CN102060344B - Multiple-effect membrane distillation method with high-efficiency inner heat recovering function - Google Patents
Multiple-effect membrane distillation method with high-efficiency inner heat recovering function Download PDFInfo
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Abstract
The invention relates to a multiple-effect membrane distillation method with a high-efficiency inner heat recovering function. In a membrane distillation operation process, condensation heat of a distillation solution is recovered in a membrane assembly. In the method, both cold fluid feeding and hot fluid feeding can be adopted. When the cold fluid feeding is adopted, an external heat source needs to be supplied, and the gained output ratio in a multi-effect membrane distillation process is 4-20; and when the hot fluid feeding is adopted, no external heat needs to be supplied, and the gained output ratio in the multi-effect membrane distillation process is 4-20. The method provided by the invention has the advantages of simple and mild operation conditions, low energy consumption and high gained output ratio, can be both implemented in a small-scale dispersion way and applied in an integration way to the fields of desalinization of seawater and brackish water, concentration of water solutions of non-volatile or semi-volatile solutes, environment protection and the like; when the method is used for the concentration of the water solutions and the antiosmosis concentrated water, of the non-volatile or semi-volatile solutes such as sodium chloride, ammonium sulfate, ammonium nitrate, sodium nitrate, sodium carbonate, sodium hydroxide, sulfuric acid, hydrochloric acid, glucose, xylitol, urea, glycerol, glycol, lactic acid, glyoxylic acid, dimethyl sulfoxide, sulfolane and the like, normal-pressure steam or hot water is used as a heat source, and the maximal gained output ratio can reach 13.7.
Description
Technical field
The invention belongs to water treatment, desalinization and environmental protection technical field, particularly a kind of multiple-effect membrane distillation method with efficient inner heat recovery function.
Background technology
Water is lifespring, is human valuable, irreplaceable natural resources, also is the lifeblood of social and economic development.China's year is approximately 2400 cubic metres of freshwater resources per capita, be the world per capita freshwater resources 1/4, occupy the 110th of 149 countries in the world, belong to serious water shortage country, wherein the North China per capita water resource belonged to areas of serious less than 400 cubic metres.The scarcity of water resource and day by day serious water pollute the bottleneck that has become restriction Chinese society progress and economic development, solve this difficult problem, are very urgent with extremely important to China's sustainable development.Seawater and brackish water desalination are to pollute an important channel that obtains new water source under the predicament from water crisis and water, and sewage, waste water advanced treatment recovery and resource in simultaneously industry, the life also will extremely be paid attention to.
Desalination technology develops rapidly in recent years, and the desalting technology of large-scale application has hyperfiltration and the way of distillation.In counter-infiltration (RO) method, the permeant flux of reverse osmosis membrane and selectively extremely sensitive to injection temperature and salinity, the operation with high pressure of reverse osmosis process makes its power consumption large, running cost is high, also may face such as seawater pollution, some difficulties that are difficult to overcome such as winter temperature is on the low side if use in northern China.The way of distillation mainly is multistage flash evaporation (MSF) and multi-effect distilling (MED), both common advantages are for enabling to measure recycling or cascade utilization, but MSF takes the method evaporation seawater of step-down dilatation flash distillation must use vaccum-pumping equipment, and the low temperature multiple-effect distillation MED process of at present industry high praise also will adopt vacuum pumping; Because both adopt metal as the heat exchange material, so plant investment is large, the fresh water cost is high, the seawater rate of recovery is low.
Film distillation (MD) is a kind of novel membrane separation technique, integrates still-process and membrane process, and the motive force of film still-process is the steam pressure difference of film both sides.In the film still-process used film be porous and not by the wetting hydrophobic membrane of feed liquid, one side of film is the pending hydrothermal solution that directly contacts with film, because the hydrophobicity of film, the aqueous solution can not pass through from fenestra, but because the existence of film both sides volatile component steam pressure difference, make volatile component in the vaporization of feed liquid high temperature side surface, steam is delivered to the opposite side of film and is condensed into liquid by micropore on the film.According to the difference of steam-condensation mode, the film distillation can be divided into direct contact type (DCMD), GAP TYPE (AGMD), the gentle four kinds of forms of formula (SGMD) of sweeping of decompression (vacuum) formula (VMD).The MD process has advantages of in, small investment simple near operation under the normal pressure, equipment; Secondly the MD process is carried out at a lower temperature, can utilize the low-grade heat sources such as various industrial waste heats, waste heat, solar energy, underground heat.But MD not yet obtains large-scale commercial Application so far, its main cause is at present also untappedly to go out the efficient MD membrane module that price reasonably can be market-oriented and film still-process and the technique that adapts with it, and the heat utilization efficiency of traditional film distillation is very low, for example the water generation ratio of VMD and DCMD is generally between 0.3～1.0, and the water generation ratio of the MSF of technical grade and MED is generally between 2～15.
By retrieval, find following publication document, emphasis is listed below:
Chinese patent (CN 101632901A, CN 101632902A, CN 201249103Y and CN 201249104Y) all introduced a kind of similar heat reclamation type pressure reducing film distillation assembly and device and method, this device has one or more groups to be spaced, the frame membrane module of series connection and frame heat-exchanging component form mutually, in the pressure reducing film distillation process, the feed liquid of preheating is by the inner chamber of hollow-fibre membrane and heat exchanger tube, and negative pressure of vacuum puts on the outside of hollow-fibre membrane and heat exchanger tube, under the effect of negative pressure of vacuum, the steam that is produced by film distillation unit flows in the adjacent with it heat-exchanging component, carry out heat exchange with the feed liquid in the heat exchanger tube, feed temperature raises, steam is condensed into liquid, and the recovery utilization rate by the method heat is greater than 70%.
United States Patent (USP) (US4545862) has been introduced a kind of sea water desalting equipment and method, utilizes in the screw type membrane module that flat plate microporous hydrophobic membrane makes feed liquid and distillate reverse flow, the condensation heat that feed liquid discharges in the time of can effectively absorbing the distillate condensation.In the example of this patent, 1 kilogram of distillate of every generation only consumes the energy of 212 kilojoules, obtains higher capacity usage ratio, and being equivalent to water generation ratio is 9.
United States Patent (USP) (US6716355B1) has been introduced a kind of block form assembly, place at one deck microporous hydrophobic membrane and one deck condenser pipe interval in this block form assembly, film is mutually vertical with pipe, incoming flow with add the hot-fluid cross-flow operation, hot feed liquid flows through membrane channels, the vapor stream that infiltrates from membrane micropore is in the outer wall condensation of condenser pipe, and the condensation heat that steam-condensation discharges passes to the cold burden liquid in the pipe, thereby improves the heat recovery and utilization rate.In the example of this patent, a plurality of block form assemblies are connected according to certain mode, the recycling better effects if of heat does not just clearly provide detailed experimental data in the example of this patent.
Present Research Emphasis mainly concentrates on these technology that how to promote, and reduces and produces water cost and pre-treatment and the last handling process relevant with these technology; In addition, any appearance about new technologies such as desalinization and sewage disposals all can cause showing great attention to of people, and particularly those have business potential, production cost is low, and energy consumption is low, and technique is simple, easy to operate, of many uses and desalination new technology non-secondary pollution is extremely paid attention to.
These are identical with multistage flash evaporation and multiple-effect evaporation or close on principle, have the characteristics of multiple-effect process but be based on film distillation separation process we be referred to as heat recovering type multiple-effect film distillation (Multi-Effect Membrane Distillation is simply referred to as MEMD).As seen, heat recovering type multiple-effect film distillation assembly and technology are collection multiple-effect evaporations (MED), the advantage of multistage flash evaporation (MSF) and conventional film distillation is in new membrane separation assembly and the technology of one, except having and multiple-effect evaporation, outside the identical even higher water generation ratio of multistage flash evaporation, also has the film distillation equipment compact, separative efficiency is high, operating condition gentle (need not HTHP and vacuum pumping), can utilize low-grade heat source (such as solar energy, underground heat, used heat etc.) advantage also is fit to the strong brine that produces in counter-infiltration and other processes is concentrated very much.Heat recovering type multiple-effect film distillation technology is expected to be widely used in the fields such as desalinization, brackish water desalination, the aqueous solution (feed liquid) concentration and environmental protection with its unique advantage.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, provide that a kind of energy consumption is low, water generation ratio is high, produce low, the simple to operate gentleness of water cost, applied range and the multiple-effect membrane distillation method with efficient inner heat recovery function that can large-scale application.
The present invention realizes that the technical scheme of purpose is:
A kind of multiple-effect membrane distillation method with efficient inner heat recovery function, step is:
(1) 60～100 ℃ feed liquid process hollow-fibre membrane import enters the inner chamber of the hollow-fibre membrane of membrane module, high temperature feed liquid moisture constantly evaporates, steam penetrates in the gap of hollow-fibre membrane in the putamina chamber and hollow fiber conduit by the micropore on the doughnut membranous wall, and condensation on the outer wall of the lower hollow fiber conduit of temperature, the condensation latent heat that discharges in the process of steam condensation on the outer wall of hollow fiber conduit is absorbed by the feed liquid in the hollow fiber conduit, the temperature of the feed liquid in the hollow fiber conduit is constantly raise, the feed liquid of hollow-fibre membrane side is because the continuous evaporation of moisture simultaneously, temperature reduces gradually, the concentration of feed liquid also constantly increases, and the backwater end from the membrane module lower end flows out at last;
(2) feed temperature that flows out from membrane module backwater end is 20～40 ℃, by external cooler the temperature of feed liquid is reduced by 2～12 ℃ again, and then feed liquid is returned the inner chamber that membrane module backwater end enters into hollow fiber conduit again;
(3) feed liquid is in the process that rises along hollow fiber conduit, constantly absorb the latent heat that the steam that sees through from the hollow-fibre membrane side discharges and cause temperature and raise gradually the process of hollow fiber conduit outer wall condensation, when feed liquid flows out from the hollow fiber conduit side upper end outlet in the putamina chamber, it is 57～97 ℃ that temperature raises again, and the distillate fresh water that forms under the steam-condensation in the putamina chamber flows out and collection from the distillate outlet;
(4) concentrate that flows out from exit, membrane module hollow fiber conduit side upper end directly enters the next stage multiple-effect film distillation assembly as new feed liquid and continues to concentrate.
A kind of multiple-effect membrane distillation method with efficient inner heat recovery function, step is:
(1) 20～60 ℃ feed liquid enters into the inner chamber of the hollow fiber conduit of membrane module from the lower end import of hollow fiber conduit, feed liquid is in the process that rises along hollow fiber conduit, the latent heat that the steam that continuous absorption sees through from the hollow-fibre membrane side discharges in the process of hollow fiber conduit outer wall condensation, feed temperature can raise gradually, and feed liquid flows out the backwater end from the hollow fiber conduit side upper end outlet of membrane module;
(2) feed temperature that flows out from the exit of membrane module backwater end hollow fiber conduit is 70～97 ℃, after by external heater the temperature of feed liquid being heated to 73～100 ℃, returning again membrane module backwater end and flow into again in the inner chamber of hollow-fibre membrane by the upper end import of hollow-fibre membrane;
(3) feed liquid is in the inner chamber along hollow-fibre membrane flows downward process, constantly evaporation and penetrating into by the micropore on the doughnut membranous wall in the gap of the hollow-fibre membrane of film device and hollow fiber conduit of steam, and condensation on the outer wall of the lower hollow fiber conduit of temperature, the condensation latent heat that discharges in the process of steam condensation on the outer wall of hollow fiber conduit is absorbed by the feed liquid in the hollow fiber conduit, the temperature of the feed liquid in the hollow fiber conduit is constantly raise, simultaneously the feed liquid of hollow-fibre membrane side reduces gradually owing to the continuous evaporation of moisture causes temperature, the concentration of feed liquid also constantly increases, concentrate after distilling from exit, the lower end outflow formation of hollow-fibre membrane at last, the distillate fresh water that forms under the steam-condensation in the putamina chamber flows out and collection from the distillate outlet;
(4) flowing out the concentrate temperature that forms after the distillation from the exit, lower end of membrane module hollow-fibre membrane is 23～63 ℃, this feed liquid directly enter continue in the next stage multiple-effect film distillation assembly concentrated.
And, cavity is made at the middle part of described putamina, two ends are shaped with an import and an outlet respectively, import and outlet all adopt binding agent to seal by end socket, cavity at putamina is built-in with by hollow-fibre membrane and hollow fiber conduit, two end connectors of hollow-fibre membrane and hollow fiber conduit connect respectively import and outlet separately, be provided with the distillate outlet in the lower end of putamina, putamina, hollow-fibre membrane and hollow fiber conduit consist of membrane module, series connection one external heater or external cooler between the import of the backwater end of membrane module and outlet.
And described hollow-fibre membrane and hollow fiber conduit form for the space is arranged in parallel in the cavity of putamina, and the cavity cross section of putamina is circular, perhaps rectangle.
And described hollow-fibre membrane is the hydrophobic hollow fiber microporous barrier, and hollow fiber conduit is doughnut non-porous film, doughnut capillary or metal capillary.
And the macromolecular material of described preparation hydrophobic hollow fiber microporous barrier is the wherein mixture of one or two or more kinds of polypropylene, polyethylene, Kynoar, polytetrafluoroethylene (PTFE), polyacrylonitrile, polytrifluorochloroethylene; The macromolecular material of described preparation hollow fiber conduit is wherein one or more the mixture of polypropylene, polyethylene, Kynoar, polytetrafluoroethylene (PTFE), polyacrylonitrile, polytrifluorochloroethylene, polyacrylic acid, polymethylacrylic acid, polyether-ether-ketone, polyamide, polyimides, polyvinyl alcohol.
And the internal diameter of described hydrophobic hollow fiber microporous barrier is 150～2000 μ m, and average pore size is 0.02～0.6 μ m, and porosity is 30～75%, and wall thickness is 30～400 μ m; The internal diameter of described hollow fiber conduit is 150～2000 μ m, and wall thickness is 30～400 μ m.
And, the mode that the even spaced and parallel of described hollow-fibre membrane and hollow fiber conduit is arranged is: every hollow-fibre membrane by hollow fiber conduit institute around, perhaps every hollow fiber conduit by hollow-fibre membrane institute around, and leave the gap in the middle of hollow-fibre membrane and the hollow fiber conduit, gap thickness is 0.2～5mm.
Advantage of the present invention and good effect are:
1, this method adopts hollow-fibre membrane and uniform the be spaced mode of hollow fiber conduit in putamina, can guarantee to reach the heat transfer of optimum and the purpose of mass transfer effect, have identical even higher water generation ratio by multiple-effect film distillation component design to realize having with multiple-effect evaporation (MED) or multistage flash evaporation (MSF).
2, this method both can adopt the cold fluid charging, also can adopt the hot fluid charging.When adopting the cold fluid charging, need the outside that thermal source is provided, the water generation ratio in the multiple-effect film still-process is 4～20; When adopting the hot fluid charging, do not need the outside that any heat is provided, and the water generation ratio in the multiple-effect film still-process is 4～20.
3, this method is simple to operate; energy consumption is low; water generation ratio is high; and whole process unit all adopts the plastic materials such as polypropylene to make; high temperature resistant, acid-alkali-corrosive-resisting both can disperse to implement on a small scale; also can integratedly use, can be used for the fields such as the concentrated and environmental protection of the aqueous solution of desalinization, brackish water desalination, fixedness or half volatile solute.When the concentrated and reverse osmosis concentrated water of the aqueous solution that is used for non-volatile and half volatile solute such as sodium chloride, ammonium sulfate, ammonium nitrate, sodium nitrate, sodium carbonate, NaOH, sulfuric acid, hydrochloric acid, glucose, xylitol, urea, glycerine, ethylene glycol, lactic acid, glyoxalic acid, dimethyl sulfoxide (DMSO), sulfolane concentrated, if adopt atmospheric steam or hot water to make thermal source, the highest water generation ratio can reach 13.7.
Description of drawings
Fig. 1 is multiple-effect distillation device of the present invention and hot feed operation chart;
Fig. 2 is multiple-effect distillation device of the present invention and cold feed operation chart;
Fig. 3 is the film silk arrangement mode schematic diagram in the multiple-effect distillation device of the present invention;
Fig. 4 is the cross section cutaway view Amplified image (cross section, putamina middle part is square) of Fig. 3.
The specific embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described further; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
In order can more clearly to illustrate the present invention, the below at first narrates multiple-effect distillation device of the present invention.This device comprises that putamina 3 and the hollow-fibre membrane 10 in putamina and hollow fiber conduit 11 consist of, and putamina, hollow-fibre membrane and hollow fiber conduit consist of membrane module.Cavity is made at the middle part of described putamina, the cavity cross-section of putamina is circular, perhaps rectangle (such as Fig. 4), its two ends are shaped with an import and an outlet respectively, and wherein, the upper end of the putamina shown in Fig. 1 is hollow-fibre membrane import 2 and hollow fiber conduit outlet 8, the lower end is hollow-fibre membrane outlet 7 and hollow fiber conduit import 5, this lower end is the backwater end of membrane module, series connection one external heat exchanger 6 between hollow-fibre membrane outlet 7 and hollow fiber conduit import 5, and this external heat exchanger is cooler.The upper end of putamina shown in Figure 2 is the backwater end, be hollow fiber conduit outlet 2a and hollow-fibre membrane import 8a, the lower end is hollow fiber conduit import 7a and hollow-fibre membrane outlet 5a, series connection one external heat exchanger 6a between hollow-fibre membrane import 8a and hollow fiber conduit outlet 2a, this external heat exchanger is heater.All imports and outlet all adopt binding agent to seal by end socket, in the cavity of putamina, be provided with hollow-fibre membrane 10 and hollow fiber conduit 11, two end connectors of hollow-fibre membrane 10 and hollow fiber conduit 11 connect respectively import and outlet separately separately, are provided with distillate outlet 4 in the lower end of putamina.
In the present embodiment, hollow-fibre membrane 10 is the hydrophobic hollow fiber microporous barrier, and the internal diameter of hydrophobic hollow fiber microporous barrier is 150～2000 μ m, and average pore size is 0.02～0.6 μ m, and porosity is 30～75%, and wall thickness is 30～400 μ m; The macromolecular material of preparation hydrophobic hollow fiber microporous barrier is the wherein mixture of one or two or more kinds of polypropylene, polyethylene, Kynoar, polytetrafluoroethylene (PTFE), polyacrylonitrile, polytrifluorochloroethylene; Described preparation doughnut macromolecular material capillaceous is wherein one or more the mixture of polypropylene, polyethylene, Kynoar, polytetrafluoroethylene (PTFE), polyacrylonitrile, polytrifluorochloroethylene, polyacrylic acid, polymethylacrylic acid, polyether-ether-ketone, polyamide, polyimides, polyvinyl alcohol.
In the present embodiment, hollow fiber conduit 11 is doughnut non-porous film, doughnut capillary or metal capillary, and the internal diameter of hollow fiber conduit 11 is 150～2000 μ m, and wall thickness is 30～400 μ m.
Hollow-fibre membrane and hollow fiber conduit form for the space is arranged in parallel in the cavity of putamina, every hollow-fibre membrane by hollow fiber conduit institute around, perhaps every hollow fiber conduit by hollow-fibre membrane institute around, and leave the gap in the middle of hollow-fibre membrane and the hollow fiber conduit, gap thickness is 0.2～5mm.
Multiple-effect membrane distillation method of the present invention is applicable to any to separate or to concentrate the aqueous solution of non-volatile or half volatile solute as the process of purpose with device.
The multiple-effect distillation device that the present invention relates to can use separately, also can organize with series, parallel or series-parallel mode more and use.
The below narrates membrane distillation method of the present invention:
One, feed liquid preliminary treatment: remove solid particle, the suspension in the feed liquid and be in saturated mode might produce crystallization or precipitation in multiple-effect film still-process material through preliminary treatment, preprocess method comprises flocculation, chemical reactivity precipitation, pH adjusting, chelating or ion-exchange, sand filtration etc. one of them or several process and micro-filtration, ultrafiltration combination, or only carry out micro-filtration, ultrafiltration pretreatment, need to select according to different water quality situations.
Two, film distillation: the temperature conditions according to feed liquid can be divided into hot feed liquid charging and cold burden liquid charging dual mode.When doughnut film during as liquor inlet, be hot feed liquid feeding manner, Applicable temperature is 60～100 ℃ feed liquid; When described hollow fiber conduit is liquor inlet, be cold burden liquid feeding manner, Applicable temperature is 20～60 ℃ feed liquid.The below is narrated respectively:
1, hot feed liquid charging: when the temperature of feed liquid 1 is 60～100 ℃, adopt hot feed mode of operation shown in Figure 1, feed liquid 1 enters into the inner chamber of hollow-fibre membrane from the upper end import 2 of hollow-fibre membrane 10 sides, feed liquid 1 is in the process that flows downward along hollow-fibre membrane 10, because the temperature of feed liquid is higher, moisture constantly evaporates, steam is in the gap of hollow-fibre membrane 10 and hollow fiber conduit 11 by the shell side that the micropore on hollow-fibre membrane 10 walls penetrates into film device, and condensation on the outer wall of the lower hollow fiber conduit 11 of temperature, the condensation latent heat that discharges in the process of steam condensation on the outer wall of hollow fiber conduit 11 is absorbed by the feed liquid 1 in the hollow fiber conduit 11, the temperature of the feed liquid 1 in the hollow fiber conduit 11 is constantly raise, the feed liquid 1 of hollow-fibre membrane 10 sides is because the continuous evaporation of moisture simultaneously, temperature reduces gradually, the concentration of the more difficult volatile component in the feed liquid 1 also constantly increases, lower end from hollow-fibre membrane 10 exports the backwater end that 7 outflows enter membrane module at last, exporting 7 feed temperatures that flow out from the lower end of hollow-fibre membrane 10 is 20～40 ℃, this feed liquid further cooler 6 by the backwater end further reduces by 2～12 ℃ with the temperature of feed liquid 1, then feed liquid is returned the inner chamber of hollow fiber conduit of membrane module from the lower end import 5 of hollow fiber conduit 11, feed liquid 1 is in the process that rises along hollow fiber conduit 11, the latent heat that the steam that the continuous absorption of meeting sees through from hollow-fibre membrane 10 sides discharges the process of hollow fiber conduit 11 outer wall condensations, thereby temperature can raise gradually, when feed liquid 1 flows out from the hollow fiber conduit 11 sides upper end outlet 8 of membrane module, it is 57～97 ℃ that temperature raises, behind this moment concentrated feed liquid 9 can through suitable heat exchange or not heat exchange directly enter continue in the next stage multiple-effect film distillation assembly concentrated.The distillate fresh water that forms under the steam-condensation in the membrane module shell side flows out and collection from distillate outlet 4.When taking hot feed to carry out the process of multiple-effect film distillation, do not need the external world that any heat is provided, and only need to from feed liquid, remove a small amount of heat so that the heat and mass motive force to be provided, the recuperation of heat utilization rate of multiple-effect distillation device is very high in this process, water generation ratio is 4～20, this generally depends on heat source temperature, also depends on kind and the concentration of solute in the feed liquid.This is because the kind of feed liquid has determined the viscosity of feed liquid and boiling point rising etc., thereby has determined heat utilization efficiency and water generation ratio.
Cold burden liquid charging: when the temperature of feed liquid 1a is 20～60 ℃, adopt cold feed mode of operation shown in Figure 2, feed liquid 1a enters into the inner chamber of hollow fiber conduit from the lower end import 7a of hollow fiber conduit 11, feed liquid 1a is in the process that rises along hollow fiber conduit 11, the latent heat that the steam that the continuous absorption of meeting sees through from hollow-fibre membrane 10 sides discharges in the process of hollow fiber conduit 11 outer wall condensations, thereby feed temperature can raise gradually, when feed liquid 1a distills the hollow fiber conduit 11 sides upper end outlet 2a outflow of assembly from the multiple-effect film, it is 70～97 ℃ that temperature raises, after by external heat exchanger 6a the temperature of feed liquid 1a being continued to be heated to 73～100 ℃, flow into by the upper end import 8a of hollow-fibre membrane 10 sides in the inner chamber of hollow-fibre membrane of membrane module; Because the feed temperature in the hollow-fibre membrane 10 exceeds the feed temperature in the adjacent hollow fiber conduit 11, in the process that flows downward along hollow-fibre membrane 10, constantly evaporation and be in the gap of hollow-fibre membrane 10 and hollow fiber conduit 11 by the shell side that the micropore on hollow-fibre membrane 10 walls penetrates into film device of steam, and condensation on the outer wall of the lower hollow fiber conduit 11 of temperature, the condensation latent heat that discharges in the process of steam condensation on the outer wall of hollow fiber conduit 11 is absorbed by the feed liquid 1a in the hollow fiber conduit 11, the temperature of feed liquid 1a in the hollow fiber conduit 11 is constantly raise, the feed liquid 1a of hollow-fibre membrane 11 sides is because the continuous evaporation of moisture simultaneously, temperature reduces gradually, the concentration of difficult volatile component also constantly increases among the feed liquid 1a, and the lower end outlet 5a from hollow-fibre membrane 10 flows out the concentrate 9a that forms after distilling at last.The distillate fresh water that forms under the steam-condensation in the membrane module shell side flows out and collection from distillate outlet 4.The process need external world that takes cold feed to carry out the distillation of multiple-effect film provides thermal source, and the recuperation of heat utilization rate of multiple-effect distillation device is very high in this process, and water generation ratio is 4～20, and this generally depends on heat source temperature, also depends on kind and the concentration of solute in the feed liquid.This is because the kind of feed liquid has determined the viscosity of feed liquid and boiling point rising etc., thereby has determined heat utilization efficiency and water generation ratio.
If pending feed liquid is hot feed liquid, when temperature is 60～100 ℃, adopt the multiple-effect film still-process of hot feed mode of operation to have unrivaled advantage, except this process has 4～20 high water generation ratio, and do not need the external world that any heat is provided, can utilize the heat of himself to carry out the enforcement of multiple-effect film still-process.
Confirm innovation height of the present invention below by 21 instantiations.
Embodiment 1:
Feed liquid: the weight percent concentration of salt is 3% sodium chloride (NaCl) aqueous solution, is equivalent to salinity in the former seawater of desalinization.
Feed liquid feeding temperature: 25～30 ℃
Thermal source: temperature is 98～100 ℃ hot water
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.28L/ (m
2H).
Water generation ratio is: 12.5.
Distilling out electrical conductivity of water is: 3.2 μ s/cm.
Embodiment 2:
Feed liquid: the weight percent concentration of salt is 6% sodium chloride (NaCl) aqueous solution, is equivalent to salinity in the traditional desalting process institute by-product strong brine.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 5.88L/ (m
2H).
Water generation ratio is: 10.4.
Distilling out electrical conductivity of water is: 7.2 μ s/cm.
Embodiment 3:
Feed liquid: the weight percent concentration of salt is 15% sodium chloride (NaCl) aqueous solution.
Feed liquid feeding temperature: 95～100 ℃.
Low-temperature receiver: underground water.
Mode of operation: adopt hot feed mode shown in Figure 1 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 4.20L/ (m
2H)
Water generation ratio is: 7.6.
Distilling out electrical conductivity of water is: 10.2 μ s/cm.
Embodiment 4:
Feed liquid: the weight percent concentration of salt is 10% sodium carbonate (Na
2CO
3) aqueous solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: atmospheric steam.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 4.70L/ (m
2H)
Water generation ratio is: 9.6.
Distilling out electrical conductivity of water is: 15.6 μ s/cm.
Embodiment 5:
Feed liquid: the weight percent concentration of salt is 15% sodium carbonate (Na
2CO
3) aqueous solution.
Feed liquid feeding temperature: 90～98 ℃.
Low-temperature receiver: underground water.
Mode of operation: adopt hot feed mode shown in Figure 1 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 4.20L/ (m
2H)
Water generation ratio is: 8.2.
Distilling out electrical conductivity of water is: 15.7 μ s/cm
Embodiment 6:
Feed liquid: the weight percent concentration of salt is 10% sodium nitrate (NaNO
3) aqueous solution.
Feed liquid feeding temperature: 90～98 ℃.
Low-temperature receiver: running water.
Mode of operation: adopt hot feed mode shown in Figure 1 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 4.12L/ (m
2H)
Water generation ratio is: 10.6.
Distilling out electrical conductivity of water is: 9.8 μ s/cm.
Embodiment 7:
Feed liquid: the weight percent concentration of salt is 5% ammonium sulfate ((NH
4)
2SO
4) aqueous solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: 98～100 ℃ of hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.50L/ (m
2H).
Water generation ratio is: 11.6.
Distilling out electrical conductivity of water is: 7.2 μ s/cm.
Embodiment 8:
Feed liquid: the weight percent concentration of salt is 1% ammonium nitrate (NH
4NO
3) aqueous solution.
Feed liquid feeding temperature: 90～98 ℃.
Low-temperature receiver: running water.
Mode of operation: adopt hot feed mode shown in Figure 1 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 7.20L/ (m
2H).
Water generation ratio is: 13.6.
Distilling out electrical conductivity of water is: 4.6 μ s/cm.
Embodiment 9:
Feed liquid: weight percent concentration is 4% NaOH (NaOH) aqueous solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: 98～100 ℃ of hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.24L/ (m
2H).
Water generation ratio is: 11.8.
Distilling out electrical conductivity of water is: 15.6 μ s/cm.
Embodiment 10:
Feed liquid: weight percent concentration is 10% D/W.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.50L/ (m
2H)
Water generation ratio is: 9.5.
Distilling out electrical conductivity of water is: 6.8 μ s/cm, concentration of glucose is lower than measuring accuracy.
Embodiment 11:
Feed liquid: weight percent concentration is 10% aqueous sulfuric acid.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 5.60L/ (m
2H).
Water generation ratio is: 10.5.
Distilling out electrical conductivity of water is: 8.3 μ s/cm, the pH value is 5.5～6.5.
Embodiment 12:
Feed liquid: the weight percent concentration of acid is 10% hydrochloric acid solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 5.60L/ (m
2H).
Water generation ratio is: 10.7.
The concentration of hydrochloric acid in the distillate: the weight percent concentration of acid is 1.92%.
Embodiment 13:
Feed liquid: weight percent concentration is 5% hydrochloric acid solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.46L/ (m
2H)
Water generation ratio is: 11.8.
The concentration of hydrochloric acid in the distillate: the weight percent concentration of acid is 0.28%.
Embodiment 14:
Feed liquid: weight percent concentration is 10% glycerine water solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.36L/ (m
2H)
Water generation ratio is: 11.8.
The glycerol content of distillation water outlet is lower than accuracy of detection.
Embodiment 15:
Feed liquid: weight percent concentration is 10% glycol water.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.63L/ (m
2H).
Water generation ratio is: 12.5.
The ethylene glycol content of distillation water outlet is lower than 0.3%.
Embodiment 16:
Feed liquid: weight percent concentration is 1% aqueous solution of urea.
Feed liquid feeding temperature: 90～92 ℃.
Low-temperature receiver: running water.
Mode of operation: adopt hot feed mode shown in Figure 1 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 7.10L/ (m
2H).
Water generation ratio is: 13.8.
The urea content of distillation water outlet is lower than 0.005%.
Embodiment 17:
Feed liquid: weight percent concentration is 2% dimethyl sulfoxide (DMSO) (DMSO) aqueous solution.
Feed liquid feeding temperature: 90～94 ℃.
Low-temperature receiver: running water.
Mode of operation: adopt hot feed mode shown in Figure 1 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 7.01L/ (m
2H)
Water generation ratio is: 13.0.
The dimethyl sulfoxide (DMSO) content of distillation water outlet is lower than 0.01%.
Embodiment 18:
Feed liquid: weight percent concentration is 10% the sulfolane aqueous solution.
Feed liquid feeding temperature: 92～94 ℃.
Low-temperature receiver: running water.
Mode of operation: adopt hot feed mode shown in Figure 1 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.10L/ (m
2H).
Water generation ratio is: 10.3.
The sulfolane content of distillation water outlet is lower than 0.02%.
Embodiment 19:
Feed liquid: weight percent concentration is 2% lactic acid aqueous solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.21L/ (m
2H)
Water generation ratio is: 12.3.
The lactic acid content of distillation water outlet is lower than 0.1%.
Embodiment 20:
Feed liquid: weight percent concentration is 2% glyoxalic acid solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.02L/ (m
2H)
Water generation ratio is: 12.1.
The Determination of Glyoxalic of distillation water outlet is lower than 0.02%.
Embodiment 21:
Feed liquid: weight percent concentration is 5% the xylitol aqueous solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ hot water.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.50L/ (m
2H)
Water generation ratio is: 11.5.
Distilling out electrical conductivity of water is: 4.8 μ s/cm, xylitol concentration is lower than measuring accuracy.
Embodiment 22:
Feed liquid: petroleum refining waste water concentrates 4 times dense water through biochemical and reverse-osmosis treated, and electrical conductivity is 3240 μ s/cm, COD
CrValue is 56.7.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: atmospheric steam.
Mode of operation: adopt cold feed mode shown in Figure 2 to carry out multiple-effect film still-process.
Experimental result:
The water flux of multiple-effect hollow fiber film assembly is: 6.73L/ (m
2H)
Water generation ratio is: 13.7.
The distillation water outlet: electrical conductivity is 5.65 μ s/cm, COD
CrValue is 44.7.
Claims (8)
1. multiple-effect membrane distillation method with efficient inner heat recovery function, it is characterized in that: step is:
⑴ the feed liquid process hollow-fibre membrane import that 60～100 ℃ enters the inner chamber of the hollow-fibre membrane of membrane module, high temperature feed liquid moisture constantly evaporates, steam penetrates in the gap of hollow-fibre membrane in the putamina chamber and hollow fiber conduit by the micropore on the doughnut membranous wall, and condensation on the outer wall of the lower hollow fiber conduit of temperature, the condensation latent heat that discharges in the process of steam condensation on the outer wall of hollow fiber conduit is absorbed by the feed liquid in the hollow fiber conduit, the temperature of the feed liquid in the hollow fiber conduit is constantly raise, the feed liquid of hollow-fibre membrane side is because the continuous evaporation of moisture simultaneously, temperature reduces gradually, concentration non-volatile and half volatile solute also constantly increases in the feed liquid, and the backwater end from the membrane module lower end flows out at last;
⑵ be 20～40 ℃ from the feed temperature that membrane module backwater end flows out, and by external cooler the temperature of feed liquid reduced by 2～12 ℃ again, and then feed liquid is returned the inner chamber that membrane module backwater end enters hollow fiber conduit;
⑶ feed liquid is in the process that rises along hollow fiber conduit, constantly absorb the latent heat that the steam that sees through from the hollow-fibre membrane side discharges and cause temperature and raise gradually the process of hollow fiber conduit outer wall condensation, when feed liquid flows out from the hollow fiber conduit side upper end outlet of membrane module, it is 57～97 ℃ that temperature raises again, and the distillate fresh water that forms under the steam-condensation in the putamina chamber flows out and collection from the distillate outlet;
⑷ the concentrate that flow out from the exit, hollow fiber conduit side upper end of membrane module directly enters the next stage multiple-effect film distillation assembly as new feed liquid and continues to concentrate.
2. multiple-effect membrane distillation method with efficient inner heat recovery function, it is characterized in that: step is:
⑴ the feed liquid that 20～60 ℃ enters into the inner chamber of the hollow fiber conduit of membrane module from the lower end import of hollow fiber conduit, feed liquid is in the process that rises along hollow fiber conduit, the latent heat that the steam that continuous absorption sees through from the hollow-fibre membrane side discharges in the process of hollow fiber conduit outer wall condensation, feed temperature can raise gradually, and feed liquid flows out the backwater end from the hollow fiber conduit side upper end outlet of membrane module;
⑵ the feed temperature that flow out from the exit of membrane module backwater end hollow fiber conduit is 70～97 ℃, after by external heater the temperature of feed liquid being heated to 73～100 ℃, returning again membrane module backwater end and flow into again in the inner chamber of hollow-fibre membrane by the upper end import of hollow-fibre membrane;
⑶ feed liquid is in the inner chamber along hollow-fibre membrane flows downward process, constantly evaporation and penetrating into by the micropore on the doughnut membranous wall in the gap of the hollow-fibre membrane of film device and hollow fiber conduit of steam, and condensation on the outer wall of the lower hollow fiber conduit of temperature, the condensation latent heat that discharges in the process of steam condensation on the outer wall of hollow fiber conduit is absorbed by the feed liquid in the hollow fiber conduit, the temperature of the feed liquid in the hollow fiber conduit is constantly raise, simultaneously the feed liquid of hollow-fibre membrane side reduces gradually owing to the continuous evaporation of moisture causes temperature, concentration non-volatile and half volatile solute also constantly increases in the feed liquid, concentrate after distilling from exit, the lower end outflow formation of hollow-fibre membrane at last, the distillate fresh water that forms under the steam-condensation in the putamina chamber flows out and collection from the distillate outlet;
⑷ the concentrate temperature after distill from exit, the lower end outflow formation of the hollow-fibre membrane of membrane module is 23～63 ℃, and this feed liquid directly enters in the next stage multiple-effect film distillation assembly and continues to concentrate.
3. according to claim 1 or 2 described multiple-effect membrane distillation methods with efficient inner heat recovery function, it is characterized in that: cavity is made at the middle part of described putamina, two ends are shaped with an import and an outlet respectively, import and outlet all adopt binding agent to seal by end socket, cavity at putamina is built-in with by hollow-fibre membrane and hollow fiber conduit, two end connectors of hollow-fibre membrane and hollow fiber conduit connect respectively import and outlet separately, be provided with the distillate outlet in the lower end of putamina, putamina, hollow-fibre membrane and hollow fiber conduit consist of membrane module, series connection one heater or cooler between the import of the backwater end of membrane module and outlet.
4. according to the multiple-effect membrane distillation method with efficient inner heat recovery function claimed in claim 3, it is characterized in that: described hollow-fibre membrane and hollow fiber conduit form for the space is arranged in parallel in the cavity of putamina, the cavity cross section of putamina is circular, perhaps rectangle.
5. according to the multiple-effect membrane distillation method with efficient inner heat recovery function claimed in claim 4, it is characterized in that: described hollow-fibre membrane is the hydrophobic hollow fiber microporous barrier, and hollow fiber conduit is doughnut non-porous film, doughnut capillary or metal capillary.
6. according to the multiple-effect membrane distillation method with efficient inner heat recovery function claimed in claim 5, it is characterized in that: the macromolecular material of described preparation hydrophobic hollow fiber microporous barrier is the wherein mixture of one or two or more kinds of polypropylene, polyethylene, Kynoar, polytetrafluoroethylene (PTFE), polyacrylonitrile, polytrifluorochloroethylene; The macromolecular material of described preparation hollow fiber conduit is wherein one or more the mixture of polypropylene, polyethylene, Kynoar, polytetrafluoroethylene (PTFE), polyacrylonitrile, polytrifluorochloroethylene, polyacrylic acid, polymethylacrylic acid, polyether-ether-ketone, polyamide, polyimides, polyvinyl alcohol.
7. according to claim 5 or 6 described multiple-effect membrane distillation methods with efficient inner heat recovery function, it is characterized in that: the internal diameter of described hydrophobic hollow fiber microporous barrier is 150～2000 μ m, average pore size is 0.02～0.6 μ m, and porosity is 30～75%, and wall thickness is 30～400 μ m; The internal diameter of described hollow fiber conduit is 150～2000 μ m, and wall thickness is 30～400 μ m.
8. according to the multiple-effect membrane distillation method with efficient inner heat recovery function claimed in claim 4, it is characterized in that: the mode that the even spaced and parallel of described hollow-fibre membrane and hollow fiber conduit is arranged is: every hollow-fibre membrane by hollow fiber conduit institute around, perhaps every hollow fiber conduit by hollow-fibre membrane institute around, and leave the gap in the middle of hollow-fibre membrane and the hollow fiber conduit, gap thickness is 0.2～5mm.
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| CN102085454B (en) * | 2010-12-02 | 2013-05-29 | 天津凯铂能膜工程技术有限公司 | Multi-effect membrane distillation device with efficient internal heat reclamation function and method |
| CN103114298B (en) * | 2013-02-20 | 2016-05-11 | 闫晓琦 | A kind of film distillation coupling alkali-making process |
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| CN104415664B (en) * | 2013-08-20 | 2017-07-28 | 中国石油化工股份有限公司 | The inner pressed vacuum membrane distillation method for concentration of ethylene glycol solution |
| CN105174219B (en) * | 2015-10-19 | 2017-07-04 | 湖州森诺膜技术工程有限公司 | The system that a kind of use vacuum type Membrane Materials system concentrates watery hydrochloric acid |
| CN106582292B (en) * | 2016-12-13 | 2019-10-29 | 北京工业大学 | A method of improving heat pump-membrane distillation thermal efficiency |
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| CN108507224A (en) * | 2018-04-16 | 2018-09-07 | 东莞理工学院 | A kind of Air Gap Membrane refrigerating plant of Driven by Solar Energy |
| CN109439807A (en) * | 2018-12-18 | 2019-03-08 | 浙江华康药业股份有限公司 | A kind of xylose production process |
| CN110496538A (en) * | 2019-09-12 | 2019-11-26 | 兰州理工大学 | A kind of efficient membrane component for desulfurization wastewater processing |
| CN112387122B (en) * | 2020-11-11 | 2021-11-05 | 四川大学 | Microchannel membrane distillation assembly and apparatus and method for enhancing membrane distillation transfer process using microchannels |
| CN114149127A (en) * | 2021-11-17 | 2022-03-08 | 克拉玛依市鑫众石油工程技术服务有限公司 | Multi-effect membrane distillation and multi-effect evaporation comprehensive crystallization device |
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