CN1686598A - Bicontrol film layer inorganic film pipe and its preparation method - Google Patents
Bicontrol film layer inorganic film pipe and its preparation method Download PDFInfo
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- CN1686598A CN1686598A CN 200510033632 CN200510033632A CN1686598A CN 1686598 A CN1686598 A CN 1686598A CN 200510033632 CN200510033632 CN 200510033632 CN 200510033632 A CN200510033632 A CN 200510033632A CN 1686598 A CN1686598 A CN 1686598A
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Abstract
An inorganic membrane pipewith dual-layer control membrane is prepared through preparing slurry A from small basic material particles, suspending agent, disperser and carrier, preparing slurry B from granular basic material, suspending agent, disperser and carrier, filing the slurry A in the pipe mould, rotating for centrifugal shaping, filling the slurry B in the pipe mould, rotating for centrifugal shaping, baking, demoulding and sintering.
Description
Technical field
The present invention relates to that inoranic membrane prepares category in the inorganic functional material field, specifically is a kind of Bicontrol film layer inorganic film pipe and preparation method thereof.
Background technology
Inoranic membrane is divided into ceramic membrane and metal film, and ceramic membrane has high temperature resistant, acid and alkali-resistance is not corroded by bacterium, intensity height, characteristics such as it is easy to regenerate.Metal film has the mechanical strength higher than ceramic membrane, good heat-conductive characteristic, particularly metal film has good toughness, is sealed to member easily.So inoranic membrane has been widely used in fields such as machinery, electronics, chemistry, atomic energy, medical and health, biology, be used for separation, clarification, degerming of fluid etc.
The membrane separating effect of the separation of inoranic membrane, clarification, degerming etc. depends primarily on the pore size and the distribution of film, and film strength is except outside the Pass having with base materials employed and sintering temperature, depend primarily on the thickness and the porosity of film, the size of membrane flux (unit interval unit are fluid is by the amount of film) has determined the practicality of film.The inoranic membrane of function admirable should be to have good membrane separating effect, high film-strength and big membrane flux.The aperture is little, the narrow then membrane separating effect of pore size distribution is good, but can cause fluid to pass through the resistance increase of film, and membrane flux is reduced.The aperture is big, pore size distribution is wide, and membrane resistance is little, and membrane flux can increase, but membrane separating effect can weaken.The porosity of film is big, and membrane resistance is also little, and membrane flux can increase, but film strength can be poor.Thickness increases, and film-strength will increase, but membrane resistance can increase.Can find out obviously that good membrane separating effect, high film-strength and big membrane flux influence each other and restrict, and can be described as conflicting.How could be under the situation that guarantees good membrane separating effect, make film have big flux, simultaneously can guarantee that again film strength is unaffected, that is to say membrane aperture and pore-size distribution, membrane porosity, film thickness are organically united, reaching optimized coupling, is the difficult point and the key of inoranic membrane preparation.
In order to solve above-mentioned film preparation difficult point, had many research workers to do many work in this respect, the structure of film also by initial symmetrical structure to development such as dissymmetrical structure, gradient-structures.Because the inoranic membrane of symmetrical structure is in the membrane aperture unanimity of whole film thickness direction, if assurance membrane separating effect, just need select for use the base-material of fine particle to prepare the film of little membrane aperture, this must cause enlarging markedly of membrane resistance, membrane flux is reduced, though can reduce membrane resistance by the attenuate thickness, but will sacrifice film strength, influence the actual serviceability of film, so the inoranic membrane of symmetrical structure can't satisfy good membrane separating effect, the whole requirement of high film-strength and big membrane flux, the porous inorganic material of present this symmetrical structure can only be the inorganic porous filter materials in some large apertures, is used for coarse filtration or pre-filtering.Inoranic membrane adopts the multilayer dissymmetrical structure more at present, and this inoranic membrane is made up of supporter, key-course and intermediate layer.The supporter aperture is bigger, has certain mechanical strength, and it is the matrix of whole film pipe, and the mechanical strength of film pipe is guaranteed by it.Have on carrier that the aperture is very little, the control rete of very thin thickness, centrifugation is mainly reached by it.Between carrier and control rete, also include one or more layers intermediate layer, the multilayer dissymmetrical structure of Here it is inoranic membrane.The asymmetric inoranic membrane of multilayer key-course or transition zone in the preparation all is on the body attached to preceding one deck macropore, because the powder granule diameter suddenlys change, following one deck powder granule will certainly stop up a part of last layer macropore, like this, will reduce the ability that sees through of inoranic membrane greatly.On the other hand, because multilayer dissymmetrical structure inoranic membrane is not one-shot forming, need repeatedly moulding and sintering process between layer and layer.At first need to prepare supporter, could descend the coating and the sintering of one deck after often needing to burn till again, the supporter behind the sintering generally can not shrink again, because the general contraction of ceramic material when sintering is all bigger, and the shrinkage factor with a last supporter of following one deck of new coating is different, so, between layer and the layer is exactly a place that is easy to generate defective most at the interface, is easy to produce peel off and shrink the crackle that causes and other defective.Influence the weight of inoranic membrane, especially long-term stability in use.Chinese invention patent " gradient ceramic-film tube and preparation method thereof " (ZL00117221.2) is shaped the powder granule in the slurry is radially descending gradually with centrifugation method, maximum particle has formed the outer surface of film pipe in the slurry, minimum particle then concentrates on the endosexine of ceramic-film tube, form the equally distributed control rete in aperture, because the aperture is a continually varying, under the same membrane separating effect, the flux of this inoranic membrane is bigger than the inoranic membrane of multilayer dissymmetrical structure.When fluid advanced in by pipe, the inner tubal wall of minimum-value aperture can effectively prevent from the especially obstruction of fenestra of pollution of film from can effectively prolong the service life of film pipe, and be easy to clean as the control rete.But this forming method can only form the control rete at the inner surface of film pipe, only when advancing in by pipe, fluid just manifests its advantage, if fluid advances outside managing, the large aperture of outer tube wall, make the pollutant in the fluid enter the duct easily, cause film to stop up, easy cleaning not, at this moment the control rete of inner tubal wall is preventing that the effect aspect the film pollution such as fenestra obstruction is just not obvious.
Summary of the invention
Purpose of the present invention is exactly the deficiency at asymmetric inoranic membrane of above multilayer and gradient ceramic-film, provides a kind of and can all have the Bicontrol film layer inorganic film pipe preparation method who controls rete at the surfaces externally and internally of porous membrane tube.
Another object of the present invention provides a kind of surfaces externally and internally at the film pipe and all has the control rete, no matter be fluid by in the pipe or pipe is outer to be advanced, can both prevent effectively that pollutant from entering the film pipe in the fenestra.
Bicontrol film layer inorganic film pipe preparation method of the present invention comprises the steps:
After the first step disposes slurry 1 and slurry 2 according to the following number of weight ratio, respectively through stirring 2～12 hours;
5～100 parts of base-materials
3～150 parts in carrier
0～0.3 part of suspending agent
The consumption of 0～0.2 part of suspending agent of dispersant and dispersant can not be zero simultaneously;
Described slurry 1 is that base-material, suspending agent, dispersant and the carrier of 0.2～5um formed by particle diameter;
Described slurry 2 is made up of base-material, suspending agent, dispersant and the carrier of 0.2um～40um particle diameter; Described base-material comprises non-metallic powder material oxidation aluminium powder, silicon dioxide powder, zirconia powder or diatomite in powder, or metal powder material nickel powder, titanium valve; Described carrier comprises water or ethanol;
The slurry 1 that second step obtained the first step is injected in the cast that rotating speed is 1000rpm～10000rpm, rotates 1～10 minute, and centrifugal forming forms outer control rete;
The 3rd step was injected into slurry 2 in the described cast of second step, and rotating speed is in the cast of 2000rpm～10000rpm, rotates 5～20 minutes, made the metal film pipe green compact of two control retes;
The 4th step green compact drying rear demoulding again at 750～1650 ℃ sintering temperature, is incubated cooling after 1～2 hour.
Suspending agent of the present invention can use general suspending agent, but optimal selection of the present invention is polyacrylamide, polyvinyl alcohol, sodium carboxymethylcellulose or gum arabic.
Of the present inventionly can use general dispersant, but optimal selection of the present invention is calgon or sodium pyrophosphate.
Principle of the present invention is as follows: slurry 1 and slurry 2 add at twice, at first add by granule inorganic powder (base-material), suspending agent, the slurry 1 that dispersant and carrier are formed, under action of centrifugal force, form a thin rete at adjacent pipe die inwall, again will be by the inorganic powder (base-material) of certain grain size distribution, suspending agent, the slurry 2 that dispersant and carrier are formed injects, under action of centrifugal force, inorganic powder particle in the slurry 2 is made travel motion, bulky grain is poly-partially to the rete that forms at the cast inner surface, adjacent outer control rete is built up moulding, and minimum particle then concentrates on the endosexine of film pipe.Formed and had inside and outside control rete, the film pipe green compact of supporter between inside and outside control rete.Carrier in forming process in the composite mortar separates with the inoranic membrane green compact of being made up of inorganic powder particle, after sloughing carrier, the non layer boundary gradient inorganic film tube green compact of making are formed in the inorganic film tube that inside and outside tube wall all has the control rete of small-bore through oven dry, the demoulding, sintering.The film sintering temperature is between 750～1650 ℃, and aperture, controlling diaphragm tunic hole is 0.1～0.5 μ m, and film pipe porosity is 38～65%, diameter 25～300mm, and length 250～2000mm, wall thickness are 2～15mm.Utilize centrifugal casting to make the novel inorganic film pipe of the control rete that outer tube wall and inner tubal wall at the film pipe respectively have one deck small-bore, the wide-aperture supporter of this inorganic film tube does not have the interface between visible layer and the layer between inner control rete and the supporter between inside and outside control rete.
Compared with prior art, the present invention has following advantage:
1. the control rete that all has the small-bore at the inside and outside wall of film pipe.
2. twice continuously shaped, primary drying, sintering, operation is simple, with short production cycle.
3. supporter does not have the interface between visible layer and the layer between inner control rete and the supporter between inside and outside key-course.
Description of drawings
Fig. 1 is the structural representation of Bicontrol film layer inorganic film pipe.The outer control rete 1 of two controlling diaphragms shown in the figure, the supporter 2 that the particle that gradient distributes is formed, inner control rete 3.
Fig. 2 is any partial structurtes enlarged drawing radially of Bicontrol film layer inorganic film pipe shown in Figure 1.
The specific embodiment
Below in conjunction with accompanying drawing, be described in further detail the present invention by embodiment, embodiments of the present invention are not limited to following manner.
Embodiment 1
With 10 weight portion particle diameters is that the water of 0.2 μ m alumina powder, 10 weight portions and the polyvinyl alcohol of 0.03 weight portion mix configuration slurry 1; Particle diameter with 85 weight portions is 0.2～40um then, and average grain diameter is 10 μ m alumina powders, and the particle diameter of 15 weight portions is water and the polyvinyl alcohol of 0.3 weight portion and the sodium pyrophosphate mixed configuration slurry 2 of 0.2 weight portion of 0.3 μ m alumina powder, 100 weight portions.Slurry 1,2 through 12 hours mechanical agitation, is made uniform slurry respectively.Start centrifugal film pipe forming machine, slurry 1 is injected in the copper alloy cast of rotation at a high speed, the cast rotating speed is 1000rpm, pass through centrifugal forming, dehydration, rotate after 2 minutes, the slurry 2 that reinjects injects, rotating speed 4000rpm rotation down made two tubular inorganic membrane green compact of controlling retes in 10 minutes, the tubular inorganic membrane green compact of making are through demoulding after drying, sintering, film pipe sintering temperature is 1600 ℃, temperature retention time 2 hours, promptly obtain after the cooling as Fig. 1, the tubular inorganic membrane of the two control retes shown in 2, wherein the material granule of the outer control rete 1 of two controlling diaphragms is thin, arranges closely, and rete is thin.The material granule of inner control rete 3 is thinner.The supporter 2 that the particle that gradient distributes is formed is near the particle maximum of outer control rete 1, near inner control rete 3 particle minimums.
After tested, the tubular inorganic membrane key-course fenestra aperture of two control retes is 0.5 μ m, film pipe porosity 48%, and diameter 60mm, length 1000mm, the film tube thickness is 8mm.The tubular inorganic membrane of this pair control rete is used to filter draft beer, can remove the small materials such as yeast, protein and polyphenol complex in the beer, improves the biology and the abiotic stability of beer.
Embodiment 2
By weight, with 10 parts of particle diameters be 0.5 μ m metal Ni powder, 6 parts water and 0.02 part polyacrylamide mixed configuration slurry 1; Be 0.2～20um with 90 parts of particle diameters then, the particle diameter of average grain diameter 3 μ m metal Ni powder, 10 weight portions is the water of 0.5 μ m metal Ni powder, 50 weight portions, the polyacrylamide of 0.1 weight portion and the calgon mixed configuration slurry 2 of 0.05 weight portion.Slurry 1,2 through 2 hours mechanical agitation, is made uniform slurry respectively.Start centrifugal film pipe forming machine, slurry 1 is injected in the porous stainless steel cast of rotation at a high speed, the cast rotating speed is 10000rpm, by centrifugal forming, dehydration, rotate after 1 minute, the slurry 2 that reinjects, rotating speed 12000rpm rotation were down made the metal film pipe green compact of two control retes in 20 minutes, and green compact are through demoulding after drying, reducing atmosphere sintering, film pipe sintering temperature is 750 ℃, temperature retention time 1 hour promptly obtains two Ni metal film pipes of controlling retes after the cooling, its cross sectional shape as shown in Figure 1.
After tested, prepared metal film key-course fenestra aperture is 0.1 μ m, film pipe porosity 38%, and diameter 25mm, length 250mm, the film tube thickness is 3mm.
Embodiment 3
With the silicon dioxide powder of 5 weight portions, 3 μ m, the water of 5 weight portions and the sodium carboxymethylcellulose mixed configuration slurry 1 of 0.01 weight portion; Be that the silicon dioxide powder of 30 μ m, the particle diameter of 10 weight portions are the water of 1 μ m silicon dioxide powder, 100 weight portions and the sodium carboxymethylcellulose mixed configuration slurry 2 of 0.2 weight portion then with 90 weight portion average grain diameters.Slurry 1,2 through 3 hours mechanical agitation, is made uniform slurry respectively.Start centrifugal film pipe forming machine, slurry 1 is injected in the lucite cast of rotation at a high speed, the cast rotating speed is 7000rpm, rotated 10 minutes, de-watering of slurries under action of centrifugal force, silica dioxide granule in the slurry is attached to the inwall of pipe die, the slurry 2 that reinjects, the cast rotating speed is 5000rpm, rotates 5 minutes, under action of centrifugal force, inorganic powder particle in the slurry 2 is made travel motion, and bulky grain is poly-partially to the rete that forms at the cast inner surface, and adjacent outer control rete is built up moulding, minimum particle then concentrates on the endosexine of film pipe, has formed to have inside and outside control rete, the film pipe green compact of supporter between inside and outside control rete.Two control rete silicon dioxide film pipe green compact of making are through demoulding after drying, sintering, and film pipe sintering temperature is 1200 ℃, and temperature retention time 2 hours promptly obtains two control rete silicon dioxide film pipes after the cooling, and its cross sectional shape as shown in Figure 1.
After testing, the silicon dioxide film management and control preparative layer fenestra aperture of making is 0.2 μ m, film pipe porosity 40%, and diameter 25mm, length 500mm, the film tube thickness is 6mm.This pair control rete silicon dioxide film pipe is used to filter mature vinegar, can remove the suspensions such as yeast, bacterium and vinegar mud in the mature vinegar, and the mature vinegar color and luster after the filter is old black, aseptic, has improved the biology and the abiotic stability of mature vinegar.
Embodiment 4
With the zirconia powder of 5 weight portions, 0.8 μ m silicon dioxide powder, the water of 10 weight portions and the gum arabic mixed configuration slurry 1 of 0.02 weight portion; Average grain diameter with 90 weight portions is that 20 μ m zirconia powders, 10 weight portion particle diameters are the water of 0.3 μ m zirconia powder, 100 weight portions and the gum arabic mixed configuration slurry 2 of 0.3 weight portion then.Slurry 1,2 through 4 hours mechanical agitation, is made uniform slurry respectively.Start centrifugal film pipe forming machine, slurry 1 is injected in the stainless steel tube cast of rotation at a high speed, the cast rotating speed is 1000rpm, rotated 10 minutes, de-watering of slurries under action of centrifugal force, zirconia particles in the slurry is attached to the inwall of pipe die, the slurry 2 that reinjects, the cast rotating speed is 4000rpm, rotates 15 minutes, under action of centrifugal force, inorganic powder particle in the slurry 2 is made travel motion, and bulky grain is poly-partially to the rete that forms at the cast inner surface, and adjacent outer control rete is built up moulding, minimum particle then concentrates on the endosexine of film pipe, has formed to have inside and outside control rete, the zirconium oxide film pipe green compact of supporter between inside and outside control rete.Green compact are through demoulding after drying, sintering, and film pipe sintering temperature is 1650 ℃, and temperature retention time 3 hours promptly obtains two zirconium oxide film pipes of controlling retes after the cooling, and its cross sectional shape as shown in Figure 1.
After testing, the zirconium oxide film management and control preparative layer fenestra aperture of prepared two control retes is 0.3 μ m, film pipe porosity 54%, and diameter 300mm, length 2000mm, the film tube thickness is 15mm.The zirconium oxide film pipe of two control retes of making can be used for air cleaning.
Embodiment 5
With 5 weight portion particle diameters is the diatomite in powder of 5 μ m, ethanol and the sodium carboxymethylcellulose of 0.05 weight portion and the calgon mixed configuration slurry 1 of 0.01 weight portion of 15 weight portions; Be 0.2～40um with 90 weight portion particle diameters then, average grain diameter is the diatomite in powder of 20 μ m, ethanol and the sodium carboxymethylcellulose of 0.2 weight portion and the calgon mixed configuration slurry 2 of 0.01 weight portion of 150 weight portions.Slurry 1,2 through 4 hours mechanical agitation, is made uniform slurry respectively.Start centrifugal film pipe forming machine, slurry 1 is injected in the stainless steel tube cast of rotation at a high speed, the cast rotating speed is 8000rpm, rotated 10 minutes, slurry is sloughed carrier ethanol under action of centrifugal force, diatomite particle in the slurry is attached to the inwall of pipe die, slurry 2 reinjects, the cast rotating speed is 8000rpm, rotated 20 minutes, under action of centrifugal force, inorganic powder particle in the slurry 2 is made travel motion, and bulky grain is poly-partially to the rete that forms at the cast inner surface, and adjacent outer control rete is built up moulding, minimum particle then concentrates on the endosexine of film pipe, has formed to have inside and outside control rete, the diatomaceous earth membrane pipe green compact of supporter between inside and outside control rete.Green compact are through demoulding after drying, sintering, and film pipe sintering temperature is 1250 ℃, and temperature retention time 2 hours promptly obtains two diatomaceous earth membrane pipes of controlling retes after the cooling, and its cross sectional shape as shown in Figure 1.
After testing, the diatomaceous earth membrane management and control preparative layer fenestra aperture of prepared two control retes is 0.5 μ m, film pipe porosity 65%, and diameter 58mm, length 500mm, the film tube thickness is 8mm.The diatomaceous earth membrane pipe of two control retes of making can be used for drinking water purification, and except that microorganisms such as the harmful suspended material in anhydrating, bacteriums, its cross sectional shape as shown in Figure 1.
Embodiment 6
With 5 weight portion particle diameters is the metallic titanium powder of 0.8um, the water of 3 weight portions and the gum arabic mixed configuration slurry 1 of 0.02 weight portion; Be the metallic titanium powder of 20um, the metallic titanium powder that 10 weight portion particle diameters are 0.5um, the water of 90 weight portions and the gum arabic mixed configuration slurry 2 of 0.2 weight portion then with 90 weight portion average grain diameters.Slurry 1,2 through 2 hours mechanical agitation, is made uniform slurry respectively.Start centrifugal film pipe forming machine, slurry 1 is injected in the stainless steel tube cast of rotation at a high speed, the cast rotating speed is 1000rpm, rotated 10 minutes, de-watering of slurries under action of centrifugal force, titanium valve particle in the slurry is attached to the inwall of pipe die, the slurry 2 that reinjects, the cast rotating speed is 8000rpm, rotates 20 minutes, under action of centrifugal force, inorganic powder particle in the slurry 2 is made travel motion, and bulky grain is poly-partially to the rete that forms at the cast inner surface, and adjacent outer control rete is built up moulding, minimum particle then concentrates on the endosexine of film pipe, has formed to have inside and outside control rete, the diatomaceous earth membrane pipe green compact of supporter between inside and outside control rete.Green compact through demoulding after drying, under vacuum atmosphere sintering, film pipe sintering temperature is 1100 ℃, temperature retention time 2 hours promptly obtains the metal titanium membrane pipes of two control retes after the cooling, its cross sectional shape is as shown in Figure 1.
After testing, the metal titanium membrane management and control preparative layer fenestra aperture of prepared two control retes is 0.3 μ m, film pipe porosity 45%, and diameter 50mm, length 500mm, the film tube thickness is 2mm.Can be used for the separation such as fluid purification, degerming, clarification of water, air etc.
Claims (6)
1, a kind of Bicontrol film layer inorganic film pipe preparation method is characterized in that comprising the steps:
After the first step disposes slurry 1 and slurry 2 according to the following number of weight ratio, respectively through stirring 2～12 hours;
5～100 parts of base-materials
3～150 parts in carrier
0～0.3 part of suspending agent
0～0.2 part of dispersant
The consumption of suspending agent and dispersant can not be zero simultaneously;
Described slurry 1 is that base-material, suspending agent, dispersant and the carrier of 0.2～5um formed by particle diameter;
Described slurry 2 is made up of base-material, suspending agent, dispersant and the carrier of 0.2um～40um particle diameter; Described base-material comprises non-metallic powder material oxidation aluminium powder, silicon dioxide powder, zirconia powder or diatomite in powder, or metal powder material nickel powder, titanium valve; Described carrier comprises water or ethanol;
The slurry 1 that second step obtained the first step is injected in the cast that rotating speed is 1000rpm～10000rpm, rotates 1～10 minute, and centrifugal forming forms outer control rete;
The 3rd step was injected into slurry 2 in the described cast of second step, and rotating speed is in the cast of 2000rpm～10000rpm, rotates 5～20 minutes, made the metal film pipe green compact of two control retes;
The 4th step green compact drying rear demoulding again at 750～1650 ℃ sintering temperature, is incubated cooling after 1～2 hour.
2, a kind of Bicontrol film layer inorganic film pipe preparation method according to claim 1, it is characterized in that: described suspending agent is polyacrylamide, sodium carboxymethylcellulose, polyvinyl alcohol or gum arabic.
3, a kind of Bicontrol film layer inorganic film pipe preparation method according to claim 1, it is characterized in that: described dispersant is calgon or sodium pyrophosphate.
4, a kind of Bicontrol film layer inorganic film pipe is by the described method preparation of claim 1.
5, Bicontrol film layer inorganic film pipe according to claim 4 is characterized in that: the inside and outside surface of described film pipe respectively has one deck aperture to control rete uniformly, is supporter between the inside and outside control rete.
6, a kind of according to the described Bicontrol film layer inorganic film pipe of claim 4, it is characterized in that: aperture, described pair of controlling diaphragm tunic hole is 0.1～0.5 μ m, and film pipe porosity is 38～65%, diameter 25～300mm, length 250～2000mm, wall thickness are 2～15mm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100415351C (en) * | 2006-08-25 | 2008-09-03 | 广州净易环保科技有限公司 | Film built-in type inorganic film tube and its preparation method |
| CN102958593A (en) * | 2010-06-30 | 2013-03-06 | 霍尼韦尔国际公司 | Variable-orifice prill plate |
| CN103521089A (en) * | 2013-10-18 | 2014-01-22 | 北京中天元环境工程有限责任公司 | Separating membrane |
| CN107051211A (en) * | 2017-02-23 | 2017-08-18 | 江苏新时高温材料股份有限公司 | High water flux ceramic membrane separation membrane layer and preparation method thereof |
| CN107308825A (en) * | 2016-04-27 | 2017-11-03 | 李月玲 | A kind of manufacture method of internal pressure tubular multilayer composite separation membrane |
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| CN104857859B (en) * | 2015-04-07 | 2018-07-17 | 南京工业大学 | Hydrophobic inorganic porous membrane and preparation method thereof |
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- 2005-03-18 CN CNB2005100336329A patent/CN100471546C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415351C (en) * | 2006-08-25 | 2008-09-03 | 广州净易环保科技有限公司 | Film built-in type inorganic film tube and its preparation method |
| CN102958593A (en) * | 2010-06-30 | 2013-03-06 | 霍尼韦尔国际公司 | Variable-orifice prill plate |
| CN103521089A (en) * | 2013-10-18 | 2014-01-22 | 北京中天元环境工程有限责任公司 | Separating membrane |
| CN103521089B (en) * | 2013-10-18 | 2015-08-05 | 北京中天元环境工程有限责任公司 | Diffusion barrier |
| CN107308825A (en) * | 2016-04-27 | 2017-11-03 | 李月玲 | A kind of manufacture method of internal pressure tubular multilayer composite separation membrane |
| CN107051211A (en) * | 2017-02-23 | 2017-08-18 | 江苏新时高温材料股份有限公司 | High water flux ceramic membrane separation membrane layer and preparation method thereof |
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