CN100393399C - DDR type zeolite membrane, and composite ddr type zeolite membrane, and method for preparation thereof - Google Patents

DDR type zeolite membrane, and composite ddr type zeolite membrane, and method for preparation thereof Download PDF

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CN100393399C
CN100393399C CNB2006100059585A CN200610005958A CN100393399C CN 100393399 C CN100393399 C CN 100393399C CN B2006100059585 A CNB2006100059585 A CN B2006100059585A CN 200610005958 A CN200610005958 A CN 200610005958A CN 100393399 C CN100393399 C CN 100393399C
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type zeolite
ddr type
gas
zeolite membrane
room temperature
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CN1824376A (en
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中山邦雄
铃木宪次
吉田学
谷岛健二
富田俊弘
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NGK Insulators Ltd
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Abstract

This invention provides a DDR type zeolite membrane, characterized in that it is formed as a membrane on a substrate and its main component is silica, and that each single gas permeance at room temperature and 100 DEG C. are different, respectively among at least two types of gases selected from a group consisting of carbon dioxide (CO2), hydrogen (H2), oxygen (O2), nitrogen (N2), methane (CH4), normal butane (n-C4H10), isobutane (i-C4H10), sulfur hexafluoride (SF6), ethane (C2H6), ethylene (C2H4), propane (C3H8), propylene (C3H6), carbon monoxide (CO), and nitrogen monoxide (NO).

Description

DDR type zeolite membrane and DDR type zeolite membrane compound and manufacture method thereof
The application is dividing an application of following application: application number: 02822549.X (PCT/JP02/09480); The applying date: on September 17th, 2002; Denomination of invention: " manufacture method of DDR type zeolite membrane, DDR type zeolite membrane and DDR type zeolite membrane compound and manufacture method thereof ".
Technical field
The present invention's (first invention) relates to the manufacture method of DDR type zeolite membrane.More particularly, the present invention relates to easy and make the method for DDR type zeolite membrane with the short time with the thickness that is fit to industrial employing.
In addition, the present invention (second invention) relates to DDR type zeolite membrane, gas separating method and gas fractionation unit.More particularly, the present invention relates to from the mist that contains specific gas composition more than 2 kinds, to separate the DDR type zeolite membrane of specific gas composition more than a kind.
The present invention's (the 3rd invention) also relates to DDR type zeolite membrane compound and manufacture method thereof.More particularly, when the present invention relates to for example use, have high mechanical properties, can prevent that the defectives such as be full of cracks that cause because of thermal stress from taking place simultaneously, and can guarantee the DDR type zeolite membrane compound and the manufacture method thereof of enough transit doses as gas separation membrane.
Background technology
Zeolite is applied as catalyst, catalyst carrier, adsorbent etc., and the zeolite layer press mold of film forming utilizes the molecular sieve effect of zeolite on the porous matrix that is made of metal or pottery, can be applicable to gas separation membrane or sees through evaporating film.Follow above-mentioned situation, people have proposed to utilize the zeolite layer press mold and the manufacture method thereof of various porous matrixes.The tympan matter that such zeolite forms can be passed through its molecular sieve effect, uses as gas separation membrane or through evaporating film equimolecular diffusion barrier.
According to the crystalline texture difference, zeolite has multiple kind such as LTA, MFI, MOR, AFI, FER, FAU, DDR to exist.Known its main component of DDR (Deca-Dodecasil 3R) wherein is the crystallization that is made of silica, its micropore is formed by the polyhedron that contains 8 yuan of rings of aerobic, the micropore diameter of 8 yuan of rings of oxygen is that 4.4 * 3.6 dusts are (with reference to W.M.Meier simultaneously, D.H.Olson, Ch.Baerlocher, Atlas of zeolite structure types, Elsevier (1996)).
DDR type zeolite with the feature on the said structure is the smaller zeolite of micropore diameter in the zeolite, have the possibility that is suitable as molecular screen membrane, this molecular screen membrane can be used for separating the carbon dioxide (CO that other zeolite as MFI, MOR, AFI, FER and FAU type is difficult to separate 2), methane (CH 4), ethane (C 2H 6) wait low molecular weight gas.
But propose about the little latest report of the manufacture method of such DDR type zeolite all the time.Though a few example reports are arranged, but for synthesizing of film not having ad hoc report about powder is synthetic.In few like this report, the synthetic concrete correlation technique of the powder of one of them has for example M.J.den Exter, J.C.Jansen, H.van Bekkum, Studies in SurfaceScience and Catalysis 84 volumes, editors such as J.Weitkamp., among Elsevier (1994) 1159-1166, disclose use tetramethoxy-silicane, 1-amantadine, ethylenediamine etc. and used, by the synthetic method of making DDR type zeolite powder of hydro-thermal as raw material.
But, according to the manufacture method of above-mentioned DDR type zeolite powder, need with the hydro-thermal of using 160 ℃ of autoclaves synthetic carry out 25 days long-time like this, also must stir etc. the easy method of can not saying so to material solution always.
And it is Powdered DDR type zeolite about 5-25 μ m that this manufacture method can only obtain grain size, therefore, for example in industrial circles such as petro chemical industry, exist and to make problems such as fine and close diffusion barrier with the enough thickness that are used to constitute gas separating step etc.
The present invention (first invention) invents in view of the problem that exists in the above-mentioned conventional art, and its purpose is: provide easy and make the method for the DDR type zeolite membrane with thickness that the gas separating step adopts in the suitable industry with the short time.
Traditional zeolite membrane does not have the methane (CH that contains in the separating natural gas respectively 4), ethane (C 2H 6), propane (C 3H 8), carbon dioxide (CO 2) micropore diameter of the molecule that equimolecular quantity is lower.
All the time, as one of purification of natural gas method, known have use and methane (CH 4) compare selective permeation carbon dioxide (CO more 2) organic substance as the method for the diffusion barrier of main component.But, organic film have bad mechanical strength, hear resistance low, produce plasticizing and because of the problem of liquid hydrocarbon deterioration because of carbon dioxide.Therefore, exist and not have to be fit to natural gas is contained this problem of film that the gas of low-molecular-weight molecule carries out the film separation like this.
The present invention's (second invention) finishes in view of the above problems, its purpose is: mechanical strength and excellent heat resistance are provided, be difficult to take place the plasticizing that carbon dioxide causes, the problems such as deterioration that liquid hydrocarbon causes, can contain the DDR type zeolite membrane of separating specific gas composition more than a kind the mist of specific gas composition more than 2 kinds from natural gas etc.; The gas separating method that uses such DDR type zeolite membrane to carry out; And the gas fractionation unit that has loaded above-mentioned DDR type zeolite membrane.
Usually, form a little less than its mechanical strength of zeolite membrane of film shape, therefore, form the zeolite membrane compound its mechanical strength is improved by making zeolite membrane film forming on the porous matrix that constitutes by metal or pottery.Such zeolite membrane not only mechanical strength is improved, and owing to can form thin zeolite membrane, compares with as the self-supported membrane of independent zeolite membrane the time during therefore as gas separation membrane, and the transit dose of gas is increased.
The above-mentioned zeolite membrane that forms on porous matrix is because the thermal expansion character of porous matrix and zeolite membrane has a great difference, and therefore when removing the structure directing agent that uses when zeolite synthesizes by calcining, the zeolite membrane on the porous matrix can produce defectives such as be full of cracks.
Therefore, the people such as Vroon of Twente university propose: by making the zeolite membrane attenuation of film forming on alumina matrix, can suppress the generation (with reference to Journal ofMembrane Science 144 (1998)) of defectives such as chapping.But, if,, can not fully reduce the probability of happening of the defectives such as be full of cracks that cause because of thermal stress at heat treatment step just with the zeolite membrane attenuation.
The Zeolite Membrane And Manufacturing Approach that the inside of porous carrier has crystallization of zeolites is disclosed in the Japanese kokai publication hei 9-202615 communique.Therefore this method is the structure that the inside of porous carrier has crystallization of zeolites, in the heat treatment step of zeolite membrane etc., can reduce the generation of the defectives such as be full of cracks that cause because of thermal stress.
But disclosed zeolite membrane can not be used in the zeolite of all kinds in the Japanese kokai publication hei 9-202615 communique etc.For example in the zeolite membrane of LTA type, just can not reduce the defectives such as be full of cracks of the zeolite membrane that on porous carrier, forms.Because the difference of porous carrier material, above-mentioned effect also has difference in addition, for example uses alumina as porous carrier and when using MFI type zeolite as zeolite membrane, and only using for several times, a zeolite membrane will produce defectives such as be full of cracks.
In addition, for disclosed zeolite membrane in the Japanese kokai publication hei 9-202615 communique, the amount that is present in the material solution of porous carrier inside is very important, and therefore wanting used thickness is the above porous carrier of 0.5mm.When the zeolite membrane compound used as gas separation membrane as constituted above, because the thickness of zeolite membrane compound is blocked up, it is big that the pressure loss becomes, and can not guarantee enough gas permeation amounts.
The present invention's (the 3rd invention) finishes in view of the above problems, purpose is: provide when for example using as gas separation membrane, has high mechanical properties, can prevent simultaneously that the defectives such as be full of cracks that cause because of thermal stress from taking place, and can guarantee the DDR type zeolite membrane compound and the manufacture method thereof of enough transit doses.
Summary of the invention
The present invention's (first invention) provides the manufacture method of DDR type zeolite membrane, it is characterized in that: the proportional (1-amantadine/SiO that contains that uses 1-amantadine and silica 2) be the proportional (water/SiO that contains of 0.03-0.4 mol ratio, water and above-mentioned silica 2) for the containing of 20-500 mol ratio and ethylenediamine and above-mentioned 1-amantadine proportional (ethylenediamine/1-amantadine) for the material solution of 5-32 mol ratio with as the DDR type zeolite powder of crystal seed, synthesize formation DDR type zeolite membrane by hydro-thermal.
Among the present invention (first invention), 1-amantadine and silica contains proportional (1-amantadine/SiO in the preferred feedstock solution 2) be the proportional (water/SiO that contains of 0.05-0.25 mol ratio, water and silica 2) for contain proportional (ethylenediamine/1-amantadine) of 28-220 mol ratio and ethylenediamine and 1-amantadine be the 8-24 mol ratio.
Among the present invention's (first invention), preferably the 1-amantadine is dissolved in the ethylenediamine, makes 1-amantadine solution, then 1-amantadine solution is mixed the preparation material solution with the silicon sol solution that contains silica.
Among the present invention's (first invention), preferably carry out hydro-thermal and synthesize at 130-200 ℃.
Among the present invention's (first invention), preferably DDR type zeolite powder is dispersed in the material solution, preferably on porous matrix, forms DDR type zeolite membrane.
Among the present invention's (first invention), DDR type zeolite powder is attached on the porous matrix, porous matrix is contacted with material solution, on porous matrix, form DDR type zeolite membrane.
Among the present invention (first invention), the thickness of the DDR type zeolite membrane that preferably forms on porous matrix is 0.1-50 μ m, and being shaped as of preferred porous matrix is tabular, the arbitrary shape of tubular, honeycomb shape or the integrated formation global shape of a plurality of tube-shaped tube.
As described above, the manufacture method of the DDR type zeolite membrane of (first invention) according to the present invention, owing to be that each raw material proportion of composing in accordance with regulations based on structure directing agent 1-amantadine is prepared material solution, and it is synthetic to use DDR type zeolite powder as crystal seed to carry out hydro-thermal, therefore can be easy and make the DDR type zeolite membrane of the thickness with suitable industrial gasses separating step with the short time.The DDR type zeolite membrane that obtains by the present invention's (first invention) manufacture method for example in petro chemical industry, by with combination such as catalyst, be suitable as diffusion barrier or the film reaction agent used in the various separating substances and use.
On the other hand, the present invention's (second invention) provides DDR type zeolite membrane, it is characterized in that: film forming on matrix, its main component is a silica, and being selected from can be different mutually with 100 ℃ of single component gas permeation rates separately in room temperature at least 2 kinds of gases in the gas of room temperature and 100 ℃ of formation mists.DDR type zeolite membrane also is provided, it is characterized in that: be selected from carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), water (H 2O), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10), sulfur hexafluoride (SF 6), ethane (C 2H 6), ethene (C 2H 4), propane (C 3H 8), propylene (C 3H 6), at least 2 kinds of gases of carbon monoxide (CO) and nitric oxide (NO) are different mutually between described at least 2 kinds of gases with 100 ℃ single component gas permeation rate in room temperature respectively.
Among the present invention's (second invention), preferably carbon dioxide (CO 2) be 1.0 * 10 at the gas permeation rate of room temperature -9(molm -2S -1Pa -1) more than.
Among the present invention's (second invention), preferably carbon dioxide (CO 2) be 5.0 * 10 at 100 ℃ gas permeation rates -10(molm -2S -1Pa -1) more than.
Among the present invention (second invention), preferably when room temperature and 100 ℃, mole of carbon dioxide (CO such as contain 2) and methane (CH 4) mist in, CO 2/ CH 4Separation (when making mist pass through DDR type zeolite membrane, CO 2The gas permeation amount of room temperature and 100 ℃ respectively with CH 4Ratio in the gas permeation amount of room temperature and 100 ℃) be more than 2.
Among the present invention's (second invention), preferably carbon dioxide (CO 2) at the single component gas permeation rate and the hydrogen (H of room temperature and 100 ℃ 2), oxygen (O 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) in any one gas be respectively more than 2 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.
Among the present invention's (second invention), preferred hydrogen (H 2) at the single component gas permeation rate and the oxygen (O of room temperature and 100 ℃ 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) in any one gas be respectively more than 2 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.
Among the present invention's (second invention), preferred oxygen (O 2) at the single component gas permeation rate and the nitrogen (N of room temperature and 100 ℃ 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) in any one gas be respectively more than 1.1 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.
Among the present invention's (second invention), preferred nitrogen (N 2) at the single component gas permeation rate and the methane (CH of room temperature and 100 ℃ 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) in any one gas be respectively more than 2 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.
Among the present invention's (second invention), optimization methane (CH 4) at the single component gas permeation rate and the normal butane (n-C of room temperature and 100 ℃ 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) in any one gas be respectively more than 2 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.
Among the present invention's (second invention), preferred normal butane (n-C 4H 10) at the single component gas permeation rate and the iso-butane (i-C of room temperature and 100 ℃ 4H 10) or sulfur hexafluoride (SF 6) in any one gas be respectively more than 1.1 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.
Among the present invention's (second invention), preferred iso-butane (i-C 4H 10) at the single component gas permeation rate and the sulfur hexafluoride (SF of room temperature and 100 ℃ 6) be respectively more than 1.1 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.
Among the present invention (second invention),, moles of hydrogen (H such as contain preferably room temperature and 100 ℃ 2) and methane (CH 4) mist in, H 2/ CH 4Separation (when making mist pass through DDR type zeolite membrane, H 2The gas permeation amount of room temperature and 100 ℃ respectively with CH 4Ratio in the gas permeation amount of room temperature and 100 ℃) be more than 2.
Among the present invention (second invention),, molar ethylene (C such as contain preferably room temperature and 100 ℃ 2H 4) and ethane (C 2H 6) mist in, C 2H 4/ C 2H 6Separation be more than 1.5.
Among the present invention (second invention), preferably room temperature and 100 ℃, O in the air 2/ N 2Separation be more than 1.5.
The present invention (second invention) provides gas separating method, this method to use above-mentioned DDR type zeolite membrane, from by being selected from carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), water (H 2O), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10), sulfur hexafluoride (SF 6), ethane (C 2H 6), ethene (C 2H 4), propane (C 3H 8), propylene (C 3H 6), separate at least a kind of gas componant in the mist that constitutes of at least 2 kinds of gas componants of carbon monoxide (CO) and nitric oxide (NO).
Among the present invention's (second invention), preferably from containing carbon dioxide (CO 2) and methane (CH 4) mist in separating carbon dioxide (CO optionally 2).
The present invention (second invention) provides gas fractionation unit, and this device uses above-mentioned DDR type zeolite membrane, and described DDR type zeolite membrane is used for from by being selected from carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), water (H 2O), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10), sulfur hexafluoride (SF 6), ethane (C 2H 6), ethene (C 2H 4), propane (C 3H 8), propylene (C 3H 6), separate at least a kind of gas componant in the mist that constitutes of at least 2 kinds of gas componants of carbon monoxide (CO) and nitric oxide (NO).
Among the present invention's (second invention), preferably used the gas fractionation unit of above-mentioned DDR type zeolite membrane, wherein said DDR type zeolite membrane is from containing carbon dioxide (CO 2) and methane (CH 4) mist in separating carbon dioxide optionally.
As mentioned above, the present invention's (second invention) DDR type zeolite membrane is because at least 2 kinds of gases single component gas permeation rate separately that is selected from the multiple specific gas is different mutually, therefore for example can separate specific gas composition more than a kind from natural gas etc. contains the mist of specific gas composition more than 2 kinds.In addition since on matrix film forming, so mechanical strength excellence.And owing to be DDR type zeolite membrane (inorganic substances), so excellent heat resistance, also can prevent the plasticizing that carbon dioxide causes, the deterioration that liquid hydrocarbon causes.
The gas separating method of (second invention) according to the present invention owing to use the present invention's's (second invention) DDR type zeolite membrane to carry out the separation of gas, therefore can separate at least a kind of specific gas composition at least 2 kinds of gases from be selected from multiple specific gas.Particularly can be from containing carbon dioxide (CO 2) and methane (CH 4) mist in separating carbon dioxide (CO optionally 2).Because the present invention's's (second invention) gas fractionation unit is to use the DDR type zeolite membrane of the present invention's (second invention),, therefore can separate at least a kind of specific gas composition at least 2 kinds of gases from be selected from multiple specific gas by this film divided gas flow.
The present invention's (the 3rd invention) also provides DDR type zeolite membrane compound, it is characterized in that possessing deposition DDR type zeolite layer in porous matrix and the matrix, deposition DDR type zeolite layer is arranged in the micropore of at least one side surface of above-mentioned porous matrix in the wherein said matrix, be made of DDR type zeolite, thickness is 5-50 times of average micropore diameter in the above-mentioned porous matrix.
In the present invention's's (the 3rd invention) the DDR type zeolite membrane compound, preferably also possesses matrix external sediment DDR type zeolite layer, wherein said matrix external sediment DDR type zeolite layer is positioned at the surface of the above-mentioned porous matrix of having arranged above-mentioned matrix deposition DDR type zeolite layer, be made of DDR type zeolite, its thickness is below the 30 μ m.
In the present invention's's (the 3rd invention) the DDR type zeolite membrane compound, the average micropore diameter of preferred above-mentioned porous matrix is 0.05-10 μ m.
On the other hand, the present invention's (the 3rd invention) provides the manufacture method of DDR type zeolite membrane compound, it is characterized in that: the mixed proportion (1-amantadine (mol)/silica (mol)) that forms 1-amantadine and silica is 0.03-0.4, and the mixed proportion of water and silica (water (mol)/silica (mol)) is the material solution that 20-500 constitutes like this; Porous matrix is dipped in the gained above-mentioned raw materials solution, it is synthetic to carry out hydro-thermal, in the micropore of at least one side surface of above-mentioned porous matrix, form by the 5-50 matrix doubly of the average micropore diameter that DDR type zeolite constitutes, thickness is above-mentioned porous matrix in deposition DDR type zeolite layer.
In the manufacture method of the present invention's (the 3rd invention) DDR type zeolite membrane compound, preferably in the layout of above-mentioned porous matrix in the above-mentioned matrix surface of deposition DDR type zeolite layer form by DDR type zeolite constitute, thickness is the matrix external sediment DDR type zeolite layer below the 30 μ m.
In the manufacture method of the present invention's (the 3rd invention) DDR type zeolite membrane compound, preferably use average micropore diameter as the porous matrix of 0.05-10 μ m as above-mentioned porous matrix.
In the manufacture method of the present invention's's (the 3rd invention) DDR type zeolite membrane compound, preferably under 130-200 ℃, carry out hydro-thermal and synthesize, to obtain above-mentioned DDR type zeolite membrane compound.
In the manufacture method of the present invention's's (the 3rd invention) DDR type zeolite membrane compound, can use the material solution that also contains as the DDR type zeolite powder of crystal seed as above-mentioned raw materials solution, also can make DDR type zeolite powder be attached to the surface of above-mentioned porous matrix, and it is dipped in the above-mentioned raw materials solution as crystal seed.
The present invention's's (the 3rd invention) DDR type zeolite membrane compound can provide when for example using as gas separation membrane, when having high mechanical properties, also can guarantee the DDR type zeolite membrane compound of enough transit doses.In addition, the manufacture method of the DDR type zeolite membrane compound of (the 3rd invention) can be made above-mentioned DDR type zeolite membrane compound easy and at low cost according to the present invention.
The accompanying drawing summary
Fig. 1 is the electron micrograph of the DDR type zeolite membrane section of preparation among the present invention's (first invention) the embodiment 13.Fig. 2 is the electron micrograph on the DDR type zeolite membrane surface of preparation among the present invention's (first invention) the embodiment 13.Fig. 3 for explanation the present invention's (first invention) gas permeation test 1., the ideograph of the structure of the gas permeation experimental rig that uses in 2..Fig. 4 sees through the bar graph of the transmitance of gas among expression the present invention (first invention) in the gas permeation test 1..Fig. 5 sees through the bar graph that sees through the transmitance of gas in the test for mist among expression the present invention (first invention).Fig. 6 is the profile of an embodiment of expression the present invention's (second invention) gas fractionation unit.Fig. 7 is among the present invention's (second invention), roughly represents the key diagram of the structure of the gas permeation experimental rig of use in the gas permeation test.Fig. 8 is the profile of the DDR type zeolite membrane compound in the embodiment roughly representing the present invention's (the 3rd invention).Fig. 9 is the electron micrograph of the section shape of the DDR type zeolite membrane compound of preparation among the embodiment 38 of expression the present invention (the 3rd invention).Figure 10 represents the electron micrograph of the surface configuration of the DDR type zeolite membrane compound of preparation among the present invention's (the 3rd invention) the embodiment 38.Figure 11 is for roughly representing among the present invention's (the 3rd invention) key diagram of the structure of the gas permeation experimental rig that uses in the gas permeation test.Figure 12 is the figure of the thermal expansion character of DDR type zeolite among expression the present invention (the 3rd invention) and alumina.
The preferred plan that carries out an invention
Below embodiment of the present invention are described, but the present invention is not limited to following embodiment, can be understood as in not breaking away from thought range of the present invention, according to those skilled in the art's general knowledge, the change that can suitably design, improvement etc.
The present invention's (first invention) relates to the manufacture method of DDR type zeolite membrane, it is characterized in that: the proportional (1-amantadine/SiO that contains that uses 1-amantadine and silica 2) be the proportional (water/SiO that contains of 0.03-0.4 mol ratio, water and silica 2) for the containing of 20-500 mol ratio and ethylenediamine and above-mentioned 1-amantadine proportional (ethylenediamine/1-amantadine) for the material solution of 5-32 mol ratio with as the DDR type zeolite powder of crystal seed, synthesize formation DDR type zeolite membrane by hydro-thermal.Below it is elaborated.Below be designated as " 1-amantadine/SiO containing of 1-amantadine and silica proportional (mol ratio) 2Than ", contain proportional (mol ratio) of water and silica be designated as " water/SiO 2Than ", contain proportional (mol ratio) of ethylenediamine and 1-amantadine be designated as " ethylenediamine/1-amantadine compares ".
Among the present invention's (first invention), use the 1-amantadine as the structure directing agent that forms DDR type zeolite membrane.At first use 1-amantadine and Ludox, water, ethylenediamine and other used as required additives to prepare material solution.For example the sodium aluminate that uses trace then can be replaced the Si that a part constitutes DDR type zeolite membrane with Al as additive.By such displacement, formed DDR type zeolite membrane can also be added catalytic action etc. except that separation function.When the preparation material solution, the present invention will strictly regulate 1-amantadine/SiO 2Ratio, water/SiO 2Ratio and ethylenediamine/1-amantadine ratio.
1-amantadine/SiO 2Ratio was less than 0.03 o'clock, and structure directing agent 1-amantadine deficiency is difficult to form DDR type zeolite membrane, thereby not preferred; And surpass at 0.4 o'clock, though can form DDR type zeolite membrane, because the 1-amantadine, therefore needs enough additions as structure directing agent, it is not preferred aspect manufacturing cost to add a large amount of expensive 1-amantadines.
From not only considering manufacturing cost but also forming the angle of DDR type zeolite membrane, preferred 1-amantadine/SiO 2Than being 0.05-0.25, further preferred 0.05-0.12.
Water/SiO 2Compare less than 20 o'clock SiO in the material solution 2Excessive concentration, be difficult to form fine and close DDR type zeolite membrane, thereby not preferred; And surpass at 500 o'clock, SiO in the material solution 2Concentration low excessively, can not form DDR type zeolite membrane, thereby not preferred.From forming the viewpoint of fine and close DDR type zeolite membrane, preferred water/SiO 2Than being 28-220, more preferably 28-120.
The 1-amantadine is solid chemical compound at normal temperatures, when the preparation material solution, may be difficult to make it to dissolve the formation homogeneous solution fully.When using the 1-amantadine to be the material solution of not complete dissolved state, may be difficult to make DDR type zeolite membrane with even grained size, thickness.Therefore prepare material solution by adding ethylenediamine, the 1-amantadine is dissolved easily, make the DDR type zeolite membrane of densification with even grained size, thickness
Ethylenediamine/1-amantadine is than less than 5 o'clock, and its quantity not sufficient surpasses at 32 o'clock so that the 1-amantadine is easy to dissolving, and reaction not have the ethylenediamine surplus of contribution, needs manufacturing cost greatly, thereby not preferred.From the easy viewpoint of dissolving the 1-amantadine and making the DDR type zeolite membrane with uniform grain size, thickness, preferred ethylenediamine/1-amantadine is than being 8-24, further preferred 10-16.
Among the present invention's (first invention),, the 1-amantadine prepares 1-amantadine solution in the ethylenediamine by being dissolved in advance.The 1-amantadine solution that use will prepare like this mixes and the material solution of preparation with the silicon sol solution that contains silica, can dissolve the 1-amantadine easier and safely, preparation has the DDR type zeolite membrane of the densification of uniform grain size, thickness, thereby preferred.Silicon sol solution can be by being dissolved in water with micro mist shape silica or preparing by the hydrolysis alkoxide, and also the silica concentration that can regulate in the Ludox commercially available product uses.
Among the present invention's (first invention), when making DDR type zeolite membrane, use DDR type zeolite powder, DDR type zeolite powder is dispersed in the material solution of making.This DDR type zeolite powder can be used as crystal seed, has the effect that promotes crystal growth.Therefore, can quicken the formation of DDR type zeolite membrane, form fine and close film easily.The method that DDR type zeolite powder is scattered in the material solution can adopt common stirring means, also can adopt methods such as ultrasonic wave processing, by making its even dispersion, can form the DDR type zeolite membrane of homogeneous film thickness more densely.
By having disperseed to pack proper container into for example in the pressure vessel etc. as the material solution of the DDR type zeolite powder of crystal seed with the appropriate carriers material that is used to form film, hydro-thermal is synthetic can make DDR type zeolite membrane.
Among the present invention's (first invention), the temperature conditions during the preferred water thermal synthesis is 130-200 ℃, further preferred 140-180 ℃, and preferred 150-160 ℃ especially.Carry out hydro-thermal under 130 ℃ when synthetic being lower than, be difficult to form DDR type zeolite membrane, thus not preferred; And under surpassing 200 ℃, carry out hydro-thermal when synthetic, and can form out-phase DOH phase, thus not preferred yet.
The synthetic processing time of hydro-thermal can be 1-10 days.Therefore the present invention (first invention) compares with the manufacture method of traditional DDR type zeolite, can make with the extremely short time have the DDR type zeolite membrane of enough thickness (40-125 μ m) as self-supported membrane.
Among the present invention's (first invention), when hydro-thermal is synthetic,, also can on this porous matrix, form DDR type zeolite membrane by using porous matrix as the carrier material that forms DDR type zeolite membrane.Porous matrix has the micropore that a lot of three-dimensionals communicate, and therefore has gas-premeable.The micropore diameter that is preferably formed the porous matrix of DDR type zeolite membrane one side is 0.003-10 μ m.Micropore diameter is when 0.003 μ m is following, and the resistance during gas permeation is excessive, and micropore diameter is easy to generate defective on the DDR zeolite membrane when surpassing 10 μ m.Among the present invention's (first invention), can preferably use with following substances is raw-material porous matrix: based on the pottery of alumina, zirconia or mullite etc., or glass, zeolite, clay, metal or carbon.Consider the porous matrix of preferred alumina material from the angle of micropore diameter and intensity.That the shape of porous matrix can have is tabular, tubular, honeycomb shape or the integrated global shape that forms of a plurality of tube-shaped tube etc. be as preference.Said " global shape " is meant and arranges a plurality of tube-shaped tubes and integrated forming among the present invention's (first invention), has the shape of a plurality of intercommunicating pores at axial direction.
Form DDR type zeolite membrane on the porous matrix, then mechanical strength is improved, so thickness can be than self-supported membrane attenuate more also.At this moment, the thickness of DDR type zeolite membrane can be 0.1-50 μ m, further preferred 1-25 μ m.
On the other hand, among the present invention's (first invention), DDR type zeolite powder is attached on the porous matrix, material solution is contacted with the porous matrix that has adhered to this DDR type zeolite powder, on porous matrix, form DDR type zeolite membrane, replace the DDR type zeolite powder that makes as crystal seed with this and be scattered in step in the material solution, also can form the DDR type zeolite membrane of densification with homogeneous film thickness, thus preferred.
Here, " DDR type zeolite powder is attached on the porous matrix " is to instigate as the surface that will form DDR type zeolite membrane on the DDR type zeolite powder of crystal seed and the porous matrix to contact and the state on it of distributing, and do not need to adhere to powerfully." material solution is contacted " with porous matrix be and instigate the surface that has distributed as the porous matrix of the DDR type zeolite powder of crystal seed to contact with material solution.Therefore, DDR type zeolite powder contacts with material solution essence.For DDR type zeolite powder is attached on the porous matrix, DDR type zeolite powder is scattered in the water, make the dispersion liquid of debita spissitudo, the dispersion liquid that this is an amount of is coated the surface that will form DDR type zeolite membrane on the porous matrix and is got final product.Coating process can select to drip method, infusion process, spin-coating method, print process etc. according to purpose.
Below, specify the present invention's (second invention) embodiment with reference to accompanying drawing.
The DDR type zeolite membrane of the present embodiment makes DDR type (Deca-Dodecasil 3R) zeolite form membranaceous (film forming) on matrix and obtains.DDR type zeolite is to be main component with silica, form a lot of micropores by the polyhedron that contains the octatomic ring that constitutes by oxygen atom, in the above-mentioned micropore, the micropore diameter of the above-mentioned formed part of octatomic ring that is made of oxygen atom is that the crystal of 4.4 * 3.6 dusts is (with reference to W.M.Meier, D.H.Olson, Ch.Baerlocher, Atlas of zeolite structure types, Elsevier (1996)).
Above-mentioned DDR type zeolite is formed membranaceous method be not particularly limited on matrix, preferred following method.
1-amantadine, silica and water mixed proportion is according to the rules mixed the preparation material solution.To disperse the liquid of DDR type zeolite powder to coat on the matrix then.The matrix that to adhere to this DDR type zeolite powder is dipped in the material solution, carries out hydro-thermal and synthesize under this state, obtains DDR type zeolite membrane thus.Can mix ethylenediamine in the material solution.As mentioned above, when forming DDR type zeolite membrane on matrix, owing to be film forming on matrix, therefore the mechanical strength excellence under high pressure also can be used.
The material of the matrix of using in the present embodiment is not particularly limited, ceramic porous matrix such as preferred alumina porous body.By adopting porous matrix, make that seeing through of gas is easy, the treatment effeciency of gas is improved.And then, by adopting ceramic porous matrix, make the mechanical strength excellence of on the matrix DDR type zeolite membrane of film forming.When separating specific gas, the preferred palladium metal matrix that sees through hydrogen, the perovskite type ceramic matrix of oxygen infiltration type etc. used have matrix through the characteristic of specific gas.
Here, porous matter is meant the material that for example has the fine aperture that a lot of three-dimensionals communicate, and preferably its aperture is 0.003-10 μ m, further preferred 0.005-5 μ m.During less than 0.003 μ m, it is big that the resistance when gas passes through becomes, and surpass 10 μ m and then be easy to generate pin hole in the DDR type zeolite membrane, thereby not preferred.
For above-mentioned DDR type zeolite membrane, be selected from room temperature and 100 ℃ and can form at least 2 kinds of gases in the gas of mist, its single component gas permeation rate separately room temperature and 100 ℃ is different mutually.Specifically, be selected from carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), water (H 2O), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10), sulfur hexafluoride (SF 6), ethane (C 2H 6), ethene (C 2H 4), propane (C 3H 8), propylene (C 3H 6), at least 2 kinds of gases of carbon monoxide (CO) and nitric oxide (NO) are different mutually between above-mentioned at least 2 kinds of gases with 100 ℃ single component gas permeation rate in room temperature respectively.
So-called gas permeation rate is meant under set point of temperature unit are (m 2), see through the molal quantity (mol) of the gas of film in unit pressure (Pa) and unit interval (s).Especially, the gas that uses a kind of single component is as test gas, and the gas permeation rate that obtains by the gas permeation test is called the single component gas permeation rate.
As mentioned above, the gas permeation rate of above-mentioned specific gas (carbon dioxide, hydrogen, oxygen, nitrogen, water vapour, methane, normal butane, iso-butane, sulfur hexafluoride, ethane, ethene, propane, propylene, carbon monoxide and nitric oxide) is different separately, therefore for example can separate the specific gas composition more than a kind from natural gas etc. contains the mist of specific gas composition more than 2 kinds.DDR type zeolite membrane excellent heat resistance, the difficult deterioration that resembles the plasticizing that causes because of carbon dioxide the film that constitutes by organic substance or cause because of liquid hydrocarbon.
The DDR type zeolite membrane of the present embodiment is to the above-mentioned specific gas gas permeation rate height of carbon dioxide particularly.Gas permeation rate under the preferred room temperature is 1.0 * 10 -9(molm -2S -1Pa -1) more than.Preferred 100 ℃ gas permeation rate is 5.0 * 10 -10(molm -2S -1Pa -1) more than.Thus can be easily with hydrogen, oxygen, nitrogen, methane, normal butane, iso-butane, sulfur hexafluoride, ethane, ethene, propane, propylene, carbon monoxide, nitric oxide and carbon dioxide separation.
In the DDR type zeolite membrane of the present embodiment,, mole of carbon dioxide (CO such as contain preferably room temperature and 100 ℃ 2) and methane (CH 4) mist in CO 2/ CH 4Separation be more than 2.Consider further preferred CO from practical standpoint 2/ CH 4Separation be more than 10, more preferably more than 20.Thus can be easily the mist of carbon dioxide and methane be separated into other gas of branch.
CO 2And CH 4Mist in CO 2/ CH 4Separation be meant under the temperature of regulation with mist when the DDR type zeolite membrane CO 2Gas permeation amount and CH 4The ratio of gas permeation amount divided by CO in the mist 2Dividing potential drop and CH 4The ratio of dividing potential drop and the value that obtains.When representing with formula then as the formula (1), here, in room temperature and 100 ℃ of values of obtaining formula (1).
(CO 2/ CH 4Separation)=(Q A/ Q B)/(P A/ P B) ... (1)
Q A: under the temperature of regulation, the CO when mist sees through film 2Gas permeation amount (molm -2S -1)
Q B: under the temperature of regulation, the CH when mist sees through film 4Gas permeation amount (molm -2S -1)
P A: under the temperature of regulation, see through CO in the film mist before 2Dividing potential drop (Pa)
P A: under the temperature of regulation, see through CH in the film mist before 4Dividing potential drop (Pa)
In the DDR type zeolite membrane of the present embodiment,, moles of hydrogen (H such as contain preferably room temperature and 100 ℃ 2) and methane (CH 4) mist in H 2/ CH 4Separation be more than 2.Thus can be easily by H 2And CH 4Mist be separated into other gas of branch.H 2/ CH 4Separation be meant under the temperature of regulation, to make to contain and wait a mole H 2And CH 4Mist when the DDR type zeolite membrane, H 2Gas permeation amount and CH 4Other ratio of the branch of gas permeation amount.
Preferably room temperature and 100 ℃, molar ethylene (C such as contain 2H 4) and ethane (C 2H 6) mist in C 2H 4/ C 2H 6Separation be more than 1.5.Thus can be easily by C 2H 4And C 2H 6Mist be separated into other gas of branch.C 2H 4/ C 2H 6Separation be meant under the temperature of regulation, to make to contain and wait a mole C 2H 4With ethane C 2H 6Mist when the DDR type zeolite membrane, C 2H 4Gas permeation amount and C 2H 6Other ratio of the branch of gas permeation amount.
Preferably room temperature and 100 ℃, O in the air 2/ N 2Separation be more than 1.5.Can easily from air, separate N thus 2And O 2O 2/ N 2Separation be meant under the temperature of regulation when making air pass through DDR type zeolite membrane O 2Gas permeation amount and N 2The ratio of gas permeation amount divided by the O that contains in the air 2Dividing potential drop and N 2The ratio (1/4) of dividing potential drop and the value that obtains.
In the DDR type zeolite membrane of the present embodiment, preferably carbon dioxide (CO 2) at the single component gas permeation rate and the hydrogen (H of room temperature and 100 ℃ 2), oxygen (O 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) in any gas be respectively more than 2 at the ratio of the single component gas permeation rate of room temperature and 100 ℃, more preferably more than 10.This ratio is less than 2 o'clock, CO 2Separative efficiency significantly reduce, do not have practicality.
The ratio of gas permeation rate is meant for example single component gas permeation rate (R of gas A A) with the single component gas permeation rate (R of gas B B) ratio, i.e. R A/ R BCalculated value.
In the DDR type zeolite membrane of the present embodiment, preferred hydrogen (H 2) at the single component gas permeation rate and the oxygen (O of room temperature and 100 ℃ 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) in any gas be respectively more than 2 at the ratio of the single component gas permeation rate of room temperature and 100 ℃, this ratio is less than 2 o'clock, H 2Be difficult to separate.
In the DDR type zeolite membrane of the present embodiment, preferred oxygen (O 2) at the single component gas permeation rate and the nitrogen (N of room temperature and 100 ℃ 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) in any gas be respectively more than 1.1 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.Also preferred nitrogen any gas in the single component gas permeation rate of room temperature and 100 ℃ and methane, normal butane, iso-butane and sulfur hexafluoride is respectively more than 2 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.Further optimization methane any gas in the single component gas permeation rate of room temperature and 100 ℃ and normal butane, iso-butane and sulfur hexafluoride is respectively more than 2 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.Further preferred normal butane any gas in the single component gas permeation rate of room temperature and 100 ℃ and iso-butane and sulfur hexafluoride is respectively more than 1.1 at the ratio of the single component gas permeation rate of room temperature and 100 ℃.Preferred iso-butane is respectively more than 1.1 at the single component gas permeation rate of room temperature and 100 ℃ and the sulfur hexafluoride ratio at the single component gas permeation rate of room temperature and 100 ℃.
Because carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10) and sulfur hexafluoride (SF 6) have above-mentioned relation respectively at the single component gas permeation rate of room temperature and 100 ℃, therefore can use the DDR type zeolite membrane of the present embodiment to separate this 8 kinds of gases effectively.
The embodiment of the present invention's (second invention) gas separating method is to use the DDR type zeolite membrane of above-mentioned embodiment, from by being selected from the gas separating method that can form separating at least one gas componant in the mist that at least 2 kinds of gas componants the gas of mist constitute room temperature and 100 ℃.Above-mentioned mixed gas composition is by being selected from carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10), sulfur hexafluoride (SF 6), ethane (C 2H 6), ethene (C 2H 4), propane (C 3H 8), propylene (C 3H 6), at least 2 kinds of gas componants of carbon monoxide (CO) and nitric oxide (NO) constitute, and separate the gas separating method of at least a kind of gas componant from this mist.
In the DDR type zeolite membrane of above-mentioned embodiment, be selected from carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10), sulfur hexafluoride (SF 6), ethane (C 2H 6), ethene (C 2H 4), propane (C 3H 8) and propylene (C 3H 6) each comfortable room temperature of at least 2 kinds of gases and 100 ℃ single component gas permeation rate different mutually between above-mentioned at least 2 kinds of gases, therefore by using this DDR type zeolite membrane can separate above-mentioned gas effectively.
The gas separating method of the present embodiment is particularly suitable for from containing carbon dioxide (CO 2) and methane (CH 4) mist in separating carbon dioxide optionally.
Fig. 6 is the profile of an embodiment of expression the present invention's (second invention) gas fractionation unit.In gas fractionation unit shown in Figure 6 240, lid shape metal parts 201 is made of annular seal gland 202 and lower cover shape stopper 203, and annular metal parts 204 are made of annular seal gland 205 and top ring-type stopper 206.Annular metal parts 204 (top ring-type stopper) engage with the flange 208 with through hole 207 by joint methods such as welding.Lid 245 is fixed on the pressure vessel 244 by fixed part 246 via flange 208.
Between lid shape metal parts 201 and the annular metal parts 204 the gas separation member 210 that has formed DDR type zeolite membrane 230 on the porous matrix 231 of tubular is housed.Be furnished with gland packing element 211,212 as seal member on lid shape metal parts 201 and the annular metal parts 204, so that its outer peripheral face of separated from the gas 210 connects.At this moment, also can arrange to possess the stuffing box 213 that can hold at least each gland packing element 211,212, hold gland packing element 211,212 with portion within it.But the outer peripheral face that gland packing element 211,212 must separated from the gas 210 directly connects.
Annular seal gland 202,205 can apply fastening pressure to gland packing element 211,212 axial directions along tubular porous matrix 231, and lower cover ring-type stopper 203 and top ring-type stopper 206 suppresses mobile along the axial direction of this gland packing element 211,212 because of gland packing element 211,212 being applied fastening pressure produces.At this moment, it moves repressed gland packing element 211,212 and in fact produces some distortion, make its internal direction radially with separated from the gas 210 of suitable pressure, promptly vertical direction tight adhesion with the face of DDR type zeolite membrane 230, thus guarantee air-tightness between gas separation member 210 and lid shape metal parts 201 and the annular metal parts 204.Stuffing box 213 can be communicated to gas separation member 210 effectively with being applied to its fastening pressure that is contained in its inner gland packing element 211,212.
For gland packing element 211,212 being applied and keeps fastening pressure, can be at position that annular seal gland 202 is connected with lower cover shape stopper 203 and the position that is connected with top ring-type stopper 206 of annular seal gland 205 form thread groove 220.Also can form chamfering 221, so that use spanner etc. to screw at the peripheral part of annular seal gland 202,205 and lower cover shape stopper 203, top ring-type stopper 206.
The porous matrix 231 that uses in the gas fractionation unit of the present embodiment can make mechanical strength improve by supporting DDR type zeolite membrane.Here said porous matter is meant to have the fine aperture that for example a lot of three-dimensionals communicate.Preferred its aperture is 0.003-10 μ m, further preferred 0.005-5 μ m.During less than 0.003 μ m, it is big that the resistance when gas passes through becomes; Surpass 10 μ m, then be easy to generate pin hole on the DDR type zeolite membrane, thus not preferred.As porous matrix, be preferably pottery, preferred especially alumina material.
Hermetically-sealed construction between the outer peripheral face of lid shape metal parts 201, annular metal parts 204 and gas separation member 210 is gland packing element not necessarily, can also be sealings such as rubber system O circle, bonding glass, wax are bonding, organic adhesive.
When using the gas fractionation unit separating mixed gas of the present embodiment, at first the ostium 242 that forms from pressure vessel 244 imports mist.The mist that imports sees through the DDR type zeolite membrane of gas separation member 210, enters gas separation member 210 inside.The gas that sees through DDR type zeolite membrane by gas separation member 210 is that special component is concentrated the gas of (separation), by the through hole 207 that forms on the flange 208, is discharged by the tap hole 241 that forms on the lid 245.Directly do not become the gas that other compositions are concentrated (separation) relatively by the gas that the tap hole 243 that forms on the pressure vessel 244 is discharged and see through DDR type zeolite membrane, the gas componant that is concentrated (separation) when wherein seeing through DDR type zeolite membrane reduces.
The gas fractionation unit of the present embodiment can be from by being selected from carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10), sulfur hexafluoride (SF 6), ethane (C 2H 6), ethene (C 2H 4), propane (C 3H 8), propylene (C 3H 6), separating at least one gas componant in the mist that constitutes of at least 2 kinds of gas componants of carbon monoxide (CO) and nitric oxide (NO).
Because the gas fractionation unit of the present embodiment is to use the gas fractionation unit of the DDR type zeolite membrane of above-mentioned embodiment, described DDR type zeolite membrane is for being selected from carbon dioxide (CO 2), hydrogen (H 2), oxygen (O 2), nitrogen (N 2), methane (CH 4), normal butane (n-C 4H 10), iso-butane (i-C 4H 10), sulfur hexafluoride (SF 6), ethane (C 2H 6), ethene (C 2H 4), propane (C 3H 8), propylene (C 3H 6), the single component gas permeation rate of each comfortable room temperature of at least 2 kinds of gases of carbon monoxide (CO) and nitric oxide (NO) and 100 ℃ is different mutually between above-mentioned at least 2 kinds of gases, therefore can separate these gas effectively.
The gas fractionation unit of the present embodiment is particularly suitable for from containing carbon dioxide (CO 2) and methane (CH 4) mist in separating carbon dioxide optionally.
Below, specifically describe the present invention's (the 3rd invention) embodiment with reference to accompanying drawing.
An embodiment to the present invention's (the 3rd invention) DDR type zeolite membrane compound describes.As shown in Figure 8, the DDR type zeolite membrane compound 301 of the present embodiment DDR type zeolite membrane 306 that has porous matrix 302 and constitute by DDR type zeolite.This DDR type zeolite membrane 306 is made of deposition DDR type zeolite layer 305 and matrix external sediment DDR type zeolite layer 304 in the matrix.Deposition DDR type zeolite layer 305 is arranged in the micropore 303 of a side surface of porous matrix 302 in the matrix, thickness be porous matrix average micropore diameter 5-50 doubly.And matrix external sediment DDR type zeolite layer 304 is arranged in the surface of having arranged deposition DDR type zeolite layer 305 in the matrix in the porous matrix 302, and thickness is below the 30 μ m.
In the present embodiment, for example the average micropore diameter of porous matrix 302 is 0.6 μ m, and then the thickness of deposition DDR type zeolite layer 305 is 10 times of average micropore diameter of porous matrix 302, i.e. 6 μ m in the matrix.The thickness of matrix external sediment DDR type zeolite layer 304 is 7 μ m.
By above-mentioned formation, the DDR type zeolite membrane compound 301 that for example uses this programme can have high mechanical strength during as gas separation membrane, can prevent that the defectives such as be full of cracks that cause because of thermal stress from producing simultaneously, and can guarantee enough transit doses.
The porous matrix 302 that uses in the present embodiment can preferably adopt the porous matrix that is formed by following substances: based on the pottery of alumina, zirconia, mullite etc., or glass, zeolite, clay, metal or carbon.Average micropore diameter to porous matrix 302 is not particularly limited, and can preferably use the porous matrix of 0.05-10 μ m.About porous matrix 302, form the porous matrix 302a in the zone of deposition DDR type zeolite layer 305 in the matrix and the porous matrix 302b in zone in addition and can be the same or different.In the porous matrix, the average micropore diameter that forms DDR type zeolite layer one side is preferably 0.05-10 μ m, and the average micropore diameter that does not form the part of DDR type zeolite layer also can be bigger than this value.
The crystallization of the main component of the DDR type zeolite that uses in the present embodiment for being made of silica, its micropore is made of the polyhedron that contains the aerobic octatomic ring.
Formation method to the matrix external sediment DDR type zeolite layer 304 of the present embodiment is not particularly limited, and for example porous matrix 302 can be contained to be dipped in to form in the used material solution of DDR type zeolite, forms by hydro-thermal is synthetic.When porous matrix 302 is dipped in this material solution,, therefore can form deposition DDR type zeolite layer 305 in the matrix because material solution infiltrates in the micropore 303 of porous matrix 302.At this moment, by using the material solution that in forming the scope that DDR type zeolite makes used material solution, has higher concentration, can promote the formation of deposition DDR type zeolite layer 305 in the micropore 303 of porous matrix 302 in the matrix.
In the present embodiment, the thickness that makes deposition DDR type zeolite layer 305 in the matrix be porous matrix 302 average micropore diameter 5-50 doubly, further preferred 5-10 thickness doubly.When the thickness of deposition DDR type zeolite layer 305 was less than 5 times of average micropore diameter in the matrix, in the steps such as heat treatment of DDR type zeolite membrane 306, the defectives such as be full of cracks that can suppress to produce because of thermal stress took place.When the thickness of deposition DDR type zeolite layer 305 surpassed 50 times of average micropore diameter in the matrix, the pressure loss was excessive, when therefore for example using this DDR type zeolite membrane compound 301 as gas separation membrane, can not guarantee enough transit doses.Deposition DDR type zeolite need cost a lot of money the time in the micropore 303 of porous matrix 302 in addition.
In the present embodiment, make the thickness of the matrix external sediment DDR type zeolite layer 304 that is arranged in porous matrix 302 surfaces is below the 30 μ m, further below the preferred 10 μ m.When depositing DDR type zeolite layer 305 in the matrix that has adequate thickness in the DDR type zeolite membrane compound 301, then be not that matrix external sediment DDR type zeolite layer 304 must be arranged.When the thickness of matrix external sediment DDR type zeolite layer 304 surpassed 30 μ m, in the steps such as heat treatment of DDR type zeolite membrane 306, the defectives such as be full of cracks that produce because of thermal stress can increase.
Thickness for porous matrix 302 is not particularly limited.
The thickness of deposition DDR type zeolite layer 305 can be realized required thickness by composition, synthesis temperature and the generated time of control material solution in the thickness of above-mentioned matrix external sediment DDR type zeolite layer 304 and the matrix.
The DDR type zeolite membrane compound 301 of Gou Chenging can be used as gas separation membrane and effectively utilizes like this, for example to carbon dioxide (CO 2) and methane (CH 4) have a high stalling characteristic.
An embodiment to the manufacture method of the present invention's (the 3rd invention) DDR type zeolite membrane compound describes below.The feature of the manufacture method of the DDR type zeolite membrane compound of the present embodiment is: form material solution, make wherein 1-amantadine and silica (SiO 2) mixed proportion (1-amantadine (mol)/silica (mol)) be 0.03-0.4, and the mixed proportion of water and silica (water (mol)/silica (mol)) is 20-500; Porous matrix is contained be dipped in the material solution of gained, it is synthetic to carry out hydro-thermal, in the micropore of at least one side surface of porous matrix, form by the 5-50 matrix doubly of the average micropore diameter that DDR type zeolite constitutes, thickness is porous matrix in deposition DDR type zeolite layer.
In the present embodiment, preferably form on the porous matrix surface that has formed deposition DDR type zeolite layer in the matrix by DDR type zeolite constitute, its thickness is the matrix external sediment DDR type zeolite layer below the 30 μ m.
By said structure, can be easy and at low cost Production Example have high strength as gas separation membrane the time, can prevent that the defectives such as be full of cracks that cause because of thermal stress from taking place simultaneously, and can guarantee the DDR type zeolite membrane compound of enough transit doses.
Above-mentioned 1-amantadine can play structure directing agent, and described structure directing agent is used to form the DDR type zeolite membrane that is made of the outer DDR type zeolite layer of deposition DDR type zeolite layer and matrix in the matrix.Can also add additive in addition in the material solution that uses in the present embodiment.
Porous matrix used in the present embodiment can preferably use the porous matrix that is formed by following substances: based on the pottery of alumina, zirconia, mullite etc., or glass, zeolite, clay, metal and carbon.
In the present embodiment, make 1-amantadine and silica (SiO 2) mixed proportion (1-amantadine (mol)/silica (mol)) be 0.03-0.4, and the mixed proportion of water and silica (water (mol)/silica (mol)) constitutes like this for 20-500.The mixed proportion of 1-amantadine and silica was less than 0.03 o'clock, and structure directing agent 1-amantadine deficiency is difficult to form DDR type zeolite membrane, thereby not preferred.And the mixed proportion of 1-amantadine and silica was above 0.4 o'clock, though can form DDR type zeolite membrane,, need enough additions because the 1-amantadine plays structure directing agent, and a large amount of 1-amantadines that add costliness are not preferred aspect manufacturing cost.
From considering the viewpoint of manufacturing cost and formation DDR type zeolite membrane, preferred 1-amantadine and silica (SiO 2) mixed proportion be 0.03-0.25, further preferred 0.05-0.125.
The mixed proportion of water and silica was less than 20 o'clock, and then concentration of silicon dioxide is too high in the material solution, be difficult to form fine and close DDR type zeolite membrane, thereby not preferred; And the mixed proportion of water and silica surpasses at 500 o'clock, and then concentration of silicon dioxide is low excessively in the material solution, is difficult to form DDR type zeolite membrane, thereby not preferred.From forming the angle of fine and close DDR type zeolite membrane, the mixed proportion of preferred water and silica is 20-224, further preferred 28-112.
In the common material solution scope used when forming DDR type zeolite, the mixed proportion of above-mentioned raw materials solution be mixed with high concentration.By using the material solution of such high concentration, can promote in the micropore of porous matrix, to form deposition DDR type zeolite layer in the matrix.
The material solution of the present embodiment preferably uses in the material solution of above-mentioned formation and adds ethylenediamine, the solution that the mixed proportion (ethylenediamine (mol)/1-amantadine (mol)) of ethylenediamine and 1-amantadine is made for 8-32.Prepare material solution by adding ethylenediamine, can easily dissolve the 1-amantadine, formation has the DDR type zeolite membrane of even grained size, thickness.
In the present embodiment, the 5-50 of the average micropore diameter that the interior thickness that deposits DDR type zeolite layer of formed matrix is porous matrix doubly further is preferably formed 5-10 thickness doubly.When the thickness of deposition DDR type zeolite layer was less than 5 times of average micropore diameter in the matrix, in the steps such as heat treatment of DDR type zeolite membrane, the defectives such as be full of cracks that can't suppress to produce because of thermal stress took place.And when the thickness of deposition DDR type zeolite layer surpassed 50 times of average micropore diameter in the matrix, the pressure loss was excessive, for example the DDR type zeolite membrane compound that obtains during as gas separation membrane, can't be guaranteed enough transit doses.And deposition DDR type zeolite need cost a lot of money the time in the micropore of porous matrix.
In the present embodiment, make the thickness of the matrix external sediment DDR type zeolite layer that is arranged in the porous matrix surface is below the 30 μ m, further below the preferred 10 μ m.When depositing DDR type zeolite layer in the matrix that has adequate thickness in the DDR type zeolite membrane compound, then be not necessarily to need matrix external sediment DDR type zeolite layer.When the thickness of matrix external sediment DDR type zeolite layer surpassed 30 μ m, in the steps such as heat treatment of DDR type zeolite membrane, the defectives such as be full of cracks that produce because of thermal stress can increase.
Thickness to porous matrix used in the present embodiment is not particularly limited.
Usually, the hydro-thermal synthesis temperature when forming DDR type zeolite is 130-200 ℃, in the present embodiment, preferably carries out hydro-thermal and synthesize under 140-180 ℃, so that form deposition DDR type zeolite layer in the matrix easily in the micropore of porous matrix.Hydro-thermal synthesis temperature just by the composition and the generated time of control material solution, also can carry out the control of the thickness of deposition DDR type zeolite layer in the thickness of matrix external sediment DDR type zeolite layer and the matrix.
In the present embodiment, material solution can also use the solution that contains as the DDR type zeolite powder of crystal seed.The formation of the auxiliary DDR type zeolite membrane of this DDR type zeolite powder.The method that the above-mentioned DDR of making type zeolite powder is scattered in material solution can adopt common stirring means, also can adopt methods such as ultrasonic wave processing, disperses equably by making it, can form the DDR type zeolite membrane of finer and close and homogeneous film thickness.
In the present embodiment, make DDR type zeolite powder as crystal seed be attached to the surface of porous matrix and immerse in the material solution, replace the DDR type zeolite powder that makes as crystal seed with this and be scattered in step in the material solution.By such formation, can have the DDR type zeolite membrane of even and enough thickness with short time formation.
Here " DDR type zeolite powder is attached on the porous matrix " is the DDR type zeolite powder and the state that the surface of the porous matrix that will form DDR type zeolite membrane contacts and distributes of instigating as crystal seed, do not need to adhere to powerfully.For DDR type zeolite powder is attached on the porous matrix, DDR type zeolite powder is scattered in the water, make the dispersion liquid of debita spissitudo, the surface that the dispersion liquid that this is an amount of is coated the porous matrix that will form DDR type zeolite membrane gets final product.Coating process can select to drip method, infusion process, spin-coating method, print process etc. according to purpose.
Embodiment
Below, specify the present invention's (first invention) by embodiment, but the present invention's (first invention) is not limited to these embodiment.
(manufacturing of DDR type zeolite powder (crystal seed))
According to M.J.den Exter, J.C.Jansen, H.van Bekkum, Studies inSurface Science and Catalysis 84 volumes, editors such as J.Weitkamp., the method of the manufacturing DDR type zeolite of putting down in writing among Elsevier (1994) 1159-1166, the DDR type zeolite powder of the about 100 μ m of manufacturing particle diameter.Being crushed into the following micro mist of 5 μ m uses as crystal seed.
(embodiment 1)
In the 100ml wide-mouth bottle that 1.80g ethylenediamine (with the pure pharmaceutical worker of light industry (the strain)) fluororesin of packing into is made, adding 0.57g 1-amantadine (sheet mountain chemical industry (strain)) then and being dissolved to does not have the precipitation of 1-amantadine residual.Adding 73.45g water in another beaker, adding 3.0g 30% quality Ludox (Snowtex S produces chemistry (strain) daily) stirs gently, and material solution is made in also powerful vibration mixing in the wide-mouth bottle with its adding ethylenediamine and the mixing of 1-amantadine then.At this moment, 1-amantadine/SiO 2Ratio be 0.25, water/SiO 2Ratio be 280, the ratio of ethylenediamine/1-amantadine is 8.
The wide-mouth bottle of material solution of will having packed into places on the shaking machine, vibrates with 500rpm again and mixes 1 hour.Add DDR type zeolite powder that 0.1mg obtains by the manufacture method of above-mentioned DDR type zeolite powder then as crystal seed, keep 65 ℃, the ultrasonic wave that carried out 5 minutes is handled and is made its dispersion.Then, the material solution that has disperseed DDR type zeolite powder is moved into in the stainless steel pressure vessel of 100ml internal volume fluororesin system inner core, will be as the diameter 35mm of film forming with brace table
Figure C20061000595800291
The fluororesin rounding dish of * thickness 10mm sinks to container bottom, carries out heat treated 5 days at 160 ℃ (hydro-thermal is synthetic).After the heat treated, take out the disk of fluororesin system, as seen formed self-supported membrane on this disk.This film is peeled off from disk, and washing, after the drying is warming up to 800 ℃ with electric furnace with the speed of 0.1 ℃/min in atmosphere, kept 4 hours, and the speed with 1 ℃/min is cooled to room temperature then.
Then, with the crystalline phase of X-ray diffraction studies gained film, crystalline phase is estimated, the result only detects the diffraction maximum of DDR type zeolite.It is observed with electron microscope, confirm that this film is that thickness is 75 μ m, the film that is made of polycrystalline, and confirm that this film is the self-supported membrane of DDR type zeolite.
" diffraction maximum of DDR type zeolite " in the X-ray diffraction is meant the diffraction maximum of being put down in writing among pairing No.38-651 of Deca-Dodecasil 3R shown in the joint committee (ICDD) " Powder Diffraction File " or the 41-571.In X-ray diffraction, about the crystalline phase of zeolite, have only wide haloing (halo) in 20-30 ° of (CuK α) zone, in the time of can not confirming clear and definite peak, can be judged as amorphous; In the time of can confirming as the peak of DDR type zeolite slightly, can be judged as crystallization midway; Clearly confirm as the peak of expression DDR type zeolite, when not having haloing, can be judged as complete crystallization.
(embodiment 2-12, comparative example 1-3)
Except that the ratio of components that changes material solution, heat-treat condition, carry out operation similarly to Example 1, attempt forming DDR type zeolite membrane.Similarly to Example 1, the film that obtains is estimated, carried out the mensuration of thickness by the observation of electron microscope by X-ray diffraction.The ratio of components of material solution (1-amantadine/SiO 2Ratio, water/SiO 2Ratio and ethylenediamine/1-amantadine ratio), the thickness of heat-treat condition (temperature, time) and formed DDR type zeolite membrane is as shown in table 1.
(comparative example 4)
Except that the DDR type zeolite powder that does not use as crystal seed, carry out operation similarly to Example 1, attempt forming DDR type zeolite membrane.As a result, though generated DDR type zeolite powder, do not form DDR type zeolite membrane (table 1).In the table 1, will use the situation of crystal seed (DDR type zeolite powder) to be labeled as " having ", the situation of not using crystal seed be labeled as " nothing ".
Figure C20061000595800311
(embodiment 13)
Except that using 1.50g ethylenediamine, 0.47g 1-amantadine, 2.50g 30% quality Ludox, 48.70g water, carry out operation similarly to Example 1, make material solution.At this moment, 1-amantadine/SiO 2Than being 0.25, water/SiO 2Than being 220, ethylenediamine/1-amantadine ratio is 8.
With average micropore diameter is that the alumina porous body (Japanese insulator (strain)) of 0.6 μ m is processed into diameter 15mm
Figure C20061000595800321
The discoid porous matrix of * thickness 1.5mm is as porous matrix.The DDR type zeolite powder that obtains with the manufacture method by above-mentioned DDR type zeolite powder adds it in entry as crystal seed, makes the dispersion liquid that concentration is 1mg/ml, one is dripped a side of coating porous matrix.This porous matrix is vertically stood in the stainless steel pressure vessel with 100ml internal volume fluororesin system inner core, be the state that is immersed in the material solution.This pressure vessel internal temperature of packing into is adjusted in 150 ℃, the drier of band oscillation device, with the state of per minute vibration 90 times with pressure vessel heat treated (hydro-thermal is synthetic) 5 days.Take out porous matrix after the heat treated, as seen form film on this porous matrix.With the washing of this porous matrix, drying, in atmosphere, be warming up to 800 ℃ with the speed of 0.1 ℃/min then with electric furnace, kept 4 hours, the speed with 1 ℃/min is cooled to room temperature then.
Then, with the crystalline phase of the film on the X-ray diffraction studies gained porous matrix, thus crystalline phase is estimated, the result detects the diffraction maximum of DDR type zeolite and porous matrix, confirms as DDR type zeolite membrane.It is observed with electron microscope, confirm that forming thickness on porous matrix is the film of the densification of 10 μ m, thereby confirm on porous matrix, to form DDR type zeolite membrane.Fig. 1, the 2nd, the electron micrograph of the crystalline texture of the DDR type zeolite membrane of making among the expression embodiment 13, Fig. 1 represents the section of film, Fig. 2 represents the crystalline texture on film surface.
(embodiment 14-26)
Except that the ratio of components that changes material solution, heat-treat condition, carry out operation similarly to Example 13, attempt on porous matrix, forming DDR type zeolite membrane.Identical with embodiment 13, by X-ray diffraction the film that forms is estimated, carry out the mensuration of thickness by the observation of electron microscope.The ratio of components of material solution (1-amantadine/SiO 2Ratio, water/SiO 2Ratio and ethylenediamine/1-amantadine ratio), the thickness of heat-treat condition (temperature, time) and formed DDR type zeolite membrane is shown in the table 2.
Figure C20061000595800341
(embodiment 27)
Except that not carrying out carrying out operation similarly to Example 13 the vibration of pressure vessel, attempt on porous matrix, forming DDR type zeolite membrane.The result shows the DDR type zeolite membrane that has formed thickness 5 μ m on porous matrix.
(embodiment 28)
The dispersion liquid that will not contain DDR type zeolite powder is coated a side of porous matrix, by operation similarly to Example 1, crystal seed is scattered in the material solution uses, in addition, carry out operation similarly to Example 13, attempt on porous matrix, forming DDR type zeolite membrane.The result shows the DDR type zeolite membrane that has formed thickness 8 μ m on porous matrix.
(embodiment 29-36)
Mix each raw material, the preparation material solution makes it have ratio of components as shown in table 3 (1-amantadine/SiO 2Ratio, water/SiO 2Ratio, ethylenediamine/1-amantadine ratio).As porous matrix, having prepared average micropore diameter is that the alumina porous body (Japanese insulator (strain)) of 0.6 μ m is processed into cylindric (external diameter 17mm
Figure C20061000595800351
Internal diameter 12mm
Figure C20061000595800352
* length 40mm) porous matrix.The DDR type zeolite powder that obtains with the manufacture method by above-mentioned DDR type zeolite powder is as crystal seed, it is added in the entry, and preparation concentration is the dispersion liquid of 1mg/ml, and porous matrix be impregnated in this dispersion liquid, 80 ℃ of dryings, make DDR type zeolite powder be attached to the surface of porous matrix then.
This porous matrix is vertically stood in the stainless steel pressure vessel with 100ml internal volume fluororesin system inner core, be the state that is dipped in the material solution, carry out vacuum outgas and handle, material solution is infiltrated in the micropore of porous matrix.It is synthetic to carry out hydro-thermal then under the heat-treat condition shown in the table 3, forms DDR type zeolite membrane on porous matrix.Similarly to Example 13, the film that forms is estimated, carried out the mensuration of thickness by the observation of electron microscope by X-ray diffraction.The thickness of the ratio of components of material solution, heat-treat condition (temperature, time) and formed DDR type zeolite membrane is as shown in table 3.
Figure C20061000595800361
(1. gas permeation is tested)
Use the DDR type zeolite membrane of preparation among the embodiment 1 to carry out the gas permeation test.Fig. 3 is the tactic pattern figure of the gas permeation experimental rig of use in the explanation gas permeation test, at detector tube 101 (the internal diameter 15mm of zirconia system ) the top DDR type zeolite membrane 102 of having carried out shape processing is installed, with furnace core tube 104 (the internal diameter 25mm of its tube furnace 103 of packing into
Figure C20061000595800372
), with internal diameter 6mm
Figure C20061000595800373
Quartz ampoule 105 lead to the inboard of detector tube 101, one near DDR type zeolite membrane 102, presents the state of triple tube structure.The outside (inboard of furnace core tube 104) at detector tube 101, at room temperature use nitrogen (50ml/min) bubbling, feed dimethylbenzene adjacent, that moles such as, each isomers are mixed as test gas, make nitrogen (purge gas, 50ml/min) flow through the quartz ampoule 105 of detector tube 101 inboards, this nitrogen is used to reclaim the gas through DDR type zeolite membrane 102.Under this state, tube furnace 103 is warming up to test temperature (100 ℃), places more than 1 hour, be stable state.The recovery gas that contains through the gas of DDR type zeolite membrane 102 is separated, analyze, estimate the transmitance (nmolm of dimethylbenzene gas with gas-chromatography -2S -1Pa -1).
Except that dimethylbenzene, use methane (CH 4) and carbon dioxide (CO 2) see through test.These test gases are gas at normal temperatures, and the gas that therefore can directly feed furnace core tube 104 feeds mouth 113.Experimental result such as table 4, shown in Figure 4.
Table 4
Test gas Transmitance (nmolm -2·s -1·Pa -1)
Dimethylbenzene 2
CH 4 10
CO 2 226
(mist sees through test)
Use gas permeation experimental rig 110 shown in Figure 3, according to above-mentioned " 1. gas permeation is tested " same operation, among the embodiment 1 preparation DDR type zeolite membrane carry out methane (CH 4), ethyl mercaptan (C 2H 5SH), dimethyl sulfide ((CH 3) 2S), tert-butyl mercaptan ((CH 3) 3CSH) seeing through of the mist of four kinds of gases (main component is that methane, other compositions are the mist of 1000ppm) tested.Test temperature is 200 ℃.Result of the test such as table 5, shown in Figure 5.
Table 5
Figure C20061000595800381
(2. gas permeation is tested)
Use gas permeation experimental rig shown in Figure 3, according to above-mentioned " 1. gas permeation is tested " same operation, the DDR type zeolite membrane of preparation among the embodiment 29 is carried out gas permeation test.Detector tube 101 (external diameter 17mm in alumina system
Figure C20061000595800382
, internal diameter 13mm
Figure C20061000595800383
) the top DDR type zeolite membrane 102 of the drum that one side opening end clogs with the vanadine plate is installed.Furnace core tube 104 (internal diameter 25mm with its tube furnace 103 of packing into
Figure C20061000595800384
), in the inboard of detector tube 101, with external diameter 6mm
Figure C20061000595800385
, internal diameter 4mm
Figure C20061000595800386
Quartz ampoule 105 1 through to the inside of DDR type zeolite membrane 102, present the structure of triple tube.The test gas (100ml/min) of moles such as methane and carbon dioxide mixing is imported to the outside (inboard of furnace core tube 104) of detector tube 101 from gas introduction port 113, make helium (purge gas, 200ml/min) flow through the quartz ampoule 105 of detector tube 101 inboards, this helium is used to reclaim the gas through DDR type zeolite membrane 102.Under this state, tube furnace 103 is warming up to test temperature (100 ℃), places more than 1 hour, be stable state.The recovery gas that contains through the gas of DDR type zeolite membrane 102 is separated, analyze, estimate the transmitance (nmolm of methane and carbon dioxide with gas-chromatography -2S -1Pa -1), obtain separation (carbon dioxide/methane) simultaneously.The separation of carbon dioxide/methane is 90 as a result.
(discussion)
By the result shown in the table 1-3 as can be known: be adjusted into forming of material solution: 1-amantadine/SiO 2Than in the 0.03-0.4 scope, ethylenediamine/1-amantadine then can be made the DDR type zeolite membrane that has as the adequate thickness of self-supported membrane than in the scope of 5-32.If water/SiO 2Than in the 20-500 scope, then can make DDR type zeolite membrane.Also as can be known: on porous matrix, can form DDR type zeolite membrane.
Heat-treat condition when synthesizing about hydro-thermal is 130-200 ℃ in temperature, and the time is in the 10 days time with interior such weak point, can make the DDR type zeolite membrane with enough thickness.
By the result shown in the table 3 as can be known:, on this surface, also can form DDR type zeolite membrane even the shape of porous matrix is made cylindric.And as can be known: this DDR type zeolite membrane shows excellent separating power (separation of carbon dioxide/methane=90) to carbon dioxide/methane blended gas.
By table 4 and result shown in Figure 4 as can be known: dimethylbenzene almost sees through DDR type zeolite membrane, but carbon dioxide and methane can see through, carbon dioxide show about 20 times to the transmitance of methane.This can think relevant with the molecular diameter of the micropore diameter of DDR type zeolite membrane and test gas.
By table 5 and result shown in Figure 5 as can be known: in the gas that constitutes mist, compare with methane, ethyl mercaptan that molecular diameter is less, the dimethyl sulfide that molecular diameter is bigger, the transmitance of tert-butyl mercaptan are little.The DDR type zeolite membrane that is gained is separated the ability excellence of dimethyl sulfide or tert-butyl mercaptan and methane, so can be used for for example separating of dimethyl sulfide and the mist of methane or the mist of tert-butyl mercaptan and methane etc.
Therefore, see through molecular sieve effect and the practicality (gas stalling characteristic) thereof that the result who tests can confirm the DDR type zeolite membrane of the manufacture method manufacturing of (first invention) according to the present invention by above-mentioned gas through test and mist.
Below, specify the present invention's (second invention) by embodiment, but the present invention's (second invention) is not limited to these embodiment.
(embodiment 37)
100ml wide-mouth bottle with ethylenediamine (with the pure pharmaceutical worker's industry of light (strain)) the fluororesin system of packing into adds 1-amantadine (sheet mountain chemical industry (strain)) then and the 1-amantadine is dissolved fully.Add ion exchange water in another beaker, add 30% quality Ludox (Snowtex S, daily output chemistry (strain)), stir gently, then it is added above-mentioned wide-mouth bottle, powerful vibration mixes, and makes material solution.At this moment, 1-amantadine/SiO 2Than (mol ratio) is 0.0625, water/SiO 2Than (mol ratio) is 42, and ethylenediamine/1-amantadine is 16 than (mol ratio).The wide-mouth bottle of material solution of will having packed into places on the shaking machine, vibrates with 500rpm again and mixes 1 hour.
As porous matrix, be that the alumina porous body (Japanese insulator (strain)) of 0.6 μ m is processed into diameter with micropore diameter
Figure C20061000595800401
15mm * thickness 1.5mm's is discoid.Preparation DDR type zeolite powder is scattered in the dispersion liquid in the ion exchange water, and it is coated a side of porous matrix.
This porous matrix is vertically stood in the stainless steel pressure vessel with 100ml internal volume fluororesin system inner core, be the state that is dipped in the material solution.This pressure vessel internal temperature of packing into is adjusted in 160 ℃ the drier, carries out 46 hours heat treated (hydro-thermal is synthetic).
After the heat treated, take out porous matrix, as seen formed film on this porous matrix.With the washing of this porous matrix, drying, in atmosphere, be warming up to 800 ℃ with the speed of 0.1 ℃/min then with electric furnace, kept 4 hours, the speed with 1 ℃/min is cooled to room temperature then.
Then, with the crystalline phase of the film on the X-ray diffraction studies gained porous matrix, thus crystalline phase is estimated, the result detects the diffraction maximum of DDR type zeolite and porous matrix, is indicated as DDR type zeolite membrane.It is observed with electron microscope, confirm that having formed thickness on porous matrix is the film of the densification of about 5 μ m.
(single component gas permeation test)
Use the DDR type zeolite membrane of preparation among the embodiment 37 to carry out the gas permeation test.Fig. 7 is a key diagram of roughly representing the structure of the gas permeation experimental rig 260 of use in the gas permeation test, at the detector tube 251 (external diameters of alumina system
Figure C20061000595800402
Top 15mm) be equipped with among the embodiment 37 preparation, on porous matrix the DDR type zeolite membrane of film forming, with the furnace core tube 254 (internal diameters of its tube furnace 253 of packing into 25mm), in the inboard of detector tube 251, with internal diameter The quartz ampoule 255 1 of 6mm presents the state of triple tube structure near DDR type zeolite membrane 252.The outside (inboard of furnace core tube 254) to detector tube 251 feeds test gas, makes nitrogen (purge gas) flow through the quartz ampoule 255 of detector tube 251 inboards, and this nitrogen is used to reclaim the gas through DDR type zeolite membrane 252.Under this state with tube furnace in adjustment to set point of temperature, place more than 1 hour, be stable state.The recovery gas that contains through the gas of DDR type zeolite membrane 252 is separated, analyze, estimate the transmitance (molm of the gas that sees through film with gas-chromatography -2S -1Pa -1).Result of the test is shown in table 6,7.Put down in writing " gas componant (the CO of A in the table 7 2, H 2, O 2, N 2, CH 4, n-C 4H 10, i-C 4H 10) the single component gas permeation rate " with " gas componant (H of B 2, O 2, N 2, CH 4, n-C 4H 10, i-C 4H 10, SF 6) the single component gas permeation rate " ratio, the value under the last line display room temperature (26 ℃) on each hurdle, the value that following line display is 100 ℃.
Table 6
(unit: 10 -9Molm -2S -1Pa -1)
Figure C20061000595800411
Table 7
The single component gas permeation rate is than (A/B)
Figure C20061000595800421
Epimere: 26 ℃, hypomere: 100 ℃
(mist sees through test)
Use gas permeation experimental rig 260 shown in Figure 7,, as test gas, see through test with the mist shown in the table 8 (waiting a mole mist) according to testing same operation with above-mentioned single component gas permeation.Result of the test is as shown in table 8.
Table 8
Figure C20061000595800422
(air sees through test)
Use gas permeation experimental rig 260 shown in Figure 7, carry out air through test by testing same operation with above-mentioned single component gas permeation.Result of the test is as shown in table 9.According to formula (2), see through test resulting gas transit dose by air and calculate O 2/ N 2Separation α.
α＝(Q A/Q B)/(P A/P B) ……(2)
Wherein, Q A, Q BBe the transit dose (molm of gas A, B -2S -1), P A, P BIt is the dividing potential drop (Pa) of gas A, B in the test gas.This air sees through in the test, and gas A represents oxygen, and gas B represents nitrogen.
That is, the following calculating of separation: when air passes through DDR type zeolite membrane, O 2Gas permeation amount and N room temperature and 100 ℃ 2The O that contains in divided by air at other ratio of branch of the gas permeation amount of room temperature and 100 ℃ 2Dividing potential drop and N 2The ratio (1/4) of dividing potential drop.
Table 9
Figure C20061000595800431
According to DDR type zeolite membrane of the present invention, owing to the single component gas permeation rate of at least 2 kinds of gases that are selected from multiple specific gas is different mutually, therefore can be by separating specific gas composition more than a kind in the mist that contains specific gas composition more than 2 kinds.
Below, specify the present invention's (the 3rd invention) by embodiment, but the present invention's (the 3rd invention) is not limited to these embodiment.
(manufacturing of DDR type zeolite powder (crystal seed))
According to M.J.den Exter, J.C.Jansen, H.van Bekkum, Studies inSurface Science and Catalysis 84 volumes, editors such as J.Weitkamp., the method of the manufacturing DDR type zeolite of putting down in writing among Elsevier (1994) 1159-1166, the DDR type zeolite powder of the about 100 μ m of manufacturing grain size.Being crushed into the following micro mist of 5 μ m uses as crystal seed.
(embodiment 38)
With the 100ml wide-mouth bottle of 6.01g ethylenediamine (with the pure pharmaceutical worker's industry of light (strain)) the fluororesin system of packing into, adding 0.95g 1-amantadine (sheet mountain chemical industry (strain)) then and being dissolved to does not have the precipitation of 1-amantadine residual.In another beaker, add 43.41g water, add the Ludox (Snowtex S, daily output chemistry (strain)) of 10.01g 30% weight, stir gently, material solution is made in also powerful vibration mixing in the wide-mouth bottle with its adding ethylenediamine and the mixing of 1-amantadine then.At this moment, 1-amantadine and silica (SiO 2) mixed proportion (1-amantadine (mol)/silica (mol)) be 0.125, the mixed proportion of water and silica (water (mol)/silica (mol)) is 56, and the mixed proportion of ethylenediamine and 1-amantadine (ethylenediamine (mol)/1-amantadine (mol)) is 16.
As porous matrix, be that the alumina porous body (Japanese insulator (strain)) of 0.6 μ m is processed into diameter 15mm with average micropore diameter
Figure C20061000595800441
* thickness 1.5mm's is discoid., as crystal seed it is added in the entry with DDR type zeolite powder, preparation concentration is the dispersion liquid of 1mg/ml, and it is coated a side of porous matrix.This porous matrix is vertically stood in the stainless steel pressure vessel with 100ml internal volume fluororesin system inner core, be the state that is dipped in the material solution.This pressure vessel internal temperature of packing into is adjusted in 160 ℃ the drier, the hydro-thermal of carrying out 48 hours is synthetic, form following DDR type zeolite membrane compound:, in the micropore on the porous matrix surface of the zeolite layer of having arranged the matrix external sediment, form deposition DDR type zeolite layer in the matrix in the zeolite layer of the surface attachment matrix external sediment of porous matrix.
After hydro-thermal is synthetic, with the washing of DDR type zeolite membrane compound, drying, in atmosphere, be warming up to 800 ℃ with the speed of 0.1 ℃/min then with electric furnace, kept 4 hours, speed with 1 ℃/min is cooled to room temperature then, forms the DDR type zeolite membrane compound that does not contain as the organic molecule of structure directing agent.
Then, the crystalline phase of the zeolite membrane of on the porous matrix that constitutes gained DDR type zeolite membrane compound, arranging with X-ray diffraction studies, crystalline phase is estimated, and the result detects the diffraction maximum of DDR type zeolite and porous matrix, confirms that the zeolite membrane that is arranged on the porous matrix is a DDR type zeolite membrane.
" diffraction maximum of DDR type zeolite " in the X-ray diffraction is meant the diffraction maximum of being put down in writing among pairing No.38-651 of Deca-Dodecasil 3R shown in the joint committee (ICDD) " Powder Diffraction File " or the 41-571.Observe with electron microscope, find that having formed thickness on porous matrix is the matrix external sediment DDR type zeolite layer of the densification of 7 μ m.And deposition DDR type zeolite layer in the micropore on the porous matrix surface of having arranged matrix external sediment DDR type zeolite layer, having formed by the matrix that DDR type zeolite constitutes, thickness is 6 μ m.Fig. 9 and Figure 10 are for showing the electron micrograph of the shape of the DDR type zeolite membrane compound of preparation among the embodiment 38, and Fig. 9 represents the section of DDR type zeolite membrane compound, and Figure 10 represents the shape of DDR type zeolite membrane composite surface.
(embodiment 39-48, comparative example 5-9)
Except that the shape of amount, heat-treat condition and the porous matrix of the ratio of components that changes material solution, material solution, carry out the operation same with embodiment 38, attempt forming DDR type zeolite membrane compound.Use the discoid porous matrix that uses among the embodiment 38 and be processed into external diameter 17mm
Figure C20061000595800451
The tubulose porous matrix of * thickness 2.5mm is as porous matrix.With embodiment 38 similarly, by X-ray diffraction formed DDR type zeolite membrane is estimated, the thickness of deposition DDR type zeolite layer in the thickness of matrix external sediment DDR type zeolite layer and the matrix is measured in the observation by electron microscope.The thickness of deposition DDR type zeolite layer is as shown in table 10 in the thickness of the matrix external sediment DDR type zeolite layer of the proportion of composing of material solution (1-amantadine (mol)/silica (mol), ethylenediamine (mol)/silica (mol) and ethylenediamine (mol)/1-amantadine (mol)), matrix shape, heat-treat condition (temperature, time), formation and the matrix.
Figure C20061000595800461
Figure C20061000595800471
(gas permeation test)
Use the DDR type zeolite membrane compound for preparing among embodiment 38-48, the comparative example 5-9 to carry out the gas permeation test.
Figure 11 is the structure skeleton diagram of the gas permeation experimental rig 320 of use in the explanation gas permeation test, at detector tube 311 (the internal diameter 15mm of alumina system
Figure C20061000595800481
) the top DDR type zeolite membrane compound 312 is installed, with furnace core tube 314 (the internal diameter 25mm of its tube furnace 313 of packing into ), in the inboard of detector tube 311, with internal diameter 6mm Quartz ampoule 315 1 near DDR type zeolite membrane compound 312, be the state of triple tube structure.With methane (CH 4) and carbon dioxide (CO 2) mist in the furnace core tube 314 of the gas permeation experimental rig that can directly feed said structure by the gas introduction port 323 that furnace core tube 314 and valve 322 cuts off.Being shaped as when discoid of porous matrix, the feeding speed of mist is 50ml/min, porous matrix be shaped as tubulose the time feeding speed be 100ml/min.
Make helium (purge gas, the speed during circular disk-shaped substrate are 100ml/min, and the speed during tubulose matrix is 200ml/min) flow through the quartz ampoule 315 of detector tube 311 inboards, this helium is used to reclaim the gas through DDR type zeolite membrane compound 312.Under this state, tube furnace 313 is warming up to test temperature (100 ℃), places more than 1 hour, be stable state.The recovery gas that contains through the gas of DDR type zeolite membrane compound 312 is separated, analyze, estimate the transmitance (nmolm of methane and carbon dioxide with gas-chromatography -2S - 1Pa -1).100 ℃ of CO 2/ CH 4Separation as shown in table 10.CO 2/ CH 4Separation α calculate according to following formula (3).
α＝(Q A/Q B)/(P A/P B) ……(3)
In the following formula (3), Q ABe CO 2Transmitance (nmolm -2S -1Pa -1), Q BBe CH 4Transmitance (nmolm -2S -1Pa -1), P ACO in the expression test gas 2Dividing potential drop (Pa), P BCH in the expression test gas 4Dividing potential drop (Pa).
(discussion)
By the result shown in the table 10 as can be known: regulate consisting of of material solution: the mixed proportion of 1-amantadine and silica in the 0.03-0.5 scope, the mixed proportion of ethylenediamine and 1-amantadine in the scope of 5-32, the mixed proportion of water and silica in the 20-500 scope, the thickness that then can make the interior DDR of deposition of matrix type zeolite layer is thickness, the 100 ℃ of CO more than 5 times (the 3 μ m) of average micropore diameter (0.6 μ m) of used porous matrix in the present embodiment 2/ CH 4Separation be more than 2, can be used as the DDR type zeolite membrane compound (embodiment 38-48) of gas separation membrane.
By the result shown in the table 10 as can be known: have thickness and be the DDR type zeolite membrane compound of deposition DDR type zeolite layer in the above matrix of 3 μ m, it is at 100 ℃ CO 2/ CH 4Separation be more than 2, especially, having formed thickness is the DDR type zeolite membrane compound of deposition DDR type zeolite layer in the above matrix of 5 μ m, it is at 100 ℃ CO 2/ CH 4Separation be more than 50, can be suitable as gas separation membrane (embodiment 38,39,43-46).The penetration speed of the thick more then molecule of thickness of deposition DDR type zeolite layer is slack-off in the matrix, and when therefore using average micropore diameter to be the porous matrix of 0.6 μ m, the thickness of deposition DDR type zeolite layer be we can say the scope of preferred 3-6 μ m in the matrix.
Having thickness is the DDR type zeolite membrane compound of the embodiment 38-48 of deposition DDR type zeolite layer in the above matrix of 3 μ m, and it is at 100 ℃ of CO 2/ CH 4Therefore the separation height can infer after removing the heat treatment of structure directing agent (roasting), also can suppress the generation of defectives such as chapping.Figure 12 represents the thermal expansion character of DDR type zeolite and alumina.As shown in figure 12, the thermal expansion character of DDR type zeolite and alumina has a great difference.Therefore the thickness of the interior deposition of matrix DDR type zeolite layer is less than 5 times of average micropore diameter, be that the thickness of DDR type zeolite layer is during less than 3 μ m, the thermal expansion character of DDR type zeolite and alumina matrix has a great difference, therefore the defective that causes because of heat treatment can take place, as comparative example 5-9, can infer the molecular separation ability and reduce.And the thickness of deposition DDR type zeolite layer is more than the 3 μ m in the matrix, when preferred 5 μ m are above, can infer deposition DDR type zeolite layer in the matrix and make the thermal expansion character difference mitigation of DDR type zeolite membrane and alumina matrix (porous matrix), can suppress the generation of the defective after the heat treatment.
Industrial applicability
DDR type zeolite membrane of the present invention can make the special component more than a kind in the mist that is made of the specific gas composition preferentially pass through by its molecular sieve effect, therefore can be suitable as gas separation membrane. Be fit to from contain carbon dioxide (CO such as natural gas etc.2) and methane (CH4) mist in separating carbon dioxide optionally. DDR type zeolite membrane of the present invention by with catalyst combination, can be used as the film reaction agent.

Claims (18)

1. DDR type zeolite membrane, it is characterized in that: film forming on matrix, its main component is a silica, and it is different mutually with each pure gas transmitance of 100 ℃ in room temperature respectively to be selected from carbon dioxide, hydrogen, oxygen, nitrogen, methane, normal butane, iso-butane, sulfur hexafluoride, ethane, ethene, propane, propylene, carbon monoxide and nitric oxide production at least 2 kinds of gases simultaneously.
2. the DDR type zeolite membrane of claim 1, wherein carbon dioxide gas permeation rate at room temperature is 1.0 * 10 -9(molm -2S -1Pa -1) or more than.
3. the DDR type zeolite membrane of claim 1, wherein carbon dioxide is 5.0 * 10 at 100 ℃ gas permeation rate -10(molm -2S -1Pa -1) or more than.
4. the DDR type zeolite membrane of claim 1 is wherein room temperature and 100 ℃, for CO in the mist that mole of carbon dioxide and methane such as contains 2/ CH 4Separation be 2 or more than.
5. the DDR type zeolite membrane of claim 1, wherein carbon dioxide in the pure gas transmitance of room temperature and 100 ℃ and hydrogen, oxygen, nitrogen, methane, normal butane, iso-butane and sulfur hexafluoride any one gas each ratio of the pure gas transmitance of room temperature and 100 ℃ be 2 or more than.
6. the DDR type zeolite membrane of claim 5, wherein hydrogen in the pure gas transmitance of room temperature and 100 ℃ and oxygen, nitrogen, methane, normal butane, iso-butane and sulfur hexafluoride any one gas each ratio of the pure gas transmitance of room temperature and 100 ℃ be 2 or more than.
7. the DDR type zeolite membrane of claim 5, wherein oxygen in the pure gas transmitance of room temperature and 100 ℃ and nitrogen, methane, normal butane, iso-butane and sulfur hexafluoride any one gas each ratio of the pure gas transmitance of room temperature and 100 ℃ be 1.1 or more than.
8. the DDR type zeolite membrane of claim 5, wherein nitrogen in the pure gas transmitance of room temperature and 100 ℃ and methane, normal butane, iso-butane and sulfur hexafluoride any one gas each ratio of the pure gas transmitance of room temperature and 100 ℃ be 2 or more than.
9. the DDR type zeolite membrane of claim 5, wherein methane in the pure gas transmitance of room temperature and 100 ℃ and normal butane, iso-butane and sulfur hexafluoride any one gas each ratio of the pure gas transmitance of room temperature and 100 ℃ be 2 or more than.
10. the DDR type zeolite membrane of claim 5, wherein normal butane in the pure gas transmitance of room temperature and 100 ℃ and iso-butane or sulfur hexafluoride any one gas each ratio of the pure gas transmitance of room temperature and 100 ℃ be 1.1 or more than.
11. the DDR type zeolite membrane of claim 5, wherein iso-butane the pure gas transmitance of room temperature and 100 ℃ and sulfur hexafluoride each ratio of the pure gas transmitance of room temperature and 100 ℃ be 1.1 or more than.
12. the DDR type zeolite membrane of claim 1 is wherein room temperature and 100 ℃, for H in the mist that moles of hydrogen and methane such as contains 2/ CH 4Separation be 2 or more than.
13. the DDR type zeolite membrane of claim 1 is wherein room temperature and 100 ℃, for C in the mist that molar ethylene and ethane such as contains 2H 4/ C 2H 6Separation be 1.5 or more than.
14. the DDR type zeolite membrane of claim 1 is wherein room temperature and 100 ℃, for O in the air 2/ N 2Separation be 1.5 or more than.
15. gas separating method, this method sees through a kind of DDR type zeolite membrane by making following mixed gas composition, be selected from carbon dioxide from containing at least two kinds, hydrogen, oxygen, nitrogen, methane, normal butane, iso-butane, sulfur hexafluoride, ethane, ethene, propane, propylene, separate at least a kind of gas componant in the mist of carbon monoxide and nitric oxide production gas componant, wherein said DDR type zeolite membrane is the film that forms on matrix, its main component is a silica, and wherein each gas componant differs from one another in the pure gas transmitance of room temperature and 100 ℃, to separate described at least a gas componant.
16. the gas separating method of claim 15, this method are separating carbon dioxides optionally from the mist that contains carbon dioxide and methane.
17. gas fractionation unit, this device comprises a kind of DDR type zeolite membrane, so that be selected from carbon dioxide from containing at least two kinds, hydrogen, oxygen, nitrogen, methane, normal butane, iso-butane, sulfur hexafluoride, ethane, ethene, propane, propylene, separate at least a kind of gas componant in the mist of carbon monoxide and nitric oxide production gas componant, wherein said DDR type zeolite membrane is the film that forms on matrix, its main component is a silica, and wherein each gas componant differs from one another in the pure gas transmitance of room temperature and 100 ℃, to separate described at least a gas componant.
18. the gas fractionation unit of claim 17, this gas fractionation unit separating carbon dioxide optionally from the mist that contains carbon dioxide and methane.
CNB2006100059585A 2001-09-17 2002-09-17 DDR type zeolite membrane, and composite ddr type zeolite membrane, and method for preparation thereof Expired - Lifetime CN100393399C (en)

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