CN104492266B - Multi-channel tubular ceramic membrane element - Google Patents

Multi-channel tubular ceramic membrane element Download PDF

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Publication number
CN104492266B
CN104492266B CN201410820927.XA CN201410820927A CN104492266B CN 104492266 B CN104492266 B CN 104492266B CN 201410820927 A CN201410820927 A CN 201410820927A CN 104492266 B CN104492266 B CN 104492266B
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powder
ceramic membrane
tubular ceramic
layer
powder body
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CN104492266A (en
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郭涛
黄智锋
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Anhui innovation Mstar Technology Ltd
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Anhui Innovation Mstar Technology Ltd
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Abstract

The invention discloses a multi-channel tubular ceramic membrane element which comprises a porous support layer and a top-layer membrane layer coating the surface of the porous support body, wherein the top-layer membrane layer is prepared by adopting a method comprising the following steps: (1) preparing a powder body I with a diameter of about 200-300nm; (2) preparing a powder body II with a particle size of 1-2 micrometers; and (3) mixing the powder body I and the powder body II, adding a dispersing agent in the mixed powder body, ball-grinding and mixing to obtain a uniform and stable top-layer membrane suspension slurry, and sintering at a temperature of 1200-1300 DEG C. According to the multi-channel tubular ceramic membrane element, the property of a coating slurry can not be influenced, the continuity of the surface of the membrane can not be damaged and the permeability is not reduced; the multi-channel tubular ceramic membrane element has a function of only forming mutually-discontinuous bulges, and a turbulent flow caused by the bulges ensures that the permeation flow around the turbulent flow is remarkably increased and kept not being attenuated.

Description

Multichannel tubular ceramic membrane elements
Technical field
The present invention relates to a kind of multichannel tubular ceramic membrane elements.
Background technology
Ceramic membrane is the separating medium with screening efficiency being manufactured using ceramic powder sintering.Height with more early industrialization Polymers seperation film is compared, and the speciality of inorganic separating film is that pore-size distribution is narrow, separating property is good, high temperature resistant, chemically stable, is not subject to Organic solvent, bacterium corrode, can soda acid cleaning, high mechanical properties, indeformable, can high pressure recoil, vapours regeneration, backwash etc.. Ceramic membrane separation element is usually to prepare one or more layers asymmetric apertures gauge structure, industry-wide on macropore supporter Change is the tubular ceramic membrane elements with rule arrangement channel design with the marketization, and this multi-passage design is on the one hand permissible Ensure that membrane component has sufficiently large mechanical strength, another aspect guarantor unit volume element has larger total filter area, Such that it is able to improving filtering efficiency and reducing manufacturing cost, reduce occupation area of equipment.
However, with the developing in application of membrane separation technology field, ceramic membrane filter technology show some unsatisfactory it Place, needs to be improved, and the pump operated amount of liquid of wherein mainly ceramic membrane separation process is big, and equipment investment and operation energy consumption are relatively High.The 19 passage ceramic separation film elements with the currently a diameter of 4mm of membrane channels of extensive commercialization and application(Outside diameter is 30mm, effective length about 100cm)As a example, the membrane module filter area of 19 film cores is about 4.4 m2.Typical at certain In sewage disposal process, when crossflow velocity is 5m/sec, stabilized flux is about 100 l/m2H, it is often little for always oozing out flow quantity When 440 L, and liquid circulation flow be about F=3.142 x (0.2cm)2x 19 x 19 x 500 cm/Sec x 3600 Sec = 81.7 m3.It can be seen that circular flow is 185.6 times of the seepage discharge flowing through film, which consumes mass energy. Several assemblies(As 3-4)Series connection, can reduce equipment and take up an area space, in principle, internal circulating load seems to reduce several times, but still For 45-60 times of efflux, moreover not only increase the resistance between assembly, improve energy consumption, because transmembrane pressure is in flowing Rapid decrement on direction, thus in fact not reaching the effect of anticipation, in actual engineering design, what multiple membrane modules were connected sets Meter is less and less.For reducing energy consumption, it is necessary for reducing crossflow velocity, and it is thick so cannot to reduce concentration gradient boundary-layer Degree, thus high fluid flux cannot be kept, so using ceramic membrane separation process waste water expense too high and be difficult on a large scale should With.
Content of the invention
It is an object of the invention to provide one kind had not both interfered with ceramic membrane coating coating slurry(Top layer film layer)Habit, also not The successional of film surface can be destroyed can be in the case of low crossflow velocity(Low energy consumption)Keep the multichannel tubulose of high permeating flux Ceramic membrane element.
The multichannel tubular ceramic membrane elements of the present invention, including porous supporting body and be coated in described porous supporting body surface Top layer film layer, described top layer film layer prepared using following methods:
(1)Take the basic zirconium chloride of molar concentration 0.1M and each 10ml of yttrium nitrate solution of molar concentration 0.1M, instilled In excess of ammonia water, form co-precipitation, after washing through washing and alcohol, calcination at 750 DEG C, obtain diameter and be about 200-300nm's Powder one;
(2)The alumina powder of quality and the zirconia powder such as take, add the deionized water with quality such as alumina powders, in shaft type Ball milling 12 hours on ball mill, obtain the powder two of 1-2 μm of particle diameter;
(3)Take above-mentioned steps(1)Gained powder one and step(2)Gained powder two mixes, and is added thereto to dispersant Acrylic acid-acrylic ester-phosphoric acid-sulfonic acid copolymer, puts into ball grinder, carries out ball milling with the porcelain ball of diameter 10mm and mix on grinding machine Close, obtain uniform and stable top layer film suspended nitride, sinter at 1200-1300 DEG C.
Preferably, step(3)The quality of described powder two is the 1%-5% of powder one mass.
Preferably, step(3)Described dispersant dosage is the 0.5%-1.5% of powder one and powder two gross mass.
During the extrusion molding of tubular ceramic film support, formation is made to have helical configuration by additional processing Film surface, may form turbulent flow with less fluid crossflow velocity.However, this manufacturing process is sufficiently complex, in fact Cannot be to this compromise face structure additional on the inner surface of thin channel.The present invention improves the technique manufacturing top layer film, is formed A kind of special surface.Most of methods preparing ceramic separation film layer all adopt so-called " suspension ceramic particle coating at present Method ", makes a kind of powdery pulp with the ceramic powder of suitable particle size, is coated in the multi-channel surface of porous supporting body, Form ceramic membrane after calcination is dried.Based on above-mentioned, the present invention is to add in the suspended particles slurry for coating top layer film The ceramic particle of the greater particle size of certain proportion number, after film layer sintering, this larger haydite can form random distribution on surface Raised structures.Due to the presence of this raised structures, under relatively low crossflow velocity, just can form turbulence-like near surface State, so as to significantly improving and keeping circulation.Above-mentioned a certain proportion of big particle, refers to its particle diameter than film layer pottery grain Big 5-10 times of footpath, its amount accounts for 1-5%.In other words, both do not interfere with the habit of coating coating slurry, will not destroy film surface yet Continuity and its permeability of reduction, its effect is to form mutually discontinuous projection, and the turbulent flow that the presence of which causes makes it The permeation flux of surrounding significantly increases and keeps unattenuated.
Specific embodiment
Following embodiments are to further illustrate using as the explaination to the technology of the present invention content for present invention, but The flesh and blood of the present invention is not limited in described in following embodiments, and those of ordinary skill in the art can and should know to appoint What simple change based on true spirit or replacement all should belong to protection domain of the presently claimed invention.
Embodiment 1
The multichannel tubular ceramic membrane elements of this example, including porous supporting body and be coated in described porous supporting body surface Top layer film layer, described top layer film layer prepared using following methods:
(1)Take the basic zirconium chloride of molar concentration 0.1M and each 10ml of yttrium nitrate solution of molar concentration 0.1M, instilled In excess of ammonia water, form co-precipitation, after washing through washing and alcohol, calcination at 750 DEG C, obtain diameter and be about 200-300nm's Powder one;
(2)The alumina powder of quality and the zirconia powder such as take, add the deionized water with quality such as alumina powders, in shaft type Ball milling 12 hours on ball mill, obtain the powder two of 1-2 μm of particle diameter;
(3)Take above-mentioned steps(1)Gained powder one 100g and step(2)Gained powder two 2g mixes, and is added thereto to Dispersant acrylic acid-acrylic ester-phosphoric acid-sulfonic acid copolymer 1g, puts into ball grinder, the porcelain ball with diameter 10mm is enterprising in grinding machine Row ball milling mixing, obtains uniform and stable top layer film suspended nitride, sinters at 1200-1300 DEG C.Gained ceramic membrane Element pure water permeation flux 1.23m3/m2.h.Br.
Embodiment 2
The multichannel tubular ceramic membrane elements of this example, including porous supporting body and be coated in described porous supporting body surface Top layer film layer, described top layer film layer prepared using following methods:
(1)Take the basic zirconium chloride of molar concentration 0.1M and each 10ml of yttrium nitrate solution of molar concentration 0.1M, instilled In excess of ammonia water, form co-precipitation, after washing through washing and alcohol, calcination at 750 DEG C, obtain diameter and be about 200-300nm's Powder one;
(2)The alumina powder of quality and the zirconia powder such as take, add the deionized water with quality such as alumina powders, in shaft type Ball milling 12 hours on ball mill, obtain the powder two of 1-2 μm of particle diameter;
(3)Take above-mentioned steps(1)Gained powder one 100g and step(2)Gained powder two 4g mixes, and is added thereto to Dispersant acrylic acid-acrylic ester-phosphoric acid-sulfonic acid copolymer 1.5g, puts into ball grinder, with the porcelain ball of diameter 10mm on grinding machine Carry out ball milling mixing, obtain uniform and stable top layer film suspended nitride, sinter at 1200-1300 DEG C.Gained pottery Membrane component pure water permeation flux 1.10m3/m2.h.Br.

Claims (2)

1. multichannel tubular ceramic membrane elements, including porous supporting body and the top layer film being coated in described porous supporting body surface Layer is it is characterised in that described top layer film layer is prepared using following methods:
(1)Take the basic zirconium chloride of molar concentration 0.1M and each 10ml of yttrium nitrate solution of molar concentration 0.1M, instilled excessive Ammoniacal liquor in, form co-precipitation, through washing with after alcohol washes, calcination at 750 DEG C, obtain the powder one of a diameter of 200-300nm;
(2)The alumina powder of quality and the zirconia powder such as take, add the deionized water with quality such as alumina powders, in shaft type ball milling Ball milling 12 hours on machine, obtain the powder two of 1-2 μm of particle diameter;
(3)Take above-mentioned steps(1)Gained powder one and step(2)Gained powder two mixes, and is added thereto to dispersant propylene Acid-acrylate-phosphoric acid-sulfonic acid copolymer, puts into ball grinder, carries out ball milling mixing with the porcelain ball of diameter 10mm on grinding machine, Obtain uniform and stable top layer film suspended nitride, sinter at 1200-1300 DEG C;Step(3)The matter of described powder two Measure the 1%-5% for powder one mass.
2. multichannel tubular ceramic membrane elements as claimed in claim 1 are it is characterised in that step(3)Described dispersant dosage is Powder one and the 0.5%-1.5% of powder two gross mass.
CN201410820927.XA 2014-12-26 2014-12-26 Multi-channel tubular ceramic membrane element Active CN104492266B (en)

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CN110423113A (en) * 2019-07-15 2019-11-08 大连理工大学 A kind of preparation method and application preparing ceramic membrane diffusion layer using yttrium stable zirconium oxide material

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DE10331049B4 (en) * 2003-07-09 2010-04-08 Saint-Gobain Industriekeramik Rödental GmbH A process for producing a porous ceramic body, then produced porous ceramic body and its use
FR2896797B1 (en) * 2006-02-01 2008-08-08 Saint Gobain Ct Recherches CERAMIC FOAM IN RECRYSTALLIZED SILICON CARBIDE IMPREGNATED.
CN101723683B (en) * 2008-10-16 2012-06-20 北京有色金属研究总院 Preparation method of yttrium oxide-stabilized zirconium oxide powder with hollow spherical nanostructure
DK177790B1 (en) * 2013-08-08 2014-07-07 Liqtech Internat A S A METHOD OF PRODUCING A CERAMIC FILTER MEMBRANE, A METHOD OF IMPROVING A CERAMIC FILTER MEMBRANE AND THE CERAMIC FILTER MEMBRANE OBTAINED BY THE METHOD
CN103638826B (en) * 2013-12-26 2016-03-30 中国科学技术大学 A kind of asymmetrical ceramic separation membrane and preparation method thereof

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