CN105344314A - Porous hollow tubular composite membrane and preparation method and application thereof - Google Patents
Porous hollow tubular composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a porous hollow tubular composite membrane and a preparation method and application thereof. The composite membrane is formed by combining a porous hollow tubular carrier and an adsorption particle gathering layer which is arranged on the outer surface of the porous hollow tubular carrier in a wrapping mode, the adsorption particle gathering layer is a porous-membrane-shaped adsorption particle gathering layer, and the thickness of the adsorption particle gathering layer is 5-50 mm; in the preparation process, the porous hollow tubular carrier is immersed in a chitosan solution containing adsorption particle powder, the adsorption particle powder is arranged on the outer surface of the porous hollow tubular carrier in a wrapping mode, then the porous hollow tubular carrier is suspended and dried, and the porous hollow tubular composite membrane can be obtained. In the application process, the porous hollow tubular composite membrane is assembled into a tube-shell type adsorption device and used for conducting defluorination on drinking water. Compared with the prior art, the porous hollow tubular composite membrane is high in adsorption rate, large in adsorption volume, large in sectional area of a work bed layer when being used for defluorination and capable of being applied to a household minitype defluorination device for drinking water.
Description
Technical field
The invention belongs to technical field of water purification, relate to a kind of porous hollow tubular composite membrane and preparation method thereof and application, especially relate to a kind of porous hollow tubular composite membrane and preparation method thereof and the application in drinking water defluorinate.
Background technology
Fluorine be in natural environment extensively distribution and with one of closely-related trace chemical elements of health.Human body is respectively organized and is all contained Trace Fluoride, and wherein the fluorine of 80-90% all concentrates in tooth and bone, and it is the important element forming bone tooth.The appropriate fluorine of absorption of human body can caries prevention, promotes the calcium metabolism of bone.But when human body absorption fluorine is excessive, the alcium and phosphor metabolization of human body can be caused again to lack of proper care, and cause " den tal fluorosis " illness, more serious meeting causes the illnesss such as textured bone.Therefore, China " standards for drinking water quality " (GB5749-2006) specifies, fluorine content of drinking water must not more than 1.0mg/L.When Oil repellent in water is more than 1.0mg/L, be referred to as high-fluorine water.At present, about the population that China drinks high-fluorine water has 5,000 ten thousand people, North China, northeast and the Northwest is mainly distributed in.These geographic coverages are extensive, sparse population, and only a few cities adopts centralized water supply, and large-scale defluorinate device can be used to carry out purifying drinking water.But, vast rural area still based on water dispersion type, certainly carry well supply water, be difficult to set up public defluorinate device.If a kind of small-sized household drinking water defluorinate device can be built, then can solve a difficult problem for vast rural area distributing drinking water defluorinate.
In recent years, the development of household small-size purifier is very fast, is wherein representative with reverse osmosis water purification units.Reverse osmosis technology can remove the ion of 80-90% in water, also comprises fluorine ion.But the former Water Sproading rate of reverse osmosis technology is too low (rate of recovery is the ratio of aquifer yield and inflow), generally only about 1/3, all the other dense water salt content of 2/3 are high, are unsuitable for drinking, cause the serious waste of water resource.Particularly the northern area of China is originally exactly water-deficient area, and this waste more exacerbates the not enough problem of water resource, meanwhile, removes various impurity to reverse osmosis unit non-selectivity, thus also can remove some element useful to human body, as selenium, calcium, magnesium etc.
The northern area of China rural potable water is based on underground water, and the water quality of underground water is better, and usually except fluorine exceeds standard, all the other projects all reach drinking water standard.If specific aim develops household small-size drinking water defluorinate device, these regional Fluorine of Drinking Waters can be solved and to exceed standard a difficult problem.Compared with reverse osmosis water purification units, this device can not cause water resource waste, and can also retain various beneficial element in former water.
At present, defluorination method is commonly used in waterworks is absorption method.Absorption method can carry out deep removal to fluorine ion in running water, makes fluorinion concentration be down to below 1mg/L.Conventional adsorbent comprises alumina balls, bone black particle, zeolite molecular sieve, zirconia and chelating resin etc.Adsorbent particle diameter mostly is 0.5-3 millimeter.Conventional drinking water defluorination flow process is ADSORPTION IN A FIXED BED, and bed height is 0.8-1.5 rice.Because there are 2 deficiencies in these conventional adsorbents, and be difficult to be applied to household small-size water purifier: the adsorption capacity of (1) adsorbent is little, conventional alumina balls adsorption capacity is 0.3-0.5wt%, and every kilogram of adsorbent can only process about 400L high-fluorine water (Funing tablet is by 10mg/L); (2) rate of adsorption of adsorbent is slow, and high-fluorine water is the time of staying more than 15min in fixed bed, Oil repellent could be down to below 1mg/L.The fixed-bed design volume of household water filter is about 1-2L, calculates by time of staying 15min, and it produces water speed and only has 67-133mL/min.Therefore, only have the adsorption capacity and the rate of adsorption that improve adsorbent further, the designing requirement of household water filter could be met.
At present, many patented technology documents are all optimized defluorinate adsorbent filtrate.
Application publication number is utilize Fe in the Chinese patent of CN104741088A
3+, Al
3+organic skeletal porous compound is formed, wherein Fe with organic carboxyl acid part
3+, Al
3+have defluorination, this adsorbent can be used for the defluorinate of industry high-concentration fluoride waste, but there is the risk and can not be used for drinking water defluorinate of dissociating because of organic carboxyl acid.Application publication number is the hydroxyapatite filtrate that the Chinese patent of CN104399426A discloses a kind of Al modification; Application publication number is that the Chinese patent of CN103833101A discloses a kind of Cu-Fe hydroxide filtrate; Authorization Notice No. is the montmorillonite that the Chinese patent of CN103071452A discloses a kind of lanthanide series metal modification; Application publication number is that the Chinese patent of CN102641730A discloses a kind of lanthanide series metal resin; Application publication number is the filtrate that the Chinese patent of CN101745362A discloses a kind of zinc carbonate, titanium dioxide and lanthanide metal oxide and mixes; Application publication number is that the Chinese patent of CN101913584A discloses a kind of hydroxyapatite filtrate.These modified adsorbents and traditional aluminium oxide or bone black adsorbent are without essential distinction, and adsorption capacity and the rate of adsorption are all without obviously promoting.
When adsorbent particle diameter be decreased to micron order even nanoscale time, its adsorption capacity and the rate of adsorption can get a promotion.Application publication number is, in the Chinese patent of CN101555078A, nanoscale adsorbent is used for defluorinate, and the rate of adsorption promotes to some extent, and the adsorbent bed time of staying is down to 7min.But the reduction of adsorbent particle diameter can cause the fluid resistance of fixed bed to rise, flow declines.
Summary of the invention
Object of the present invention be exactly provide that a kind of rate of adsorption is fast to overcome defect that above-mentioned prior art exists, adsorption capacity is large, the porous hollow tubular composite membrane being suitable for household small-size drinking water defluorinate device and preparation method thereof and the application in drinking water defluorinate.
Object of the present invention can be achieved through the following technical solutions:
A kind of porous hollow tubular composite membrane, this composite membrane is combined by porous hollow tubular carrier and the adsorption particle Guinier-Preston zone be coated on porous hollow tubular carrier outer surface, described adsorption particle Guinier-Preston zone is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of described adsorption particle Guinier-Preston zone is 5-50mm, preferred 5-30mm.
Described porous hollow tubular carrier is the one in Porous hollow alumina ceramic tube or Porous hollow alumina fibre.
The external diameter of described Porous hollow alumina ceramic tube is 5-20mm, and wall thickness is 1-3mm, and length is 5-20cm, and the external diameter of described Porous hollow alumina fibre is 0.5-5mm, and wall thickness is 0.1-1mm, and length is 5-20cm.
Preferably, the external diameter of described Porous hollow alumina ceramic tube is 5-10mm, and wall thickness is 1mm, and length is 10cm, and the external diameter of described Porous hollow alumina fibre is 1-2mm, and wall thickness is 0.1-0.2mm, and length is 10cm.
Described adsorption particle Guinier-Preston zone mutually to be bondd by shitosan by adsorption particle powder and forms, and the particle diameter of described adsorption particle powder is 5-500 μm, preferred 5-100 μm.
Described adsorption particle powder by molecular sieve, calcium phosphate and aluminium oxide in mass ratio for 0.01-1:0.01-1:0.1-1 mixes.
Preferably, described molecular sieve, calcium phosphate, aluminium oxide three mass ratio are 0.5-1:0.5-1:0.5-1.
Described molecular sieve comprises one or more of 4A molecular sieve, 10X molecular sieve or 13X molecular sieve, described aluminium oxide comprise gama-alumina, Hollow nanofibre shape aluminium oxide, fast shedding or boehmite one or more.
Described Hollow nanofibre shape aluminium oxide is prepared from by method of electrostatic spinning, and external diameter is 400-500nm, and internal diameter is 300-400nm, and length is 1-20 μm.
Preferably, described molecular sieve is 4A molecular sieve, and described aluminium oxide is in gama-alumina or Hollow nanofibre shape aluminium oxide.
A preparation method for porous hollow tubular composite membrane, the method specifically comprises the following steps:
(1) shitosan is dissolved in aqueous acetic acid, is configured to the chitosan solution that concentration is 0.5-1wt%;
(2) add in chitosan solution by adsorption particle powder, be uniformly dispersed, obtained adsorption particle powder quality concentration is the suspension of 0.01-0.3g/mL;
(3) blocked porous hollow tubular carrier one end, another termination Vacuum filtration device, then be immersed in suspension by whole porous hollow tubular carrier, regulate vacuum, the flow velocity controlling suction filtration liquid is 10-100L/ (m
2min) (the m wherein, in flow rate
2refer to the lateral area of porous hollow tubular carrier), make adsorption particle powder be coated on the outer surface of porous hollow tubular carrier gradually, form one deck adsorption particle Guinier-Preston zone;
(4) when the thickness of particle aggregation layer upon adsorption reaches 5-50mm, transferring to mass fraction is in the ammonia spirit of 1-3wt%, continue suction filtration, ammonia spirit is made to flow through adsorption particle Guinier-Preston zone 5-30min, shitosan in adsorption particle Guinier-Preston zone is separated out, adsorption particle powder adhesion is got up;
(5) Surface coating is had that the porous hollow tubular carrier of adsorption particle Guinier-Preston zone is unsettled to be positioned in baking oven, 100-120 DEG C is warming up to 1-5 DEG C/min, freeze-day with constant temperature 1-3h, then be cooled to room temperature with 1-5 DEG C/min, described porous hollow tubular composite membrane can be obtained.
An application for porous hollow tubular composite membrane, is assembled into shell-and-tube adsorbent equipment by described porous hollow tubular composite membrane, for carrying out defluorinate process to drinking water.
Described shell-and-tube adsorbent equipment assembles by the following method:
By the two ends of described porous hollow tubular composite membrane cover upper sealing washer, and be fixed on bracing frame at two ends, then be fixed in cylinder-like shell by bracing frame, finally, two ends connect end socket, are namely assembled into described shell-and-tube adsorbent equipment.
When described shell-and-tube adsorbent equipment is used for carrying out defluorinate process to drinking water, will treat the water of defluorinate, slow inflow pipe shell-type adsorbent equipment, in radial inflow composite membrane central tube, coutroi velocity is 0.1L/ (m
2min)-10L/ (m
2min) (the m in flow rate
2refer to the lateral area of porous hollow tubular composite membrane), water is through the particle aggregation layer duct of perforated tubular composite membrane, and fluorine ion is adsorbed in particle, and the water through defluorinate comes together in carrier center pipeline and flows out.
The described water until defluorinate comprises dense water after reverse osmosis membrane processing of running water, running water or dissolvability solid amount and is less than 1500mg/L and pH is one or more in the underground water of 4-10, after treatment in water Oil repellent lower than 1mg/L.
In actual application, in described shell-and-tube adsorbent equipment, the porous hollow tubular composite membrane be fixed on bracing frame is 1 or 7, is symmetric around bracing frame center, described shell-and-tube adsorbent equipment can used aloned, also can multiple parallel connection or series connection use.
Porous hollow tubular composite membrane of the present invention can make adsorbent while particle diameter reduces, and ensures larger flow, is suitable as household small-size drinking water defluorinate device.
Compared with prior art, the present invention has following characteristics:
1) absorbent particles is directly fixed on central shaft tube surface, form the sorbing material powder adhesion layer of thick layer, compared with " radial fixed-bed " of being fixed by inside and outside two porous cylindrical wall with traditional packing layer, structure is compacter, can existing fixed bed be substituted, for household small-size drinking water defluorinate device.
2) traditional " porous ceramic film " tube wall is thinner, mainly plays filtration; And the thickness of the sorbing material powder adhesion layer of porous hollow tubular composite membrane of the present invention is comparatively large, mainly play suction-operated, expand the application of tradition " porous ceramic film ".
3) sorbent used particle diameter is micron order, and compared with traditional grade adsorbent, the external surface area that micron order adsorbent contacts with water is larger, and faster to the rate of adsorption of fluorine, adsorption capacity is also larger.
4), when traditional fixed bed takes off removing fluorine in water, water axially flows into from fixed bed one end, after flowing through sorbing material layer, flows out from the other end; And the present invention's shell-and-tube adsorbent equipment used is when taking off removing fluorine in water, water comes together in central tube and flows out after radially flowing through sorbing material layer, its operation bed layer cross section amasss (lateral area of elongated cylinder) operation bed layer cross section long-pending (elongated cylinder floor space) much larger than traditional fixed bed.
5) because the present invention uses micron order sorbing material, the rate of adsorption of defluorinate is faster, and its operation bed layer cross section is long-pending larger, and therefore in this shell-and-tube adsorbent equipment unit interval, the amount of production defluorinate water is larger.
6) the porous hollow tubular composite membrane be fixed on bracing frame can be 1 or 7, and shell-and-tube adsorbent equipment can used aloned, also multiple parallel connection or series connection can use, therefore can select flexibly according to different drinking water classification and demand of processing quantity.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 prepares gained porous hollow tubular structure of composite membrane schematic diagram;
Fig. 2 is the shell-and-tube adsorbent equipment structural representation described in embodiment 1;
Fig. 3 is support frame structure schematic diagram in the shell-and-tube adsorbent equipment described in embodiment 1;
Fig. 4 is water (flow) direction schematic diagram in the shell-and-tube adsorbent equipment described in embodiment 1;
Fig. 5 is that embodiment 1 is prepared gained porous hollow tubular composite membrane working sections and amassed schematic diagram;
Fig. 6 amasss schematic diagram for the fixed bed packing layer working sections described in comparative example 1;
Fig. 7 is that embodiment 2 prepares gained porous hollow tubular structure of composite membrane schematic diagram;
Fig. 8 is support frame structure schematic diagram in the shell-and-tube adsorbent equipment described in embodiment 2;
Description of symbols in figure:
1-porous hollow tubular composite membrane, 11-porous hollow tubular carrier, 12-adsorption particle Guinier-Preston zone, 2-seal washer, 3-bracing frame, 4-cylindrical shell, 5-end socket, 6-fixed bed packing layer.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
Porous hollow tubular composite membrane device removes the fluorine in running water
The preparation of porous hollow tubular composite membrane 1: be dissolved in by shitosan in 1wt% aqueous acetic acid, is configured to concentration 0.5% chitosan solution 2L.The absorbent particles powder of 400g is added wherein, is configured to suspension; Absorbent particles is mixed by the mass ratio of 1:1:0.8:0.2 by 4A molecular sieve, calcium phosphate, gama-alumina particle, fast shedding, and often kind of absorbent particles particle diameter is 40 microns-50 microns.Select Porous hollow alumina ceramic tube to make porous hollow tubular carrier 11, earthenware external diameter is 10mm, wall thickness 1mm, length 150mm.Porous hollow tubular carrier 11 one end is blocked, another termination Vacuum filtration device, whole porous hollow tubular carrier 11 is immersed in above-mentioned suspension, suction filtration, powder granule is made to be attached to porous hollow tubular carrier 11 outer surface gradually, form one deck adsorption particle Guinier-Preston zone 12, when the thickness of particle aggregation layer 12 upon adsorption reaches 30mm, porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirit, continuing suction filtration makes ammoniacal liquor flow through adsorption particle Guinier-Preston zone 1210min, the unsettled baking oven Program that is positioned over of porous hollow tubular carrier 11 that attached to adsorption particle Guinier-Preston zone 12 heats up dry, 105 DEG C are warming up to 1 DEG C/min, keep 105 DEG C of dry 2h, room temperature is cooled to again with 1 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, forms porous hollow tubular composite membrane, as shown in Figure 1.
Shell-and-tube adsorbent equipment is assembled: 1 above-mentioned porous hollow tubular composite membrane 1 is formed shell-and-tube adsorbent equipment with internal diameter 80mm cylindrical shell 4, seal washer 2, bracing frame 3 and end socket 5, as shown in Figure 2.Its support frame structure as shown in Figure 3.
Running water defluorinate: add a certain amount of NaF solution in running water, makes wherein Oil repellent be 2.6mg/L.Running water is with 0.3L/min through adsorption particle Guinier-Preston zone 12 duct of perforated tubular composite membrane 1, and fluorine ion is wherein adsorbed in particle, flows out in the central tube that the water of defluorinate comes together in porous hollow tubular carrier 11.Treat the flow direction of the water of defluorinate in this shell-and-tube adsorbent equipment as shown in Figure 4, the working sections of this porous hollow tubular composite membrane 1 is long-pending as shown in Figure 5.
Oil repellent in detection outflow water, with the change of flowing out the water yield, lists in table 1.Wherein fluorinion concentration fluorine ion selective electrode determining.As shown in Table 1, as flow of inlet water 0.3L/min, in water outlet, Funing tablet can be down in 1mg/L, meets Drinking Water in China standard.
Table 1 fluorinion concentration is with the change of flowing out the water yield
| Processing time | 1min | 10min | 1h | 2h | 5h | 10h |
| Flow out the water yield, L | 0.3L | 3L | 18L | 36L | 90L | 180L |
| Funing tablet, mg/L | 0.86 | 0.85 | 0.88 | 0.86 | 0.91 | 0.95 |
。
Comparative example 1:
Tradition fixed bed device removes the fluorine in running water
Fixed bed device is assembled: select internal diameter 80mm fixed bed, wherein fixed bed packing layer 6 height 150mm (identical with the composite membrane length in embodiment 1), 0.5mm-0.6mm activated alumina adsorbents selected by adsorbent.
Running water defluorinate: add a certain amount of NaF solution in running water, makes wherein Oil repellent be 2.6mg/L.Running water flows through fixed bed with 0.05L/min, and the Oil repellent in detection outflow water, with the change of flowing out the water yield, lists in table 2.After 10 hours, flow velocity is adjusted to 0.3L/min, (identical with the flow velocity in embodiment 1), the Oil repellent in detection outflow water, with the change of flowing out the water yield, lists in table 3.Wherein fluorinion concentration fluorine ion selective electrode determining.The working sections of this fixed bed packing layer 6 is long-pending as shown in Figure 6.
Compared with embodiment 1, comparative example 1 is (0.05L/min) when flow of inlet water is less, within Funing tablet can be down to 1mg/L in water outlet, meets Drinking Water in China standard; But when flow of inlet water is larger (0.3L/min), in water outlet, Funing tablet is then more than 1mg/L, cannot meet potable water guidelines.
Table 2 fluorinion concentration is with the change (flow velocity 0.05L/min) of flowing out the water yield
| Processing time | 1min | 10min | 1h | 2h | 5h | 10h |
| Flow out the water yield, L | 0.05L | 0.5L | 3L | 6L | 15L | 30L |
| Funing tablet, mg/L | 0.76 | 0.72 | 0.81 | 0.83 | 0.85 | 0.89 |
。
Table 3 fluorinion concentration is with the change (flow velocity 0.3L/min) of flowing out the water yield
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out the water yield, L | 0.3L | 3L | 18L | 36L | 90L |
| Funing tablet, mg/L | 1.22 | 1.62 | 1.88 | 2.03 | 2.21 |
。
Comparative example 2:
Tradition fixed bed device removes the fluorine in running water
Fixed bed device is assembled: select internal diameter 80mm fixed bed, wherein fixed bed packing layer 6 height 150mm (identical with the composite membrane length in embodiment 1), 40 microns-50 microns mixed adsorbent particles (mixed adsorbent particle is mixed by the mass ratio of 1:1:0.8:0.2 by 4A molecular sieve, calcium phosphate, gama-alumina particle, fast shedding, and often kind of absorbent particles particle diameter is 40 microns-50 microns) selected by adsorbent.Various filler is fully mixed in rear loading fixed bed.
Running water defluorinate: add a certain amount of NaF solution in running water, makes wherein Oil repellent be 2.6mg/L.Running water flows through fixed bed with 0.05L/min, and the Oil repellent in detection outflow water, with the change of flowing out the water yield, lists in table 4.Wherein fluorinion concentration fluorine ion selective electrode determining.
Compared with embodiment 1, comparative example 2 is (0.05L/min) when flow of inlet water is less, within Funing tablet can be down to 1mg/L in water outlet, meets Drinking Water in China standard; But the resistance of the bed of fixed bed is comparatively large, fixed bed is imported and exported pressure drop and is about 6bar.And fixed bed import and export pressure drop is less than 1bar in embodiment 1.
Table 4 fluorinion concentration is with the change of flowing out the water yield
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out the water yield, L | 0.05L | 0.5L | 3L | 6L | 15L |
| Funing tablet, mg/L | 0.12 | 0.12 | 0.13 | 0.15 | 0.19 |
。
Embodiment 2:
Hollow porous composite film device remove reverse osmosis process discharge fluorine in dense water
The preparation of porous hollow tubular composite membrane 1: be dissolved in by shitosan in 1wt% aqueous acetic acid, is configured to concentration 1% chitosan solution 2L.The absorbent particles powder of 400g is added wherein, is configured to suspension; Absorbent particles by 4A molecular sieve, calcium phosphate, gama-alumina particle, (external diameter is about 500nm to hollow nano-alumina fiber, internal diameter 300nm, length 20 microns), boehmite mixes by the mass ratio of 1:1:0.4:0.4:0.2, except hollow nano-alumina fiber, all the other four kinds of absorbent particles particle diameters are 40 microns-50 microns.Select Porous hollow alumina fibre to make porous hollow tubular carrier 11, alumina fibre external diameter is 5mm, wall thickness 1mm, length 100mm.Reference example 1, suction filtration mode is used to make alumina fibre surface form one deck adsorption particle Guinier-Preston zone 12, when the thickness of particle aggregation layer 12 upon adsorption reaches 5mm, porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirit, continue suction filtration, ammoniacal liquor is made to flow through adsorption particle Guinier-Preston zone 125min, the unsettled baking oven Program that is positioned over of porous hollow tubular carrier 11 that attached to adsorption particle Guinier-Preston zone 12 heats up dry, 105 DEG C are warming up to 1 DEG C/min, keep 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, forms porous hollow tubular composite membrane 1, as shown in Figure 7.
Shell-and-tube adsorbent equipment is assembled: above-mentioned porous hollow tubular composite membrane 1 seven and internal diameter 80mm cylindrical shell 4, seal washer 2, bracing frame 3, end socket 5 etc. are formed shell-and-tube adsorbent equipment.Its bracing frame 3 structure as shown in Figure 8.Two shell-and-tube adsorbent equipment series connection used, namely the delivery port of a shell-and-tube adsorbent equipment is connected with the water inlet of another shell-and-tube adsorbent equipment.
Reverse osmosis process discharges dense water defluorinate: measuring fluorinion concentration in dense water is 6.8mg/L.Dense water is with 0.1L/min through perforated tubular composite membrane device, and the Oil repellent in detection outflow water, with the change of flowing out the water yield, lists in table 5.Wherein fluorinion concentration fluorine ion selective electrode determining.
As shown in Table 5, as flow of inlet water 0.1L/min, in water outlet, Funing tablet can be down in 1mg/L.
Table 5 fluorinion concentration is with the change of flowing out the water yield
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out the water yield, L | 0.1L | 1L | 6L | 12L | 30L |
| Funing tablet, mg/L | 0.82 | 0.78 | 0.83 | 0.85 | 0.91 |
。
Comparative example 3:
Tradition fixed bed device removes the fluorine in running water
Fixed bed device is assembled: select internal diameter 80mm fixed bed, wherein fixed bed packing layer 6 height 200mm (2 times for the composite membrane length in embodiment 2), adsorbent is 0.5mm-0.6mm activated alumina adsorbents.
Reverse osmosis process discharges dense water defluorinate: measuring fluorinion concentration in dense water is 6.8mg/L.Dense water is with 0.1L/min through perforated tubular composite membrane device, and the Oil repellent in detection outflow water, with the change of flowing out the water yield, lists in table 6.Wherein fluorinion concentration fluorine ion selective electrode determining.
As shown in Table 6, as flow of inlet water 0.1L/min, in water outlet, Funing tablet fails to be down in 1mg/L.Compared with embodiment 2, the speed that comparative example 3 removes fluorine obviously reduces.
Table 6 fluorinion concentration is with the change of flowing out the water yield
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out the water yield, L | 0.1L | 1L | 6L | 12L | 30L |
| Funing tablet, mg/L | 1.52 | 1.48 | 1.63 | 1.72 | 2.33 |
。
Embodiment 3:
Hollow porous composite film device removes the fluorine in underground water
The preparation of porous hollow tubular composite membrane 1: the preparation process reference example 2 of porous hollow tubular composite membrane 1.
Shell-and-tube adsorbent equipment is assembled: above-mentioned porous hollow tubular composite membrane 1 seven and internal diameter 80mm cylindrical shell 4, seal washer 2, bracing frame 3, end socket 5 etc. are formed shell-and-tube adsorbent equipment.The parallel connection of two shell-and-tube adsorbent equipments used, namely the water inlet of a shell-and-tube adsorbent equipment, delivery port are connected with the water inlet of another shell-and-tube adsorbent equipment, delivery port respectively.To increase the disposal ability of whole system.
Underground water defluorinate: measuring fluorinion concentration in underground is 3.8mg/L.Underground water is with 0.2L/min through perforated tubular composite membrane device, and the Oil repellent in detection outflow water, with the change of flowing out the water yield, lists in table 7.Wherein fluorinion concentration fluorine ion selective electrode determining.
As shown in Table 7, as flow of inlet water 0.2L/min, in water outlet, Funing tablet can be down in 1mg/L, reaches Drinking Water in China standard-required.
Table 7 fluorinion concentration is with the change of flowing out the water yield
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out the water yield, L | 0.2L | 2L | 12L | 24L | 60L |
| Funing tablet, mg/L | 0.52 | 0.63 | 0.68 | 0.75 | 0.77 |
。
Embodiment 4:
Hollow porous composite film device removes the fluorine in underground water
The preparation of porous hollow tubular composite membrane 1: the preparation process reference example 1 of porous hollow tubular composite membrane 1.
Shell-and-tube adsorbent equipment is assembled: above-mentioned porous hollow tubular composite membrane 1 one and internal diameter 80mm cylindrical shell 4, seal washer 2, bracing frame 3, end socket 5 etc. are formed shell-and-tube adsorbent equipment.Two shell-and-tube adsorbent equipment series connection used, namely the delivery port of a shell-and-tube adsorbent equipment is connected with the water inlet of another shell-and-tube adsorbent equipment.
Underground water defluorinate: measuring fluorinion concentration in underground is 3.9mg/L.Underground water is with 0.3L/min through perforated tubular composite membrane device, and the Oil repellent in detection outflow water, with the change of flowing out the water yield, lists in table 8.Wherein fluorinion concentration fluorine ion selective electrode determining.
As shown in Table 8, as flow of inlet water 0.3L/min, in water outlet, Funing tablet can be down in 1mg/L, reaches Drinking Water in China standard-required.
Table 8 fluorinion concentration is with the change of flowing out the water yield
Embodiment 5:
The present embodiment porous hollow tubular composite membrane 1, combined by porous hollow tubular carrier 11 and the adsorption particle Guinier-Preston zone 12 be coated on porous hollow tubular carrier 11 outer surface, described adsorption particle Guinier-Preston zone 12 is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of described adsorption particle Guinier-Preston zone 12 is 15mm.
Described adsorption particle powder by molecular sieve, calcium phosphate, aluminium oxide three in mass ratio 0.01:0.01:1 form.
Described molecular sieve is 10X molecular sieve, and described aluminium oxide is Hollow nanofibre shape aluminium oxide, and described Hollow nanofibre shape aluminium oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 400nm, and internal diameter is 300nm, and length is 1 micron.
Described porous hollow tubular carrier 11 is Porous hollow alumina ceramic tube.
The particle diameter of described adsorption particle powder is 5 microns, and described Porous hollow alumina ceramic tube external diameter is 5mm, and wall thickness is 3mm, and length is 5cm.
The preparation method of the present embodiment porous hollow tubular composite membrane 1, specifically comprises the following steps:
(1) shitosan is dissolved in 1wt% aqueous acetic acid, is configured to the chitosan solution that concentration is 0.9wt%;
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, fully stir, powder is suspended good;
(3) blocked porous hollow tubular carrier 11 one end, another termination Vacuum filtration device, is immersed in above-mentioned suspension by whole porous hollow tubular carrier 11, regulates vacuum, controls the flow velocity 60L/ (m of suction filtration liquid
2min) (the m in flow rate
2refer to carrier side area), make powder granule be attached to porous hollow tubular carrier 11 outer surface gradually, form one deck adsorption particle Guinier-Preston zone 12;
(4) when the thickness of particle aggregation layer 12 upon adsorption reaches 15mm, porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirit, continue suction filtration, ammoniacal liquor is made to flow through adsorption particle Guinier-Preston zone 1220min, shitosan in adsorption particle Guinier-Preston zone 12 is separated out, powder granule bonding is got up;
(5) unsettled for the porous hollow tubular carrier 11 that the attached to adsorption particle Guinier-Preston zone 12 baking oven Program that is positioned over is heated up dry, be warming up to 105 DEG C with 1 DEG C/min, keep 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, forms porous membrane structure, obtains porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is add 10g powder in every 100mL chitosan solution.
The application of porous hollow tubular composite membrane 1 in drinking water defluorinate, this application process specifically comprises the following steps:
A () shell-and-tube adsorbent equipment is assembled: by described porous hollow tubular composite membrane 1 two ends cover upper sealing washer 2; Then two ends are fixed on bracing frame 3; Be fixed on by bracing frame in cylinder-like shell 4, two ends connect end socket 5 more again, obtain shell-and-tube adsorbent equipment.
B defluorinate in () drinking water: will treat the water of defluorinate, slowly flows into the shell-and-tube adsorbent equipment described in step (a), in radial inflow porous hollow tubular composite membrane 1 central tube, coutroi velocity is 8L/ (m
2min) (the m in flow rate
2refer to the outside area of porous hollow tubular composite membrane 1), water is through the adsorption particle Guinier-Preston zone duct of porous hollow tubular composite membrane 1, fluorine ion is wherein adsorbed in particle, flows out in the central tube that the water of defluorinate comes together in porous hollow tubular carrier 11.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 be fixed on bracing frame 3 is one, 3 parallel connections of described shell-and-tube.
The water until defluorinate described in step (b) is the dense water of running water after reverse osmosis membrane processing, after treatment in water Oil repellent lower than 1mg/L.
Embodiment 6:
The present embodiment porous hollow tubular composite membrane 1, combined by porous hollow tubular carrier 11 and the adsorption particle Guinier-Preston zone 12 be coated on porous hollow tubular carrier 11 outer surface, described adsorption particle Guinier-Preston zone 12 is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of described adsorption particle Guinier-Preston zone 12 is 40mm.
Described adsorption particle powder by molecular sieve, calcium phosphate, aluminium oxide three in mass ratio 0.01:1:1 form.
Described molecular sieve is 13X molecular sieve, and described aluminium oxide is Hollow nanofibre shape aluminium oxide, and described Hollow nanofibre shape aluminium oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 500nm, and internal diameter is 400nm, and length is 10 microns.
Described porous hollow tubular carrier 11 is Porous hollow alumina ceramic tube.
The particle diameter of described adsorption particle powder is 500 microns, and described Porous hollow alumina ceramic tube external diameter is 20mm, and wall thickness is 2mm, and length is 20cm.
The preparation method of the present embodiment porous hollow tubular composite membrane 1, specifically comprises the following steps:
(1) shitosan is dissolved in 1wt% aqueous acetic acid, is configured to the chitosan solution that concentration is 0.6wt%;
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, fully stir, powder is suspended good;
(3) blocked porous hollow tubular carrier 11 one end, another termination Vacuum filtration device, is immersed in above-mentioned suspension by whole porous hollow tubular carrier 11, regulates vacuum, controls the flow velocity 70L/ (m of suction filtration liquid
2min) (the m in flow rate
2refer to carrier side area), make powder granule be attached to porous hollow tubular carrier 11 outer surface gradually, form one deck adsorption particle Guinier-Preston zone 12;
(4) when the thickness of particle aggregation layer 12 upon adsorption reaches 40mm, porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirit, continue suction filtration, ammoniacal liquor is made to flow through adsorption particle Guinier-Preston zone 1225min, shitosan in adsorption particle Guinier-Preston zone 12 is separated out, powder granule bonding is got up;
(5) unsettled for the porous hollow tubular carrier 11 that the attached to adsorption particle Guinier-Preston zone 12 baking oven Program that is positioned over is heated up dry, be warming up to 105 DEG C with 1 DEG C/min, keep 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, forms porous membrane structure, obtains porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is add 18g powder in every 100mL chitosan solution.
The application of porous hollow tubular composite membrane 1 in drinking water defluorinate, this application process specifically comprises the following steps:
A () shell-and-tube adsorbent equipment is assembled: by described porous hollow tubular composite membrane 1 two ends cover upper sealing washer 2; Then two ends are fixed on bracing frame 3; Be fixed on by bracing frame in cylinder-like shell 4, two ends connect end socket 5 more again, obtain shell-and-tube adsorbent equipment.
B defluorinate in () drinking water: will treat the water of defluorinate, slowly flows into the shell-and-tube adsorbent equipment described in step (a), in the central tube of radial inflow porous hollow tubular composite membrane 1, coutroi velocity is 8L/ (m
2min) (the m in flow rate
2refer to the outside area of porous hollow tubular composite membrane 1), water is through adsorption particle Guinier-Preston zone 12 duct of porous hollow tubular composite membrane 1, fluorine ion is wherein adsorbed in particle, flows out in the central tube that the water of defluorinate comes together in porous hollow tubular carrier 11.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 be fixed on bracing frame 3 is one, and described shell-and-tube adsorbent equipment 3 series connection uses.
The water treating defluorinate described in step (b) is that dissolvability solid amount is less than 1500mg/L and pH is the underground water of 7, after treatment in water Oil repellent lower than 1mg/L.
Embodiment 7:
The present embodiment porous hollow tubular composite membrane 1, combined by porous hollow tubular carrier 11 and the adsorption particle Guinier-Preston zone 12 be coated on porous hollow tubular carrier 11 outer surface, described adsorption particle Guinier-Preston zone 12 is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of described adsorption particle Guinier-Preston zone 12 is 30mm.
Described adsorption particle powder by molecular sieve, calcium phosphate, aluminium oxide three in mass ratio 1:0.01:1 form.
Described molecular sieve is 4A molecular sieve and 10X molecular sieve, and described aluminium oxide is Hollow nanofibre shape aluminium oxide, and described Hollow nanofibre shape aluminium oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 400nm, and internal diameter is 400nm, and length is 1 micron.
Described porous hollow tubular carrier 11 is Porous hollow alumina fibre.
The particle diameter of described adsorption particle powder is 50 microns, and described Porous hollow alumina fibre external diameter is 0.5mm, and wall thickness is 0.1mm, and length is 5cm.
The preparation method of porous hollow tubular composite membrane 1, specifically comprises the following steps:
(1) shitosan is dissolved in 1wt% aqueous acetic acid, is configured to the chitosan solution that concentration is 0.6wt%;
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, fully stir, powder is suspended good;
(3) blocked porous hollow tubular carrier 11 one end, another termination Vacuum filtration device, is immersed in above-mentioned suspension by whole porous hollow tubular carrier 11, regulates vacuum, controls the flow velocity 30L/ (m of suction filtration liquid
2min) (the m in flow rate
2refer to carrier side area), make powder granule be attached to porous hollow tubular carrier 11 outer surface gradually, form one deck adsorption particle Guinier-Preston zone 12;
(4) when the thickness of particle aggregation layer 12 upon adsorption reaches 30mm, porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirit, continue suction filtration, ammoniacal liquor is made to flow through adsorption particle Guinier-Preston zone 1215min, shitosan in adsorption particle Guinier-Preston zone 12 is separated out, powder granule bonding is got up;
(5) unsettled for the porous hollow tubular carrier 11 that the attached to adsorption particle Guinier-Preston zone 12 baking oven Program that is positioned over is heated up dry, be warming up to 105 DEG C with 1 DEG C/min, keep 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, forms porous membrane structure, obtains porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is add 15g powder in every 100mL chitosan solution.
The application of porous hollow tubular composite membrane 1 in drinking water defluorinate, this application process specifically comprises the following steps:
A () shell-and-tube adsorbent equipment is assembled: by described porous hollow tubular composite membrane 1 two ends cover upper sealing washer 2; Then two ends are fixed on bracing frame 3; Be fixed on by bracing frame in cylinder-like shell 4, two ends connect end socket 5 more again, obtain shell-and-tube adsorbent equipment.
B defluorinate in () drinking water: will treat the water of defluorinate, slowly flows into the shell-and-tube adsorbent equipment described in step (a), in the central tube of radial inflow porous hollow tubular composite membrane 1, coutroi velocity is 3L/ (m
2min) (the m in flow rate
2refer to the outside area of porous hollow tubular composite membrane 1), water is through adsorption particle Guinier-Preston zone 12 duct of porous hollow tubular composite membrane 1, fluorine ion is wherein adsorbed in particle, flows out in the central tube that the water of defluorinate comes together in porous hollow tubular carrier 11.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 be fixed on bracing frame 3 is one, described shell-and-tube adsorbent equipment used aloned.
The water treating defluorinate described in step (b) is that dissolvability solid amount is less than 1500mg/L and pH is the underground water of 10, after treatment in water Oil repellent lower than 1mg/L.
Embodiment 8:
The present embodiment porous hollow tubular composite membrane 1, combined by porous hollow tubular carrier 11 and the adsorption particle Guinier-Preston zone 12 be coated on porous hollow tubular carrier 11 outer surface, described adsorption particle Guinier-Preston zone 12 is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of described adsorption particle Guinier-Preston zone 12 is 50mm.
Described adsorption particle powder by molecular sieve, calcium phosphate, aluminium oxide three in mass ratio 0.01:1:0.1 form.
Described molecular sieve is 10X molecular sieve and 13X molecular sieve, and described aluminium oxide is Hollow nanofibre shape aluminium oxide, and described Hollow nanofibre shape aluminium oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 500nm, and internal diameter is 400nm, and length is 20 microns.
Described porous hollow tubular carrier 11 is Porous hollow alumina fibre.
The particle diameter of described adsorption particle powder is 50 microns, and described Porous hollow alumina fibre external diameter is 2mm, and wall thickness is 0.5mm, and length is 20cm.
The preparation method of porous hollow tubular composite membrane, specifically comprises the following steps:
(1) shitosan is dissolved in 1wt% aqueous acetic acid, is configured to the chitosan solution that concentration is 0.8wt%;
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, fully stir, powder is suspended good;
(3) blocked porous hollow tubular carrier 11 one end, another termination Vacuum filtration device, is immersed in above-mentioned suspension by whole porous hollow tubular carrier 11, regulates vacuum, controls the flow velocity 65L/ (m of suction filtration liquid
2min) (the m in flow rate
2refer to carrier side area), make powder granule be attached to porous hollow tubular carrier 11 outer surface gradually, form one deck adsorption particle Guinier-Preston zone 12;
(4) when the thickness of particle aggregation layer 12 upon adsorption reaches 50mm, porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirit, continue suction filtration, ammoniacal liquor is made to flow through adsorption particle Guinier-Preston zone 1220min, shitosan in adsorption particle Guinier-Preston zone 12 is separated out, powder granule bonding is got up;
(5) unsettled for the porous hollow tubular carrier 11 that the attached to adsorption particle Guinier-Preston zone 12 baking oven Program that is positioned over is heated up dry, be warming up to 105 DEG C with 1 DEG C/min, keep 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, forms porous membrane structure, obtains porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is add 10g powder in every 100mL chitosan solution.
The application of porous hollow tubular composite membrane 1 in drinking water defluorinate, this application process specifically comprises the following steps:
A () shell-and-tube adsorbent equipment is assembled: by described porous hollow tubular composite membrane 1 two ends cover upper sealing washer 2; Then two ends are fixed on bracing frame 3; Be fixed on by bracing frame in cylinder-like shell 4, two ends connect end socket 5 more again, obtain shell-and-tube adsorbent equipment.
B defluorinate in () drinking water: will treat the water of defluorinate, slowly flows into the shell-and-tube adsorbent equipment described in step (a), in the central tube of radial inflow porous hollow tubular composite membrane 1, coutroi velocity is 5L/ (m
2min) (the m in flow rate
2refer to the outside area of porous hollow tubular composite membrane 1), water is through adsorption particle Guinier-Preston zone 12 duct of porous hollow tubular composite membrane 1, fluorine ion is wherein adsorbed in particle, flows out in the central tube that the water of defluorinate comes together in porous hollow tubular carrier 11.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 be fixed on bracing frame 3 is one, described shell-and-tube adsorbent equipment used aloned.
The water treating defluorinate described in step (b) is that dissolvability solid amount is less than 1500mg/L and pH is the underground water of 4, after treatment in water Oil repellent lower than 1mg/L.
Embodiment 9:
The present embodiment porous hollow tubular composite membrane 1, combined by porous hollow tubular carrier 11 and the adsorption particle Guinier-Preston zone 12 be coated on porous hollow tubular carrier 11 outer surface, described adsorption particle Guinier-Preston zone 12 is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of described adsorption particle Guinier-Preston zone 12 is 5mm.
Described adsorption particle powder by molecular sieve, calcium phosphate, aluminium oxide three in mass ratio 1:0.01:0.1 form.
Described molecular sieve is 4A molecular sieve and 13X molecular sieve, and described aluminium oxide is Hollow nanofibre shape aluminium oxide, and described Hollow nanofibre shape aluminium oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 450nm, and internal diameter is 350nm, and length is 10 microns.
Described porous hollow tubular carrier 11 is Porous hollow alumina ceramic tube.
The particle diameter of described adsorption particle powder is 100 microns, and described Porous hollow alumina ceramic tube external diameter is 15mm, and wall thickness is 1.5mm, and length is 15cm.
The preparation method of porous hollow tubular composite membrane 1, specifically comprises the following steps:
(1) shitosan is dissolved in 1wt% aqueous acetic acid, is configured to the chitosan solution that concentration is 0.6wt%;
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, fully stir, powder is suspended good;
(3) blocked porous hollow tubular carrier 11 one end, another termination Vacuum filtration device, is immersed in above-mentioned suspension by whole porous hollow tubular carrier 11, regulates vacuum, controls the flow velocity 100L/ (m of suction filtration liquid
2min) (the m in flow rate
2refer to carrier side area), make powder granule be attached to porous hollow tubular carrier 11 outer surface gradually, form one deck adsorption particle Guinier-Preston zone 12;
(4) when the thickness of particle aggregation layer 12 upon adsorption reaches 5mm, porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirit, continue suction filtration, make ammoniacal liquor flow through adsorption particle Guinier-Preston zone 1230min, shitosan in adsorption particle Guinier-Preston zone 12 is separated out, powder granule bonding is got up;
(5) unsettled for the porous hollow tubular carrier 11 that the attached to adsorption particle Guinier-Preston zone 12 baking oven Program that is positioned over is heated up dry, be warming up to 105 DEG C with 1 DEG C/min, keep 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, forms porous membrane structure, obtains porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is add 30g powder in every 100mL chitosan solution.
The application of porous hollow tubular composite membrane 1 in drinking water defluorinate, this application process specifically comprises the following steps:
A () shell-and-tube adsorbent equipment is assembled: by described porous hollow tubular composite membrane 1 two ends cover upper sealing washer 2; Then two ends are fixed on bracing frame 3; Be fixed on by bracing frame in cylinder-like shell 4, two ends connect end socket 5 more again, obtain shell-and-tube adsorbent equipment.
B defluorinate in () drinking water: will treat the water of defluorinate, slowly flows into the shell-and-tube adsorbent equipment described in step (a), in the central tube of radial inflow porous hollow tubular composite membrane 1, coutroi velocity is 10L/ (m
2min) (the m in flow rate
2refer to the outside area of porous hollow tubular composite membrane 1), water is through adsorption particle Guinier-Preston zone 12 duct of porous hollow tubular composite membrane 1, fluorine ion is wherein adsorbed in particle, flows out in the central tube that the water of defluorinate comes together in porous hollow tubular carrier 11.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 be fixed on bracing frame 3 is seven, described shell-and-tube adsorbent equipment used aloned.
The water until defluorinate described in step (b) is the dense water of running water after reverse osmosis membrane processing, after treatment in water Oil repellent lower than 1mg/L.
Embodiment 10:
The present embodiment porous hollow tubular composite membrane 1, combined by porous hollow tubular carrier 11 and the adsorption particle Guinier-Preston zone 12 be coated on porous hollow tubular carrier 11 outer surface, described adsorption particle Guinier-Preston zone 12 is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of described adsorption particle Guinier-Preston zone 12 is 25mm.
Described adsorption particle powder by molecular sieve, calcium phosphate, aluminium oxide three in mass ratio 1:1:0.1 form.
Described molecular sieve is 4A molecular sieve, 10X molecular sieve and 13X molecular sieve, described aluminium oxide is Hollow nanofibre shape aluminium oxide, and described Hollow nanofibre shape aluminium oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 400nm, internal diameter is 400nm, and length is 1 micron.
Described porous hollow tubular carrier 11 is Porous hollow alumina fibre.
The particle diameter of described adsorption particle powder is 300 microns, and described Porous hollow alumina fibre external diameter is 3mm, and wall thickness is 0.6mm, and length is 12cm.
The preparation method of porous hollow tubular composite membrane 1, specifically comprises the following steps:
(1) shitosan is dissolved in 1wt% aqueous acetic acid, is configured to the chitosan solution that concentration is 0.7wt%;
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, fully stir, powder is suspended good;
(3) blocked porous hollow tubular carrier 11 one end, another termination Vacuum filtration device, is immersed in above-mentioned suspension by whole porous hollow tubular carrier 11, regulates vacuum, controls the flow velocity 10L/ (m of suction filtration liquid
2min) (the m in flow rate
2refer to carrier side area), make powder granule be attached to porous hollow tubular carrier 11 outer surface gradually, form one deck adsorption particle Guinier-Preston zone 12;
(4) when the thickness of particle aggregation layer 12 upon adsorption reaches 25mm, porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirit, continue suction filtration, make ammoniacal liquor flow through adsorption particle Guinier-Preston zone 125min, shitosan in adsorption particle Guinier-Preston zone 12 is separated out, powder granule bonding is got up;
(5) unsettled for the porous hollow tubular carrier 11 that the attached to adsorption particle Guinier-Preston zone 12 baking oven Program that is positioned over is heated up dry, be warming up to 120 DEG C with 2 DEG C/min, keep 120 DEG C of dry 1h, then be cooled to room temperature with 2 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, forms porous membrane structure, obtains porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is add 1g powder in every 100mL chitosan solution.
The application of porous hollow tubular composite membrane 1 in drinking water defluorinate, this application process specifically comprises the following steps:
A () shell-and-tube adsorbent equipment is assembled: by described porous hollow tubular composite membrane 1 two ends cover upper sealing washer 2; Then two ends are fixed on bracing frame 3; Be fixed on by bracing frame in cylinder-like shell 4, two ends connect end socket 5 more again, obtain shell-and-tube adsorbent equipment.
B defluorinate in () drinking water: will treat the water of defluorinate, slowly flows into the shell-and-tube adsorbent equipment described in step (a), in the central tube of radial inflow porous hollow tubular composite membrane 1, coutroi velocity is 0.1L/ (m
2min) (the m in flow rate
2refer to the outside area of porous hollow tubular composite membrane 1), water is through adsorption particle Guinier-Preston zone 12 duct of porous hollow tubular composite membrane 1, fluorine ion is wherein adsorbed in particle, flows out in the central tube that the water of defluorinate comes together in porous hollow tubular carrier 11.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 be fixed on bracing frame 3 is seven, is symmetric around bracing frame center, described shell-and-tube adsorbent equipment used aloned.
The water treating defluorinate described in step (b) is running water, after treatment in water Oil repellent lower than 1mg/L.
Embodiment 11:
In this enforcement, porous hollow tubular composite membrane 1 is combined by porous hollow tubular carrier 11 and the adsorption particle Guinier-Preston zone 12 be coated on porous hollow tubular carrier 11 outer surface, adsorption particle Guinier-Preston zone 12 is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of adsorption particle Guinier-Preston zone 12 is 35mm.
Wherein, porous hollow tubular carrier 11 is Porous hollow alumina ceramic tube, and the external diameter of this hollow aluminium earthenware is 20mm, and wall thickness is 2mm, and length is 16cm.Adsorption particle Guinier-Preston zone 12 mutually to be bondd by shitosan by adsorption particle powder and forms, and the particle diameter of adsorption particle powder is 5-500 μm.
Adsorption particle powder by molecular sieve, calcium phosphate and aluminium oxide in mass ratio for 0.8:0.6:1 mixes.Wherein, molecular sieve is 13X molecular sieve, and aluminium oxide is boehmite
The preparation method of the present embodiment porous hollow tubular composite membrane 1, specifically comprises the following steps:
(1) shitosan is dissolved in aqueous acetic acid, is configured to the chitosan solution that concentration is 0.5wt%;
(2) add in chitosan solution by adsorption particle powder, be uniformly dispersed, obtained adsorption particle powder quality concentration is the suspension of 0.1g/mL;
(3) blocked porous hollow tubular carrier 11 one end, another termination Vacuum filtration device, then be immersed in suspension by whole porous hollow tubular carrier 11, regulate vacuum, the flow velocity controlling suction filtration liquid is 60L/ (m
2min), make adsorption particle powder be coated on the outer surface of porous hollow tubular carrier 11 gradually, form one deck adsorption particle Guinier-Preston zone 12;
(4) when the thickness of particle aggregation layer 12 upon adsorption reaches 35mm, transferring to mass fraction is in the ammonia spirit of 3wt%, continue suction filtration, ammonia spirit is made to flow through adsorption particle Guinier-Preston zone 1230min, shitosan in adsorption particle Guinier-Preston zone 12 is separated out, adsorption particle powder adhesion is got up;
(5) Surface coating is had that the porous hollow tubular carrier 11 of adsorption particle Guinier-Preston zone 12 is unsettled to be positioned in baking oven, be warming up to 100 DEG C with 5 DEG C/min, freeze-day with constant temperature 3h, then be cooled to room temperature with 5 DEG C/min, porous hollow tubular composite membrane 1 can be obtained.
Porous hollow tubular composite membrane 1, when practical application, is assembled into shell-and-tube adsorbent equipment, for carrying out defluorinate process to drinking water by the porous hollow tubular composite membrane 1 that the present embodiment obtains.Shell-and-tube adsorbent equipment assembles by the following method:
By the two ends of porous hollow tubular composite membrane 1 cover upper sealing washer 2, and be fixed on bracing frame 3 at two ends, then be fixed on by bracing frame in cylinder-like shell 4, finally, two ends connect end socket 5, are namely assembled into shell-and-tube adsorbent equipment.
Claims (10)
1. a porous hollow tubular composite membrane, it is characterized in that, this composite membrane is combined by porous hollow tubular carrier (11) and the adsorption particle Guinier-Preston zone (12) be coated on porous hollow tubular carrier (11) outer surface, described adsorption particle Guinier-Preston zone (12) is the membranaceous adsorption particle Guinier-Preston zone of porous, and the thickness of described adsorption particle Guinier-Preston zone (12) is 5-50mm.
2. a kind of porous hollow tubular composite membrane according to claim 1, is characterized in that, described porous hollow tubular carrier (11) is the one in Porous hollow alumina ceramic tube or Porous hollow alumina fibre.
3. a kind of porous hollow tubular composite membrane according to claim 2, it is characterized in that, the external diameter of described Porous hollow alumina ceramic tube is 5-20mm, wall thickness is 1-3mm, length is 5-20cm, the external diameter of described Porous hollow alumina fibre is 0.5-5mm, and wall thickness is 0.1-1mm, and length is 5-20cm.
4. a kind of porous hollow tubular composite membrane according to claim 1, it is characterized in that, described adsorption particle Guinier-Preston zone (12) mutually to be bondd by shitosan by adsorption particle powder and forms, and the particle diameter of described adsorption particle powder is 5-500 μm.
5. a kind of porous hollow tubular composite membrane according to claim 4, is characterized in that, described adsorption particle powder by molecular sieve, calcium phosphate and aluminium oxide in mass ratio for 0.01-1:0.01-1:0.1-1 mixes.
6. a kind of porous hollow tubular composite membrane according to claim 5, it is characterized in that, described molecular sieve comprises one or more of 4A molecular sieve, 10X molecular sieve or 13X molecular sieve, described aluminium oxide comprise gama-alumina, Hollow nanofibre shape aluminium oxide, fast shedding or boehmite one or more.
7. a kind of porous hollow tubular composite membrane according to claim 6, is characterized in that, the external diameter of described Hollow nanofibre shape aluminium oxide is 400-500nm, and internal diameter is 300-400nm, and length is 1-20 μm.
8. a preparation method for the porous hollow tubular composite membrane as described in any one of claim 1 to 7, it is characterized in that, the method specifically comprises the following steps:
(1) shitosan is dissolved in aqueous acetic acid, is configured to the chitosan solution that concentration is 0.5-1wt%;
(2) add in chitosan solution by adsorption particle powder, be uniformly dispersed, obtained adsorption particle powder quality concentration is the suspension of 0.01-0.3g/mL;
(3) porous hollow tubular carrier (11) one end is blocked, another termination Vacuum filtration device, be immersed in suspension by whole porous hollow tubular carrier (11) again, regulate vacuum, the flow velocity controlling suction filtration liquid is 10-100L/ (m
2min), make adsorption particle powder be coated on the outer surface of porous hollow tubular carrier (11) gradually, form one deck adsorption particle Guinier-Preston zone (12);
(4) when the thickness of particle aggregation layer (12) upon adsorption reaches 5-50mm, transferring to mass fraction is in the ammonia spirit of 1-3wt%, continue suction filtration, ammonia spirit is made to flow through adsorption particle Guinier-Preston zone (12) 5-30min, shitosan in adsorption particle Guinier-Preston zone (12) is separated out, adsorption particle powder adhesion is got up;
(5) Surface coating is had that the porous hollow tubular carrier (11) of adsorption particle Guinier-Preston zone (12) is unsettled to be positioned in baking oven, 100-120 DEG C is warming up to 1-5 DEG C/min, freeze-day with constant temperature 1-3h, be cooled to room temperature with 1-5 DEG C/min again, described porous hollow tubular composite membrane (1) can be obtained.
9. an application for the porous hollow tubular composite membrane as described in any one of claim 1 to 7, is characterized in that, described porous hollow tubular composite membrane (1) is assembled into shell-and-tube adsorbent equipment, for carrying out defluorinate process to drinking water.
10. the application of a kind of porous hollow tubular composite membrane according to claim 9, is characterized in that, described shell-and-tube adsorbent equipment assembles by the following method:
By the two ends of described porous hollow tubular composite membrane (1) cover upper sealing washer (2), and two ends are fixed on bracing frame (3), again bracing frame is fixed in cylinder-like shell (4), finally, two ends connect end socket (5), are namely assembled into described shell-and-tube adsorbent equipment.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110002545A (en) * | 2019-05-22 | 2019-07-12 | 深圳中清环境科技有限公司 | A kind of dynamic membrane reactor and preparation method thereof for removing fluor in water |
| CN115251456A (en) * | 2022-08-26 | 2022-11-01 | 云南中烟工业有限责任公司 | Preparation method of porous aerosol generation substrate rod with volatile aroma-enhancing substances |
| CN115251455A (en) * | 2022-08-19 | 2022-11-01 | 云南中烟工业有限责任公司 | Method for preparing porous aerosol-generating substrate rod with channel structure |
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| CN115251455A (en) * | 2022-08-19 | 2022-11-01 | 云南中烟工业有限责任公司 | Method for preparing porous aerosol-generating substrate rod with channel structure |
| CN115251456A (en) * | 2022-08-26 | 2022-11-01 | 云南中烟工业有限责任公司 | Preparation method of porous aerosol generation substrate rod with volatile aroma-enhancing substances |
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| CN105344314B (en) | 2017-10-27 |
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