CN108554178A - The novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count for Liquid-liquid separation is 11 - Google Patents
The novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count for Liquid-liquid separation is 11 Download PDFInfo
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- CN108554178A CN108554178A CN201810431276.3A CN201810431276A CN108554178A CN 108554178 A CN108554178 A CN 108554178A CN 201810431276 A CN201810431276 A CN 201810431276A CN 108554178 A CN108554178 A CN 108554178A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/021—Pore shapes
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Abstract
The present invention relates to a kind of novel tree-shaped nanoscale cylindrical hole filter membranes that branch's hole count for liquid-liquid separation is 11, there are many an equally distributed tree cylindrical holes for manufacture in one layer of solid material, each through-hole is including a larger trunk hole and 11 compared with subbranch hole, this 11 branched holes are parallel with their trunk hole and are connected to completely with this trunk hole, and trunk hole surface material is identical with its branched hole surfacing；Each branched hole is filter opening, its length determines according to filter opening intensity requirement, and trunk hole is for reducing filter membrane flow resistance, and physical absorption is weak between a kind of liquid and trunk hole surface in liquid mixture to be separated, physical absorption is strong between remaining liquid and trunk hole surface, and each branch's pore radius is：RB, 1=(0.1~0.2) Rcr, RcrTo make that liquid in the liquid mixture that physical absorption is weak between trunk hole surface become critical cylindrical hole radius needed for continuous media flowing, this layer of solid material is filter membrane.
Description
Technical field
The present invention relates to filter membrane field, specifically a kind of branch's hole count for Liquid-liquid separation be 11 it is new
Type tree-shaped nanoscale cylindrical hole filter membrane.
Background technology
Filtering film, abbreviation filter membrane have important application in industry and daily life, it can be used for filtering out solid
Grain, impurity purify liquid, it can also be used to filter out bacterium, macromolecular substances, or the separation for realizing two kinds of liquid.It is daily
In life, filter membrane can be used for purifying drinking water, purify various beverages, it can also be used to impurity, the various ions in seawater are filtered out, it is real
Existing seawater cleaning.Existing typical filter ways and means have：
One, activated carbon filters
Activated carbon is a kind of industrial adsorbents that purposes is extremely wide, it be using charcoal, various shells and fat coal etc. as
Raw material, raw material is crushed by physics and chemical method, is sieved, activation of catalyst, rinsing, drying and screening etc. it is a series of
Process fabricates.The adsorptivity of activated carbon is derived from its unique molecular configuration, and there are many holes in the inside of activated carbon, often
If the internal void drawout of gram activated carbon can reach 500~1700 square metres, exactly this unique internal structure makes
Obtaining activated carbon has excellent adsorption capacity.When activated carbon filters, due to the fine content in the adsorbable various liquid of its porosity
Matter, decoloration, deodorization, dechlorination, organics removal and the heavy metal being usually used in water process remove synthetic detergent, bacterium, virus
And the polluters such as radioactivity, it is also commonly used for the tertiary treatment of waste water.
The common application range of activated carbon filtering：(1) water treatment facilities filtering, sewage disposal, Treated sewage reusing etc. are used for.
It is widely used in chemical industry, food, medicine, electronics photovoltaic etc..(2) it is used to require delivery turbidity≤5mg/L that can meet drinking water quality
Industrial water, domestic water and the municipal water supply system of standard.(3) removal of the suspended matter, solids in trade effluent.(4)
It can be used as the pre-processing device in ion-exchange softening, desalting system, the coarse filtration of the industrial water supply not high to water quality requirement
Equipment.(5) swimming pool circulating treating system, cooling cycle water purification system etc. are used in.The advantage and disadvantage of activated carbon filtering：Advantage：
Activated carbon price is relatively inexpensive, and it is relatively low that activated carbon filters cost, can meet general industry and the common filtration needs of daily life, resistance to
Pressure, heat-resisting, sexual valence is relatively high.Disadvantage：The hole of activated carbon is larger, it is difficult to realize fine filtering, cannot filter out micron order and receive
The substance of meter level size, is usually used in coarse filtration.
Two, micro-pore-film filtration
It is close and numerous on microporous barrier to be evenly distributed with each micropore, the diameter in this hole usually 0.1 micron and 100 microns it
Between.Therefore, microporous barrier can filter out liquid, gas 0.1um or more particle and bacterium, it has, and filtering accuracy is high, transition speed
Degree is fast, absorption falls off less, without medium, acid-alkali-corrosive-resisting, it is easy to operate the advantages that.Be widely used in medicine, chemical industry, electronics,
The required equipment of the industry such as beverage, fruit wine, biochemical water process, environmental protection.
Common microporous membrane filter element has：Polytetrafluoroethylene film (PTFE) filter core gathers inclined film (PVDF) filter core, polypropylene screen
(PP) filter core, cellulose acetate film (CN-CA) filter core, nylon (PN6) filter core, alloy stud, Wire-wound filter core, melt-blown filter, PA/PE
Sintered filter core.These filter core features are：It is small, light-weight, easy to use, filter area is big, plugging rate is low, the rate of filtration
Soon, pollution-free, the dilute stability of heat and chemical stability are good, can filter out most particles, be widely used in refined filtration and degerming work
Skill.
The shortcomings that micro-pore-film filtration：Compared to nano-pore filter membrane, the diameter in filtering hole is still bigger than normal on microporous barrier, although energy
Meet many refined filtration requirements in daily industry and life, but cannot be used for filtering superfine small substance such as blood purification, protein
Middle virus purification, liquid intermediate ion filter out, the super purification etc. of water.
Three, sock filtration
Micron order liquid filter bag is made using high-quality filtrate, can effectively remove the solid for needing to remove in liquid
Matter.When by micron order filter bag, impurities are accurately captured in filter bag deep layer liquid, complete filter process.Filter material
Matter：Different according to institute's filtering solution, PE felts or PP felts may be selected in filter material, and the filtrates such as nylon monofilament, polyester monofilament also can be selected, from
And it is widely used in height different temperatures, soda acid varying environment.
Similar with micro-pore-film filtration, the shortcomings that sock filtration, is：The diameter in filtering hole is still bigger than normal on filter bag, although can be full
Many refined filtration requirements in the daily industry of foot and life, but cannot be used for filtering in superfine small substance such as blood purification, protein
Virus purification, liquid intermediate ion filter out, the super purification etc. of water.
Four, nano-pore membrane filtration
In order to filter pole subtitle substance, isolated viral, separation larger molecular organics etc., nano-pore filter membrane mistake must be just used
Filter.Compared to miillpore filter, the hole in nano-pore filter membrane is much smaller, and diameter is in nanometer scale, often less than by filter impurity
Molecular dimension, therefore be usually used in hyperfine filtering, impurity, bacterium, virus, organic macromolecule etc. can thoroughly be filtered out.Nanometer
Kong Changwei cylindrical holes, conical bore in the filter membrane of hole.To improve this filter membrane permeability, also have using two layers of filter membrane, upper layer is to receive
Metre hole filter membrane, lower layer are miillpore filter.Also someone develops very thin monolayer nano-pore graphene filter membrane, this filter membrane
Permeability is preferable.
Although the filter capacity of nano-pore filter membrane is strong, since filter opening is minimum, this permeability of the membrane is poor, its filtering
Efficiency is relatively low, and this film is very thin, and the mechanical strength of film also often faces the challenge, not high pressure resistant, high temperature.Filter capacity is oozed
Permeability and mechanical strength are difficult to realize well simultaneously on nano-pore filter membrane；One of which performance is met, must be reduced
Remaining performance.
Five, Liquid-liquid separating and filtering
It often needs the liquid for being blended in two kinds one piece to separate in daily life and production, realizes Liquid-liquid separation
Filtering.In the past, the common means of Liquid-liquid isolation of purified had：
(1) Gravity Separation：The two kind liquid larger and immiscible suitable for density difference.It is larger in two kinds of fluid density differences
In the case of, the larger liquid of density can be deposited on bottom, and the smaller liquid of density can float on upper layer, can be achieved with two kinds in this way
The separation of liquid.
(2) centrifugal force separate：The two kind liquid larger and immiscible suitable for density difference.It is generated using rotary drum high speed rotation
Powerful centrifugal force field, keep density different and two kinds of immiscible liquid mixtures achieve the purpose that separation.
(3) it extracts：Suitable for the little two kinds of miscible liquid of solubility.With another solvent from the mixture of both liquid
Extract solute.Precondition is：Two kinds of solvents are immiscible, and solubility of the solute in two kinds of solvents differs greatly.
(4) it distills：Two kinds of liquid of larger suitable for boiling point difference and mutual phased soln.Make that lower liquid of boiling point by heating
Evacuator body realizes the separation of both liquid.
Liquid-liquid separating and filtering is a more difficult technical barrier in filtering.The common Liquid-liquid of above-mentioned introduction
Separation means are limited to two kinds of specific physical property and differ larger liquid, for example density difference is big and mutually insoluble or boiling point phase
Solubility of the poor big or solute in two kinds of solvents differs greatly.The two kinds of liquid to mix in daily life or production are often
Do not have these conditions, these liquid of isolation of purified just face larger technical barrier.It mixes for example, density difference is little and mutually
Solution, two kinds of liquid mix similar in boiling point, and how detaching both liquid, to be conventional means presented hereinbefore cannot solve
's.
Invention content
The object of the present invention is to provide a kind of novel tree-shaped nanoscales that branch's hole count for Liquid-liquid separation is 11
Cylindrical hole filter membrane, solves to be only limited to two kinds of specific physical property of separation in the prior art to differ larger liquid and be difficult to partition density
It is not much different and mutually phased soln, two kinds of this technical barriers of liquid similar in boiling point.
Technical solution of the invention is：
The novel tree-shaped nanoscale cylindrical hole filter membrane that a kind of branch's hole count for Liquid-liquid separation is 11, such as Fig. 1 and
Shown in Fig. 2, in the inner manufacture of one layer of solid material (1), there are many through-hole of equally distributed tree, each trees
Through-hole include a trunk hole (2) and 11 branched hole, that is, branched holes (3), branched hole (4), branched hole (5), branched hole
(6), branched hole (7), branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole
(13), this 11 branched holes are mutually parallel with trunk hole (2) and are connected to completely with trunk hole (2), trunk hole (2) and this
11 branched holes are cylindrical hole, the surfacing all same of the surfacing of trunk hole (2) and this 11 branched holes, respectively
Branched hole is filter opening, and each branch's pore radius is RB, 1, each branch's hole length is l1, trunk hole (2) and its 11 points
The surface coatings in branch hole are not coated by coating, a kind of liquid in mixture made of several liquid to be separated mix
Physical absorption between body and trunk hole (2) and the surface of its branched hole is weak, remaining liquid in liquid mixture and trunk hole
(2) physical absorption between the surface of its branched hole is strong, between liquid here and trunk hole (2) surface strong physical absorption instigate
Liquid flowing becomes liquid and trunk of critical trunk hole (2) diameter not less than 30nm of continuous media flowing in trunk hole (2)
Liquid in trunk hole (2) is instigated in weak physical absorption between physical absorption between hole (2) surface, liquid here and trunk hole (2) surface
Body flowing becomes between liquid and trunk hole (2) surface of critical trunk hole (2) diameter no more than 10nm of continuous media flowing
Physical absorption；Branched hole (3) diameter is in nanometer scale, branched hole (3) radius RB, 1It is taken as (0.1~0.2) Rcr, R herecrFor
That liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) is set to become needed for continuous media flowing
Critical cylindrical hole radius.Each branch's hole length l1It is as small as possible to reduce the flow resistance of filter opening, l1Value wanted according to filter opening intensity
Ask determining, the axial line of each branched hole and the parallelism tolerance of the axial line in their trunk hole (2) are not more than 0.1l1.Trunk
The radius R in hole (2)B, 2Than its branch pore radius RB, 1Bigger, trunk hole (2) radius RB, 2According to its branch pore radius RB, 1With
Maximum penetrating power requirement of that liquid in filter membrane between trunk hole (2) surface in the weak liquid mixture of physical absorption
It is calculate by the following formula determination：
Here, λ0=l1/ l, l are the thickness of solid material (1),Req=c1RB, 1, RcrTo make and trunk
That liquid between the surface in hole (2) in the weak liquid mixture of physical absorption becomes the critical cylinder needed for continuous media flowing
Pore radius, c1Value range be：1.63~1.99, c1Preferred value be 1.81,
ρ is the body of that liquid between the surface of trunk hole (2) in the weak liquid mixture of physical absorption under environment temperature and pressure
Phase density,That liquid between the surface of trunk hole (2) in the weak liquid mixture of physical absorption is in radius
For ReqHole radial direction averag density, this averag density withIt is related,η
For the body phase of that liquid under environment temperature and pressure between the surface of trunk hole (2) in the weak liquid mixture of physical absorption
Viscosity,That liquid between the surface of trunk hole (2) in the weak liquid mixture of physical absorption is in radius
ReqHole radial direction equivalent viscosity, this equivalent viscosity withIt is related,For the table for describing with trunk hole (2)
That liquid between face in the weak liquid mixture of physical absorption is R in radiuseqHole radial direction present discontinuous Jie
The parameter of mass effect.
Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7), branched hole (8), branched hole
(9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) are evenly distributed on the surface of solid material (1)
On one circumference, the radius of the circumference is Rd, this branched hole (3), branched hole (4), branched hole (5), branched hole (6), branch
Hole (7), branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) are in solid
The distribution circle on the surface of material (1) and the concentricity tolerance of trunk hole (2) are not more than 0.1Rd, contiguous branch hole is on the circumference
Spacing be Δ1, Δ1With RB, 1Ratio value range be：ks=Δ1/RB, 1=0.05~0.5, RdWith RB, 1Ratio be：Rd/
RB, 1=(22+11ks)/(2π)。
The thickness l of solid material (1) is determined according to the requirement of mechanical strength of solid material (1)；Trunk hole (2) and its ten
The through-hole for the tree that one branched hole is formed runs through solid material (1), trunk hole in the thickness direction of solid material (1)
(2) it is used to reduce that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) in solid material (1)
In flow resistance, increase solid material (1) penetrating power.Under the conditions of in this way, due to a kind of liquid in liquid mixture
Physical absorption between body and trunk hole (2) and its branch's hole surface is weak and remaining liquid and trunk hole (2) in liquid mixture
Physical absorption between its branch's hole surface is strong, the liquid in liquid mixture the inner flow resistance of solid material (1) just
It differs greatly, that liquid energy between trunk hole (2) and its branch's hole surface in the weak liquid mixture of physical absorption
Solid material (1) is passed through, and remaining liquid in liquid mixture is then difficult to through solid material (1).This solid material
(1) it is novel tree-shaped nanoscale cylindrical hole filter membrane that the signified branch's hole count for Liquid-liquid separation of the present invention is 11.
Further, filter membrane uses plane or curved surface filter membrane.
Further, the thickness of filter membrane is identical everywhere or differs.
Further, filter membrane is fabricated by silica or graphene.
The novel tree-shaped nanoscale cylindrical hole filter membrane that this kind is 11 for branch's hole count of Liquid-liquid separation, with one layer
Solid material manufactures filter membrane, and filter membrane can be plane filter membrane, can also be curved surface filter membrane.Filter membrane thickness can be equal everywhere,
It can be variation.
The beneficial effects of the invention are as follows：
Compared to traditional liquid-liquid separation technology, present invention does not require each fluid density differences in liquid mixture
Big or boiling point differs greatly, and does not also require each liquid in liquid mixture immiscible, has specific tree by design
The filter membrane of through-hole makes flow resistance of the liquid in liquid mixture in filter membrane differ greatly, to realize Liquid-liquid point
From；Filter membrane of the present invention can not only realize the separating and filtering of Liquid-liquid, moreover it is possible to meet requirement of mechanical strength when filtering；This hair
Bright filter membrane anufacturability is good, of low cost, to the good separating effect of Liquid-liquid.These are advantages of the present invention.The present invention
There is important application in the fields such as sewage disposal, oil-oil separation, biology, pharmacy, petrochemical industry, chemical industry.
Description of the drawings
Fig. 1 is the novel tree-shaped nanoscale cylinder that the embodiment of the present invention is 11 for branch's hole count of Liquid-liquid separation
The front view of hole filter membrane structure；Fig. 2 is the novel tree-shaped that the embodiment of the present invention is 11 for branch's hole count of Liquid-liquid separation
The left view of nanoscale cylindrical hole filter membrane structure；
Fig. 3 is the water in embodiment when filter membrane of the present invention is manufactured with silica, detached to water and machine oil mixture
With dimensionless flow resistance I of the machine oil in filter membrane of the present inventionfWith filter opening, that is, branched hole (3) radius RB, 1Relational graph；
Fig. 4 be when filter membrane of the present invention is manufactured with graphene, is detached to water and machine oil mixture in embodiment water and
Dimensionless flow resistance I of the machine oil in filter membrane of the present inventionfWith filter opening, that is, branched hole (3) radius RB, 1Relational graph.
In Fig. 1 and Fig. 2：1- solid materials, 2- trunks hole, 3- branched holes, 4- branched holes, 5- branched holes, 6- branched holes, 7-
Branched hole, 8- branched holes, 9- branched holes, 10- branched holes, 11- branched holes, 12- branched holes, 13- branched holes
Wherein, l1For each branch's hole length, l2For the length of main dry hole (2), l is thickness, that is, embodiment of solid material (1)
The thickness of filter membrane of the present invention, RdFor branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7), branched hole
(8), the surface of branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) in solid material (1)
Distribution circle radius, Δ1For spacing of the contiguous branch hole on the circumference of the distribution circle on the surface of circle material (1).
Specific implementation mode
The preferred embodiment that the invention will now be described in detail with reference to the accompanying drawings.
Embodiment
The novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count for Liquid-liquid separation of embodiment is 11, such as
Shown in Fig. 1 and Fig. 2, in the inner manufacture of one layer of solid material (1), there are many through-holes of equally distributed tree, each tree-shaped
The through-hole of structure includes a trunk hole (2) and 11 branched hole, that is, branched holes (3), branched hole (4), branched hole (5), branch
Hole (6), branched hole (7), branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole
(13), this 11 branched holes are mutually parallel with trunk hole (2) and are connected to completely with trunk hole (2), trunk hole (2) and this
11 branched holes are cylindrical hole, the surfacing all same of the surfacing of trunk hole (2) and this 11 branched holes, respectively
Branched hole is filter opening, and each branch's pore radius is RB, 1, each branch's hole length is l1, trunk hole (2) and its 11 points
The surface coatings in branch hole are not coated by coating, a kind of liquid in mixture made of several liquid to be separated mix
Physical absorption between body and trunk hole (2) and the surface of its branched hole is weak, remaining liquid in liquid mixture and trunk hole
(2) physical absorption between the surface of its branched hole is strong, between liquid here and trunk hole (2) surface strong physical absorption instigate
Liquid flowing becomes liquid and trunk of critical trunk hole (2) diameter not less than 30nm of continuous media flowing in trunk hole (2)
Liquid in trunk hole (2) is instigated in weak physical absorption between physical absorption between hole (2) surface, liquid here and trunk hole (2) surface
Body flowing becomes between liquid and trunk hole (2) surface of critical trunk hole (2) diameter no more than 10nm of continuous media flowing
Physical absorption；Branched hole (3) diameter is in nanometer scale, branched hole (3) radius RB, 1It is taken as (0.1~0.2) Rcr, R herecrFor
That liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) is set to become needed for continuous media flowing
Critical cylindrical hole radius.Each branch's hole length l1It is as small as possible to reduce the flow resistance of filter opening, l1Value wanted according to filter opening intensity
Ask determining, the axial line of each branched hole and the parallelism tolerance of the axial line in their trunk hole (2) are not more than 0.1l1.Trunk
The radius R in hole (2)B, 2Than its branch pore radius RB, 1Bigger, trunk hole (2) radius RB, 2According to its branch pore radius RB, 1With
Maximum penetrating power requirement of that liquid in filter membrane between trunk hole (2) surface in the weak liquid mixture of physical absorption
It is calculate by the following formula determination：
Here, λ0=l1/ l, l are the thickness of solid material (1),Req=c1RB, 1, RcrTo make and trunk
That liquid between the surface in hole (2) in the weak liquid mixture of physical absorption becomes the critical cylinder needed for continuous media flowing
Pore radius, c1Value range be：1.63~1.99, c1Preferred value be 1.81,
ρ is the body of that liquid between the surface of trunk hole (2) in the weak liquid mixture of physical absorption under environment temperature and pressure
Phase density,That liquid between the surface of trunk hole (2) in the weak liquid mixture of physical absorption is in radius
For ReqHole radial direction averag density, this averag density withIt is related,η
For the body phase of that liquid under environment temperature and pressure between the surface of trunk hole (2) in the weak liquid mixture of physical absorption
Viscosity,That liquid between the surface of trunk hole (2) in the weak liquid mixture of physical absorption is in radius
ReqHole radial direction equivalent viscosity, this equivalent viscosity withIt is related,For the table for describing with trunk hole (2)
That liquid between face in the weak liquid mixture of physical absorption is R in radiuseqHole radial direction present discontinuous Jie
The parameter of mass effect.
Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7), branched hole (8), branched hole
(9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) are evenly distributed on the surface of solid material (1)
On one circumference, the radius of the circumference is Rd, this branched hole (3), branched hole (4), branched hole (5), branched hole (6), branch
Hole (7), branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) are in solid
The distribution circle on the surface of material (1) and the concentricity tolerance of trunk hole (2) are not more than 0.1Rd, contiguous branch hole is on the circumference
Spacing be Δ1, Δ1With RB, 1Ratio value range be：ks=Δ1/RB, 1=0.05~0.5, RdWith RB, 1Ratio be：Rd/
RB, 1=(22+11ks)/(2π)。
The thickness l of solid material (1) is determined according to the requirement of mechanical strength of solid material (1)；Trunk hole (2) and its ten
The through-hole for the tree that one branched hole is formed runs through solid material (1), trunk hole in the thickness direction of solid material (1)
(2) it is used to reduce that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) in solid material (1)
In flow resistance, increase solid material (1) penetrating power.Under the conditions of in this way, due to a kind of liquid in liquid mixture
Physical absorption between body and trunk hole (2) and its branch's hole surface is weak and remaining liquid and trunk hole (2) in liquid mixture
Physical absorption between its branch's hole surface is strong, the liquid in liquid mixture the inner flow resistance of solid material (1) just
It differs greatly, that liquid energy between trunk hole (2) and its branch's hole surface in the weak liquid mixture of physical absorption
Solid material (1) is passed through, and remaining liquid in liquid mixture is then difficult to through solid material (1).This solid material
(1) it is novel tree-shaped nanoscale cylindrical hole filter membrane that the signified branch's hole count for Liquid-liquid separation of the present invention is 11.
In one preferred embodiment, filter membrane is plane filter membrane, and filter membrane is fabricated by graphene, for detaching water and machine oil
Mixture (the hydrophobic close machine oil of graphene).Select branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7),
Branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) radius, that is, filter opening half
Diameter RB, 1=0.7nm, takes ks=Δ1/RB, 1=0.5, c1=1.81, λ0=l1/ l=1 × 10-2, whole film, that is, solid material (1)
Thickness be l=1 μm, then：Each branch's hole length l1=10nm, trunk hole (2) radius RB, 2=4.4nm, each branched hole is solid
The distribution radius of circle R on the surface of body material (1)d=3.1nm, separation delta of the contiguous branch hole on the circumferential spread1=
0.35nm；It is 1.0nm to take the parallelism tolerance of the axial line of each branched hole and the axial line in their trunk hole (2), takes each point
Branch hole is 0.3nm in the distribution circle on the surface of solid material (1) and the concentricity tolerance of trunk hole (2).Water is in this filter membrane
Flow resistance is smaller, can pass through filter membrane；And machine oil flow resistance in this filter membrane is very big, cannot pass through filter membrane.In this way
It can be achieved with the separation of water and machine oil.
In one preferred embodiment, filter membrane is plane filter membrane, and filter membrane is fabricated by silica, for detaching water and machine
Oil mixture (silicon dioxide drainage parent machine oil).Select branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole
(7), branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) radius are filtered
Pore radius RB, 1=0.7nm, takes ks=Δ1/RB, 1=0.5, c1=1.81, λ0=l1/ l=1 × 10-4, whole film, that is, solid material
(1) thickness is l=0.1mm, then：Each branch's hole length l1=10nm, trunk hole (2) radius RB, 2=15nm, each branched hole
Distribution radius of circle R on the surface of solid material (1)d=3.1nm, separation delta of the contiguous branch hole on the circumferential spread1=
0.35nm；It is 1.0nm to take the parallelism tolerance of the axial line of each branched hole and the axial line in their trunk hole (2), takes each point
Branch hole is 0.3nm in the distribution circle on the surface of solid material (1) and the concentricity tolerance of trunk hole (2).Water is in this filter membrane
Flow resistance is smaller, can pass through filter membrane；And machine oil flow resistance in this filter membrane is very big, cannot pass through filter membrane.In this way
It can be achieved with the separation of water and machine oil.
In one preferred embodiment, filter membrane is plane filter membrane, and filter membrane is fabricated by graphene, for detaching water and alcohol
Mixture (the hydrophobic close alcohol of graphene).Select branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7),
Branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) radius, that is, filter opening half
Diameter RB, 1=0.5nm, takes ks=Δ1/RB, 1=0.5, c1=1.81, λ0=l1/ l=1 × 10-2, whole film, that is, solid material (1)
Thickness be l=1 μm, then：Each branch's hole length l1=10nm, trunk hole (2) radius RB, 2=2.7nm, each branched hole is solid
The distribution radius of circle R on the surface of body material (1)d=2.2nm, separation delta of the contiguous branch hole on the circumferential spread1=
0.25nm；It is 1.0nm to take the parallelism tolerance of the axial line of each branched hole and the axial line in their trunk hole (2), takes each point
Branch hole is 0.21nm in the distribution circle on the surface of solid material (1) and the concentricity tolerance of trunk hole (2).Water is in this filter membrane
Flow resistance is smaller, can pass through filter membrane；And alcohol flow resistance in this filter membrane is very big, cannot pass through filter membrane.In this way
It can be achieved with the separation of water and alcohol.
In one preferred embodiment, filter membrane is plane filter membrane, and filter membrane is fabricated by silica, for detaching water and vapour
Oil mixture (silicon dioxide drainage parent gasoline).Select branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole
(7), branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) radius are filtered
Pore radius RB, 1=0.6nm, takes ks=Δ1/RB, 1=0.5, c1=1.81, λ0=l1/ l=1 × 10-4, whole film, that is, solid material
(1) thickness is l=0.1mm, then：Each branch's hole length l1=10nm, trunk hole (2) radius RB, 2=11nm, each branched hole
Distribution radius of circle R on the surface of solid material (1)d=2.6nm, separation delta of the contiguous branch hole on the circumferential spread1=
0.3nm；It is 1.0nm, Qu Ge branches to take the parallelism tolerance of the axial line of each branched hole and the axial line in their trunk hole (2)
Hole is 0.25nm in the distribution circle on the surface of solid material (1) and the concentricity tolerance of trunk hole (2).Water flows in this filter membrane
Dynamic resistance is smaller, can pass through filter membrane；And gasoline flow resistance in this filter membrane is very big, cannot pass through filter membrane.Thus
It can realize the separation of water and gasoline.
Principle of this kind for the novel tree-shaped nanoscale cylindrical hole filter membrane that branch's hole count of Liquid-liquid separation is 11 is said
It is bright as follows：
Filter membrane of the present invention is used for Liquid-liquid separating and filtering, and a kind of liquid in liquid mixture is allowed to pass through filter membrane,
And remaining liquid in liquid mixture is allowed to be difficult to through filter membrane, to reach Liquid-liquid separation.The principle of the invention is to utilize
The larger physical absorption of difference of each liquid in the small nano-size pores (filter opening) of filter membrane between orifice surface in liquid mixture
Characteristic is so that each liquid has the prodigious flow resistance of difference in filter membrane in liquid mixture.To realize Liquid-liquid
Purpose is detached, the present invention claims：A kind of liquid and filter membrane in mixture made of several liquid to be separated mix
Physical absorption between small nano-size pores (filter opening) surface is weak, and the small nano-size pores of remaining liquid and filter membrane in liquid mixture
Physical absorption between surface is strong.Here strong physical absorption instigates liquid flowing in filter opening to become continuous between liquid and filter opening surface
Physical absorption between liquid and filter opening surface of the critical filter opening diameter of media flow not less than 30nm, liquid here and filter opening
Weak physical absorption instigates liquid flowing in filter opening to become the critical filter opening diameter of continuous media flowing no more than 10nm's between surface
Physical absorption between liquid and filter opening surface.
The filter opening radius of filter membrane of the present invention, that is, branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole
(7), the radius R of branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13)B, 1
Value range be (0.1~0.2) Rcr, R herecrTo make that in the liquid mixture that physical absorption is weak between filter opening surface
Kind liquid becomes the critical cylindrical hole radius needed for continuous media flowing.Filter opening diameter 2R of the present inventionB, 1It is generally in 1nm magnitudes
It is horizontal.Different liquids in liquid mixture to be separated just have the flow resistance to differ greatly in the filter membrane designed in this way
To realize the Liquid-liquid separation function of filter membrane.
The requirement of mechanical strength proposed to filter membrane during Liquid-liquid separating and filtering is considered, with conventional material such as dioxy
The thickness l of filter membrane of the present invention made of SiClx need to usually reach 50 μm or more.If penetrating filter of the present invention using single filter opening
The whole thickness l of film, then filter opening seem very deep, the draw ratio of filter opening greatly (reaches 104).Liquid is it is difficult to flow through this and thin
And long filter opening, the penetrating power of such filter membrane just becomes very poor.In fact, the axial direction of filter opening, that is, each branched hole is long in the present invention
Spend l1(i.e. the depth of filter opening) need not reach the thickness l of filter membrane, only need to consider filter opening intensity requirement, it is long to reserve necessary filter opening
Spend l1.In this way, can achieve the purpose that Liquid-liquid separating and filtering.On the other hand, in order to reduce and filter opening i.e. branched hole
(3) resistance of that liquid flow filter membrane between surface in the weak liquid mixture of physical absorption, increases the penetrating power of filter membrane,
Fluid flow in 11 filter openings of dense distribution i.e. 11 branched holes can be pooled to the trunk hole (2) of a bigger
In, filter membrane is flowed out by trunk hole (2) by the liquid of separating and filtering, material is thus formed the through-holes of tree in filter membrane.
According to nanochannel fluid flow theory, 11 branched hole, that is, branched holes (3) shown in Fig. 2, branched hole (4),
Branched hole (5), branched hole (6), branched hole (7), branched hole (8), branched hole (9), branched hole (10), branched hole (11), branch
It is l that hole (12) and branched hole (13), which are equivalent to a length,1Radius with hole is ReqStraight cylindrical hole.The half of trunk hole (2)
Diameter RB, 2It is bad if too small, the resistance for effectively lowering liquid flow filter membrane cannot be reached and effectively increase filter membrane penetrating power
Purpose.And the radius R of trunk hole (2)B, 2It is excessive, it is also bad；The radius R of trunk hole although (2)B, 2Increase can reduce liquid flow
The resistance of single tree through-hole in filter membrane, still, for a given filter membrane, its surface area is given, master
The radius R of dry hole (2)B, 2Increase the sum of trunk hole (2) in filter membrane can be made to reduce, make the penetrating power of filter membrane instead in this way
It is deteriorated, the flow for flowing liquid through filter membrane reduces.Therefore, the radius R in trunk hole (2) how is chosen in the present inventionB, 2It is crucial.
The radius R in trunk hole (2)B, 2It need to make that in the liquid mixture that physical absorption is weak between trunk hole (2) surface
Liquid has maximum penetrating power in filter membrane, and according to this requirement, based on fluid flow theory in nanochannel, the present invention obtains
To the radius R of trunk hole (2)B, 2With all branched holes of trunk hole (2) it is equivalent at cylindrical hole radius ReqIt need to meet with ShiShimonoseki
It is formula：
Here, λ0=l1/ l, l are that the thickness of solid material (1) is the thickness of filter membrane of the present invention,Req=
c1RB, 1, RcrTo make that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) become continuous media
Critical cylindrical hole radius needed for flowing, c1Value range be：1.63~1.99, c1Preferred value be 1.81,ρ is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure
Liquid mixture in that liquid body phase density,Physical absorption is weak between the surface of trunk hole (2)
That liquid in liquid mixture is R in radiuseqHole radial direction averag density, this averag density withHave
It closes,η is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure
Liquid mixture in that liquid bulk viscosity,Physical absorption is weak between the surface of trunk hole (2)
That liquid in liquid mixture is R in radiuseqHole radial direction equivalent viscosity, this equivalent viscosity withHave
It closes,It is R to describe that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) in radiuseq
Hole radial direction present Discontinuous transmission effect parameter.
By the radius R of the counted trunk hole (2) of above formulaB, 2Than its branch pore radius RB, 1It is much greater, in remaining filter
Film thickness (l-l1) on open up trunk hole (2), allow liquid by trunk hole (2) flow out filter membrane can be substantially reduced filter membrane flowing hinder
Power, the penetrating power for significantly increasing filter membrane.For ensure trunk hole (2) 11 branched holes dense distribution and meet these points
The manufacturing process in branch hole requires, here the circumferential distance Δ in contiguous branch hole1It should meet：ks=Δ1/RB, 1=0.05~0.5, this
Distribution radius of circle R of 11 branched holes in filter membrane surfacedIt should meet：Rd/RB, 1=(22+11ks)/(2π).In this way, of the invention
The filter membrane of design just has the advantages that more tree number of through-holes, good penetrability, high mechanical strength, anufacturability are good.This
It is exactly the principle of the present invention.
When filter membrane of the present invention is manufactured with silica, is detached to water and machine oil mixture, reality is set forth in Fig. 3
Apply the dimensionless flow resistance I of water and machine oil in filter membrane of the present invention in examplefWith filter opening, that is, branched hole (3) radius RB, 1Relationship.
In Fig. 3,Here, Rr=10nm, ρ and η are respectively the body phase of water or machine oil under environment temperature and pressure
Density and bulk viscosity, l are the thickness of filter membrane of the present invention in embodiment, AmFilter opening is distributed with for filter membrane of the present invention in embodiment
The area on surface, χ are the drilling rate on the surface that trunk hole (2) is distributed in filter membrane of the present invention in embodiment, ifFor this in embodiment
The dimension flow resistance of invention filter membrane, if=Δ p/qm, qmTo flow through the water or machine of filter membrane of the present invention in embodiment in the unit time
The mass flow of oil, Δ p are the pressure difference applied on filter membrane of the present invention in embodiment.As can be seen from Figure 3, work as RB, 1When≤2nm,
Flow resistance of the machine oil in filter membrane of the present invention is more than 80~1000 times of flow resistance of the water in filter membrane of the present invention；This display
Flow resistance difference of both liquid in filter membrane of the present invention is very big.Fig. 3 shows that water can smoothly lead in filter membrane of the present invention
It crosses, and machine oil is then difficult to filter membrane through the invention.Fig. 3 supports the present invention.
When filter membrane of the present invention is manufactured with graphene, is detached to water and machine oil mixture, implementation is set forth in Fig. 4
The dimensionless flow resistance I of water and machine oil in filter membrane of the present invention in examplefWith filter opening, that is, branched hole (3) radius RB, 1Relationship.Figure
In 4, IfDefinition it is identical as in Fig. 3, as can be seen from Figure 4, work as RB, 1When≤2nm, flow resistance of the machine oil in filter membrane of the present invention
It is more than 80~1000 times of flow resistance of the water in filter membrane of the present invention；Which show both liquid in filter membrane of the present invention
Flow resistance difference is very big.Fig. 4 shows that water can pass through in filter membrane of the present invention, and machine oil is then difficult to filter through the invention
Film.Fig. 4 supports the present invention.
Claims (8)
1. the novel tree-shaped nanoscale cylindrical hole filter membrane that a kind of branch's hole count for Liquid-liquid separation is 11, feature exist
In：In the inner manufacture of one layer of solid material (1), there are many through-hole of equally distributed tree, the through-holes of each tree
Including a trunk hole (2) and 11 branched hole, that is, branched holes (3), branched hole (4), branched hole (5), branched hole (6), branch
Hole (7), branched hole (8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13), this 11
A branched hole is mutually parallel with trunk hole (2) and is connected to completely with trunk hole (2), trunk hole (2) and this 11 branches
Hole is cylindrical hole, the surfacing all same of the surfacing of trunk hole (2) and this 11 branched holes, and each branched hole is
Filter opening, each branch's pore radius is RB, 1, each branch's hole length is l1, the surface of trunk hole (2) and its 11 branched holes
Applying coating is not coated by coating, a kind of liquid in mixture made of several liquid to be separated mix and trunk hole
(2) physical absorption between the surface of its branched hole is weak, remaining liquid in liquid mixture and trunk hole (2) and its point
Physical absorption between the surface in branch hole is strong, between liquid here and trunk hole (2) surface strong physical absorption instigate in trunk hole (2)
Liquid flowing becomes between liquid and trunk hole (2) surface of critical trunk hole (2) diameter not less than 30nm of continuous media flowing
Physical absorption, between liquid here and trunk hole (2) surface weak physical absorption instigate in trunk hole (2) liquid flowing to become and connect
Physical absorption between liquid and trunk hole (2) surface of critical trunk hole (2) diameter no more than 10nm of continuous media flow；Branch
Hole (3) diameter is in nanometer scale, branched hole (3) radius RB, 1It is taken as (0.1~0.2) Rcr, R herecrTo make and trunk hole (2)
Surface between that liquid in the weak liquid mixture of physical absorption become the critical cylindrical hole half needed for continuous media flowing
Diameter；Each branch's hole length l1It is as small as possible to reduce the flow resistance of filter opening, l1Value according to filter opening intensity requirement determine, trunk
The radius R in hole (2)B, 2Than its branch pore radius RB, 1The tree-shaped knot that bigger, trunk hole (2) and its 11 branched holes are formed
The through-hole of structure runs through solid material (1) in the thickness direction of solid material (1), and trunk hole (2) are for reducing by isolation of purified liquid
Body is to filter in the inner flow resistance of solid material (1), the penetrating power of increase solid material (1), this layer of solid material (1)
Film.
2. the novel tree-shaped nanoscale that a kind of branch's hole count for Liquid-liquid separation as described in claim 1 is 11 is justified
Post holes filter membrane, it is characterised in that：Trunk hole (2) radius RB, 2According to its branch pore radius RB, 1And between trunk hole (2) surface
Maximum penetrating power of that liquid in filter membrane in the weak liquid mixture of physical absorption requires to be calculate by the following formula determination：
Here, λ0=l1/ l, l are the thickness of thickness, that is, filter membrane of solid material (1),Req=c1RB, 1,
RcrInstitute is flowed to make that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) become continuous media
The critical cylindrical hole radius needed, c1Value range be：1.63~1.99, c1Preferred value be 1.81,ρ is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure
Liquid mixture in that liquid body phase density,Physical absorption is weak between the surface of trunk hole (2)
That liquid in liquid mixture is R in radiuseqHole radial direction averag density, this averag density withHave
It closes,η is that physical absorption is weak between the surface of trunk hole (2) under environment temperature and pressure
Liquid mixture in that liquid bulk viscosity,Physical absorption is weak between the surface of trunk hole (2)
That liquid in liquid mixture is R in radiuseqHole radial direction equivalent viscosity, this equivalent viscosity withHave
It closes,It is R to describe that liquid in the liquid mixture that physical absorption is weak between the surface of trunk hole (2) in radiuseq
Hole radial direction present Discontinuous transmission effect parameter.
3. the novel tree-shaped nanoscale that a kind of branch's hole count for Liquid-liquid separation as described in claim 1 is 11 is justified
Post holes filter membrane, it is characterised in that：Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7), branched hole
(8), branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) are evenly distributed on solid material
(1) on a circumference on surface, the radius of the circumference is Rd, spacing of the contiguous branch hole on the circumference is Δ1, Δ1With
RB, 1Ratio value range be：ks=Δ1/RB, 1=0.05~0.5, RdWith RB, 1Ratio be：Rd/RB, 1=(22+11ks)/(2
π)。
4. the novel tree-shaped nanoscale that a kind of branch's hole count for Liquid-liquid separation as described in claim 1 is 11 is justified
Post holes filter membrane, it is characterised in that：Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7), branched hole
(8), the master of the axial line and they of branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13)
The parallelism tolerance of the axial line of dry hole (2) is not more than 0.1l1。
5. the novel tree-shaped nanoscale that a kind of branch's hole count for Liquid-liquid separation as claimed in claim 3 is 11 is justified
Post holes filter membrane, it is characterised in that：Branched hole (3), branched hole (4), branched hole (5), branched hole (6), branched hole (7), branched hole
(8), the surface of branched hole (9), branched hole (10), branched hole (11), branched hole (12) and branched hole (13) in solid material (1)
Distribution circle and trunk hole (2) concentricity tolerance be not more than 0.1Rd。
6. the novel tree-shaped that a kind of branch's hole count for Liquid-liquid separation as described in any one in claim 1-5 is 11
Nanoscale cylindrical hole filter membrane, it is characterised in that：Filter membrane is plane or curved surface filter membrane.
7. the novel tree-shaped that a kind of branch's hole count for Liquid-liquid separation as described in any one in claim 1-5 is 11
Nanoscale cylindrical hole filter membrane, it is characterised in that：The thickness of filter membrane is identical everywhere or differs.
8. the novel tree-shaped that a kind of branch's hole count for Liquid-liquid separation as described in any one in claim 1-5 is 11
Nanoscale cylindrical hole filter membrane, it is characterised in that：Filter membrane is fabricated by silica or graphene.
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| US5985146A (en) * | 1997-07-23 | 1999-11-16 | Trisep Corporation | Sanitary rigid shell spiral wound element |
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| CN105080361A (en) * | 2015-08-20 | 2015-11-25 | 张哲夫 | Polypropylene hollow fiber ultrafiltration membrane coated with polymer composite coating |
| CN107875860A (en) * | 2017-11-08 | 2018-04-06 | 袁虹娣 | Nanoscale bicylindrical hole filter membrane |
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2018
- 2018-04-27 CN CN201810431276.3A patent/CN108554178A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5985146A (en) * | 1997-07-23 | 1999-11-16 | Trisep Corporation | Sanitary rigid shell spiral wound element |
| CN201216922Y (en) * | 2008-06-12 | 2009-04-08 | 刘镇江 | Seven-aperture PVC ultra-filtration membrane |
| CN204261563U (en) * | 2014-10-20 | 2015-04-15 | 江西成必信生物科技有限公司 | The aseptic micro-pore-film filtration device of a kind of veterinary drug injection |
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