CA2237436A1 - Water removal device - Google Patents
Water removal device Download PDFInfo
- Publication number
- CA2237436A1 CA2237436A1 CA002237436A CA2237436A CA2237436A1 CA 2237436 A1 CA2237436 A1 CA 2237436A1 CA 002237436 A CA002237436 A CA 002237436A CA 2237436 A CA2237436 A CA 2237436A CA 2237436 A1 CA2237436 A1 CA 2237436A1
- Authority
- CA
- Canada
- Prior art keywords
- zeolite membrane
- equipment
- membrane
- water
- liquid mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910001868 water Inorganic materials 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000012528 membrane Substances 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 34
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000010457 zeolite Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 125000005624 silicic acid group Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HYUJIYRRLKBBBT-UHFFFAOYSA-N COO[Si](OOC)(OOC)OOC Chemical compound COO[Si](OOC)(OOC)OOC HYUJIYRRLKBBBT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01D71/028—Molecular sieves
- B01D71/0281—Zeolites
-
- 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
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
- B01D63/062—Tubular membrane modules with membranes on a surface of a support tube
-
- 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
- B01D71/028—Molecular sieves
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A device for removing water from liquid mixtures which comprises a tubular cylinder closed at one end formed from a support matrix on which is crystallised a zeolite membrane over at least its lower part, in use the cylinder is placed in the liquid mixture with the zeolite membrane in contact with the liquid mixture so that the water passes through the membrane into the cylinder, optionally there can be a reduced pressure inside the cylinder.
Description
CA 02237436 l998-0~-l2 Water Removal Device The present invention relates to equipment for separating liquids, moreparticularly it relates to equipment which can be used to separate water from other liquids.
It is known that zeolite membranes can be used to separate water from othçr liquids and European Patent application 0481660 discloses and di~c~l~5es prior art zeo-type membranes and refers in particular to US Patents 3244643, 3730910 and 4578372, Applied Catalysts 49(1989) 1-25, DE-A-3827049, CA1235684, JP-A-63Z87504, JP-A-63291809, EP-A-135069 Conventional use of membranes in liquid separation either involves through-flow methods, where the liquids to be separated are one side of the m~ e and by the use of pressure diLrel-enl;al or gravity one liquid is passed through the membrane leaving the liquid mixture on the other side of the membrane.
Alternatively, cross-flow separation is used, where the liquid mixture is passedacross the surface of the membrane in a continuous or semi-continuous stream and one liquid is removed from the stream by a pressure differential appiied across the membrane.
The equipment used in such applications is purpose built and can involve complex pumping and control systems and the liquids are poured into the equipment.
We have devised a simpler and more convenient means of separating liquids which is easier to use in situ.
According to the invention there is provided equipment for separating liquids, which comprises a tubular means which is closed at one end and open at the other and in which part of the tube comprises a zeolite membrane.
The tubular means can be of any cross-sectional shape, e.g. circular, oval, ellipsoidal, rect~n~ul~r, square, etc., although circular or oval cross-sectional CA 02237436 1998-0~-12 shapes are preferred. The ratio of length to cross-sectional area of the tubularmeans is not critical and, depending on its application, a very wide range of shapes can be used, e.g. from long thin tubes to shorter ~vider tubes.
The part of the tubular means cont5lining a zeolite membrane is p~ere,~bly a zeolite membrane on a supported matrix such as a metal mesh or sieve, ceramic, a polymer such as a polvsulphone or a polyether sulphone etc. as disclosed in th~
above references. In the present invention the supported membrane can be forrned into the desired shape to cornprise part of the tubular means.
Preferably the zeolite membrane part of the tubular means is ~ acf?nt to the closed end and, if desired, the end can be formed of a zeolite membrane.
The other part of the tubular means can comprise the uncoated membrane support or it can be made of a metal, ceramic, plastic, etc. material. The material is not critical but it should be sufficiently strong enough and dimensionally stable to be suitable. It can be porous or non-porous, depending on how it is to be used.
The zeolite membranes should be substantially free of defects so as to provide an effective separation and zeolite membranes as described in our co-pendin~
application PCT/GB95/02221 in which zeolite membranes are treated with a silicic acid are preferred.
Methods of making silicic acids are described in ~B Patent Application 2269377 and a ~leïel.ed method is by acidification of a sodium silicate solution followed by separation of the silicic acid by phase separation using an organic solvent such as tetrahydrofuran. The organic phase can then be dried and anhydrous silicic acid separated e.g. by addition of n-butanol to obtain a substantially anhydroussolution of silicic acid. The degree of polymerisation of the silicic acid depends on the actual conditions used e.g. the time the sodium silicate solution is in contact with the acid before addition of the organic solvent, temperature etc.
The silicic acid used in the present invention preferably has an average molecular weight in the range of 96 to 10,000 and more preferably of 96 to 3220.
CA 02237436 1998-0~-12 As well as treatment with silicic acids the zeo-type materials can be treated with alkylorthosilicates such as tetra ethyl ortho silicate ~TEOS) and tetra isopropyl ortho silicate (TIPOT) akoxyorthosilicates such as tetramethoxyortho silicate which form a polysilicic acid when applied to the zeo-type m.aterial. These alkylorthosilicates and alkoxyorthocilic~tçs form mesoporous silica compounds which consist f~ssçnti~lly of a series of polysilicic acid units linked together, each unit comprising a polysilicic acid molecule as described in GB Patent Application 2269377 and comprising a plurality of three dimensional species linked together with each species either having silicon atom bridges with an oxygen atom between each silicon atom or hydroxyl groups on the silicon In one embodiment the tubular means is formed from a matrix which can be used as a support for a zeolite membrane and a zeolite membrane is then deposited, grown, crystallised or formed on part of the support, leaving the other part untreated.
The equipment of the invention can be used in two dirre~ ways. In the first way, the device of the invention is placed within a receptacle and the liquid mixture placed within the tubular means so that the liquid mixLure is only in contact with the zeolite membrane or non-porous part of the tubular means. The liquid, which can pass through the zeolite membrane, e.g. water, passes through the membrane into the receptacle, thus separating the liquids. A pressure di~e.~,lLial is preferably applied across the membrane to ~ilit~te the separation.
In an alternative way of operation, the liquid mixture is contained in a receptacle and the device is placed in the liquid, with a portion of the tubular means comprising the zeolite membrane in contact with the liquid mixture. The liquid, which can pass through the membrane, will then pass into the tubular means and can be removed. A pressure differential can be applied across the membrane to facilitate the separation.
The device is particularly useful in removing water from liquid mixtures co,.~ g water, for example, to lower the water content to acceptably low levels, e.g. in solvents, thinners and other liquids which can be cont~min~ted with CA 02237436 1998-0~-12 water and biological and pharmaceutical materials and other thermally sensitive rnaterials. In one example, the liquid cont~ining water is cnnt~ined in a receptacle such as a beaker, Winchester, etc., the device of the invention placed within the liquid and a vacuum applied to the tubular means. The water in the liquid mixture is then drawn through the membrane. The system can be left running until the required degree of dehydration in the li~uid mixture is obtained.
The device can then be removed, cleaned and used again, or if co.~ le-l e.g.
by biological or pharmaceutical material, thrown away.
Thus, an easily transportable device can be obtained for removing water from water cont~ininsg liquid mixtures, which is adaptable, easy to use and can be employed at the point of use of the liquid mixtures.
It is a feature of the invention that it enables water to be removed from liquidmixtures without the need for high pressure difrelenlials across the membrane asin previously disclosed uses of zeolite membranes.
The invention is described in the Examples and drawing in which the Examples exemplify the plepalalion ofthe membrane and the drawing illustrates apparatus for application of the membranes.
F,Ys-mple 1 Membrane Growth The substrate used was a Pall PSS (Trade Mark) CP 1606 PO5 3t6L porous sintered stainless steel cylinder filter as illustrated in fig. I in which (7) is the cylinder filter and (8~ is a screw thread ( see Example 3.) The cylinder was placed in a I litre glass vessel which had previously been cleaned by washing with de-ionised water, acetone, toluene and finally acetone before being dried in an oven at 90 degrees C. for 3 hours.
CA 02237436 1998-0~-12 (a) Cobalt pre-treatment:
The cylinder was placed in a I litre glass vessel to which was added 800ml of 0.1 M cobalt nitrate solution and le~ to soak for I hour, after which the cobalt nitrate solution was decanted and the beaker was placed in an oven at 90~C to dry, the cylinder was removed from the beaker and fired at 250~C for 4 hours. The cylinder was removed from the furnace and allowed to cool.
This procedure was repeated 2 more times to obtain a good cobalt oxide coating.
(b) Zeolite Pre-treatment Zeolite 4A powder was rubbed into the outside of the substrate, wh;ch had already been cobalt coated as above, using a gloved finger, until no more zeolite will rub into the surface, any excess zeolite was tapped off.
Two solutions A and B were prepared separately in two 500 ml glass bottles as follows:-Solution A
73.47g Sodium ~IIlmin~t~, 11.25g Sodium Hydroxide and 445.8g de-ionised water were rnechanically shaken until dissolved. The Sodium Ahlmin~te had an actual composition 62.48% A12O3, 35.24% Na2O, and 2.28% H2O.
Solution B
151.71g Sodium Silicate of composition 14.21% Na2O, 35.59~~0 SiO2 and 50.20% H2O was dissolved in 445.80g de-ionised water.
Solution A was added slowly to solution B with both stirring and shaking by hand to ensure complete and even mixing ~it is important that no lumps of hydrogel are formed~. This resulted in a hydrogel having a molar composition 2.01 Na2O: A12O3: 2.0 SiO2: 120.0 H20 CA 02237436 1998-0~-12 W ~97/18886 PCT/GB96/02861 800 ml of the hydrogel was slowly poured into a growth vessel Co..~ the cobalt oxide treated and zeolite rubbed cylinder in a vertical position. The growth vessel was placed in a pressure cooker together with a beaker cont~ining the ~ g hydrogel solution. The pressure cooker was placed in an oven preheated to 100 degrees C. for 5 hours. Subsequently it was removed from the oven and allowed to cool for 30 minutes. The growth vessel was removed and the solution poured away.
The cylinder was carefully removed from the vessel. The cylinder was placed in a glass vessel and washed three times with 800ml aliquots of de-ionised water~ swirling the solution each time to ensure complete removal of residues and the membrane was allowed to air dry in air at 70~C for 2 hours.
The surface of the dried coated cylinder was subsequently wiped clean with a clean lens tissue in order to remove any loose powdery deposits which may have formed on the surface. It was then washed with de-ionised water and left to in an oven at 70()C for 2 hours. This growth and washing process was repeated two more times.
X-ray Analysis showed this to be a Zeolite 4A
F.xsn~ple 2 Preparation of TEOS ~or Post Treatment of Membrane The post treatment solution was prepared by placing 120ml of (TEOS) into a clean, dry beaker, adding 540 ml of deionised water and 540ml of ethanol.
The mixture was then stirred at 300r.p.m. for a period of 5 mins.
~,Ys~le 3 Membrane Test Procedure The cylinder was placed in a I litre glass vessel on a heater/stirrer hot plate and a vacuum line was ~tt~ched to the end of the cylinder by a screw thread.
The glass vessel cell was filled with an isopropanoVwater (IPA/H20) mixture (90/10 wt. % respectively). The membrane was tested at ap~oloxhllalely 70~C.
CA 02237436 1998-0~-12 W ~ 97/18886 PCT/GB96/02861 The pressure on the side of the membrane remote from the liquid i.e. inside the cylinder was reduced to 4 mbar (0.4 kN). Permeate was collected over periods of 8 hours and weighed, and small aliquots were analysed, feed water concentration was monitored throughout.
~Y~Imple 4 Post-treatment Procedure of Membrane After the initial test of the untreated membrane in the appa~L-Is of Example 3 with IPA/Water, the glass vessel was emptied, rinsed with 2 x 100 ml aliquots of ethanol and then another 1 00ml aliquot of ethanol was placed into the glass vessel and cylinder was then placed under vacuum for 30 mins.
The ethanol was removed from the glass vessel and the TEOS
post-LI~aLllle~l solution prepared as in Example 2 was poured into the glass vessel. The cylinder cell was then treated at 70~)C for a period of 24 hours, with the inside of the cylinder under vacuum. After this period, the mix was removed, the heat switched off, vacuum removed and then co--lplt;ssed air was passed over the membrane for a period of one hour.
Example 5 A membrane produced by the method of Example I was treated under pervaporation conditions described in Example 3 and the post treatment described in example 4 and the results shown in Table 1 below CA 02237436 1998-0~-12 Table I
Isopropanol/Water mixture at 70~C.
Time on Stream Feed Water Permeate Water Perrneate Water Flux (hours) % Weight% Weight (J) Kg/m2/day 0.5 7.99 82.18 27.25 1.0 7.60 80.40 23.26 1.5 7.3~ 78. ~4 ~.3g 2.0 6.45 75.38 21.14 2.5 5.84 72.52 19.79 3.0 5.23 69.45 18.36 3.5 4.88 66.14 18.46 4.0 4.41 60.90 16.14 4.5 3.75 57.61 15.05 5.0 3.46 57.32 13.25 5.5 3.16 48.26 13.18 6.0 2.69 45.93 12.30 6.5 2.19 42.16 8.76 7.0 1.90 38.42 8.27 7.5 1.59 33.15 8.44 8.0 1.47 29.51 7.89 8.5 1.18 26.44 6.98 9.0 1.16 25.77 6.44 9.5 1.00 22.02 5.56 10.0 0.86 21.31 4.87 10.5 0.75 20.34 4.35 11.0 0.66 18.16 3.91 11.5 0.60 16.06 3.26 12.0 0.52 13.98 2.68 12.5 0.44 10.59 1.89 An embodiment of the invention showing equipment in use is shown if fig. 2 in which a receptacle (1) contains a liquid mixture (2) cont~ining water. A tube ~3) made of metal mesh has a lower portion (4) on which is deposited a zeolite membrane.
In use the tube is placed in the water-cont~inins~ liquid in the receptacle and a vacuum is applied at (5). Water is drawn through membrane (4) into the tube, as shown at (6), from where it can be removed. Thus, the liquid (2) lef'c behind, contains a lower proportion of water.
In an alternative application the water cont~inin~ liquid is placed within the tube (3) and the pressure reduced outside the tube. Water then passes through the Illelllblcll~e leaving a liquid with reduced water content in the tube.
It is known that zeolite membranes can be used to separate water from othçr liquids and European Patent application 0481660 discloses and di~c~l~5es prior art zeo-type membranes and refers in particular to US Patents 3244643, 3730910 and 4578372, Applied Catalysts 49(1989) 1-25, DE-A-3827049, CA1235684, JP-A-63Z87504, JP-A-63291809, EP-A-135069 Conventional use of membranes in liquid separation either involves through-flow methods, where the liquids to be separated are one side of the m~ e and by the use of pressure diLrel-enl;al or gravity one liquid is passed through the membrane leaving the liquid mixture on the other side of the membrane.
Alternatively, cross-flow separation is used, where the liquid mixture is passedacross the surface of the membrane in a continuous or semi-continuous stream and one liquid is removed from the stream by a pressure differential appiied across the membrane.
The equipment used in such applications is purpose built and can involve complex pumping and control systems and the liquids are poured into the equipment.
We have devised a simpler and more convenient means of separating liquids which is easier to use in situ.
According to the invention there is provided equipment for separating liquids, which comprises a tubular means which is closed at one end and open at the other and in which part of the tube comprises a zeolite membrane.
The tubular means can be of any cross-sectional shape, e.g. circular, oval, ellipsoidal, rect~n~ul~r, square, etc., although circular or oval cross-sectional CA 02237436 1998-0~-12 shapes are preferred. The ratio of length to cross-sectional area of the tubularmeans is not critical and, depending on its application, a very wide range of shapes can be used, e.g. from long thin tubes to shorter ~vider tubes.
The part of the tubular means cont5lining a zeolite membrane is p~ere,~bly a zeolite membrane on a supported matrix such as a metal mesh or sieve, ceramic, a polymer such as a polvsulphone or a polyether sulphone etc. as disclosed in th~
above references. In the present invention the supported membrane can be forrned into the desired shape to cornprise part of the tubular means.
Preferably the zeolite membrane part of the tubular means is ~ acf?nt to the closed end and, if desired, the end can be formed of a zeolite membrane.
The other part of the tubular means can comprise the uncoated membrane support or it can be made of a metal, ceramic, plastic, etc. material. The material is not critical but it should be sufficiently strong enough and dimensionally stable to be suitable. It can be porous or non-porous, depending on how it is to be used.
The zeolite membranes should be substantially free of defects so as to provide an effective separation and zeolite membranes as described in our co-pendin~
application PCT/GB95/02221 in which zeolite membranes are treated with a silicic acid are preferred.
Methods of making silicic acids are described in ~B Patent Application 2269377 and a ~leïel.ed method is by acidification of a sodium silicate solution followed by separation of the silicic acid by phase separation using an organic solvent such as tetrahydrofuran. The organic phase can then be dried and anhydrous silicic acid separated e.g. by addition of n-butanol to obtain a substantially anhydroussolution of silicic acid. The degree of polymerisation of the silicic acid depends on the actual conditions used e.g. the time the sodium silicate solution is in contact with the acid before addition of the organic solvent, temperature etc.
The silicic acid used in the present invention preferably has an average molecular weight in the range of 96 to 10,000 and more preferably of 96 to 3220.
CA 02237436 1998-0~-12 As well as treatment with silicic acids the zeo-type materials can be treated with alkylorthosilicates such as tetra ethyl ortho silicate ~TEOS) and tetra isopropyl ortho silicate (TIPOT) akoxyorthosilicates such as tetramethoxyortho silicate which form a polysilicic acid when applied to the zeo-type m.aterial. These alkylorthosilicates and alkoxyorthocilic~tçs form mesoporous silica compounds which consist f~ssçnti~lly of a series of polysilicic acid units linked together, each unit comprising a polysilicic acid molecule as described in GB Patent Application 2269377 and comprising a plurality of three dimensional species linked together with each species either having silicon atom bridges with an oxygen atom between each silicon atom or hydroxyl groups on the silicon In one embodiment the tubular means is formed from a matrix which can be used as a support for a zeolite membrane and a zeolite membrane is then deposited, grown, crystallised or formed on part of the support, leaving the other part untreated.
The equipment of the invention can be used in two dirre~ ways. In the first way, the device of the invention is placed within a receptacle and the liquid mixture placed within the tubular means so that the liquid mixLure is only in contact with the zeolite membrane or non-porous part of the tubular means. The liquid, which can pass through the zeolite membrane, e.g. water, passes through the membrane into the receptacle, thus separating the liquids. A pressure di~e.~,lLial is preferably applied across the membrane to ~ilit~te the separation.
In an alternative way of operation, the liquid mixture is contained in a receptacle and the device is placed in the liquid, with a portion of the tubular means comprising the zeolite membrane in contact with the liquid mixture. The liquid, which can pass through the membrane, will then pass into the tubular means and can be removed. A pressure differential can be applied across the membrane to facilitate the separation.
The device is particularly useful in removing water from liquid mixtures co,.~ g water, for example, to lower the water content to acceptably low levels, e.g. in solvents, thinners and other liquids which can be cont~min~ted with CA 02237436 1998-0~-12 water and biological and pharmaceutical materials and other thermally sensitive rnaterials. In one example, the liquid cont~ining water is cnnt~ined in a receptacle such as a beaker, Winchester, etc., the device of the invention placed within the liquid and a vacuum applied to the tubular means. The water in the liquid mixture is then drawn through the membrane. The system can be left running until the required degree of dehydration in the li~uid mixture is obtained.
The device can then be removed, cleaned and used again, or if co.~ le-l e.g.
by biological or pharmaceutical material, thrown away.
Thus, an easily transportable device can be obtained for removing water from water cont~ininsg liquid mixtures, which is adaptable, easy to use and can be employed at the point of use of the liquid mixtures.
It is a feature of the invention that it enables water to be removed from liquidmixtures without the need for high pressure difrelenlials across the membrane asin previously disclosed uses of zeolite membranes.
The invention is described in the Examples and drawing in which the Examples exemplify the plepalalion ofthe membrane and the drawing illustrates apparatus for application of the membranes.
F,Ys-mple 1 Membrane Growth The substrate used was a Pall PSS (Trade Mark) CP 1606 PO5 3t6L porous sintered stainless steel cylinder filter as illustrated in fig. I in which (7) is the cylinder filter and (8~ is a screw thread ( see Example 3.) The cylinder was placed in a I litre glass vessel which had previously been cleaned by washing with de-ionised water, acetone, toluene and finally acetone before being dried in an oven at 90 degrees C. for 3 hours.
CA 02237436 1998-0~-12 (a) Cobalt pre-treatment:
The cylinder was placed in a I litre glass vessel to which was added 800ml of 0.1 M cobalt nitrate solution and le~ to soak for I hour, after which the cobalt nitrate solution was decanted and the beaker was placed in an oven at 90~C to dry, the cylinder was removed from the beaker and fired at 250~C for 4 hours. The cylinder was removed from the furnace and allowed to cool.
This procedure was repeated 2 more times to obtain a good cobalt oxide coating.
(b) Zeolite Pre-treatment Zeolite 4A powder was rubbed into the outside of the substrate, wh;ch had already been cobalt coated as above, using a gloved finger, until no more zeolite will rub into the surface, any excess zeolite was tapped off.
Two solutions A and B were prepared separately in two 500 ml glass bottles as follows:-Solution A
73.47g Sodium ~IIlmin~t~, 11.25g Sodium Hydroxide and 445.8g de-ionised water were rnechanically shaken until dissolved. The Sodium Ahlmin~te had an actual composition 62.48% A12O3, 35.24% Na2O, and 2.28% H2O.
Solution B
151.71g Sodium Silicate of composition 14.21% Na2O, 35.59~~0 SiO2 and 50.20% H2O was dissolved in 445.80g de-ionised water.
Solution A was added slowly to solution B with both stirring and shaking by hand to ensure complete and even mixing ~it is important that no lumps of hydrogel are formed~. This resulted in a hydrogel having a molar composition 2.01 Na2O: A12O3: 2.0 SiO2: 120.0 H20 CA 02237436 1998-0~-12 W ~97/18886 PCT/GB96/02861 800 ml of the hydrogel was slowly poured into a growth vessel Co..~ the cobalt oxide treated and zeolite rubbed cylinder in a vertical position. The growth vessel was placed in a pressure cooker together with a beaker cont~ining the ~ g hydrogel solution. The pressure cooker was placed in an oven preheated to 100 degrees C. for 5 hours. Subsequently it was removed from the oven and allowed to cool for 30 minutes. The growth vessel was removed and the solution poured away.
The cylinder was carefully removed from the vessel. The cylinder was placed in a glass vessel and washed three times with 800ml aliquots of de-ionised water~ swirling the solution each time to ensure complete removal of residues and the membrane was allowed to air dry in air at 70~C for 2 hours.
The surface of the dried coated cylinder was subsequently wiped clean with a clean lens tissue in order to remove any loose powdery deposits which may have formed on the surface. It was then washed with de-ionised water and left to in an oven at 70()C for 2 hours. This growth and washing process was repeated two more times.
X-ray Analysis showed this to be a Zeolite 4A
F.xsn~ple 2 Preparation of TEOS ~or Post Treatment of Membrane The post treatment solution was prepared by placing 120ml of (TEOS) into a clean, dry beaker, adding 540 ml of deionised water and 540ml of ethanol.
The mixture was then stirred at 300r.p.m. for a period of 5 mins.
~,Ys~le 3 Membrane Test Procedure The cylinder was placed in a I litre glass vessel on a heater/stirrer hot plate and a vacuum line was ~tt~ched to the end of the cylinder by a screw thread.
The glass vessel cell was filled with an isopropanoVwater (IPA/H20) mixture (90/10 wt. % respectively). The membrane was tested at ap~oloxhllalely 70~C.
CA 02237436 1998-0~-12 W ~ 97/18886 PCT/GB96/02861 The pressure on the side of the membrane remote from the liquid i.e. inside the cylinder was reduced to 4 mbar (0.4 kN). Permeate was collected over periods of 8 hours and weighed, and small aliquots were analysed, feed water concentration was monitored throughout.
~Y~Imple 4 Post-treatment Procedure of Membrane After the initial test of the untreated membrane in the appa~L-Is of Example 3 with IPA/Water, the glass vessel was emptied, rinsed with 2 x 100 ml aliquots of ethanol and then another 1 00ml aliquot of ethanol was placed into the glass vessel and cylinder was then placed under vacuum for 30 mins.
The ethanol was removed from the glass vessel and the TEOS
post-LI~aLllle~l solution prepared as in Example 2 was poured into the glass vessel. The cylinder cell was then treated at 70~)C for a period of 24 hours, with the inside of the cylinder under vacuum. After this period, the mix was removed, the heat switched off, vacuum removed and then co--lplt;ssed air was passed over the membrane for a period of one hour.
Example 5 A membrane produced by the method of Example I was treated under pervaporation conditions described in Example 3 and the post treatment described in example 4 and the results shown in Table 1 below CA 02237436 1998-0~-12 Table I
Isopropanol/Water mixture at 70~C.
Time on Stream Feed Water Permeate Water Perrneate Water Flux (hours) % Weight% Weight (J) Kg/m2/day 0.5 7.99 82.18 27.25 1.0 7.60 80.40 23.26 1.5 7.3~ 78. ~4 ~.3g 2.0 6.45 75.38 21.14 2.5 5.84 72.52 19.79 3.0 5.23 69.45 18.36 3.5 4.88 66.14 18.46 4.0 4.41 60.90 16.14 4.5 3.75 57.61 15.05 5.0 3.46 57.32 13.25 5.5 3.16 48.26 13.18 6.0 2.69 45.93 12.30 6.5 2.19 42.16 8.76 7.0 1.90 38.42 8.27 7.5 1.59 33.15 8.44 8.0 1.47 29.51 7.89 8.5 1.18 26.44 6.98 9.0 1.16 25.77 6.44 9.5 1.00 22.02 5.56 10.0 0.86 21.31 4.87 10.5 0.75 20.34 4.35 11.0 0.66 18.16 3.91 11.5 0.60 16.06 3.26 12.0 0.52 13.98 2.68 12.5 0.44 10.59 1.89 An embodiment of the invention showing equipment in use is shown if fig. 2 in which a receptacle (1) contains a liquid mixture (2) cont~ining water. A tube ~3) made of metal mesh has a lower portion (4) on which is deposited a zeolite membrane.
In use the tube is placed in the water-cont~inins~ liquid in the receptacle and a vacuum is applied at (5). Water is drawn through membrane (4) into the tube, as shown at (6), from where it can be removed. Thus, the liquid (2) lef'c behind, contains a lower proportion of water.
In an alternative application the water cont~inin~ liquid is placed within the tube (3) and the pressure reduced outside the tube. Water then passes through the Illelllblcll~e leaving a liquid with reduced water content in the tube.
Claims (9)
1. Equipment for separating liquids which comprises a tubular means which is closed at one end and open at the other and in which part of the tube comprises a zeolite membrane.
2. Equipment as claimed in claim 1 in which the tubular means containing a zeolite membrane is a zeolite membrane formed on a supported matrix.
3. Equipment as claimed in claim 2 in which the supported matrix is a metal mesh or sieve or a ceramic or a polymeric material.
4. Equipment as claimed in claim 3 in which the tubular means has been made by forming the supported matrix into the desired shape and crystallising the zeolite membrane on to the supported matrix.
5. Equipment as claimed in any one of claims 1 to 4 in which the zeolite membrane has been treated by being contacted with a silicic acid to form a membrane substantially free of holes.
6. Equipment as claimed in any one of claims 1 to 5 which comprises a substantially cylindrical supported matrix on which is deposited a zeolite membrane so that the zeolite membrane is formed on at least the lower part of the equipment adjacent its closed end.
7. A method of removing water from a liquid mixture which comprises placing equipment as claimed in any one of claims 1 to 6 in contact with the liquid mixture so that substantially the only water permeable part of the equipment in contact with the liquid mixture is that comprising the zeolite membrane, so thatwater passes through the zeolite membrane and is separated from the liquid mixture.
8. A method as claimed in claim 7 in which the liquid mixture is contained in a vessel.
9. A method as claimed in claim 7. in which the liquid mixture is put inside theequipment so that water passes out through the zeolite membrane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9523854.9 | 1995-11-22 | ||
| GBGB9523854.9A GB9523854D0 (en) | 1995-11-22 | 1995-11-22 | Water removal device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2237436A1 true CA2237436A1 (en) | 1997-05-29 |
Family
ID=10784255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002237436A Abandoned CA2237436A1 (en) | 1995-11-22 | 1996-11-20 | Water removal device |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0863791A1 (en) |
| JP (1) | JP2000500394A (en) |
| KR (1) | KR19990071526A (en) |
| CN (1) | CN1202839A (en) |
| AU (1) | AU713866B2 (en) |
| CA (1) | CA2237436A1 (en) |
| GB (1) | GB9523854D0 (en) |
| WO (1) | WO1997018886A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9723253D0 (en) * | 1997-11-04 | 1998-01-07 | Bratton Graham J | Water treatment process |
| GB9821706D0 (en) * | 1998-10-07 | 1998-12-02 | Bratton Graham J | Membrane structure |
| AU2009268532B2 (en) * | 2008-07-10 | 2013-01-10 | Board Of Regents, The University Of Texas System | Water purification membranes with improved fouling resistance |
| CN101898089B (en) * | 2009-05-27 | 2013-11-06 | 三菱重工业株式会社 | Dehydration system |
| CN103861459A (en) * | 2014-03-25 | 2014-06-18 | 湖州森诺氟材料科技有限公司 | Filtering device with polytetrafluoroethylene membrane |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4995967A (en) * | 1987-11-06 | 1991-02-26 | Akzo N.V. | Separator for cell-containing liquids |
| DE3827049A1 (en) * | 1988-08-10 | 1990-02-15 | Schulten Rudolf Prof Dr | Zeolite molecular sieve for separating fluids |
| GB9022836D0 (en) * | 1990-10-19 | 1990-12-05 | British Petroleum Co Plc | Membranes |
| SE469031B (en) * | 1991-10-31 | 1993-05-03 | Electrolux Ab | DEVICE FOR WATER PURIFICATION MEDIUM REVERSE OSMOS |
| JP3431973B2 (en) * | 1993-12-27 | 2003-07-28 | 三井造船株式会社 | Method for producing liquid mixture separation membrane |
| US5464798A (en) * | 1994-02-24 | 1995-11-07 | Jia; Meng-Dong | Ceramic-zeolite composite membranes and use for separation of vapor/gas mixtures |
-
1995
- 1995-11-22 GB GBGB9523854.9A patent/GB9523854D0/en active Pending
-
1996
- 1996-11-20 WO PCT/GB1996/002861 patent/WO1997018886A1/en not_active Application Discontinuation
- 1996-11-20 AU AU76318/96A patent/AU713866B2/en not_active Ceased
- 1996-11-20 CN CN96198500A patent/CN1202839A/en active Pending
- 1996-11-20 JP JP9519502A patent/JP2000500394A/en active Pending
- 1996-11-20 EP EP96939178A patent/EP0863791A1/en not_active Withdrawn
- 1996-11-20 KR KR1019980703799A patent/KR19990071526A/en not_active Application Discontinuation
- 1996-11-20 CA CA002237436A patent/CA2237436A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990071526A (en) | 1999-09-27 |
| AU7631896A (en) | 1997-06-11 |
| EP0863791A1 (en) | 1998-09-16 |
| GB9523854D0 (en) | 1996-01-24 |
| JP2000500394A (en) | 2000-01-18 |
| WO1997018886A1 (en) | 1997-05-29 |
| AU713866B2 (en) | 1999-12-09 |
| CN1202839A (en) | 1998-12-23 |
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