CN102060344A - 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, sea water desaltination 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 about 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 resources belonged to areas of serious less than 400 cubic metres.The scarcity of water resources and serious day by day 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 utilization in industry simultaneously, 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 reverse osmosis method and distillation method.In reverse osmosis (RO) method, the product water flux and the selectivity of reverse osmosis membrane are extremely sensitive to injection temperature and salinity, the high top pressure operation of reverse osmosis process makes its current consumption big, the running cost height also may face such as sea pollution, some difficulties that are difficult to overcome such as winter temperature is on the low side if use in northern China.Distillation method mainly is multistage flash evaporation (MSF) and multi-effect distilling (MED), both common advantages obtain recycling or cascade utilization for making energy, 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 industry high praise at present also will adopt vacuum pumping; Because the both adopts metal as the heat exchange material, so plant investment is big, fresh water cost height, the seawater rate of recovery is low.
Membrane distillation (MD) is a kind of novel membrane separation technique, integrates still-process and membrane process, and the impellent of membrane distillation process is the steam pressure difference of film both sides.Used film is the porous and the hydrophobic membrane of quilting liquid wetting not in the membrane distillation process, 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 constituent steam pressure difference, make volatile constituent 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 vapor condensation mode, membrane 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 in advantage simple near operation under the normal pressure, equipment, less investment; Secondly the MD process is carried out at a lower temperature, can utilize low-grade heat sources such as various industrial waste heats, waste heat, sun power, underground heat.But MD does not obtain large-scale industrial application as yet so far, its major cause is at present also untapped go out efficient MD membrane module that price reasonably can be market-oriented and membrane distillation process and the technology that adapts with it, and the heat utilization efficiency of traditional membrane 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, mutual placed in-line frame membrane module and frame heat-exchanging component are formed, in the pressure reducing film distillation process, the feed liquid of preheating is by the inner chamber of hollow-fibre membrane and heat transfer tube, and negative pressure of vacuum puts on the outside of hollow-fibre membrane and heat transfer tube, under the effect of negative pressure of vacuum, the steam that is produced by the membrane distillation unit flows in the adjacent with it heat-exchanging component, carry out heat exchange with the feed liquid in the heat transfer tube, feed temperature raises, steam is condensed into liquid, and the recovery utilization rate by this 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 spiral type membrane module that flat plate microporous hydrophobic membrane makes feed liquid and distillate reversed flow, the heat of condensation 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 high energy utilization rate, and being equivalent to water generation ratio is 9.
United States Patent (USP) (US6716355B1) has been introduced a kind of block form assembly, one deck microporous hydrophobic membrane and one deck prolong are placed at interval in this block form assembly, film is vertical mutually with pipe, incoming flow with add the hot-fluid cross-flow operation, hot feed liquid flows through membrane channel, the vapour stream that infiltrates from membrane micropore is in the outer wall condensation of prolong, and the heat of condensation that vapor 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 the detailed experiments data in the example of this patent.
Present research and development 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 sea water desaltination 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 technology 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 membrane distillation sepn process we be referred to as heat recovering type multiple-effect membrane distillation (Multi-Effect Membrane Distillation is simply referred to as MEMD).As seen, heat recovering type multiple-effect membrane distillation assembly and technology are new membrane separation assembly and the technology that integrates multiple-effect evaporation (MED), multistage flash evaporation (MSF) and conventional film distillatory advantage, except having the water generation ratio identical even higher with multiple-effect evaporation, multistage flash evaporation, also have membrane distillation facility compact, separation efficiency height, operational condition gentleness (need not High Temperature High Pressure and vacuum pumping), can utilize the advantage of low-grade heat source (as sun power, underground heat, used heat etc.), also be fit to very much the strong brine that produces in reverse osmosis and other processes is concentrated.Heat recovering type multiple-effect film distillation technology is expected to be widely used in fields such as sea water desaltination, brackish water desalination, the aqueous solution (feed liquid) concentration and environment 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 multiple-effect membrane distillation method that can large-scale application with efficient inner heat recovery function.
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 tubular fibre 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) be 20～40 ℃ from the effusive feed temperature of membrane module backwater end, by external cooler the temperature of feed liquid reduced by 2～12 ℃ again, feed liquid is returned the inner chamber that membrane module backwater end enters into hollow fiber conduit more then;
(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 discharged and cause temperature and raise gradually the process of hollow fiber conduit outer wall condensation, when the hollow fiber conduit side upper end outlet of feed liquid in the putamina chamber flowed out, it is 57～97 ℃ that temperature raises again, and the distillate fresh water that forms under the vapor condensation in the putamina chamber flows out and collection from the distillate outlet;
(4) directly enter as new feed liquid from the effusive concentrated solution in exit, membrane module hollow fiber conduit side upper end and continue the next stage multiple-effect membrane distillation assembly 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 is discharged 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) the effusive feed temperature in exit from 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 membrane module backwater end again 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 tubular fibre membranous wall in the gap of the hollow-fibre membrane of film device and hollow fiber conduit of water vapour, 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, concentrated solution after distilling from exit, the lower end outflow formation of hollow-fibre membrane at last, the distillate fresh water that forms under the vapor condensation in the putamina chamber flows out and collection from the distillate outlet;
(4) flowing out the concentrated solution temperature that forms after distilling from the exit, lower end of membrane module hollow-fibre membrane is 23～63 ℃, and this feed liquid directly enters and continues in the next stage multiple-effect membrane distillation assembly to concentrate.
And, cavity is made at the middle part of described putamina, two ends are shaped on 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 import and outlet separately respectively, be provided with the distillate outlet in the lower end of putamina, putamina, hollow-fibre membrane and hollow fiber conduit constitute 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 membrane, and hollow fiber conduit is tubular fibre non-porous film, tubular fibre kapillary or metal capillary.
And the macromolecular material of described preparation hydrophobic hollow fiber microporous membrane is the wherein mixture of one or two or more kinds of polypropylene, polyethylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyacrylonitrile, voltalef; The macromolecular material of described preparation hollow fiber conduit is wherein one or more the mixture of polypropylene, polyethylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyacrylonitrile, voltalef, polyacrylic acid, polymethyl acrylic acid, polyether-ether-ketone, polymeric amide, polyimide, polyvinyl alcohol.
And the internal diameter of described hydrophobic hollow fiber microporous membrane is 150～2000 μ m, and mean 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 positively effect are:
1, present 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 to realize having with multiple-effect evaporation (MED) or multistage flash evaporation (MSF) by multiple-effect membrane distillation component design.
2, present 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 membrane distillation 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 membrane distillation process is 4～20.
3, present method is simple to operate; energy consumption is low; the water generation ratio height; and whole process unit all adopts 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, the aqueous solution that can be used for sea water desaltination, brackish water desalination, non-volatility or half volatile solute concentrates and field such as environment protection.When the aqueous solution that is used for non-volatile and half volatile solute such as sodium-chlor, ammonium sulfate, ammonium nitrate, SODIUMNITRATE, yellow soda ash, sodium hydroxide, sulfuric acid, hydrochloric acid, glucose, Xylitol, urea, glycerine, ethylene glycol, lactic acid, oxoethanoic acid, dimethyl sulfoxide (DMSO), tetramethylene sulfone concentrate and during reverse osmosis concentrated water 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 synoptic 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.
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, at first narrate multiple-effect distillation device of the present invention below to the present invention.This device comprises that putamina 3 and the hollow-fibre membrane 10 in putamina and hollow fiber conduit 11 constitute, and putamina, hollow-fibre membrane and hollow fiber conduit constitute membrane module.Cavity is made at the middle part of described putamina, the cavity cross-section of putamina is circular, perhaps rectangle (as Fig. 4), its two ends are shaped on 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 a water 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 a well 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 import and outlet separately respectively 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 membrane, and the internal diameter of hydrophobic hollow fiber microporous membrane is 150～2000 μ m, and mean 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 membrane is the wherein mixture of one or two or more kinds of polypropylene, polyethylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyacrylonitrile, voltalef; Described preparation tubular fibre macromolecular material capillaceous is wherein one or more the mixture of polypropylene, polyethylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyacrylonitrile, voltalef, polyacrylic acid, polymethyl acrylic acid, polyether-ether-ketone, polymeric amide, polyimide, polyvinyl alcohol.
In the present embodiment, hollow fiber conduit 11 is tubular fibre non-porous film, tubular fibre kapillary 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 that with device any is the process of purpose to separate or to concentrate the aqueous solution non-volatile or half volatile solute.
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.
Narrate membrane distillation method of the present invention below:
One, feed liquid pre-treatment: the process pre-treatment is removed solid particulate, the suspended substance in the feed liquid and is in saturated mode and might produce crystallization or sedimentary material in multiple-effect membrane distillation process, pretreatment process comprises flocculation, chemical reactivity precipitation, pH regulator, chelating or ion-exchange, sand filtration etc. one of them or plurality of processes and micro-filtration, ultrafiltration combination, or only carry out micro-filtration, ultrafiltration pretreatment, need to select according to different water quality situations.
Two, membrane distillation: the temperature condition according to feed liquid can be divided into hot feed liquid charging and cold burden liquid charging dual mode.When tubular fibre film during as liquor inlet, be hot feed liquid feeding manner, Applicable temperature is 60～100 ℃ a feed liquid; When described hollow fiber conduit is liquor inlet, be cold burden liquid feeding manner, Applicable temperature is 20～60 ℃ a feed liquid.Narrated respectively below:
1, hot feed liquid charging: when the temperature of feed liquid 1 is 60～100 ℃, adopt hot feed operating method 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 than 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 in the hollow fiber conduit 11 1, 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 volatiles 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 water cooler 6 by the backwater end further reduces by 2～12 ℃ with the temperature of feed liquid 1, 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 then, 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 is discharged the process of hollow fiber conduit 11 outer wall condensations, thereby temperature can raise gradually, when feed liquid 1 exports 8 outflows on hollow fiber conduit 11 sides of membrane module, it is 57～97 ℃ that temperature raises, and the concentrated back feed liquid 9 of this moment can directly enter through suitable heat exchange or not heat exchange and continue in the next stage multiple-effect membrane distillation assembly to concentrate.The distillate fresh water that forms under the vapor 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 membrane distillation, do not need the external world that any heat is provided, and only need from feed liquid, remove little heat so that the heat and mass impellent to be provided, the pick up the heat 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 the 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 operating method 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 is discharged in the process of hollow fiber conduit 11 outer wall condensations, thereby feed temperature can raise gradually, when feed liquid 1a exports the 2a outflow on hollow fiber conduit 11 sides of multiple-effect membrane distillation assembly, 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 of water vapour 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 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 volatiles also constantly increases among the feed liquid 1a, and the lower end outlet 5a from hollow-fibre membrane 10 flows out the concentrated solution 9a that forms after distilling at last.The distillate fresh water that forms under the vapor 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 multiple-effect membrane distillation provides thermal source, and the pick up the heat 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 the 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 membrane distillation process of hot feed operating method to have incomparable 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 membrane distillation process.
Confirm innovation height of the present invention below by 21 specific exampless.
Embodiment 1:
Feed liquid: the weight percent concentration of salt is 3% sodium-chlor (NaCl) aqueous solution, is equivalent to salt concn in the former seawater of sea water desaltination.
Feed liquid feeding temperature: 25～30 ℃
Thermal source: temperature is 98～100 ℃ a hot water
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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-chlor (NaCl) aqueous solution, is equivalent to salt concn in the traditional desalting process institute by-product strong brine.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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-chlor (NaCl) aqueous solution.
Feed liquid feeding temperature: 95～100 ℃.
Low-temperature receiver: underground water.
Operating method: adopt hot feed mode shown in Figure 1 to carry out multiple-effect membrane distillation 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% yellow soda ash (Na
2CO
3) aqueous solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: atmospheric steam.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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% yellow soda ash (Na
2CO
3) aqueous solution.
Feed liquid feeding temperature: 90～98 ℃.
Low-temperature receiver: underground water.
Operating method: adopt hot feed mode shown in Figure 1 to carry out multiple-effect membrane distillation 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% SODIUMNITRATE (NaNO
3) aqueous solution.
Feed liquid feeding temperature: 90～98 ℃.
Low-temperature receiver: tap water.
Operating method: adopt hot feed mode shown in Figure 1 to carry out multiple-effect membrane distillation 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.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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: tap water.
Operating method: adopt hot feed mode shown in Figure 1 to carry out multiple-effect membrane distillation 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% sodium hydroxide (NaOH) aqueous solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: 98～100 ℃ of hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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, glucose concn 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 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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 soln.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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 soln.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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% aqueous glycerin solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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% aqueous glycol solution.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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: tap water.
Operating method: adopt hot feed mode shown in Figure 1 to carry out multiple-effect membrane distillation 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: tap water.
Operating method: adopt hot feed mode shown in Figure 1 to carry out multiple-effect membrane distillation 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 tetramethylene sulfone aqueous solution.
Feed liquid feeding temperature: 92～94 ℃.
Low-temperature receiver: tap water.
Operating method: adopt hot feed mode shown in Figure 1 to carry out multiple-effect membrane distillation 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 tetramethylene sulfone 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 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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% aqueous glyoxylic acid.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: temperature is 98～100 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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 oxoethanoic acid content 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 ℃ a hot water.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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: refining of petroleum waste water concentrates 4 times dense water through biochemical and reverse-osmosis treated, and specific conductivity is 3240 μ s/cm, COD
CrValue is 56.7.
Feed liquid feeding temperature: 25～30 ℃.
Thermal source: atmospheric steam.
Operating method: adopt cold feed mode shown in Figure 2 to carry out multiple-effect membrane distillation 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: specific 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:
(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 tubular fibre 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;
(2) be 20～40 ℃ from the effusive feed temperature of membrane module backwater end, by external cooler the temperature of feed liquid reduced by 2～12 ℃ again, feed liquid is returned the inner chamber that membrane module backwater end enters hollow fiber conduit then;
(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 discharged and cause temperature and raise gradually the process of hollow fiber conduit outer wall condensation, when feed liquid exports outflow on the hollow fiber conduit side of membrane module, it is 57～97 ℃ that temperature raises again, and the distillate fresh water that forms under the vapor condensation in the putamina chamber flows out and collection from the distillate outlet;
(4) directly enter as new feed liquid from the effusive concentrated solution in the hollow fiber conduit side of membrane module exit, upper end and continue the next stage multiple-effect membrane distillation assembly to concentrate.
2. multiple-effect membrane distillation method with efficient inner heat recovery function, it is characterized in that: 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 is discharged 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) be 70～97 ℃ from the effusive feed temperature of membrane module backwater end, the temperature of feed liquid raise after 2～12 ℃, return membrane module backwater end and flow into again in the inner chamber of hollow-fibre membrane by external heat exchanger;
(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 tubular fibre membranous wall in the gap of the hollow-fibre membrane of film device and hollow fiber conduit of water vapour, 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, concentrated solution after distilling from exit, the lower end outflow formation of hollow-fibre membrane at last, the distillate fresh water that forms under the vapor condensation in the putamina chamber flows out and collection from the distillate outlet;
(4) flowing out the concentrated solution temperature that forms after the distillation from the exit, lower end of the hollow-fibre membrane of membrane module is 23～63 ℃, and this feed liquid directly enters and continues in the next stage multiple-effect membrane distillation assembly 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 on 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 import and outlet separately respectively, be provided with the distillate outlet in the lower end of putamina, putamina, hollow-fibre membrane and hollow fiber conduit constitute membrane module, series connection one well heater or water cooler between the import of the backwater end of membrane module and outlet.
4. according to the described multiple-effect membrane distillation method of claim 3 with efficient inner heat recovery function, 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 described multiple-effect membrane distillation method of claim 4 with efficient inner heat recovery function, it is characterized in that: described hollow-fibre membrane is the hydrophobic hollow fiber microporous membrane, and hollow fiber conduit is tubular fibre non-porous film, tubular fibre kapillary or metal capillary.
6. according to the described multiple-effect membrane distillation method with efficient inner heat recovery function of claim 5, it is characterized in that: the macromolecular material of described preparation hydrophobic hollow fiber microporous membrane is the wherein mixture of one or two or more kinds of polypropylene, polyethylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyacrylonitrile, voltalef; The macromolecular material of described preparation hollow fiber conduit is wherein one or more the mixture of polypropylene, polyethylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyacrylonitrile, voltalef, polyacrylic acid, polymethyl acrylic acid, polyether-ether-ketone, polymeric amide, polyimide, 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 membrane is 150～2000 μ m, mean 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 described multiple-effect membrane distillation method of claim 4 with efficient inner heat recovery function, 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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