CN105344314B - A kind of porous hollow tubular composite membrane and preparation method and application - Google Patents
A kind of porous hollow tubular composite membrane and preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of porous hollow tubular composite membrane and preparation method and application, described composite membrane is combined by porous hollow tubular carrier and the adsorption particle Guinier-Preston zone being coated on porous hollow tubular carrier outer surface, described adsorption particle Guinier-Preston zone is porous membranaceous adsorption particle Guinier-Preston zone, and the thickness of described adsorption particle Guinier-Preston zone is 5 50mm；During preparation, porous hollow tubular carrier is immersed in the chitosan solution containing adsorption particle powder, adsorption particle powder is coated on porous hollow tubular carrier outer surface, is dried by hanging；Using when, porous hollow tubular composite membrane is assembled into shell-and-tube adsorbent equipment, for drinking water carry out defluorinate processing.Compared with prior art, porous hollow tubular composite membrane of the present invention can be applied to household small-size drinking water defluorinate device for the rate of adsorption of defluorinate to be fast, adsorption capacity is big, operation bed layer cross section product is big.
Description
Technical field
The invention belongs to technical field of water purification, it is related to a kind of porous hollow tubular composite membrane and preparation method thereof with answering
With more particularly, to a kind of porous hollow tubular composite membrane and preparation method thereof and the application in drinking water defluorinate.
Background technology
Fluorine is one of widely distributed and closely related with health trace chemical elements in natural environment.Human body each group
Knit and all contain Trace Fluoride, wherein 80-90% fluorine is all concentrated in tooth and bone, it is the important element for constituting bone tooth.People
Body absorbs appropriate fluorine can pre- anti-caries, the calcium metabolism of promotion bone.But when human body intake fluorine is excessive, human body can be caused again
Alcium and phosphor metabolization imbalance, cause " den tal fluorosis " illness, more serious meeting causes the illnesss such as textured bone.Therefore, China《Life drink
Use water hygiene standard》(GB5749-2006) provide, fluorine content of drinking water must not exceed 1.0mg/L.When Oil repellent exceedes in water
During 1.0mg/L, referred to as high-fluorine water.At present, China, which drinks the population of high-fluorine water, 5 million peoples or so, be mainly distributed on North China,
Northeast and the Northwest.Extensively, sparse population, only a few cities use centralized water supply to these geographic coverages, can be used large-scale
Defluorinate device carrys out purifying drinking water.However, vast rural area still with water dispersion type, pick up by oneself well supply water based on, it is difficult to set up
Public defluorinate device.If a kind of small-sized household drinking water defluorinate device can be built, vast rural area distributing can be solved
The problem of drinking water defluorinate.
In recent years, household small-size purifier have developed rapidly, wherein using reverse osmosis water purification units as representative.Reverse osmosis technology
The ion of 80-90% in water can be removed, also including fluorine ion.But, the too low (rate of recovery of the raw water rate of recovery of reverse osmosis technology
For aquifer yield and the ratio of inflow), normally only 1/3 or so, remaining 2/3 concentrated water salt content is high, is unsuitable for drinking, causes water
The serious waste of resource.Particularly the northern area of China is originally water-deficient area, and this waste more exacerbates water resource deficiency and asked
Topic, meanwhile, various impurity are removed to reverse osmosis unit non-selectivity, thus some elements beneficial to human body can be also removed, such as
Selenium, calcium, magnesium etc..
The northern area of China rural potable water is based on underground water, and preferably, usual fluorine removal is exceeded outer for the water quality of underground water, its
Remainder mesh reaches drinking water standard.If specific aim develops household small-size drinking water defluorinate device, you can solve these areas
The exceeded problem of Fluorine of Drinking Water.Compared with reverse osmosis water purification units, this device does not result in water resource waste, and can also retain
Various beneficial elements in raw water.
At present, waterworks is often absorption method with defluorination method.Absorption method can carry out depth to fluorine ion in running water and take off
Remove, fluorinion concentration is down to below 1mg/L.Conventional adsorbent includes alumina balls, bone black particle, zeolite molecular sieve, oxidation
Zirconium and chelating resin etc..Adsorbent particle diameter is generally 0.5-3 millimeters.Conventional drinking water defluorination flow is ADSORPTION IN A FIXED BED, and bed is high
Spend for 0.8-1.5 meters.These conventional adsorbents are not enough because having at 2 points, and are dfficult to apply to household small-size water purifier：(1) adsorb
The adsorption capacity of agent is small, and conventional alumina balls adsorption capacity is 0.3-0.5wt%, and every kilogram of adsorbent can only handle about 400L
High-fluorine water (Funing tablet is based on 10mg/L)；(2) rate of adsorption of adsorbent is slow, high-fluorine water residence time 15min in fixed bed
More than, Oil repellent could be down to below 1mg/L.The fixed-bed design volume about 1-2L of household water filter, by the residence time
15min is calculated, and it produces water speed rate and there was only 67-133mL/min.Therefore, adsorption capacity and the suction of adsorbent are only further improved
Attached speed, could meet the design requirement of household water filter.
At present, all defluorinate adsorbent filtrate is optimized for many patented technology documents.
Fe is utilized in the Chinese patent that application publication number is CN104741088A3+、Al3+It is formed with organic carboxyl acid part
Machine skeletal porous compound, wherein Fe3+、Al3+With defluorination, the adsorbent can be used for industry high-concentration fluoride waste
Defluorinate, but cannot be used for drinking water defluorinate because organic carboxyl acid there is dissociation risk.Application publication number is CN104399426A's
Chinese patent discloses the hydroxyapatite filtrate that a kind of Al is modified；Application publication number is public for CN103833101A Chinese patent
A kind of Cu-Fe hydroxide filtrate is opened；Authorization Notice No. discloses a kind of group of the lanthanides gold for CN103071452A Chinese patent
Belong to modified montmorillonite；Application publication number discloses a kind of lanthanide series metal resin for CN102641730A Chinese patent；Application
Publication No. CN101745362A Chinese patent disclose a kind of zinc carbonate, titanium dioxide and lanthanide metal oxide mixing and
Into filtrate；Application publication number discloses a kind of hydroxyapatite filtrate for CN101913584A Chinese patent.These are modified
Adsorbent is obviously improved with traditional aluminum oxide or bone black adsorbent without essential distinction, adsorption capacity and the rate of adsorption nothing.
When adsorbent particle diameter is decreased to micron order even nanoscale, its adsorption capacity and the rate of adsorption can get a promotion.
Nanoscale adsorbent is is used for defluorinate by application publication number in CN101555078A Chinese patent, and the rate of adsorption has been lifted,
The adsorbent bed residence time is down to 7min.However, adsorbent particle diameter reduces the fluid resistance of fixed bed can be caused to rise, under flow
Drop.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of rate of adsorption is fast, inhale
Porous hollow tubular composite membrane that attached capacity is big, be suitable for household small-size drinking water defluorinate device and preparation method thereof and in drink
With the application in water defluorinate.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of porous hollow tubular composite membrane, the composite membrane is by porous hollow tubular carrier and is coated on Porous hollow pipe
Adsorption particle Guinier-Preston zone on shape carrier outer surface is combined, and described adsorption particle Guinier-Preston zone is porous membranaceous adsorption particle
Guinier-Preston zone, and the thickness of described adsorption particle Guinier-Preston zone is 5-50mm, preferably 5-30mm.
Described porous hollow tubular carrier is in Porous hollow alumina ceramic tube or Porous hollow alumina fibre
It is a kind of.
The external diameter of described Porous hollow alumina ceramic tube is 5-20mm, and wall thickness is 1-3mm, and length is 5-20cm, institute
The external diameter for the Porous hollow alumina fibre stated is 0.5-5mm, and wall thickness is 0.1-1mm, and length is 5-20cm.
It is preferred that, the external diameter of described Porous hollow alumina ceramic tube is 5-10mm, and wall thickness is 1mm, and length is 10cm,
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 is formed by adsorption particle powder by chitosan mutually bonding, described absorption
The particle diameter of grain powder is 5-500 μm, preferably 5-100 μm.
Described adsorption particle powder is 0.01-1 in mass ratio by molecular sieve, calcium phosphate and aluminum oxide：0.01-1：0.1-
1 mixes.
It is preferred that, described molecular sieve, calcium phosphate, aluminum oxide three mass ratio are 0.5-1：0.5-1：0.5-1.
Described molecular sieve includes the one or more of 4A molecular sieves, 10X molecular sieves or 13X molecular sieves, described oxidation
Aluminium includes the one or more of gama-alumina, Hollow nanofibre shape aluminum oxide, fast shedding or boehmite.
Described Hollow nanofibre shape aluminum oxide is prepared from by method of electrostatic spinning, and external diameter is 400-500nm, and internal diameter is
300-400nm, length is 1-20 μm.
It is preferred that, described molecular sieve is 4A molecular sieves, and described aluminum oxide is gama-alumina or Hollow nanofibre shape
In aluminum oxide.
A kind of preparation method of porous hollow tubular composite membrane, this method specifically includes following steps：
(1) dissolve the chitosan in aqueous acetic acid, be configured to the chitosan solution that concentration is 0.5-1wt%；
(2) adsorption particle powder is added in chitosan solution, be uniformly dispersed, adsorption particle powder quality concentration, which is made, is
0.01-0.3g/mL suspension；
(3) porous hollow tubular carrier one end is blocked, another termination Vacuum filtration device, then by whole Porous hollow pipe
Shape carrier is immersed in suspension, adjusts vacuum, and the flow velocity for controlling suction filtration liquid is 10-100L/ (m2Min) (wherein, flow
M in fast unit2Refer to the lateral area of porous hollow tubular carrier), adsorption particle powder is gradually coated on porous hollow tubular
The outer surface of carrier, forms one layer of adsorption particle Guinier-Preston zone；
(4) when the thickness of particle aggregation layer to be adsorbed reaches 5-50mm, the ammoniacal liquor that mass fraction is 1-3wt% is transferred to
In solution, continue suction filtration, ammonia spirit is flowed through adsorption particle Guinier-Preston zone 5-30min, gather the shell in adsorption particle Guinier-Preston zone
Sugar is separated out, and adsorption particle powder adhesion is got up；
(5) the porous hollow tubular carrier that Surface coating has adsorption particle Guinier-Preston zone is vacantly positioned in baking oven, with 1-5
DEG C/min is warming up to 100-120 DEG C, freeze-day with constant temperature 1-3h, then is cooled to room temperature with 1-5 DEG C/min, you can it is made described porous
Hollow tubular composite membrane.
A kind of application of porous hollow tubular composite membrane, is assembled into shell-and-tube by described porous hollow tubular composite membrane and inhales
Adsorption device, for carrying out defluorinate processing to drinking water.
Described shell-and-tube adsorbent equipment assembles by the following method：
The two ends of described porous hollow tubular composite membrane are covered into upper sealing washer, and two ends are fixed on support frame,
Support frame is fixed in cylinder-like shell again, finally, two ends connect end socket, that is, is assembled into described shell-and-tube adsorbent equipment.
When described shell-and-tube adsorbent equipment is used to carry out defluorinate processing to drinking water, the water of defluorinate will be treated, flowed slowly into
In shell-and-tube adsorbent equipment, radial inflow composite membrane central tube, coutroi velocity is 0.1L/ (m2·min)-10L/(m2·min)
(the m in flow rate2Refer to the lateral area of porous hollow tubular composite membrane), particle aggregation layer of the water through perforated tubular composite membrane
Duct, fluorine ion is adsorbed in particle, and the water through defluorinate, which is come together in carrier center pipeline, to flow out.
It is total that the described water after defluorinate includes the concentrated water or soluble solid of running water, running water after reverse osmosis membrane processing
Amount is less than 1500mg/L and pH is the one or more in 4-10 underground water, and Oil repellent is less than 1mg/L in water after processing.
In actual application, in described shell-and-tube adsorbent equipment, the porous hollow tubular being fixed on support frame
Composite membrane is 1 or 7, is symmetric around support frame center, described shell-and-tube adsorbent equipment can with used aloned,
It can be used in parallel or in series with multiple.
Porous hollow tubular composite membrane of the present invention can make adsorbent while particle diameter reduces, it is ensured that larger flow, fit
Share and make household small-size drinking water defluorinate device.
Compared with prior art, the invention has the characteristics that：
1) absorbent particles are directly fixed on central shaft tube surface, form the sorbing material powder adhesion layer of a thickness, with
" radial fixed-bed " that traditional packing layer is fixed by inside and outside two porous cylindrical walls is compared, and structure is compacter, can substitute existing
There is fixed bed, for household small-size drinking water defluorinate device.
2) traditional " porous ceramic film " tube wall is relatively thin, primarily serves filtration；And porous hollow tubular of the present invention is multiple
The thickness for closing the sorbing material powder adhesion layer of film is larger, mainly plays suction-operated, has expanded answering for traditional " porous ceramic film "
Use field.
3) sorbent used particle diameter is micron order, compared with traditional grade adsorbent, micron order adsorbent and water
The external surface area of contact is bigger, and to the rate of adsorption of fluorine faster, adsorption capacity is also bigger.
4) when traditional fixed bed takes off removing fluorine in water, water is axially flowed into from fixed bed one end, is flowed through after sorbing material layer,
From other end outflow；And shell-and-tube adsorbent equipment used in the present invention is when taking off removing fluorine in water, water is along flowing radially across sorbing material
Central tube outflow is come together in after layer, its operation bed layer cross section product (lateral area of elongated cylinder) is much larger than the work of traditional fixed bed
Bed sectional area (elongated cylinder floor space).
5) due to the present invention use micron order sorbing material, the rate of adsorption of defluorinate faster, and its operation bed layer cross section accumulate
It is bigger, therefore it is bigger that the amount of defluorinate water is produced in the shell-and-tube adsorbent equipment unit interval.
6) the porous hollow tubular composite membrane being fixed on support frame can be 1 or 7, and shell-and-tube adsorbent equipment can be single
It is individual to use, multiple it can also be used in parallel or in series, therefore can flexibly be selected according to different drinking water classifications and demand of processing quantity.
Brief description of the drawings
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 current direction schematic diagram in the shell-and-tube adsorbent equipment described in embodiment 1；
Fig. 5 is that embodiment 1 prepares gained porous hollow tubular composite membrane working sections product schematic diagram；
Fig. 6 is the fixed bed packing layer working sections product schematic diagram 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-sealing
Packing ring, 3-support frame, 4-cylinder, 5-end socket, 6-fixed bed packing layer.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
Fluorine in porous hollow tubular composite membrane device removing running water
The preparation of porous hollow tubular composite membrane 1：Dissolve the chitosan in 1wt% aqueous acetic acids, be configured to concentration
0.5% chitosan solution 2L.400g absorbent particles powder is added thereto, suspension is configured to；Absorbent particles are by 4A
Molecular sieve, calcium phosphate, gama-alumina particle, fast shedding press 1：1：0.8：0.2 mass ratio is mixed, every kind of adsorbent
Grain particle diameter is 40 microns -50 microns.Made from Porous hollow alumina ceramic tube outside porous hollow tubular carrier 11, earthenware
Footpath is 10mm, wall thickness 1mm, length 150mm.The one end of porous hollow tubular carrier 11 is blocked, another termination Vacuum filtration device,
Whole porous hollow tubular carrier 11 is immersed in above-mentioned suspension, suction filtration makes powder granule gradually be attached to Porous hollow
The outer surface of tubular carrier 11, forms one layer of adsorption particle Guinier-Preston zone 12, when the thickness of particle aggregation layer 12 to be adsorbed reaches 30mm,
Porous hollow tubular carrier 11 is transferred in 1wt% ammonia spirits, continuing suction filtration makes ammoniacal liquor flow through adsorption particle Guinier-Preston zone 12
10min, the porous hollow tubular carrier 11 for being attached to adsorption particle Guinier-Preston zone 12 is vacantly positioned over the heating drying of baking oven Program,
105 DEG C are warming up to 1 DEG C/min, 105 DEG C of dry 2h are kept, then room temperature is cooled to 1 DEG C/min.The phase of adsorption particle Guinier-Preston zone 12
Mutual adhesion, forms porous hollow tubular composite membrane, as shown in Figure 1.
Shell-and-tube adsorbent equipment is assembled：By 1 above-mentioned porous hollow tubular composite membrane 1 and internal diameter 80mm cylinders 4, sealing gasket
Circle 2, support frame 3 and the composition shell-and-tube adsorbent equipment of end socket 5, as shown in Figure 2.Its support frame structure is as shown in Figure 3.
Running water defluorinate：A certain amount of NaF solution is added into running water, it is 2.6mg/L to make wherein Oil repellent.Running water
The duct of adsorption particle Guinier-Preston zone 12 of perforated tubular composite membrane 1 is passed through with 0.3L/min, fluorine ion therein is adsorbed on particle
Interior, the water through defluorinate, which is come together in the central tube of porous hollow tubular carrier 11, to flow out.Treat that the water of defluorinate is inhaled in the shell-and-tube
Flow direction in adsorption device is as shown in figure 4, the working sections product of the porous hollow tubular composite membrane 1 is as shown in Figure 5.
Detect that the Oil repellent in outflow water, with the change of outflow water, is listed in table 1.Wherein fluorinion concentration is selected with fluorine ion
Selecting property determination of electrode.As shown in Table 1, when in flow of inlet water 0.3L/min, water outlet Funing tablet can be down in 1mg/L, meet China
Drinking water standard.
The fluorinion concentration of table 1 is with the change for flowing out water
| Processing time | 1min | 10min | 1h | 2h | 5h | 10h |
| Flow out water, 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：
Fluorine in traditional fixed bed device removing running water
Fixed bed device is assembled：From internal diameter 80mm fixed beds, the wherein height 150mm of fixed bed packing layer 6 (with embodiment
Compound film length in 1 is identical), adsorbent selects 0.5mm-0.6mm activated alumina adsorbents.
Running water defluorinate：A certain amount of NaF solution is added into running water, it is 2.6mg/L to make wherein Oil repellent.Running water
Fixed bed is flowed through with 0.05L/min, detects that the Oil repellent in outflow water, with the change of outflow water, is listed in table 2.Treat 10 hours
Afterwards, flow velocity is adjusted to 0.3L/min, (identical with the flow velocity in embodiment 1) detects the Oil repellent in outflow water with outflow water
Change, be listed in table 3.Wherein fluorinion concentration fluorine ion selective electrode determining.The working sections of the fixed bed packing layer 6
Product is as shown in Figure 6.
Compared with Example 1, comparative example 1 is when flow of inlet water is smaller (0.05L/min), and Funing tablet can be down in water outlet
Within 1mg/L, meet Drinking Water in China standard；But when flow of inlet water is larger (0.3L/min), Funing tablet then exceedes in water outlet
1mg/L, it is impossible to meet potable water guidelines.
The fluorinion concentration of table 2 is with the change (flow velocity 0.05L/min) for flowing out water
| Processing time | 1min | 10min | 1h | 2h | 5h | 10h |
| Flow out water, 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 |
The fluorinion concentration of table 3 is with the change (flow velocity 0.3L/min) for flowing out water
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out water, L | 0.3L | 3L | 18L | 36L | 90L |
| Funing tablet, mg/L | 1.22 | 1.62 | 1.88 | 2.03 | 2.21 |
Comparative example 2：
Fluorine in traditional fixed bed device removing running water
Fixed bed device is assembled：From internal diameter 80mm fixed beds, the wherein height 150mm of fixed bed packing layer 6 (with embodiment
Compound film length in 1 is identical), (mixed adsorbent particle is by 4A from 40 microns of -50 microns of mixed adsorbent particles for adsorbent
Molecular sieve, calcium phosphate, gama-alumina particle, fast shedding press 1：1：0.8：0.2 mass ratio is mixed, every kind of adsorbent
Grain particle diameter is 40 microns -50 microns).It is fitted into after various fillers are sufficiently mixed in fixed bed.
Running water defluorinate：A certain amount of NaF solution is added into running water, it is 2.6mg/L to make wherein Oil repellent.Running water
Fixed bed is flowed through with 0.05L/min, detects that the Oil repellent in outflow water, with the change of outflow water, is listed in table 4.Wherein fluorine ion
Concentration fluorine ion selective electrode determining.
Compared with Example 1, comparative example 2 is when flow of inlet water is smaller (0.05L/min), and Funing tablet can be down in water outlet
Within 1mg/L, meet Drinking Water in China standard；But the bed resistance of fixed bed is larger, and it is about 6bar that fixed bed, which imports and exports pressure drop,.And it is real
Apply fixed bed in example 1 and import and export pressure drop less than 1bar.
The fluorinion concentration of table 4 is with the change for flowing out water
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out water, 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 removing reverse osmosis process discharges the fluorine in concentrated water
The preparation of porous hollow tubular composite membrane 1：Dissolve the chitosan in 1wt% aqueous acetic acids, be configured to concentration
1% chitosan solution 2L.400g absorbent particles powder is added thereto, suspension is configured to；Absorbent particles are by 4A points
Sub- sieve, calcium phosphate, gama-alumina particle, (external diameter about 500nm, internal diameter 300nm, length 20 is micro- for hollow nano-alumina fiber
Rice), boehmite press 1：1：0.4：0.4：0.2 mass ratio is mixed, in addition to hollow nano-alumina fiber, and remaining four
It is 40 microns -50 microns to plant absorbent particles particle diameter.Make porous hollow tubular carrier 11 from Porous hollow alumina fibre,
Alumina fibre external diameter is 5mm, wall thickness 1mm, length 100mm.Reference implementation example 1, makes alumina fibre table using suction filtration mode
Face forms one layer of adsorption particle Guinier-Preston zone 12, and when the thickness of particle aggregation layer 12 to be adsorbed reaches 5mm, porous hollow tubular is carried
Body 11 is transferred in 1wt% ammonia spirits, is continued suction filtration, ammoniacal liquor is flowed through the 5min of adsorption particle Guinier-Preston zone 12, is attached to absorption
The porous hollow tubular carrier 11 of particle aggregation layer 12 is hanging to be positioned over the heating drying of baking oven Program, is warming up to 1 DEG C/min
105 DEG C, 105 DEG C of dry 2h are kept, then room temperature is cooled to 1 DEG C/min.Adsorption particle Guinier-Preston zone 12 is inter-adhesive, is formed porous
Hollow tubular composite membrane 1, as shown in Figure 7.
Shell-and-tube adsorbent equipment is assembled：By above-mentioned porous hollow tubular composite membrane 1 seven and internal diameter 80mm cylinders 4, sealing
Packing ring 2, support frame 3, end socket 5 etc. constitute shell-and-tube adsorbent equipment.Its structure of support frame 3 is as shown in Figure 8.Two shell-and-tubes are inhaled
Adsorption device is used in series, i.e., the water inlet phase of the delivery port of one shell-and-tube adsorbent equipment and another shell-and-tube adsorbent equipment
Even.
Reverse osmosis process discharges concentrated water defluorinate：It is 6.8mg/L to determine fluorinion concentration in concentrated water.Concentrated water is with 0.1L/min
Through perforated tubular composite membrane device, detect that the Oil repellent in outflow water, with the change of outflow water, is listed in table 5.Wherein fluorine from
Sub- concentration fluorine ion selective electrode determining.
As shown in Table 5, when in flow of inlet water 0.1L/min, water outlet Funing tablet can be down in 1mg/L.
The fluorinion concentration of table 5 is with the change for flowing out water
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out water, L | 0.1L | 1L | 6L | 12L | 30L |
| Funing tablet, mg/L | 0.82 | 0.78 | 0.83 | 0.85 | 0.91 |
Comparative example 3：
Fluorine in traditional fixed bed device removing running water
Fixed bed device is assembled：(it is embodiment from internal diameter 80mm fixed beds, the wherein height 200mm of fixed bed packing layer 6
2 times of compound film length in 2), adsorbent is 0.5mm-0.6mm activated alumina adsorbents.
Reverse osmosis process discharges concentrated water defluorinate：It is 6.8mg/L to determine fluorinion concentration in concentrated water.Concentrated water is with 0.1L/min
Through perforated tubular composite membrane device, detect that the Oil repellent in outflow water, with the change of outflow water, is listed in table 6.Wherein fluorine from
Sub- concentration fluorine ion selective electrode determining.
As shown in Table 6, when in flow of inlet water 0.1L/min, water outlet Funing tablet fail to be down in 1mg/L.With the phase of embodiment 2
Than the speed of the removing fluorine of comparative example 3 is substantially reduced.
The fluorinion concentration of table 6 is with the change for flowing out water
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out water, L | 0.1L | 1L | 6L | 12L | 30L |
| Funing tablet, mg/L | 1.52 | 1.48 | 1.63 | 1.72 | 2.33 |
Embodiment 3：
Fluorine in hollow porous composite film device removing underground water
The preparation of porous hollow tubular composite membrane 1：The preparation process reference implementation example 2 of porous hollow tubular composite membrane 1.
Shell-and-tube adsorbent equipment is assembled：By above-mentioned porous hollow tubular composite membrane 1 seven and internal diameter 80mm cylinders 4, sealing
Packing ring 2, support frame 3, end socket 5 etc. constitute shell-and-tube adsorbent equipment.Two shell-and-tube adsorbent equipments are used in parallel, i.e., one pipe
Water inlet, water inlet, the delivery port of delivery port respectively with another shell-and-tube adsorbent equipment of shell-type adsorbent equipment are connected.To increase
Plus the disposal ability of whole system.
Underground water defluorinate：It is 3.8mg/L to determine fluorinion concentration in underground.Underground water passes through perforated tubular with 0.2L/min
Oil repellent in composite membrane device, detection outflow water is listed in table 7 with the change of outflow water.Wherein fluorinion concentration fluorine from
Sub- electrodes selective is determined.
As shown in Table 7, when in flow of inlet water 0.2L/min, water outlet Funing tablet can be down in 1mg/L, reach Drinking Water in China
Standard requirement.
The fluorinion concentration of table 7 is with the change for flowing out water
| Processing time | 1min | 10min | 1h | 2h | 5h |
| Flow out water, L | 0.2L | 2L | 12L | 24L | 60L |
| Funing tablet, mg/L | 0.52 | 0.63 | 0.68 | 0.75 | 0.77 |
Embodiment 4：
Fluorine in hollow porous composite film device removing underground water
The preparation of porous hollow tubular composite membrane 1：The preparation process reference implementation example 1 of porous hollow tubular composite membrane 1.
Shell-and-tube adsorbent equipment is assembled：By above-mentioned porous hollow tubular composite membrane 1 one and internal diameter 80mm cylinders 4, sealing
Packing ring 2, support frame 3, end socket 5 etc. constitute shell-and-tube adsorbent equipment.Two shell-and-tube adsorbent equipments are used in series, i.e., one pipe
The delivery port of shell-type adsorbent equipment is connected with the water inlet of another shell-and-tube adsorbent equipment.
Underground water defluorinate：It is 3.9mg/L to determine fluorinion concentration in underground.Underground water passes through perforated tubular with 0.3L/min
Oil repellent in composite membrane device, detection outflow water is listed in table 8 with the change of outflow water.Wherein fluorinion concentration fluorine from
Sub- electrodes selective is determined.
As shown in Table 8, when in flow of inlet water 0.3L/min, water outlet Funing tablet can be down in 1mg/L, reach Drinking Water in China
Standard requirement.
The fluorinion concentration of table 8 is with the change for flowing out water
Embodiment 5：
The present embodiment porous hollow tubular composite membrane 1, by porous hollow tubular carrier 11 and is coated on Porous hollow pipe
Adsorption particle Guinier-Preston zone 12 on the outer surface of shape carrier 11 is combined, and described adsorption particle Guinier-Preston zone 12 is porous membranaceous suction
Attached particle aggregation layer, and the thickness of described adsorption particle Guinier-Preston zone 12 is 15mm.
Described adsorption particle powder is by molecular sieve, calcium phosphate, aluminum oxide three in mass ratio 0.01：0.01：1 composition.
Described molecular sieve is 10X molecular sieves, and described aluminum oxide is Hollow nanofibre shape aluminum oxide, described nanometer
Hollow fiber aluminum 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,
Wall thickness is 3mm, and length is 5cm.
The preparation method of the present embodiment porous hollow tubular composite membrane 1, specifically includes following steps：
(1) dissolve the chitosan in 1wt% aqueous acetic acids, be configured to the chitosan solution that concentration is 0.9wt%；
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, be sufficiently stirred for, hang powder
It is floating good；
(3) one end of porous hollow tubular carrier 11 is blocked, another termination Vacuum filtration device, by whole Porous hollow pipe
Shape carrier 11 is immersed in above-mentioned suspension, adjusts vacuum, controls the flow velocity 60L/ (m of suction filtration liquid2Min) (flow velocity list
M in position2Refer to carrier side area), powder granule is gradually attached to the outer surface of porous hollow tubular carrier 11, form one layer of suction
Attached particle aggregation layer 12；
(4) when the thickness of particle aggregation layer 12 to be adsorbed reaches 15mm, porous hollow tubular carrier 11 is transferred to 1wt%
In ammonia spirit, continue suction filtration, ammoniacal liquor is flowed through the 20min of adsorption particle Guinier-Preston zone 12, make the shell in adsorption particle Guinier-Preston zone 12
Glycan is separated out, and powder granule is bonded；
(5) the porous hollow tubular carrier 11 for being attached to adsorption particle Guinier-Preston zone 12 is vacantly positioned over baking oven Program liter
Temperature is dried, and 105 DEG C are warming up to 1 DEG C/min, keeps 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle gathers
Collect layer 12 inter-adhesive, form porous membrane structure, produce porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is per addition 10g powder in 100mL chitosan solutions
Body.
Application of the porous hollow tubular composite membrane 1 in drinking water defluorinate, the application process specifically includes following steps：
(a) shell-and-tube adsorbent equipment is assembled：The described two ends of porous hollow tubular composite membrane 1 are covered into upper sealing washer 2；So
Two ends are fixed on support frame 3 afterwards；Support frame is fixed in cylinder-like shell 4 again, two ends connect end socket 5 again, produce pipe
Shell-type adsorbent equipment.
(b) defluorinate in drinking water：The water of defluorinate will be treated, flow slowly into the shell-and-tube adsorbent equipment described in step (a), radially
Flow into the central tube of porous hollow tubular composite membrane 1, coutroi velocity is 8L/ (m2Min the) (m in flow rate2Refer to porous
The outside area of hollow tubular composite membrane 1), water passes through the adsorption particle Guinier-Preston zone duct of porous hollow tubular composite membrane 1, wherein
Fluorine ion be adsorbed in particle, the water through defluorinate, which is come together in the central tube of porous hollow tubular carrier 11, to flow out.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 being fixed on support frame 3 is
One, described 3 parallel connections of shell-and-tube.
The water after defluorinate described in step (b) is concentrated water of the running water after reverse osmosis membrane processing, the fluorine in water after processing
Content is less than 1mg/L.
Embodiment 6：
The present embodiment porous hollow tubular composite membrane 1, by porous hollow tubular carrier 11 and is coated on Porous hollow pipe
Adsorption particle Guinier-Preston zone 12 on the outer surface of shape carrier 11 is combined, and described adsorption particle Guinier-Preston zone 12 is porous membranaceous suction
Attached particle aggregation layer, and the thickness of described adsorption particle Guinier-Preston zone 12 is 40mm.
Described adsorption particle powder is by molecular sieve, calcium phosphate, aluminum oxide three in mass ratio 0.01：1：1 composition.
Described molecular sieve is 13X molecular sieves, and described aluminum oxide is Hollow nanofibre shape aluminum oxide, described nanometer
Hollow fiber aluminum 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, wall thickness is 2mm, and length is 20cm.
The preparation method of the present embodiment porous hollow tubular composite membrane 1, specifically includes following steps：
(1) dissolve the chitosan in 1wt% aqueous acetic acids, be configured to the chitosan solution that concentration is 0.6wt%；
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, be sufficiently stirred for, hang powder
It is floating good；
(3) one end of porous hollow tubular carrier 11 is blocked, another termination Vacuum filtration device, by whole Porous hollow pipe
Shape carrier 11 is immersed in above-mentioned suspension, adjusts vacuum, controls the flow velocity 70L/ (m of suction filtration liquid2Min) (flow velocity list
M in position2Refer to carrier side area), powder granule is gradually attached to the outer surface of porous hollow tubular carrier 11, form one layer of suction
Attached particle aggregation layer 12；
(4) when the thickness of particle aggregation layer 12 to be adsorbed reaches 40mm, porous hollow tubular carrier 11 is transferred to 1wt%
In ammonia spirit, continue suction filtration, ammoniacal liquor is flowed through the 25min of adsorption particle Guinier-Preston zone 12, make the shell in adsorption particle Guinier-Preston zone 12
Glycan is separated out, and powder granule is bonded；
(5) the porous hollow tubular carrier 11 for being attached to adsorption particle Guinier-Preston zone 12 is vacantly positioned over baking oven Program liter
Temperature is dried, and 105 DEG C are warming up to 1 DEG C/min, keeps 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle gathers
Collect layer 12 inter-adhesive, form porous membrane structure, produce porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is per addition 18g powder in 100mL chitosan solutions
Body.
Application of the porous hollow tubular composite membrane 1 in drinking water defluorinate, the application process specifically includes following steps：
(a) shell-and-tube adsorbent equipment is assembled：The described two ends of porous hollow tubular composite membrane 1 are covered into upper sealing washer 2；So
Two ends are fixed on support frame 3 afterwards；Support frame is fixed in cylinder-like shell 4 again, two ends connect end socket 5 again, produce pipe
Shell-type adsorbent equipment.
(b) defluorinate in drinking water：The water of defluorinate will be treated, flow slowly into the shell-and-tube adsorbent equipment described in step (a), radially
In the central tube for flowing into porous hollow tubular composite membrane 1, coutroi velocity is 8L/ (m2Min the) (m in flow rate2Refer to many
The outside area of hole hollow tubular composite membrane 1), water passes through the duct of adsorption particle Guinier-Preston zone 12 of porous hollow tubular composite membrane 1,
Fluorine ion therein is adsorbed in particle, and the water through defluorinate, which is come together in the central tube of porous hollow tubular carrier 11, to flow
Go out.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 being fixed on support frame 3 is
One, described shell-and-tube adsorbent equipment 3 is used in series.
The water for treating defluorinate described in step (b) is the underground water that dissolvability solid amount is less than that 1500mg/L and pH are 7, warp
Oil repellent is less than 1mg/L in water after processing.
Embodiment 7：
The present embodiment porous hollow tubular composite membrane 1, by porous hollow tubular carrier 11 and is coated on Porous hollow pipe
Adsorption particle Guinier-Preston zone 12 on the outer surface of shape carrier 11 is combined, and described adsorption particle Guinier-Preston zone 12 is porous membranaceous suction
Attached particle aggregation layer, and the thickness of described adsorption particle Guinier-Preston zone 12 is 30mm.
Described adsorption particle powder is by molecular sieve, calcium phosphate, aluminum oxide three in mass ratio 1：0.01：1 composition.
Described molecular sieve is 4A molecular sieves and 10X molecular sieves, and described aluminum oxide is Hollow nanofibre shape aluminum oxide,
Described Hollow nanofibre shape aluminum oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 400nm, and internal diameter is 400nm, length
For 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,
Wall thickness is 0.1mm, and length is 5cm.
The preparation method of porous hollow tubular composite membrane 1, specifically includes following steps：
(1) dissolve the chitosan in 1wt% aqueous acetic acids, be configured to the chitosan solution that concentration is 0.6wt%；
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, be sufficiently stirred for, hang powder
It is floating good；
(3) one end of porous hollow tubular carrier 11 is blocked, another termination Vacuum filtration device, by whole Porous hollow pipe
Shape carrier 11 is immersed in above-mentioned suspension, adjusts vacuum, controls the flow velocity 30L/ (m of suction filtration liquid2Min) (flow velocity list
M in position2Refer to carrier side area), powder granule is gradually attached to the outer surface of porous hollow tubular carrier 11, form one layer of suction
Attached particle aggregation layer 12；
(4) when the thickness of particle aggregation layer 12 to be adsorbed reaches 30mm, porous hollow tubular carrier 11 is transferred to 1wt%
In ammonia spirit, continue suction filtration, ammoniacal liquor is flowed through the 15min of adsorption particle Guinier-Preston zone 12, make the shell in adsorption particle Guinier-Preston zone 12
Glycan is separated out, and powder granule is bonded；
(5) the porous hollow tubular carrier 11 for being attached to adsorption particle Guinier-Preston zone 12 is vacantly positioned over baking oven Program liter
Temperature is dried, and 105 DEG C are warming up to 1 DEG C/min, keeps 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle gathers
Collect layer 12 inter-adhesive, form porous membrane structure, produce porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is per addition 15g powder in 100mL chitosan solutions
Body.
Application of the porous hollow tubular composite membrane 1 in drinking water defluorinate, the application process specifically includes following steps：
(a) shell-and-tube adsorbent equipment is assembled：The described two ends of porous hollow tubular composite membrane 1 are covered into upper sealing washer 2；So
Two ends are fixed on support frame 3 afterwards；Support frame is fixed in cylinder-like shell 4 again, two ends connect end socket 5 again, produce pipe
Shell-type adsorbent equipment.
(b) defluorinate in drinking water：The water of defluorinate will be treated, flow slowly into the shell-and-tube adsorbent equipment described in step (a), radially
In the central tube for flowing into porous hollow tubular composite membrane 1, coutroi velocity is 3L/ (m2Min the) (m in flow rate2Refer to many
The outside area of hole hollow tubular composite membrane 1), water passes through the duct of adsorption particle Guinier-Preston zone 12 of porous hollow tubular composite membrane 1,
Fluorine ion therein is adsorbed in particle, and the water through defluorinate, which is come together in the central tube of porous hollow tubular carrier 11, to flow
Go out.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 being fixed on support frame 3 is
One, described shell-and-tube adsorbent equipment used aloned.
The water for treating defluorinate described in step (b) is the underground water that dissolvability solid amount is less than that 1500mg/L and pH are 10,
Oil repellent is less than 1mg/L in water after processing.
Embodiment 8：
The present embodiment porous hollow tubular composite membrane 1, by porous hollow tubular carrier 11 and is coated on Porous hollow pipe
Adsorption particle Guinier-Preston zone 12 on the outer surface of shape carrier 11 is combined, and described adsorption particle Guinier-Preston zone 12 is porous membranaceous suction
Attached particle aggregation layer, and the thickness of described adsorption particle Guinier-Preston zone 12 is 50mm.
Described adsorption particle powder is by molecular sieve, calcium phosphate, aluminum oxide three in mass ratio 0.01：1：0.1 composition.
Described molecular sieve is 10X molecular sieves and 13X molecular sieves, and described aluminum oxide aoxidizes for Hollow nanofibre shape
Aluminium, described Hollow nanofibre shape aluminum oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 500nm, and internal diameter is 400nm,
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, wall
Thickness is 0.5mm, and length is 20cm.
The preparation method of porous hollow tubular composite membrane, specifically includes following steps：
(1) dissolve the chitosan in 1wt% aqueous acetic acids, be configured to the chitosan solution that concentration is 0.8wt%；
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, be sufficiently stirred for, hang powder
It is floating good；
(3) one end of porous hollow tubular carrier 11 is blocked, another termination Vacuum filtration device, by whole Porous hollow pipe
Shape carrier 11 is immersed in above-mentioned suspension, adjusts vacuum, controls the flow velocity 65L/ (m of suction filtration liquid2Min) (flow velocity list
M in position2Refer to carrier side area), powder granule is gradually attached to the outer surface of porous hollow tubular carrier 11, form one layer of suction
Attached particle aggregation layer 12；
(4) when the thickness of particle aggregation layer 12 to be adsorbed reaches 50mm, porous hollow tubular carrier 11 is transferred to 1wt%
In ammonia spirit, continue suction filtration, ammoniacal liquor is flowed through the 20min of adsorption particle Guinier-Preston zone 12, make the shell in adsorption particle Guinier-Preston zone 12
Glycan is separated out, and powder granule is bonded；
(5) the porous hollow tubular carrier 11 for being attached to adsorption particle Guinier-Preston zone 12 is vacantly positioned over baking oven Program liter
Temperature is dried, and 105 DEG C are warming up to 1 DEG C/min, keeps 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle gathers
Collect layer 12 inter-adhesive, form porous membrane structure, produce porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is per addition 10g powder in 100mL chitosan solutions
Body.
Application of the porous hollow tubular composite membrane 1 in drinking water defluorinate, the application process specifically includes following steps：
(a) shell-and-tube adsorbent equipment is assembled：The described two ends of porous hollow tubular composite membrane 1 are covered into upper sealing washer 2；So
Two ends are fixed on support frame 3 afterwards；Support frame is fixed in cylinder-like shell 4 again, two ends connect end socket 5 again, produce pipe
Shell-type adsorbent equipment.
(b) defluorinate in drinking water：The water of defluorinate will be treated, flow slowly into the shell-and-tube adsorbent equipment described in step (a), radially
In the central tube for flowing into porous hollow tubular composite membrane 1, coutroi velocity is 5L/ (m2Min the) (m in flow rate2Refer to many
The outside area of hole hollow tubular composite membrane 1), water passes through the duct of adsorption particle Guinier-Preston zone 12 of porous hollow tubular composite membrane 1,
Fluorine ion therein is adsorbed in particle, and the water through defluorinate, which is come together in the central tube of porous hollow tubular carrier 11, to flow
Go out.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 being fixed on support frame 3 is
One, described shell-and-tube adsorbent equipment used aloned.
The water for treating defluorinate described in step (b) is the underground water that dissolvability solid amount is less than that 1500mg/L and pH are 4, warp
Oil repellent is less than 1mg/L in water after processing.
Embodiment 9：
The present embodiment porous hollow tubular composite membrane 1, by porous hollow tubular carrier 11 and is coated on Porous hollow pipe
Adsorption particle Guinier-Preston zone 12 on the outer surface of shape carrier 11 is combined, and described adsorption particle Guinier-Preston zone 12 is porous membranaceous suction
Attached particle aggregation layer, and the thickness of described adsorption particle Guinier-Preston zone 12 is 5mm.
Described adsorption particle powder is by molecular sieve, calcium phosphate, aluminum oxide three in mass ratio 1：0.01：0.1 composition.
Described molecular sieve is 4A molecular sieves and 13X molecular sieves, and described aluminum oxide is Hollow nanofibre shape aluminum oxide,
Described Hollow nanofibre shape aluminum oxide is prepared by method of electrostatic spinning, and its fiber outer diameter is 450nm, and internal diameter is 350nm, length
For 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, wall thickness is 1.5mm, and length is 15cm.
The preparation method of porous hollow tubular composite membrane 1, specifically includes following steps：
(1) dissolve the chitosan in 1wt% aqueous acetic acids, be configured to the chitosan solution that concentration is 0.6wt%；
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, be sufficiently stirred for, hang powder
It is floating good；
(3) one end of porous hollow tubular carrier 11 is blocked, another termination Vacuum filtration device, by whole Porous hollow pipe
Shape carrier 11 is immersed in above-mentioned suspension, adjusts vacuum, controls the flow velocity 100L/ (m of suction filtration liquid2Min) (flow velocity list
M in position2Refer to carrier side area), powder granule is gradually attached to the outer surface of porous hollow tubular carrier 11, form one layer of suction
Attached particle aggregation layer 12；
(4) when the thickness of particle aggregation layer 12 to be adsorbed reaches 5mm, porous hollow tubular carrier 11 is transferred to 1wt%
In ammonia spirit, continue suction filtration, ammoniacal liquor is flowed through the 30min of adsorption particle Guinier-Preston zone 12, make the shell in adsorption particle Guinier-Preston zone 12
Glycan is separated out, and powder granule is bonded；
(5) the porous hollow tubular carrier 11 for being attached to adsorption particle Guinier-Preston zone 12 is vacantly positioned over baking oven Program liter
Temperature is dried, and 105 DEG C are warming up to 1 DEG C/min, keeps 105 DEG C of dry 2h, then be cooled to room temperature with 1 DEG C/min.Adsorption particle gathers
Collect layer 12 inter-adhesive, form porous membrane structure, produce porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is per addition 30g powder in 100mL chitosan solutions
Body.
Application of the porous hollow tubular composite membrane 1 in drinking water defluorinate, the application process specifically includes following steps：
(a) shell-and-tube adsorbent equipment is assembled：The described two ends of porous hollow tubular composite membrane 1 are covered into upper sealing washer 2；So
Two ends are fixed on support frame 3 afterwards；Support frame is fixed in cylinder-like shell 4 again, two ends connect end socket 5 again, produce pipe
Shell-type adsorbent equipment.
(b) defluorinate in drinking water：The water of defluorinate will be treated, flow slowly into the shell-and-tube adsorbent equipment described in step (a), radially
In the central tube for flowing into porous hollow tubular composite membrane 1, coutroi velocity is 10L/ (m2Min the) (m in flow rate2Refer to many
The outside area of hole hollow tubular composite membrane 1), water passes through the duct of adsorption particle Guinier-Preston zone 12 of porous hollow tubular composite membrane 1,
Fluorine ion therein is adsorbed in particle, and the water through defluorinate, which is come together in the central tube of porous hollow tubular carrier 11, to flow
Go out.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 being fixed on support frame 3 is
Seven, described shell-and-tube adsorbent equipment used aloned.
The water after defluorinate described in step (b) is concentrated water of the running water after reverse osmosis membrane processing, the fluorine in water after processing
Content is less than 1mg/L.
Embodiment 10：
The present embodiment porous hollow tubular composite membrane 1, by porous hollow tubular carrier 11 and is coated on Porous hollow pipe
Adsorption particle Guinier-Preston zone 12 on the outer surface of shape carrier 11 is combined, and described adsorption particle Guinier-Preston zone 12 is porous membranaceous suction
Attached particle aggregation layer, and the thickness of described adsorption particle Guinier-Preston zone 12 is 25mm.
Described adsorption particle powder is by molecular sieve, calcium phosphate, aluminum oxide three in mass ratio 1：1：0.1 composition.
Described molecular sieve is 4A molecular sieves, 10X molecular sieves and 13X molecular sieves, and described aluminum oxide is fine for hollow nano
Shape aluminum oxide is tieed up, described Hollow nanofibre shape aluminum oxide is prepared by method of electrostatic spinning, its fiber outer diameter is 400nm, internal diameter
For 400nm, 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,
Wall thickness is 0.6mm, and length is 12cm.
The preparation method of porous hollow tubular composite membrane 1, specifically includes following steps：
(1) dissolve the chitosan in 1wt% aqueous acetic acids, be configured to the chitosan solution that concentration is 0.7wt%；
(2) adsorption particle powder is scattered in above-mentioned chitosan solution, obtains suspension, be sufficiently stirred for, hang powder
It is floating good；
(3) one end of porous hollow tubular carrier 11 is blocked, another termination Vacuum filtration device, by whole Porous hollow pipe
Shape carrier 11 is immersed in above-mentioned suspension, adjusts vacuum, controls the flow velocity 10L/ (m of suction filtration liquid2Min) (flow velocity list
M in position2Refer to carrier side area), powder granule is gradually attached to the outer surface of porous hollow tubular carrier 11, form one layer of suction
Attached particle aggregation layer 12；
(4) when the thickness of particle aggregation layer 12 to be adsorbed reaches 25mm, porous hollow tubular carrier 11 is transferred to 1wt%
In ammonia spirit, continue suction filtration, ammoniacal liquor is flowed through the 5min of adsorption particle Guinier-Preston zone 12, make the shell in adsorption particle Guinier-Preston zone 12
Glycan is separated out, and powder granule is bonded；
(5) the porous hollow tubular carrier 11 for being attached to adsorption particle Guinier-Preston zone 12 is vacantly positioned over baking oven Program liter
Temperature is dried, and 120 DEG C are warming up to 2 DEG C/min, keeps 120 DEG C of dry 1h, then be cooled to room temperature with 2 DEG C/min.Adsorption particle gathers
Collect layer 12 inter-adhesive, form porous membrane structure, produce porous hollow tubular composite membrane 1.
The amount of adsorption particle powder contained by suspension described in step (2) is per addition 1g powder in 100mL chitosan solutions
Body.
Application of the porous hollow tubular composite membrane 1 in drinking water defluorinate, the application process specifically includes following steps：
(a) shell-and-tube adsorbent equipment is assembled：The described two ends of porous hollow tubular composite membrane 1 are covered into upper sealing washer 2；So
Two ends are fixed on support frame 3 afterwards；Support frame is fixed in cylinder-like shell 4 again, two ends connect end socket 5 again, produce pipe
Shell-type adsorbent equipment.
(b) defluorinate in drinking water：The water of defluorinate will be treated, flow slowly into the shell-and-tube adsorbent equipment described in step (a), radially
In the central tube for flowing into porous hollow tubular composite membrane 1, coutroi velocity is 0.1L/ (m2Min the) (m in flow rate2Refer to
The outside area of porous hollow tubular composite membrane 1), water passes through the hole of adsorption particle Guinier-Preston zone 12 of porous hollow tubular composite membrane 1
Road, fluorine ion therein is adsorbed in particle, and the water through defluorinate is come together in the central tube of porous hollow tubular carrier 11
Outflow.
In shell-and-tube adsorbent equipment described in step (a), the porous hollow tubular composite membrane 1 being fixed on support frame 3 is
Seven, it is symmetric around support frame center, described shell-and-tube adsorbent equipment used aloned.
The water for treating defluorinate described in step (b) is running water, and Oil repellent is less than 1mg/L in water after processing.
Embodiment 11：
Porous hollow tubular composite membrane 1 is by porous hollow tubular carrier 11 in this implementation and is coated on porous hollow tubular
Adsorption particle Guinier-Preston zone 12 on the outer surface of carrier 11 is combined, and adsorption particle Guinier-Preston zone 12 is poly- for porous membranaceous adsorption particle
Collect layer, and the thickness of adsorption particle Guinier-Preston zone 12 is 35mm.
Wherein, porous hollow tubular carrier 11 is outside Porous hollow alumina ceramic tube, the hollow aluminium earthenware
Footpath is 20mm, and wall thickness is 2mm, and length is 16cm.Adsorption particle Guinier-Preston zone 12 is mutually glued by adsorption particle powder by chitosan
Knot is formed, and the particle diameter of adsorption particle powder is 5-500 μm.
Adsorption particle powder is 0.8 in mass ratio by molecular sieve, calcium phosphate and aluminum oxide：0.6：1 mixes.Wherein,
Molecular sieve is 13X molecular sieves, and aluminum oxide is boehmite
The preparation method of the present embodiment porous hollow tubular composite membrane 1, specifically includes following steps：
(1) dissolve the chitosan in aqueous acetic acid, be configured to the chitosan solution that concentration is 0.5wt%；
(2) adsorption particle powder is added in chitosan solution, be uniformly dispersed, adsorption particle powder quality concentration, which is made, is
0.1g/mL suspension；
(3) one end of porous hollow tubular carrier 11 is blocked, another termination Vacuum filtration device, then by whole Porous hollow
Tubular carrier 11 is immersed in suspension, adjusts vacuum, and the flow velocity for controlling suction filtration liquid is 60L/ (m2Min), absorption is made
Granular powder is gradually coated on the outer surface of porous hollow tubular carrier 11, forms one layer of adsorption particle Guinier-Preston zone 12；
(4) when the thickness of particle aggregation layer 12 to be adsorbed reaches 35mm, the ammoniacal liquor that mass fraction is 3wt% is transferred to molten
In liquid, continue suction filtration, ammonia spirit is flowed through the 30min of adsorption particle Guinier-Preston zone 12, gather the shell in adsorption particle Guinier-Preston zone 12
Sugar is separated out, and adsorption particle powder adhesion is got up；
(5) the porous hollow tubular carrier 11 that Surface coating has adsorption particle Guinier-Preston zone 12 is vacantly positioned in baking oven,
100 DEG C are warming up to 5 DEG C/min, freeze-day with constant temperature 3h, then room temperature is cooled to 5 DEG C/min, you can porous hollow tubular is made and answers
Close film 1.
Porous hollow tubular composite membrane 1 made from the present embodiment is in practical application, by 1 group of porous hollow tubular composite membrane
Shell-and-tube adsorbent equipment is dressed up, for carrying out defluorinate processing to drinking water.Shell-and-tube adsorbent equipment assemble by the following method and
Into：
The two ends of porous hollow tubular composite membrane 1 are covered into upper sealing washer 2, and two ends are fixed on support frame 3, then will
Support frame is fixed in cylinder-like shell 4, finally, and two ends connect end socket 5, that is, is assembled into shell-and-tube adsorbent equipment.
Claims (10)
1. a kind of porous hollow tubular composite membrane, it is characterised in that the composite membrane is by porous hollow tubular carrier (11) and bag
The adsorption particle Guinier-Preston zone (12) overlayed on porous hollow tubular carrier (11) outer surface is combined, and described adsorption particle gathers
It is porous membranaceous adsorption particle Guinier-Preston zone to collect layer (12), and the thickness of described adsorption particle Guinier-Preston zone (12) is 5-50mm；
The preparation method of described porous hollow tubular composite membrane specifically includes following steps：
(1) dissolve the chitosan in aqueous acetic acid, be configured to the chitosan solution that concentration is 0.5-1wt%；
(2) adsorption particle powder is added in chitosan solution, be uniformly dispersed, adsorption particle powder quality concentration, which is made, is
0.01-0.3g/mL suspension；
(3) porous hollow tubular carrier (11) one end is blocked, another termination Vacuum filtration device, then by whole Porous hollow pipe
Shape carrier (11) is immersed in suspension, adjusts vacuum, and the flow velocity for controlling suction filtration liquid is 10-100L/ (m2Min), make
Adsorption particle powder is gradually coated on the outer surface of porous hollow tubular carrier (11), forms one layer of adsorption particle Guinier-Preston zone
(12)；
(4) when the thickness of particle aggregation layer (12) to be adsorbed reaches 5-50mm, the ammoniacal liquor that mass fraction is 1-3wt% is transferred to
In solution, continue suction filtration, ammonia spirit is flowed through adsorption particle Guinier-Preston zone (12) 5-30min, make adsorption particle Guinier-Preston zone (12)
In chitosan separate out, adsorption particle powder adhesion is got up；
(5) the porous hollow tubular carrier (11) that Surface coating has adsorption particle Guinier-Preston zone (12) is vacantly 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 room temperature is cooled to 1-5 DEG C/min, you can it is made described
Porous hollow tubular composite membrane (1).
2. a kind of porous hollow tubular composite membrane according to claim 1, it is characterised in that described porous hollow tubular
Carrier (11) is one kind 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 characterised in that described Porous hollow oxidation
The external diameter of aluminium earthenware is 5-20mm, and wall thickness is 1-3mm, and length is 5-20cm, described Porous hollow alumina fibre it is outer
Footpath 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 characterised in that described adsorption particle aggregation
Layer (12) is formed by adsorption particle powder by chitosan mutually bonding, 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, it is characterised in that described adsorption particle powder
It is 0.01-1 in mass ratio by molecular sieve, calcium phosphate and aluminum oxide：0.01-1：0.1-1 is mixed.
6. a kind of porous hollow tubular composite membrane according to claim 5, it is characterised in that described molecular sieve includes 4A
The one or more of molecular sieve, 10X molecular sieves or 13X molecular sieves, it is fine that described aluminum oxide includes gama-alumina, hollow nano
Tie up the one or more of shape aluminum oxide, fast shedding or boehmite.
7. a kind of porous hollow tubular composite membrane according to claim 6, it is characterised in that described Hollow nanofibre
The external diameter of shape aluminum oxide is 400-500nm, and internal diameter is 300-400nm, and length is 1-20 μm.
8. a kind of preparation method of porous hollow tubular composite membrane as described in any one of claim 1 to 7, it is characterised in that
This method specifically includes following steps：
(1) dissolve the chitosan in aqueous acetic acid, be configured to the chitosan solution that concentration is 0.5-1wt%；
(2) adsorption particle powder is added in chitosan solution, be uniformly dispersed, adsorption particle powder quality concentration, which is made, is
0.01-0.3g/mL suspension；
(3) porous hollow tubular carrier (11) one end is blocked, another termination Vacuum filtration device, then by whole Porous hollow pipe
Shape carrier (11) is immersed in suspension, adjusts vacuum, and the flow velocity for controlling suction filtration liquid is 10-100L/ (m2Min), make
Adsorption particle powder is gradually coated on the outer surface of porous hollow tubular carrier (11), forms one layer of adsorption particle Guinier-Preston zone
(12)；
(4) when the thickness of particle aggregation layer (12) to be adsorbed reaches 5-50mm, the ammoniacal liquor that mass fraction is 1-3wt% is transferred to
In solution, continue suction filtration, ammonia spirit is flowed through adsorption particle Guinier-Preston zone (12) 5-30min, make adsorption particle Guinier-Preston zone (12)
In chitosan separate out, adsorption particle powder adhesion is got up；
(5) the porous hollow tubular carrier (11) that Surface coating has adsorption particle Guinier-Preston zone (12) is vacantly 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 room temperature is cooled to 1-5 DEG C/min, you can it is made described
Porous hollow tubular composite membrane (1).
9. the application of a kind of porous hollow tubular composite membrane as described in any one of claim 1 to 7, it is characterised in that by institute
The porous hollow tubular composite membrane (1) stated is assembled into shell-and-tube adsorbent equipment, for carrying out defluorinate processing to drinking water.
10. a kind of application of porous hollow tubular composite membrane according to claim 9, it is characterised in that described shell
Formula adsorbent equipment assembles by the following method：
By the two ends set upper sealing washer (2) of described porous hollow tubular composite membrane (1), and support frame is fixed at two ends
(3) on, then support frame is fixed in cylinder-like shell (4), finally, two ends connect end socket (5), that is, is assembled into described shell
Formula adsorbent equipment.
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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 |
| 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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| CN1108583A (en) * | 1994-03-15 | 1995-09-20 | 中国科学院大连化学物理研究所 | Method for preparation of complex film |
| CN1272391A (en) * | 1998-12-04 | 2000-11-08 | 陶瓷技术公司 | Membrane containing porous carrier and molecular sieve layer and its preparing method |
| CN101254420A (en) * | 2008-04-11 | 2008-09-03 | 北京碧水源科技股份有限公司 | Reinforced tubular porous body compound film, method of preparing the same and use thereof |
| CN204619758U (en) * | 2015-05-27 | 2015-09-09 | 杭州凯宏膜技术有限公司 | A kind of hollow fiber film assembly being applicable to external membrane bioreactor |
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| JP5033328B2 (en) * | 2005-12-26 | 2012-09-26 | 本田技研工業株式会社 | Hydrogen storage tank |
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|---|---|---|---|---|
| CN1108583A (en) * | 1994-03-15 | 1995-09-20 | 中国科学院大连化学物理研究所 | Method for preparation of complex film |
| CN1272391A (en) * | 1998-12-04 | 2000-11-08 | 陶瓷技术公司 | Membrane containing porous carrier and molecular sieve layer and its preparing method |
| CN101254420A (en) * | 2008-04-11 | 2008-09-03 | 北京碧水源科技股份有限公司 | Reinforced tubular porous body compound film, method of preparing the same and use thereof |
| CN204619758U (en) * | 2015-05-27 | 2015-09-09 | 杭州凯宏膜技术有限公司 | A kind of hollow fiber film assembly being applicable to external membrane bioreactor |
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