core solution and the membrane casting solution is 5-80 ℃, the temperature of a spinning nozzle is 5-80 ℃, the speed of a wire winding wheel is 1-50m/min, and the temperature of a solidification pool is 5-80 ℃, so that the hollow fiber pervaporation membrane obtained by the method has better performance compared with other membranes due to the control of the preparation conditions.
The outer layer membrane casting solution comprises hydrophilic polymers and a solvent, wherein the hydrophilic polymers comprise but are not limited to sulfonated polysulfone, sulfonated polyphenylsulfone, sulfonated polyethersulfone, sulfonated polyamide and sulfonated polyimide, polyvinyl alcohol, polyoxyethylene, cellulose acetate, hydrolyzed polyacrylonitrile, polyvinylpyrrolidone, chitosan, polyetheramine and polyethyleneimine; such solvents include, but are not limited to, N-methyl-2-pyrrolidone, N-dimethylacetamide, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dichloromethane, trichloromethane;
wherein the inner layer casting solution comprises polymer macromolecules, solvents and auxiliaries, wherein the polymer macromolecules include but are not limited to polysulfone, polyethersulfone, polyphenylsulfone, polyamide, polyimide, polyamide-imide, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, polypropylene, polycarbonate, polybenzimidazole, polyurethane; such solvents include, but are not limited to, N-methyl-2-pyrrolidone, N-dimethylacetamide, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dichloromethane, trichloromethane; and the adjuvants include, but are not limited to, polyethylene glycol, ethylene glycol, glycerol, polyvinylpyrrolidone, water, ethanol, acetone, lithium chloride, lithium bromide, calcium chloride;
wherein the bore fluid comprises a solvent, a non-solvent and an auxiliary agent, wherein the auxiliary agent comprises but is not limited to polyethylene glycol, ethylene glycol, glycerol, polyvinylpyrrolidone, ethanol, acetone and N-butanol, wherein the solvent comprises but is not limited to N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane and trichloromethane, and the non-solvent is water.
The structure is as follows:
as shown in fig. 6 and 7, the conventional hollow fiber pervaporation membrane sequentially forms a conventional inner support layer, a conventional transition support layer, and a conventional selective separation layer from inside to outside, that is, the conventional selective separation layer is located at the outermost layer of the conventional hollow fiber pervaporation membrane, and in practical application, problems such as swelling, chemical decomposition, and physical damage of the separation layer easily occur, so that the membrane structural integrity of the pervaporation membrane is damaged, and the separation efficiency is reduced. The hollow fiber pervaporation membrane provided by the invention sequentially forms an inner supporting layer, a selective separation layer and an outer protection layer from inside to outside, namely, the selective separation layer is positioned in the outer protection layer and protected, and the outer protection layer has good hydrophilicity, so that the problems of chemical and physical damage and the like are avoided. The hollow structure of the hollow fiber pervaporation membrane provided by the invention is achieved by controlling the formulas of the inner layer membrane casting solution and the outer layer membrane casting solution, if the compatibility of the inner layer and the outer layer is good, the intermediate selective separation layer cannot be formed, if the compatibility of the inner layer and the outer layer is too poor, the inner layer and the outer layer can be delaminated and peeled, and the separation effect and the stability are poor. The inventor tries a plurality of sets of formulas, finally determines a series of formulas of inner layer casting solution and outer layer casting solution, so that the inner layer and the outer layer can reach the ideal state of semi-compatibility, and the cross-sectional view of the actually obtained hollow fiber pervaporation membrane is shown in fig. 6 and 7.
The specific selection series of formulations are as follows:
the first group of formulas: the formula of the outer layer casting solution is as follows: the mixed solution of sulfonated polyphenylsulfone and n-methyl-2-pyrrolidone, wherein the mass ratio of the sulfonated polyphenylsulfone is 10-35%, the mass ratio of the n-methyl-2-pyrrolidone is 65-90%, and the combined proportion of the two is 100%;
the formula of the inner layer casting solution is as follows: the mixed solution of polyphenylsulfone, ethylene glycol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyphenylsulfone is 10-30%, the mass ratio of the ethylene glycol is 2-20%, the mass ratio of the n-methyl-2-pyrrolidone is 50-88%, and the combined ratio of the three formulas is 100%;
the formula of the core liquid is as follows: the water-soluble film comprises n-methyl-2-pyrrolidone, water and glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-4%, the mass ratio of the glycol is 0-10%, and the total proportion of the three formulas is 100%.
The second group of formulas:
the outer layer of casting solution: the mixed solution of cellulose acetate and n-methyl-2-pyrrolidone, wherein the mass ratio of the cellulose acetate is between 1 and 15 percent, the mass ratio of the n-methyl-2-pyrrolidone is between 85 and 99 percent, and the combined ratio of the two formulas is 100 percent;
the inner layer membrane casting solution: the mixed solution of polyetherimide, polyethylene glycol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyphenylsulfone is 10-30%, the mass ratio of the polyethylene glycol is 1-10%, the mass ratio of the n-methyl-2-pyrrolidone is 60-89%, and the combined ratio of the three formulas is 100%;
the core liquid is as follows: the water-soluble organic solvent comprises n-methyl-2-pyrrolidone, water and polyethylene glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-40%, the mass ratio of the polyethylene glycol is 0-10%, and the combined ratio of the three formulas is 100%.
The formula of the outer layer casting solution is as follows: the mixed solution of cellulose acetate and n-methyl-2-pyrrolidone, wherein the mass ratio of the cellulose acetate is between 1 and 15 percent, the mass ratio of the n-methyl-2-pyrrolidone is between 85 and 99 percent, and the combined proportion of the two formulas is 100 percent;
the formula of the inner layer casting solution is as follows: the mixed solution of polyetherimide, ethanol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyphenylsulfone is 10-30%, the mass ratio of the ethanol is 1-10%, the mass ratio of the n-methyl-2-pyrrolidone is 60-89%, and the combined ratio of the three formulas is 100%;
the formula of the core liquid is as follows: the water-soluble organic solvent comprises n-methyl-2-pyrrolidone, water and polyethylene glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-40%, the mass ratio of the polyethylene glycol is 0-10%, and the combined ratio of the three formulas is 100%.
Compared with the prior art, the invention has the beneficial effects that:
1. the process of ultrafiltration and pervaporation is adopted to replace the traditional energy-consuming processes such as reduced-pressure multistage distillation and the like, so that the waste of production energy consumption is greatly reduced, the equipment investment cost is reduced, the ethanol production cost is further reduced, and the operation cost is reduced by more than 50% compared with the traditional process.
2. The inventive hollow fiber pervaporation membrane has high flux and rejection rate, the flux can reach 5-10 times of that of the cross-linked polyvinyl alcohol membrane and 2-5 times of that of the inorganic membrane, thereby greatly improving the processing capacity of the hollow fiber pervaporation membrane, having high separation efficiency,
3. the hollow fiber pervaporation membrane has strong tolerance to pH, conductivity and water content, and can directly dehydrate and concentrate crude glycerol with water content of more than 50-90%.
3. The glycerol concentration equipment comprises a pervaporation membrane group, a heating device, a condenser and other equipment which are combined, the equipment investment is small, the occupied space is saved, the corresponding process is simple and practical, and the glycerol concentration equipment has good practicability.
4. The glycerol product concentrated by the novel process is stable, glycerol is dehydrated and concentrated at the temperature lower than 100 ℃, no glyceraldehyde and polyglycerol are generated, no by-product is generated, the product recovery rate is high, and the environmental influence is extremely small.
Drawings
Fig. 1 is an apparatus schematic view of a glycerol concentrating apparatus based on a hollow fiber pervaporation membrane according to an embodiment of the present invention.
Fig. 2 is an apparatus schematic view of a glycerol concentrating apparatus based on a hollow fiber pervaporation membrane according to another embodiment of the present invention.
Fig. 3 is a surface morphology of an ultrafiltration membrane according to an embodiment of the invention.
Fig. 4 and 5 are schematic structural views of an ultrafiltration membrane according to another embodiment of the present invention.
Fig. 6 and 7 are schematic structural views of a hollow fiber pervaporation membrane according to an embodiment of the present invention.
Fig. 8 is a change in water content of glycerin according to the experimental result of example 3 of the present invention.
In the figure: the system comprises a first delivery pump 1, an ultrafiltration unit 2, a buffer tank 3, a second delivery pump 4, a preheater 5, a heater 6, a pervaporation membrane group 7, a first condenser 8, a product tank 9, a fourth delivery pump 10, a second condenser 11, a permeate liquid tank 12, a third delivery pump 13, a vacuum unit 14 and a heating device 15.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
The following describes an example of the actual dehydration concentration of glycerin using the hollow fiber pervaporation membrane-based glycerin concentration apparatus and method of the present invention:
example 1:
a crude glycerol solution from a certain manufacturing company is taken, the water content is about 80 wt%, the turbidity is 300NTU, the continuous operation process is realized, and the schematic diagram of the equipment in FIG. 1 is shown.
The crude glycerol solution is conveyed to an ultrafiltration unit 2 by a first conveying pump 1, and is filtered to obtain an inorganic ceramic membrane with the aperture of 0.05-0.1 micron and the operating pressure of 0.1-0.2bar, so as to obtain clear liquid with the water content of 80 percent, the turbidity of the clear liquid is less than 10NTU, and the clear liquid is stored in a buffer tank 3. At this point, a recovery of 97-99% was obtained for ultrafiltration unit 2.
The glycerol clear liquid in the buffer tank 3 is heated to 90 ℃ by a preheater 5 and a heater 6, and is conveyed into a permeable gasification membrane group 7 for dehydration and concentration.
The concentrated product is stored in a product tank 9 and is conveyed to a use site by a fourth conveying pump 10, and finally the product purity is 95 wt% and the yield is 99%.
Moisture diffuses to the vacuum side of the pervaporation module 7, liquefies in the condenser 11, is stored in the permeate line 12, and is transported elsewhere by the transport pump 13. The vacuum of the vacuum pump 14 was set at 20mbar and the temperature of the condenser 11 was controlled at less than 5 ℃.
Example 2:
waste liquid generated in the process of using glycerol of a certain enterprise, which has the water content of about 70 wt% and contains 3% of lignocellulose, and the turbidity is 500NTU, is a continuous operation process, and is shown in a schematic diagram of equipment in figure 1.
The crude glycerol solution is delivered to an ultrafiltration unit 2 for filtration by a first delivery pump 1, the ultrafiltration membrane is an organic hollow fiber membrane, the aperture is 0.01-0.1 micron, the operating pressure is 1bar, clear liquid with the water content of 70% is obtained, the turbidity is less than 10NTU, and the clear liquid is stored in a buffer tank 3. At this point, a recovery of 95% was obtained for ultrafiltration unit 2.
The glycerol clear liquid in the buffer tank 3 is heated to 80 ℃ by a preheater 5 and a heater 6, and is conveyed into a permeable gasification membrane group 7 for dehydration and concentration.
The concentrated product is stored in a product tank 9 and is conveyed to a use site by a fourth conveying pump 10, and finally the product with the purity of 92 wt% and the recovery yield of more than 99% is obtained.
Moisture diffuses to the vacuum side of the pervaporation module 7, liquefies in the condenser 11, is stored in the permeate line 12, and is transported elsewhere by the transport pump 13. The vacuum of the vacuum pump 14 was set at 15-20mbar and the temperature of the condenser 11 was controlled at less than 5 ℃.
Example 3:
the glycerol and water solution is prepared by itself to be 15kg, and at the moment, the prepared glycerol water solution does not have the water content of about 80 wt%, which is an intermittent operation process and is shown in a schematic diagram of equipment in FIG. 2. Putting the glycerol aqueous solution into the feed liquid tank 3, opening the heating device 15, and allowing the temperature of the feed liquid to rise to 90 ℃. The delivery pump 4 is turned on, and the feed liquid is delivered to the pervaporation module 7 and then flows back to the feed liquid tank 3. And opening a vacuum unit 14, controlling the vacuum degree to be 20mbar and the temperature of the condenser 11 to be not less than 5 ℃, and performing dehydration concentration. The water content of the feed liquid in the feed liquid tank 3 was measured, and the experiment was stopped when the water content was reduced to about 6 wt%. The change in water content of glycerol is shown in FIG. 8. The purity of the final product is 94 wt%, and the yield is about 99%.
Example 4:
12kg of waste liquid generated in the use process of glycerol of a certain enterprise is taken, the water content is about 70 wt%, the waste liquid contains 3% of lignocellulose, the turbidity is 500NTU, and the waste liquid is an intermittent operation process.
And (3) filtering the glycerol waste liquid to obtain clear liquid, placing the clear liquid into a feed liquid tank 3, opening a heating device 15, and heating the feed liquid to 90 ℃. The delivery pump 4 is turned on, and the feed liquid is delivered to the pervaporation module 7 and then flows back to the feed liquid tank 3. And opening a vacuum unit 14, controlling the vacuum degree to be 20mbar and the temperature of the condenser 11 to be not less than 5 ℃, and performing dehydration concentration. The water content of the feed liquid in the feed liquid tank 3 was measured, and the experiment was stopped when the water content was reduced to about 8 wt%. The final product had a purity of 92.5 wt% and a yield of about 99%.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by anyone in the light of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as those of the present application, fall within the protection scope of the present invention.
Claims (12)
1. The glycerol concentration method based on the hollow fiber pervaporation membrane is characterized by comprising the following steps of:
s1: filtering the crude liquid containing 20-50% of glycerol by ultrafiltration (TSS) to obtain a filtered clear liquid;
s2: heating the filtered clear liquid at 60-100 deg.C;
s3: and (2) dewatering, concentrating and filtering clear liquid by adopting a hollow fiber pervaporation membrane to obtain the recovered 92-95% glycerol, wherein the preparation process of the hollow fiber pervaporation membrane is as follows: step 1: preparing an inner layer membrane casting solution, an outer layer membrane casting solution and a core solution, wherein the inner layer membrane casting solution, the outer layer membrane casting solution and the core solution form a hollow tubular liquid membrane through a spinning nozzle; step 2: the hollow tubular liquid film enters a coagulation bath pool after passing through an air gap to be subjected to phase change coagulation, so that hollow fiber film filaments are obtained; and step 3: processing the hollow fiber membrane filaments to obtain a hollow fiber pervaporation membrane;
wherein the outer layer membrane casting solution is a mixed solution of sulfonated polyphenylsulfone and n-methyl-2-pyrrolidone, wherein the mass ratio of the sulfonated polyphenylsulfone is 10-35%, the mass ratio of the n-methyl-2-pyrrolidone is 65-90%, and the combined ratio of the two is 100%;
the inner layer casting solution is a mixed solution of polyphenylsulfone, ethylene glycol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyphenylsulfone is 10-30%, the mass ratio of the ethylene glycol is 2-20%, the mass ratio of the n-methyl-2-pyrrolidone is 50-88%, and the combined ratio of the three formulas is 100%;
the core liquid is a mixed liquid of n-methyl-2-pyrrolidone, water and glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-4%, the mass ratio of the glycol is 0-10%, and the combined ratio of the three formulas is 100%; the hollow fiber pervaporation membrane sequentially forms an inner supporting layer, a selective separation layer and an outer protective layer from inside to outside of the membrane, wherein the selective separation layer is arranged between the inner supporting layer and the outer protective layer, and the outer protective layer has hydrophilicity.
2. The glycerol concentration method based on the hollow fiber pervaporation membrane is characterized by comprising the following steps of:
s1: filtering the crude liquid containing 20-50% of glycerol by ultrafiltration (TSS) to obtain a filtered clear liquid;
s2: heating the filtered clear liquid at 60-100 deg.C;
s3: and (2) dewatering, concentrating and filtering clear liquid by adopting a hollow fiber pervaporation membrane to obtain the recovered 92-95% glycerol, wherein the preparation process of the hollow fiber pervaporation membrane is as follows: step 1: preparing an inner layer membrane casting solution, an outer layer membrane casting solution and a core solution, wherein the inner layer membrane casting solution, the outer layer membrane casting solution and the core solution form a hollow tubular liquid membrane through a spinning nozzle; step 2: the hollow tubular liquid film enters a coagulation bath pool after passing through an air gap to be subjected to phase change coagulation, so that hollow fiber film filaments are obtained; and step 3: processing the hollow fiber membrane filaments to obtain a hollow fiber pervaporation membrane;
the outer layer membrane casting solution is a mixed solution of cellulose acetate and n-methyl-2-pyrrolidone, wherein the mass ratio of the cellulose acetate is 1-15%, the mass ratio of the n-methyl-2-pyrrolidone is 85-99%, and the combined ratio of the two is 100%;
the inner layer membrane casting solution is a mixed solution of polyetherimide, polyethylene glycol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyetherimide is 10-30%, the mass ratio of the polyethylene glycol is 1-10%, the mass ratio of the n-methyl-2-pyrrolidone is 60-89%, and the combined ratio of the three formulas is 100%;
the core liquid is a mixed liquid of n-methyl-2-pyrrolidone, water and polyethylene glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-40%, the mass ratio of the polyethylene glycol is 0-10%, and the combined ratio of the three formulas is 100%; the hollow fiber pervaporation membrane sequentially forms an inner supporting layer, a selective separation layer and an outer protective layer from inside to outside of the membrane, wherein the selective separation layer is arranged between the inner supporting layer and the outer protective layer, and the outer protective layer has hydrophilicity.
3. The hollow fiber pervaporation membrane-based glycerol concentration method according to any one of claims 1 or 2, wherein in step S1, the crude solution containing 20% to 50% glycerol is first introduced into an ultrafiltration unit to filter TSS, wherein the ultrafiltration unit is an ultrafiltration membrane, and when the ultrafiltration membrane is selected from a hollow fiber membrane, a plate-type membrane, a single-channel tubular membrane or a multi-channel tubular membrane, the pore size of the ultrafiltration membrane is 0.01 to 0.2 μm.
4. The hollow fiber pervaporation membrane based glycerol concentration method according to claim 3, wherein when said ultrafiltration membrane is a ceramic ultrafiltration membrane, the pore size of said ceramic ultrafiltration membrane is 0.01 to 0.1 μm.
5. The hollow fiber pervaporation membrane based glycerol concentration method according to any of claims 1 or 2, wherein the operating pressure at ultrafiltration is 0.1-5 bar; the gauge pressure at the retentate side of the pervaporation module is 0-3bar and the absolute pressure at the permeate side is 5-30 mbar.
6. The hollow fiber pervaporation membrane based glycerol concentration method according to any of claims 1 or 2, wherein the membrane outer diameter of said hollow fiber pervaporation membrane is 0.8 to 1.5mm, the inner diameter is 0.5 to 1.2mm, and the wall thickness is 0.1 to 0.2 mm.
7. Glycerol concentration device based on hollow fiber pervaporation membrane, characterized by comprising:
the device comprises an ultrafiltration unit (2), a buffer tank (3), a preheater (5), a heater (6) and a pervaporation membrane group (7) which are connected in sequence, wherein the permeation side of the pervaporation membrane group (7) is connected with a vacuum unit (14), a second condenser (11) is arranged between the vacuum unit (14) and the pervaporation membrane group (7), and the second condenser (11) is connected with a permeate liquid tank (12); wherein the interception side of the pervaporation membrane group (7) is connected with a product tank (9), a first condenser (8) is arranged between the product tank (9) and the pervaporation membrane group (7), the pervaporation module consists of a hollow fiber pervaporation membrane, and the preparation process of the hollow fiber pervaporation membrane is as follows: step 1: preparing an inner layer membrane casting solution, an outer layer membrane casting solution and a core solution, wherein the inner layer membrane casting solution, the outer layer membrane casting solution and the core solution form a hollow tubular liquid membrane through a spinning nozzle; step 2: the hollow tubular liquid film enters a coagulation bath pool after passing through an air gap to be subjected to phase change coagulation, so that hollow fiber film filaments are obtained; and step 3: processing the hollow fiber membrane filaments to obtain a hollow fiber pervaporation membrane;
wherein the outer layer membrane casting solution is a mixed solution of sulfonated polyphenylsulfone and n-methyl-2-pyrrolidone, wherein the mass ratio of the sulfonated polyphenylsulfone is 10-35%, the mass ratio of the n-methyl-2-pyrrolidone is 65-90%, and the combined ratio of the two is 100%;
the inner layer casting solution is a mixed solution of polyphenylsulfone, ethylene glycol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyphenylsulfone is 10-30%, the mass ratio of the ethylene glycol is 2-20%, the mass ratio of the n-methyl-2-pyrrolidone is 50-88%, and the combined ratio of the three formulas is 100%;
the core liquid is a mixed liquid of n-methyl-2-pyrrolidone, water and glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-4%, the mass ratio of the glycol is 0-10%, and the combined ratio of the three formulas is 100%; the hollow fiber pervaporation membrane sequentially forms an inner supporting layer, a selective separation layer and an outer protective layer from inside to outside of the membrane, wherein the selective separation layer is arranged between the inner supporting layer and the outer protective layer, and the outer protective layer has hydrophilicity.
8. Glycerol concentration device based on hollow fiber pervaporation membrane, characterized by comprising:
the device comprises an ultrafiltration unit (2), a buffer tank (3), a preheater (5), a heater (6) and a pervaporation membrane group (7) which are connected in sequence, wherein the permeation side of the pervaporation membrane group (7) is connected with a vacuum unit (14), a second condenser (11) is arranged between the vacuum unit (14) and the pervaporation membrane group (7), and the second condenser (11) is connected with a permeate liquid tank (12); wherein the interception side of the pervaporation membrane group (7) is connected with a product tank (9), a first condenser (8) is arranged between the product tank (9) and the pervaporation membrane group (7), the pervaporation module consists of a hollow fiber pervaporation membrane, and the preparation process of the hollow fiber pervaporation membrane is as follows: step 1: preparing an inner layer membrane casting solution, an outer layer membrane casting solution and a core solution, wherein the inner layer membrane casting solution, the outer layer membrane casting solution and the core solution form a hollow tubular liquid membrane through a spinning nozzle; step 2: the hollow tubular liquid film enters a coagulation bath pool after passing through an air gap to be subjected to phase change coagulation, so that hollow fiber film filaments are obtained; and step 3: processing the hollow fiber membrane filaments to obtain a hollow fiber pervaporation membrane;
the outer layer membrane casting solution is a mixed solution of cellulose acetate and n-methyl-2-pyrrolidone, wherein the mass ratio of the cellulose acetate is 1-15%, the mass ratio of the n-methyl-2-pyrrolidone is 85-99%, and the combined ratio of the two is 100%;
the inner layer membrane casting solution is a mixed solution of polyetherimide, polyethylene glycol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyetherimide is 10-30%, the mass ratio of the polyethylene glycol is 1-10%, the mass ratio of the n-methyl-2-pyrrolidone is 60-89%, and the combined ratio of the three formulas is 100%;
the core liquid is a mixed liquid of n-methyl-2-pyrrolidone, water and polyethylene glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-40%, the mass ratio of the polyethylene glycol is 0-10%, and the combined ratio of the three formulas is 100%; the hollow fiber pervaporation membrane sequentially forms an inner supporting layer, a selective separation layer and an outer protective layer from inside to outside of the membrane, wherein the selective separation layer is arranged between the inner supporting layer and the outer protective layer, and the outer protective layer has hydrophilicity.
9. The hollow fiber pervaporation membrane based glycerol concentration device according to any of claims 7 or 8, comprising: the ultrafiltration unit (2) is an ultrafiltration membrane, the ultrafiltration membrane is an inorganic ceramic membrane or an organic membrane, the ultrafiltration membrane is selected from a hollow fiber membrane, a plate-type membrane, a single-channel tubular membrane or a multi-channel tubular membrane, and the aperture of the ultrafiltration membrane is 0.01-0.2 microns.
10. The hollow fiber pervaporation membrane based glycerol concentration apparatus according to claim 9, wherein when said ultrafiltration membrane is a ceramic ultrafiltration membrane, the pore size of said ceramic ultrafiltration membrane is 0.01 to 0.1 μm.
11. Glycerol concentration device based on hollow fiber pervaporation membrane, characterized by comprising:
the system comprises a feed liquid tank (3), a heating device (15), a second delivery pump (4), a pervaporation membrane group (7), a second condenser (11), a permeate liquid tank (12) and a vacuum unit (14); one side of the feed liquid tank (3) is connected with a heating device (15), the other side of the feed liquid tank (3) is connected with a pervaporation membrane group (7), wherein the permeation side of the pervaporation membrane group (7) is connected with a vacuum unit (14), a second condenser (11) is arranged between the vacuum unit (14) and the pervaporation membrane group (7), and the second condenser (11) is connected with a pervaporation liquid tank (12); the interception side of the pervaporation membrane group (7) is connected with the feed liquid tank (3), a second delivery pump (4) is arranged between the feed liquid tank (3) and the pervaporation membrane group (7), and the glycerol concentrated from the pervaporation membrane group (7) is delivered back to the feed liquid tank (3); the pervaporation module consists of a hollow fiber pervaporation membrane, wherein the preparation process of the hollow fiber pervaporation membrane is as follows: step 1: preparing an inner layer membrane casting solution, an outer layer membrane casting solution and a core solution, wherein the inner layer membrane casting solution, the outer layer membrane casting solution and the core solution form a hollow tubular liquid membrane through a spinning nozzle; step 2: the hollow tubular liquid film enters a coagulation bath pool after passing through an air gap to be subjected to phase change coagulation, so that hollow fiber film filaments are obtained; and step 3: processing the hollow fiber membrane filaments to obtain a hollow fiber pervaporation membrane;
wherein the outer layer membrane casting solution is a mixed solution of sulfonated polyphenylsulfone and n-methyl-2-pyrrolidone, wherein the mass ratio of the sulfonated polyphenylsulfone is 10-35%, the mass ratio of the n-methyl-2-pyrrolidone is 65-90%, and the combined ratio of the two is 100%;
the inner layer casting solution is a mixed solution of polyphenylsulfone, ethylene glycol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyphenylsulfone is 10-30%, the mass ratio of the ethylene glycol is 2-20%, the mass ratio of the n-methyl-2-pyrrolidone is 50-88%, and the combined ratio of the three formulas is 100%;
the core liquid is a mixed liquid of n-methyl-2-pyrrolidone, water and glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-4%, the mass ratio of the glycol is 0-10%, and the combined ratio of the three formulas is 100%; the hollow fiber pervaporation membrane sequentially forms an inner supporting layer, a selective separation layer and an outer protective layer from inside to outside of the membrane, wherein the selective separation layer is arranged between the inner supporting layer and the outer protective layer, and the outer protective layer has hydrophilicity.
12. Glycerol concentration device based on hollow fiber pervaporation membrane, characterized by comprising:
the system comprises a feed liquid tank (3), a heating device (15), a second delivery pump (4), a pervaporation membrane group (7), a second condenser (11), a permeate liquid tank (12) and a vacuum unit (14); one side of the feed liquid tank (3) is connected with a heating device (15), the other side of the feed liquid tank (3) is connected with a pervaporation membrane group (7), wherein the permeation side of the pervaporation membrane group (7) is connected with a vacuum unit (14), a second condenser (11) is arranged between the vacuum unit (14) and the pervaporation membrane group (7), and the second condenser (11) is connected with a pervaporation liquid tank (12); the interception side of the pervaporation membrane group (7) is connected with the feed liquid tank (3), a second delivery pump (4) is arranged between the feed liquid tank (3) and the pervaporation membrane group (7), and the glycerol concentrated from the pervaporation membrane group (7) is delivered back to the feed liquid tank (3); the pervaporation module consists of a hollow fiber pervaporation membrane, wherein the preparation process of the hollow fiber pervaporation membrane is as follows: step 1: preparing an inner layer membrane casting solution, an outer layer membrane casting solution and a core solution, wherein the inner layer membrane casting solution, the outer layer membrane casting solution and the core solution form a hollow tubular liquid membrane through a spinning nozzle; step 2: the hollow tubular liquid film enters a coagulation bath pool after passing through an air gap to be subjected to phase change coagulation, so that hollow fiber film filaments are obtained; and step 3: processing the hollow fiber membrane filaments to obtain a hollow fiber pervaporation membrane;
the outer layer membrane casting solution is a mixed solution of cellulose acetate and n-methyl-2-pyrrolidone, wherein the mass ratio of the cellulose acetate is 1-15%, the mass ratio of the n-methyl-2-pyrrolidone is 85-99%, and the combined ratio of the two is 100%;
the inner layer membrane casting solution is a mixed solution of polyetherimide, polyethylene glycol and n-methyl-2-pyrrolidone, wherein the mass ratio of the polyetherimide is 10-30%, the mass ratio of the polyethylene glycol is 1-10%, the mass ratio of the n-methyl-2-pyrrolidone is 60-89%, and the combined ratio of the three formulas is 100%;
the core liquid is a mixed liquid of n-methyl-2-pyrrolidone, water and polyethylene glycol, wherein the mass ratio of the n-methyl-2-pyrrolidone is 50-99%, the mass ratio of the water is 1-40%, the mass ratio of the polyethylene glycol is 0-10%, and the combined ratio of the three formulas is 100%; the hollow fiber pervaporation membrane sequentially forms an inner supporting layer, a selective separation layer and an outer protective layer from inside to outside of the membrane, wherein the selective separation layer is arranged between the inner supporting layer and the outer protective layer, and the outer protective layer has hydrophilicity.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910148084.6A CN109809965B (en) | 2019-02-28 | 2019-02-28 | Glycerol concentration equipment and method based on hollow fiber pervaporation membrane |
| PCT/CN2020/087360 WO2020173510A2 (en) | 2019-02-28 | 2020-04-28 | Hollow fibre pervaporation membrane-based glycerol concentration device and method |
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| CN109809965B (en) * | 2019-02-28 | 2021-08-20 | 南京惟新环保装备技术研究院有限公司 | Glycerol concentration equipment and method based on hollow fiber pervaporation membrane |
| CN111203109A (en) * | 2020-01-15 | 2020-05-29 | 南京工业大学 | Novel pervaporation circulation heat exchange system and method |
| CN113617117A (en) * | 2021-07-21 | 2021-11-09 | 武汉智宏思博环保科技有限公司 | Dehydration equipment and process for comprehensively recovering liquid phase membrane from organic solvent |
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| CN101121639A (en) * | 2007-07-13 | 2008-02-13 | 天津大学 | Membrane distillation dehydration method for polyatomic alcohol water solution produced from corn |
| CN102229521A (en) * | 2011-05-14 | 2011-11-02 | 江门市鸿捷精细化工有限公司 | Process for refining crude glycerin and recovering byproducts |
| CN103785310A (en) * | 2014-03-11 | 2014-05-14 | 中南大学 | Method for preparing composite double-layer hollow fiber membrane with polysiloxane imide-polyether imide |
| CN105906476A (en) * | 2016-05-26 | 2016-08-31 | 淮南天力生物工程开发有限公司 | Method for extraction of glycerin from biodiesel production wastewater |
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| CN101642683B (en) * | 2009-09-10 | 2012-05-02 | 苏州信望膜技术有限公司 | Double-layer composite hollow fiber nano-filtration membrane and preparation method and special tool thereof |
| EP3016733A1 (en) * | 2013-07-04 | 2016-05-11 | Basf Se | Multiple channel membranes |
| CN105218316A (en) * | 2014-11-28 | 2016-01-06 | 杭州奇纯膜技术有限公司 | A kind of hollow fiber pervaporation membrane prepares the device and method of dehydrated alcohol |
| CN109809965B (en) * | 2019-02-28 | 2021-08-20 | 南京惟新环保装备技术研究院有限公司 | Glycerol concentration equipment and method based on hollow fiber pervaporation membrane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121639A (en) * | 2007-07-13 | 2008-02-13 | 天津大学 | Membrane distillation dehydration method for polyatomic alcohol water solution produced from corn |
| CN102229521A (en) * | 2011-05-14 | 2011-11-02 | 江门市鸿捷精细化工有限公司 | Process for refining crude glycerin and recovering byproducts |
| CN103785310A (en) * | 2014-03-11 | 2014-05-14 | 中南大学 | Method for preparing composite double-layer hollow fiber membrane with polysiloxane imide-polyether imide |
| CN105906476A (en) * | 2016-05-26 | 2016-08-31 | 淮南天力生物工程开发有限公司 | Method for extraction of glycerin from biodiesel production wastewater |
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| WO2020173510A2 (en) | 2020-09-03 |
| WO2020173510A3 (en) | 2020-10-15 |
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