CN103285736B - Preparation method of inorganic membrane element having high membrane area/volume ratio, and preparation method of membrane assembly of inorganic membrane element - Google Patents
Preparation method of inorganic membrane element having high membrane area/volume ratio, and preparation method of membrane assembly of inorganic membrane element Download PDFInfo
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- CN103285736B CN103285736B CN201310246667.5A CN201310246667A CN103285736B CN 103285736 B CN103285736 B CN 103285736B CN 201310246667 A CN201310246667 A CN 201310246667A CN 103285736 B CN103285736 B CN 103285736B
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Abstract
The invention discloses an inorganic membrane element having a high membrane area/volume ratio. The inorganic membrane element comprises a cellular inorganic membrane, the cellular inorganic membrane is formed by a porous support body and a filtering channel, and the interior surface of the filtering channel is a separate film; and a hollow fiber inorganic membrane is arranged in the filtering channel of the cellular inorganic membrane, and the hollow fiber inorganic membrane is hollow and cylindrical in shape, and has an inner channel and an exterior surface as a separation film. The invention also discloses a preparation method of the inorganic membrane element, and a preparation method of a membrane assembly of the inorganic membrane element. In the invention, the membrane area/volume ratio of the inorganic membrane is substantially increased, a contradiction between the configuration and the filtering mode of the hollow fiber inorganic membrane is effectively solved, and the inorganic membrane element and the membrane assembly have a good adaptability to present apparatus, so it is helpful for the large scale popularization and application.
Description
Technical field
The present invention relates to technical field of membrane separation, particularly relate to a kind of configuration of inorganic membrane element and the preparation method of membrane module thereof.
Background technology
UF membrane is that a kind of operation is relatively simple, consume energy low separating technology, can reclaim in principle and recycle the component in mixture, is thus widely used in bioengineering, oil, chemical industry, metallurgy, medicine and other fields.UF membrane is realized by membrane module, and its core is filtration membrane elements.Compared with organic film, chemical stability is good, mechanical strength is large, anti-microbe ability is strong, high temperature resistant, pore-size distribution is narrow, separative efficiency advantages of higher as ceramic membrane has for inoranic membrane, but as organic film, cannot improve membrane area/volume ratio (the membrane filtration area in elementary membrane component size) by folding mode.For improving membrane area/volume ratio, currently available technology ceramic membrane is adopt the mode (as 7,19 and 37 passages) increasing duct number mostly, or uses ceramic honey comb film, hollow fiber ceramic membrane.
But, in prior art multi-pore channel/ceramic honey comb film configuration, problem is discharged for solving penetrating fluid, need the spread configuration considering infiltration lane, so just, make 1/3 of ceramic honey comb the film even passage of half need be used for the discharge of penetrating fluid, thus cause the actual effective filtration area decreasing ceramic honey comb film.For hollow fiber ceramic membrane, adopt pattern separation membrane layer being prepared in doughnut film outer surface, higher membrane area/volume ratio can be obtained and bear higher intermembranous pressure, but this pattern needs to adopt external-compression type membrane filtration pattern (to act on feed liquid by pressure, feed liquid flows at film outer surface, penetrating fluid flows out in film internal channel), therefore there is following technical problem: it is different that (1) and organic film have good morphotropism, the violent turbulence of feed liquid makes the inorganic hollow fibers ceramic membrane had compared with big L/D ratio and lower morphotropism easily rupture.Especially for meeting the needs of membrane module, usually inorganic hollow fibers ceramic membrane two ends are fixed, the disturbance caused by feed liquid and the destruction produced is stronger.(2) generally speaking, hollow-fibre membrane arrangement is relatively tightr, and the disturbance of feed liquid easily causes rubbing between film pipe, colliding, thus causes the destruction of separation membrane layer.Therefore, the contradiction between the configuration of prior art hollow fiber ceramic membrane and its filtered model is unusual distinct issues.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of inorganic membrane element with high membrane area/volume ratio is provided, while the membrane area/volume ratio effectively improving inoranic membrane, effectively solve the contradiction between the configuration of doughnut inoranic membrane and its filtered model.Another object of the present invention is to the preparation method that above-mentioned inorganic membrane element and membrane module are provided.
Object of the present invention is achieved by the following technical programs:
A kind of inorganic membrane element with high membrane area/volume ratio provided by the invention, comprises honeycomb inoranic membrane, and described honeycomb inoranic membrane is made up of porous supporting body and filtration duct, and the inner surface in described filtration duct is separation membrane layer; In addition, be provided with doughnut inoranic membrane in the filtration duct of described honeycomb inoranic membrane, described doughnut inoranic membrane is hollow columnar and has internal channel and the outer surface as separation membrane layer.
Inorganic membrane element of the present invention, separation membrane layer is distributed in the outer surface of doughnut inoranic membrane and the inner surface in its filtration duct of honeycomb inoranic membrane, passage between the two namely between doughnut inoranic membrane outer surface and honeycomb inorganic membrane filtration duct is feed liquid passage, and the internal channel of doughnut inoranic membrane and the porous supporting body of honeycomb inoranic membrane are permeate passageway.Like this, just substantially increase the membrane area/volume ratio of inoranic membrane, meanwhile, the filtration duct due to honeycomb inoranic membrane gives the supporting of doughnut inoranic membrane, the fracture of doughnut inoranic membrane can be avoided, be thus conducive to solving the contradiction between the configuration of doughnut inoranic membrane and its filtered model.
For reducing the impact of feed liquid turbulence on doughnut inoranic membrane further, its inwall filtering duct of honeycomb inoranic membrane described in inorganic membrane element of the present invention contacts with doughnut inoranic membrane.Following concrete measure can be taked: described honeycomb inoranic membrane is provided with at least one doughnut inoranic membrane in its single filtration duct, namely assembly that is only single or many doughnut inoranic membranes is filled in the filtration duct of honeycomb inoranic membrane as much as possible, make to keep less space between the two, increase honeycomb inorganic membrane filtration duct to the supporting of doughnut inoranic membrane.
In such scheme, for ease of end-blocking, the two ends of doughnut inoranic membrane of the present invention are stretched out outside honeycomb inoranic membrane; Described its one end of doughnut inoranic membrane is provided with end-blocking thing in internal channel, and its other end is provided with end-blocking thing between outside.
Another object of the present invention is achieved by the following technical programs:
A kind of preparation method with the inorganic membrane element of high membrane area/volume ratio provided by the invention, the honeycomb inoranic membrane adopting the filtration duct that is separation membrane layer by porous supporting body and inner surface to form and have the doughnut inoranic membrane that internal channel and outer surface are separation membrane layer, comprises the following steps:
(1) described doughnut inoranic membrane is filled in the filtration duct of honeycomb inoranic membrane, and the two ends of doughnut inoranic membrane are stretched out outside honeycomb inoranic membrane;
(2) be immersed in epoxy resin by the upper end of described doughnut inoranic membrane, be cured after taking-up, epoxy resin filling is sealed in the internal channel port of doughnut inoranic membrane upper end;
(3) be immersed in epoxy resin by the lower end of described doughnut inoranic membrane, be cured after taking-up, epoxy resin filling is sealed in the internal channel port of doughnut inoranic membrane lower end;
(4) be immersed in epoxy resin by mould by the lower end of the doughnut inoranic membrane after step (3) process, its submergence is highly greater than the height of institute's filling epoxy resin in its internal channel of step (3) doughnut inoranic membrane lower end; Then submerged state is kept to be cured; Remove mould after having solidified, epoxy resin filling, between the outside of doughnut inoranic membrane lower end, makes the lower end of doughnut inoranic membrane be global shape and form doughnut inoranic membrane bundle;
(5) the height and position place that described doughnut inoranic membrane bundle is being greater than internal channel institute filling epoxy resin is carried out transverse cuts, the internal channel port at doughnut inoranic membrane bundle place is exposed, thus obtains the inorganic membrane element with high membrane area/volume ratio.
Another object of the present invention is achieved by the following technical programs:
A kind of preparation method with the inorganic membrane assembly of high membrane area/volume ratio provided by the invention, adopt above-mentioned inorganic membrane element, with one end of described doughnut inoranic membrane internal channel port sealing for upper end, the doughnut inoranic membrane Shu Yiduan that doughnut inoranic membrane internal channel port exposes is lower end; Comprise the following steps:
A. at the sheathed shell in outside of described honeycomb inoranic membrane; Described shell is provided with permeate outlet;
B. in the upper surface of described honeycomb inoranic membrane with arrange trapezoidal O RunddichtringO between lower surface place and shell;
C. gondola water faucet type stainless steel gripper shoe is inserted in the lower end of described doughnut inoranic membrane;
D. adopt the supportive stainless steel coil with up big and down small two layers of installing ring, after its upper strata installing ring entangles the hypomere of doughnut inoranic membrane, fixed by the lower end of bolt and shell;
E. trapezoidal O RunddichtringO is set between the lower surface place and lower floor's installing ring of supportive stainless steel coil of described doughnut inoranic membrane; Interior end housing is fixed by bolt and lower floor's installing ring; Described interior end housing is provided with permeate outlet;
F. lower end shield is secured by bolts on the lower end of shell and the upper strata installing ring of supportive stainless steel coil; Described lower end shield is provided with feed liquid port;
G. upper end shield is secured by bolts in the upper end of shell; Described upper end shield is provided with material liquid outlet.
The present invention has following beneficial effect:
(1) effectively improve the membrane area/volume ratio of membrane component
In the configuration of inorganic membrane element of the present invention, in identical volume, for honeycomb inoranic membrane, its all filtration inner surfaces of pores is effective membrane area.Although the discharge resistance of penetrating fluid increases to some extent, membrane area is 1.3 ~ 1.5 times of original honeycomb inoranic membrane configuration, and total permeation flux increases on the contrary.In addition, adding of doughnut inoranic membrane, further increase the effective area of membrane filtration, make the membrane area/volume ratio of inorganic membrane element configuration of the present invention be 2 ~ 5 times of conventional film configuration.
(2) contradiction between the film configuration of doughnut inoranic membrane and filtered model is efficiently solved
In the configuration of inorganic membrane element of the present invention, doughnut inoranic membrane contacts as far as possible with honeycomb inoranic membrane, decreases because of the doughnut inoranic membrane resonance problem caused by feed liquid disturbance, avoids the fracture of doughnut inoranic membrane.Meanwhile, under the constraint in honeycomb inorganic membrane filtration duct, feed liquid along the flowing of doughnut inoranic membrane axial direction, thus decreases the impact of feed liquid turbulence on doughnut inoranic membrane.
(3) there is good existing equipment adaptability
The present invention, for honeycomb inoranic membrane, adopts feed liquid circulation pattern, therefore, it is possible to be applicable to existing most of membrane filter system; For doughnut inoranic membrane, the filtration duct of honeycomb inoranic membrane is equivalent to outer die pressing type, without the need to additionally adding supercharging equipment to feed liquid, thus can effectively reduce film device cost.
Accompanying drawing explanation
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail:
Fig. 1 is the structural representation of embodiment of the present invention inorganic membrane element;
Fig. 2 is the A-A sectional view of Fig. 1;
Fig. 3 is the enlarged diagram at honeycomb inorganic membrane filtration duct place in Fig. 2;
Fig. 4 is the structural representation of embodiment of the present invention inorganic membrane assembly;
Fig. 5 is the three-dimensional view of supportive stainless steel coil in Fig. 4.
In figure: honeycomb inoranic membrane 1, porous supporting body 1a, filters duct 1b, doughnut inoranic membrane 2, internal channel 2a, outer surface 2b, doughnut inoranic membrane bundle 2c, end-blocking thing 3,4, shell 5, permeate outlet 6,6 ＇, trapezoidal O RunddichtringO 7,11, gondola water faucet type stainless steel gripper shoe 8, supportive stainless steel coil 9, upper strata installing ring 9a, lower floor installing ring 9b, bolt 10,12,17, interior end housing 13, feed liquid port 14, lower end shield 15, upper end shield 16; Material liquid outlet 18.
Detailed description of the invention
Fig. 1 ~ Figure 5 shows that a kind of embodiment with the high inorganic membrane element of membrane area/volume ratio and the preparation method of membrane module thereof of the present invention.
1, the present embodiment inorganic membrane element
As shown in Figure 1, Figure 2 and Figure 3, the present embodiment inorganic membrane element by honeycomb inoranic membrane 1(as ceramic honey comb film) and doughnut inoranic membrane 2(as hollow fiber ceramic membrane) form.Wherein, honeycomb inoranic membrane 1 is made up of porous supporting body 1a and filtration duct 1b, and the inner surface filtering duct 1b is separation membrane layer; Doughnut inoranic membrane 2 has internal channel 2a and the outer surface 2b as separation membrane layer in hollow columnar.As shown in Figures 2 and 3, doughnut inoranic membrane 2 is filled in (can be only single or the filling of the assembly of many doughnut inoranic membranes 2) in the filtration duct 1b of honeycomb inoranic membrane 1, and its inwall filtering duct 1b of honeycomb inoranic membrane 1 contacts with doughnut inoranic membrane 2.
As shown in Figure 1, the two ends of doughnut inoranic membrane 2 are stretched out outside honeycomb inoranic membrane 1.Its one end of doughnut inoranic membrane 2 is provided with end-blocking thing 3 in internal channel 2a, and its other end is provided with end-blocking thing 4 between outside.
2, the preparation method of the present embodiment inorganic membrane element is as follows:
(1) doughnut inoranic membrane 2 is filled in the filtration duct 1b of honeycomb inoranic membrane 1, and the two ends of doughnut inoranic membrane 2 are stretched out outside honeycomb inoranic membrane 1;
(2) be immersed in the less epoxy resin of viscosity the upper end of doughnut inoranic membrane 2, immersion length is 2 ~ 8mm, is cured after taking-up, and epoxy resin filling is sealed in the internal channel 2a port of doughnut inoranic membrane 2 upper end;
(3) be immersed in the less epoxy resin of viscosity the lower end of doughnut inoranic membrane 2, immersion length is no more than 2mm, is cured after taking-up, and epoxy resin filling is sealed in the internal channel 2a port of doughnut inoranic membrane 2 lower end;
(4) be immersed in the larger epoxy resin of viscosity by mould (as square or circular, to be adapted to shell 5 shape of membrane module) by the lower end of the doughnut inoranic membrane 2 after step (3) process, its submergence is highly 25 ~ 80mm; Then submerged state is kept to be cured; Remove mould after having solidified, epoxy resin filling, between the outside of doughnut inoranic membrane 2 lower end, makes the lower end of doughnut inoranic membrane 2 be global shape and form doughnut inoranic membrane bundle 2c;
(5) by doughnut inoranic membrane bundle 2c apart from 2 ~ 5mm place, epoxy resin outer face transverse cuts, the internal channel 2a port at doughnut inoranic membrane bundle 2c place is exposed, thus acquisition has the inorganic membrane element of high membrane area/volume ratio.
3, the preparation method of the present embodiment inorganic membrane assembly
The present embodiment inorganic membrane assembly as shown in Figure 4, adopts above-mentioned inorganic membrane element, and with one end of doughnut inoranic membrane 2 internal channel 2a port sealing for upper end, doughnut inoranic membrane bundle 2c one end that doughnut inoranic membrane 2 internal channel 2a port exposes is lower end; Its step is as follows:
A. at the outside of honeycomb inoranic membrane 1 sheathed straight tube shape stainless steel casing 5; Shell 5 is provided with permeate outlet 6;
B. in the upper surface of honeycomb inoranic membrane 1 with arrange trapezoidal O RunddichtringO 7 between lower surface place and shell 5;
C. the lower end of doughnut inoranic membrane 2 is inserted in gondola water faucet type stainless steel gripper shoe 8;
D. the supportive stainless steel coil 9(with up big and down small two layers of installing ring is adopted to see Fig. 5), after its upper strata installing ring 9a entangles the hypomere of doughnut inoranic membrane 2, fixed by the lower end of bolt 10 with shell 5;
E. trapezoidal O RunddichtringO 11 is set between the lower surface place of doughnut inoranic membrane 2 and the lower floor installing ring 9b of supportive stainless steel coil 9; Interior end housing 13 is fixed with lower floor installing ring 9b by bolt 12; Interior end housing 13 is provided with permeate outlet 6 ＇;
F. lower end shield 15 is fixed on the lower end of shell 5 and the upper strata installing ring 9a of supportive stainless steel coil 9 by bolt 10; Lower end shield 15 is provided with feed liquid port 14;
G. upper end shield 16 is fixed on the upper end of shell 5 by bolt 17; Upper end shield 16 is provided with material liquid outlet 18.
Its operation principle following (as shown in Figure 4, solid arrow is that feed liquid flows to, dotted arrow be permeate flow to):
Feed liquid enters from feed liquid port 14, from between lower end shield 15 and interior end housing 13, through supportive stainless steel coil 9, entering honeycomb inoranic membrane 1 filters in the 1b of duct and space between doughnut inoranic membrane 2 outer surface 2b, filters the inner surface of duct 1b and the outer surface 2b of doughnut inoranic membrane 2 for separation membrane layer filter with honeycomb inoranic membrane 1.The penetrating fluid filtered to isolate enters the internal channel 2a of doughnut the inoranic membrane 2 and porous supporting body 1a of honeycomb inoranic membrane 1.Wherein, the penetrating fluid entering its internal channel of doughnut inoranic membrane 2 2a flows into inner shell 13, then discharges from permeate outlet 6 ＇; The penetrating fluid entering its porous supporting body of honeycomb inoranic membrane 1 1a flows into shell 5, then discharges from permeate outlet 6.Filter complete feed liquid and enter end shield 16 li, then discharge from material liquid outlet 18.
Claims (6)
1. one kind has the inorganic membrane element of high membrane area/volume ratio, comprise honeycomb inoranic membrane (1), described honeycomb inoranic membrane (1) is made up of porous supporting body (1a) and filtration duct (1b), and the inner surface of described filtration duct (1b) is separation membrane layer; It is characterized in that: be provided with doughnut inoranic membrane (2) in the filtration duct (1b) of described honeycomb inoranic membrane (1), described doughnut inoranic membrane (2) has internal channel (2a) and the outer surface (2b) as separation membrane layer in hollow columnar.
2. the inorganic membrane element with high membrane area/volume ratio according to claim 1, is characterized in that: its inwall filtering duct (1b) of described honeycomb inoranic membrane (1) contacts with doughnut inoranic membrane (2).
3. the inorganic membrane element with high membrane area/volume ratio according to claim 2, is characterized in that: its single filtration duct (1b) of described honeycomb inoranic membrane (1) is inner is provided with at least one doughnut inoranic membrane (2).
4. the inorganic membrane element with high membrane area/volume ratio according to claim 1, is characterized in that: the two ends of described doughnut inoranic membrane (2) are stretched out outside honeycomb inoranic membrane (1); Described its one end of doughnut inoranic membrane (2) is provided with end-blocking thing (3) internal channel (2a) is inner, and its other end is provided with end-blocking thing (4) between the outside of doughnut inoranic membrane (2).
5. there is described in one of claim 1-4 the preparation method of the inorganic membrane element of high membrane area/volume ratio, it is characterized in that: the honeycomb inoranic membrane (1) that the filtration duct (1b) that to adopt by porous supporting body (1a) and inner surface be separation membrane layer is formed and there is the doughnut inoranic membrane (2) that internal channel (2a) and outer surface (2b) are separation membrane layer, comprise the following steps:
(1) described doughnut inoranic membrane is filled in the filtration duct of honeycomb inoranic membrane, and the two ends of doughnut inoranic membrane are stretched out outside honeycomb inoranic membrane;
(2) be immersed in epoxy resin by the upper end of described doughnut inoranic membrane (2), be cured after taking-up, epoxy resin filling is sealed in internal channel (2a) port of doughnut inoranic membrane (2) upper end;
(3) be immersed in epoxy resin by the lower end of described doughnut inoranic membrane (2), be cured after taking-up, epoxy resin filling is sealed in internal channel (2a) port of doughnut inoranic membrane (2) lower end;
(4) be immersed in epoxy resin by mould by the lower end of the doughnut inoranic membrane (2) after step (3) process, its submergence is highly greater than the height of step (3) doughnut inoranic membrane (2) lower end its internal channel (2a) inner institute filling epoxy resin; Then submerged state is kept to be cured; Remove mould after having solidified, epoxy resin filling, between the outside of doughnut inoranic membrane (2) lower end, makes the lower end of doughnut inoranic membrane (2) be global shape and form doughnut inoranic membrane bundle (2c);
(5) the height and position place that described doughnut inoranic membrane bundle (2c) is being greater than internal channel (2a) institute filling epoxy resin is carried out transverse cuts, internal channel (2a) port at doughnut inoranic membrane bundle (2c) place is exposed, thus obtains the inorganic membrane element with high membrane area/volume ratio.
6. one kind has the preparation method of the inorganic membrane assembly of high membrane area/volume ratio, it is characterized in that: adopt inorganic membrane element prepared by claim 5, with one end of described doughnut inoranic membrane (2) internal channel (2a) port sealing for upper end, doughnut inoranic membrane bundle (2c) one end that doughnut inoranic membrane (2) internal channel (2a) port exposes is lower end; Comprise the following steps:
A. in the sheathed shell in the outside (5) of described honeycomb inoranic membrane (1); Described shell (5) is provided with permeate outlet (6);
B. in the upper surface of described honeycomb inoranic membrane (1) with arrange trapezoidal O RunddichtringO (7) between lower surface place and shell (5);
C. gondola water faucet type stainless steel gripper shoe (8) is inserted in the lower end of described doughnut inoranic membrane (2);
D. the supportive stainless steel coil (9) with up big and down small two layers of installing ring is adopted, after its upper strata installing ring (9a) entangles the hypomere of doughnut inoranic membrane (2), fixed by the lower end of bolt (10) with shell (5);
E. trapezoidal O RunddichtringO (11) is set between the lower surface place and lower floor's installing ring (9b) of supportive stainless steel coil (9) of described doughnut inoranic membrane (2); Interior end housing (13) is fixed by bolt (12) and lower floor's installing ring (9b); Described interior end housing (13) is provided with permeate outlet (6 ＇);
F. lower end shield (15) is fixed on the lower end of shell (5) and the upper strata installing ring (9a) of supportive stainless steel coil (9) by bolt (10); Described lower end shield (15) is provided with feed liquid port (14)
G. upper end shield (16) is fixed on the upper end of shell (5) by bolt (17); Described upper end shield (16) is provided with material liquid outlet (18).
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Address after: 333001 Jingdezhen ceramic University, Tao Yang South Road, Zhuzhan, Jingdezhen, Jiangxi Patentee after: JINGDEZHEN CERAMIC INSTITUTE Address before: 333001 Tao Yang South Road, Jingdezhen, Jiangxi, Jingdezhen Patentee before: Jingdezhen Ceramic Institute |
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Effective date of registration: 20190201 Address after: 402460 Guangfu Industrial Park Avenue, Rongchang District, Chongqing Patentee after: CHONGQING WUDUN NANO TECHNOLOGY Co.,Ltd. Address before: 333001 Taoyang Road, Zhushan District, Jingdezhen City, Jiangxi Province Patentee before: Science and Technology Development Center of Jingdezhen Ceramic University Effective date of registration: 20190201 Address after: 333001 Taoyang Road, Zhushan District, Jingdezhen City, Jiangxi Province Patentee after: Science and Technology Development Center of Jingdezhen Ceramic University Address before: 333001 Jingdezhen ceramic University, Tao Yang South Road, Zhuzhan, Jingdezhen, Jiangxi Patentee before: JINGDEZHEN CERAMIC INSTITUTE |