CN110605029A - Method for synthesizing DDR molecular sieve membrane - Google Patents
Method for synthesizing DDR molecular sieve membrane Download PDFInfo
- Publication number
- CN110605029A CN110605029A CN201910779384.4A CN201910779384A CN110605029A CN 110605029 A CN110605029 A CN 110605029A CN 201910779384 A CN201910779384 A CN 201910779384A CN 110605029 A CN110605029 A CN 110605029A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- ddr molecular
- ddr
- sieve membrane
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/04—Tubular membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/104—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/548—Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention relates to a method for synthesizing a DDR molecular sieve membrane, DDR molecular sieve powder is subjected to ball milling to obtain submicron DDR molecular sieve crystal seeds; mixing a silicon source, amantadine, tetraethyl ammonium hydroxide and water to obtain a DDR molecular sieve membrane synthesis mother liquor; coating DDR molecular sieve seed crystals on a porous carrier tube; placing DDR molecular sieve membrane synthesis mother liquor and a porous carrier tube in a crystallization kettle for hydro-thermal synthesis treatment, and after the synthesis is finished, washing and drying the obtained membrane tube; roasting under ozone atmosphere to remove tetraethyl oxyhydrogenAnd (4) carrying out ammonium activation to obtain the activated DDR molecular sieve membrane. Compared with the prior art, the invention utilizes the mixed template agent of the amantadine and the tetraethyl ammonium hydroxide, and the addition of the tetraethyl ammonium hydroxide inhibits the generation of miscellaneous items, thereby quickly synthesizing the DDR molecular sieve membrane at high temperature, greatly shortening the crystallization time, and obtaining the DDR molecular sieve membrane with higher CO2‑CH4Selectivity of separation.
Description
Technical Field
The invention relates to a preparation method of a molecular sieve membrane, in particular to a method for synthesizing a DDR molecular sieve membrane.
Background
The molecular sieve membrane is obtained by preparing a layer of continuous, compact and uniform molecular sieve on a porous carrier. The inorganic molecular sieve membrane has the advantages of uniform pore diameter, high temperature resistance, chemical solvent resistance, capability of ion exchange and the like, so the inorganic molecular sieve membrane has great application potential in the fields of membrane catalytic reaction, gas separation, liquid pervaporation separation, environmental protection and the like. For example, in CO2The membrane separation device has the advantages of low energy consumption, continuous operation, low equipment investment, small volume, easy maintenance and the like, so the membrane separation device is very suitable for high CO2Content of harsh separation environment. The DDR molecular sieve (the structure code of the International molecular Sieve Association is DDR) is an all-silicon type oxygenate with a three-dimensional pore channel structure, the framework structure is basically silicon-oxygen tetrahedron, the pore channel size is 0.36 multiplied by 0.44nm, and the kinetic diameter of the common small molecular gas is close. DDR molecular sieve membranes are suitable for separation of small molecule mixtures, such as CO, based on molecular sieving effects2-CH4、O2-N2Propylene-propane, water-alcohol, etc. (Journal of Membrane Science 316(2008) 35-45). The DDR molecular sieve is of an all-Si framework structure and has extremely high hydrothermal, chemical and solvent stability and strong hydrophobicity, so that the DDR molecular sieve can be applied to environments of high temperature, high pressure, corrosive conditions, organic solvents, high humidity and the like, and has important application value in the fields of adsorption-separation, gas purification and the like. The DDR molecular sieve membrane has better stability than other hydrophilic molecular sieve membranes (such as SAPO-34 molecular sieve membrane), is not sensitive to water in raw materials, and is not sensitive to CO2-CH4The separation field has better application prospect. However, the synthesis of the DDR molecular sieve membrane (like the synthesis of DDR molecular sieve powder) is difficult, the synthesis time is long, and a large amount of ethylenediamine needs to be added as a solvent (toxic). In the process of addingOn the premise of the seed crystal, 3 days (160 ℃) are usually needed to obtain the DDR molecular sieve membrane with high quality. While increasing the synthesis temperature leads to the formation of a hetero-phase. These unfavorable conditions greatly hinder the industrial application of DDR molecular sieve membranes.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synthesizing a DDR molecular sieve membrane aiming at the problems that the traditional DDR molecular sieve membrane has long synthesis time, and toxic ethylenediamine is used as a solvent.
The purpose of the invention can be realized by the following technical scheme:
a method for synthesizing a DDR molecular sieve membrane aims at solving the problems that the traditional DDR molecular sieve membrane is long in synthesis time, toxic ethylenediamine is used as a solvent and the like, and adopts a mixed template agent of amantadine and tetraethylammonium hydroxide to quickly synthesize the DDR molecular sieve membrane at high temperature. The addition of tetraethyl ammonium hydroxide inhibits the generation of a heterogeneous phase, and the high-temperature synthesis greatly improves the crystallization rate, so that the synthesis time is greatly shortened. In addition, the use of toxic ethylene diamine is avoided, which is beneficial to environmental protection. The prepared DDR molecular sieve membrane has higher CO2-CH4The separation performance specifically adopts the following method:
(1) performing ball milling on DDR molecular sieve powder (generally large particles of 5-10 micrometers) to obtain submicron DDR molecular sieve seed crystals with the particle size of less than 300 nanometers;
(2) mixing a silicon source, amantadine, tetraethyl ammonium hydroxide and water to obtain a DDR molecular sieve membrane synthesis mother liquor;
(3) coating DDR molecular sieve seed crystals on a porous carrier tube;
(4) placing DDR molecular sieve membrane synthesis mother liquor and a porous carrier tube in a reaction container;
(5) carrying out hydro-thermal synthesis treatment on the reaction container, and washing and drying the obtained membrane tube after synthesis is finished;
(6) roasting and removing tetraethyl ammonium hydroxide under the ozone atmosphere to obtain the activated DDR molecular sieve membrane.
Further, the silicon source is selected from one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, sodium silicate, sodium metasilicate, silica sol and white carbon black.
Further, SiO of silicon source2The molar ratio of amantadine to tetraethylammonium hydroxide to water is 1: (0.005-0.5): (0.01-0.2): (0.05-100).
Further, the DDR molecular sieve seed crystal coating method comprises brush coating, dip coating, spray coating or spin coating.
Furthermore, when dip coating is adopted, the concentration of the DDR molecular sieve seed crystal is 0.01-1 wt%.
Furthermore, the shape of the porous carrier tube comprises a single-channel tube shape, a multi-channel tube shape, a flat plate shape or a hollow fiber tube shape, the material comprises ceramics, stainless steel, aluminum oxide, titanium dioxide, zirconium dioxide, silicon carbide or silicon nitride, and the aperture is 2-2000 nm.
Furthermore, the temperature of the hydrothermal reaction is 200-240 ℃ and the time is 1-12 hours.
Further, the temperature is controlled to be 100-300 ℃ during roasting, the roasting time is 1-10 days, the roasting atmosphere is an ozone atmosphere, and the concentration of ozone is 1-200 mg/L.
Compared with the prior art, the invention adopts the mixed template agent of amantadine and tetraethyl ammonium hydroxide to rapidly synthesize the DDR molecular sieve membrane at high temperature aiming at the problems that the traditional DDR molecular sieve membrane has long synthesis time, and toxic ethylenediamine is adopted as a solvent. The addition of tetraethyl ammonium hydroxide inhibits the generation of a heterogeneous phase, so that the synthesis temperature can be increased from 160 to 220 ℃, and the high-temperature synthesis greatly increases the crystallization rate, thereby greatly shortening the synthesis time. In addition, tetraethyl ammonium hydroxide can improve the alkalinity of the mother liquor and promote the dissolution of a silicon source. The use of toxic ethylene diamine is avoided, so that the method is beneficial to environmental protection. The prepared DDR molecular sieve membrane has higher CO2-CH4Separation performance.
Drawings
Fig. 1 is an SEM (scanning electron microscope) photograph of the surface and cross section of the DDR molecular sieve membrane prepared in example 1. Wherein, the picture (a) is an SEM picture of the surface of the membrane; (b) the figure is an SEM photograph of a cross section of the membrane.
Fig. 2 is an SEM photograph of the surface and cross section of the DDR molecular sieve membrane prepared in example 2. Wherein, the picture (a) is an SEM picture of the surface of the membrane; (b) the figure is an SEM photograph of a cross section of the membrane.
Fig. 3 is an SEM photograph of the surface and cross section of the DDR molecular sieve membrane prepared in example 3. Wherein, the picture (a) is an SEM picture of the surface of the membrane; (b) the figure is an SEM photograph of a cross section of the membrane.
Fig. 4 is an SEM photograph of the surface and cross section of the DDR molecular sieve membrane prepared in example 4. Wherein, the picture (a) is an SEM picture of the surface of the membrane; (b) the figure is an SEM photograph of a cross section of the membrane.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A method for synthesizing a DDR molecular sieve membrane aims at solving the problems that the traditional DDR molecular sieve membrane is long in synthesis time, toxic ethylenediamine is used as a solvent and the like, and adopts a mixed template agent of amantadine and tetraethylammonium hydroxide to quickly synthesize the DDR molecular sieve membrane at high temperature. The addition of tetraethyl ammonium hydroxide inhibits the generation of a heterogeneous phase, and the high-temperature synthesis greatly improves the crystallization rate, so that the synthesis time is greatly shortened. In addition, the use of toxic ethylene diamine is avoided, which is beneficial to environmental protection. The prepared DDR molecular sieve membrane has higher CO2-CH4The separation performance specifically adopts the following method:
(1) performing ball milling on DDR molecular sieve powder (generally large particles of 5-10 micrometers) to obtain submicron DDR molecular sieve seed crystals with the particle size of less than 300 nanometers;
(2) mixing silicon source (according to SiO in silicon source)2Calculated), amantadine, tetraethylammonium hydroxide and water in a molar ratio of 1: (0.005-0.5): (0.01-0.2): (0.05-100) mixing to obtain DDR molecular sieve membrane synthesis mother liquor, wherein the adopted silicon source is selected from tetramethyl orthosilicate, tetraethyl orthosilicate and sodium silicateOne or more of sodium metasilicate, silica sol and white carbon black;
(3) coating the prepared DDR molecular sieve seed crystal on a porous carrier tube in a mode of brushing, dip coating, spray coating or spin coating, wherein the shape of the porous carrier tube which can be used comprises a single-channel tube shape, a multi-channel tube shape, a flat plate shape or a hollow fiber tube shape, the material comprises ceramic, stainless steel, aluminum oxide, titanium dioxide, zirconium dioxide, silicon carbide or silicon nitride, and the aperture is 2-2000 nm;
(4) placing DDR molecular sieve membrane synthetic mother liquor and a porous carrier tube in a crystallization kettle;
(5) placing the crystallization kettle in an oven for hydrothermal synthesis for 1-12 hours, wherein the synthesis temperature is 200-240 ℃; after the synthesis is finished, washing and drying the obtained membrane tube;
(6) and (3) roasting to remove the template agent tetraethylammonium hydroxide under the ozone atmosphere, wherein the roasting temperature is 200 ℃, and the roasting time is 4 days, so as to obtain the activated DDR molecular sieve membrane.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1:
a method for synthesizing DDR molecular sieve membrane with mole ratio of 1SiO2:50H2And (3) crystallizing the mother solution of 0.4Adam:0.2TEAOH at 220 ℃ for 2 hours to prepare the all-silicon DDR molecular sieve membrane.
In the embodiment, a traditional oven is adopted to heat and synthesize the SSZ-13 molecular sieve membrane, and the specific steps are as follows:
step 1: the synthesis formula of the all-silicon DDR molecular sieve is as follows: 1.0SiO2:4.0EDA:0.5ADA:100H2O (EDA: ethylenediamine, ADA: amantadine). Mixing ethylenediamine, water and amantadine, stirring for 1 hour, adding ethyl orthosilicate, and stirring at room temperature overnight to obtain a synthetic mother liquor. Crystallizing at 433K for 24 days to obtain the all-silicon DDR molecular sieve. The molecular sieve crystals were large, about 8 microns. After ball milling by a ball mill, the crystal is crushed to below 500 nanometers.
Step 2: selecting a porous ceramic tube with the aperture of 100nm as a carrier, sealing glaze at two ends of the carrier, cleaning and drying, sealing the outer surface by using a tetrafluoro belt, and dip-coating DDR molecular sieve seed crystals onto the inner surface of the ceramic tube, wherein the DDR seed crystal concentration of the dip-coating liquid is 0.1 wt%. After dip coating, the membrane tube is dried at room temperature and then dried at 110 ℃.
And step 3: and mixing amantadine, tetraethylammonium hydroxide and water, adding tetraethoxysilane, and stirring overnight to obtain the synthetic mother liquor of the DDR molecular sieve membrane. The preferable molar ratio of the mother liquor is as follows: 1SiO2:50H2O:0.4Adam:0.2TEAOH。
And 4, step 4: and (3) placing the porous carrier coated with the all-silicon DDR molecular sieve seed crystal prepared in the step (2) into a crystallization kettle, pouring a synthetic mother solution, and directly contacting the mother solution with a carrier tube. Crystallizing in an oven at 220 ℃ for 12 hours, cooling the reaction kettle, and taking out the porous carrier.
And 5: and (4) roasting the DDR molecular sieve membrane tube obtained in the step (4) at 200 ℃ for 4 days under the ozone atmosphere to remove the template agent (the heating rate and the cooling rate are both 1K/min, and the ozone concentration is 15 mg/L), so as to obtain the DDR molecular sieve membrane. The surface and the section of the obtained DDR molecular sieve membrane are shown in a figure 1, and the surface of a carrier is completely covered by rhombic DDR crystals, and the cross-linking among the crystals is perfect (see a picture); the thickness of the film was relatively uniform, about 24 microns (see panel b).
Subjecting the obtained DDR molecular sieve membrane to CO2/CH4Gas separation test, the test conditions were: the temperature was 25 ℃, the atmospheric pressure was 102.4kPa, the feed gas flow was 4000mL/min, and the molar composition was 50/50%. Measuring the gas flow at the permeation side by using a soap film flowmeter; the gas composition on the permeate side was analyzed by gas chromatography (Shimadzu-2014C).
Calculation formula of gas permeability: p is V/(sxp). Wherein V is a permeate gas (CO)2Or CH4) The flow rate of (2) is in mol/S, S is the membrane area, m2(ii) a P is the pressure difference between the feed side and the permeate side of the membrane tube, in Pa.
Separation selectivity calculation formula: f ═ pCO2/pCH4I.e. CO2And CH4The permeability of (c).
CO of the DDR molecular sieve membrane tube2/CH4The results of the gas separation test are shown below, at 0.2MPa, for their CO2Has an average value of 0.18X 10-7mol/(m2·s·Pa)，CO2/CH4The separation selectivity of (2) was an average value of 166.
Example 2
A method for synthesizing a DDR molecular sieve membrane, which is different from example 1 in that: crystallizing at 220 deg.C for 4 hr to obtain the final product. The rest of the procedure was the same as in example 1.
The surface and the section of the obtained SSZ-13 molecular sieve membrane are shown in FIG. 2, and the surface of the carrier is completely covered by rhombic DDR crystals, and the cross-linking among the crystals is good (see a picture); the thickness of the film was relatively uniform, about 8.9 microns (see panel b).
CO of the SSZ-13 molecular sieve membrane tube2/CH4The results of the gas separation test are shown below, at 0.2MPa, for their CO2Has an average value of 0.78X 10-7mol/(m2·s·Pa)，CO2/CH4The separation selectivity of (a) was an average value of 165.
Example 3
A method for synthesizing a DDR molecular sieve membrane, which is different from example 1 in that: crystallizing at 220 deg.C for 3 hr to obtain the final product. The rest of the procedure was the same as in example 1.
The surface and the section of the obtained DDR molecular sieve membrane are shown in FIG. 3, and it can be seen from the figure that the surface of the carrier is completely covered by the rhombic DDR crystals, and the cross-linking among the crystals is good (see a picture); the thickness of the film was relatively uniform, about 4.3 microns (see b).
CO of the DDR molecular sieve membrane tube2/CH4The results of the gas separation test are shown below, at 0.2MPa, for their CO2Has an average value of 1.5X 10-7mol/(m2·s·Pa)，CO2/CH4The separation selectivity of (a) was an average value of 155.
Example 4
A method for synthesizing a DDR molecular sieve membrane, which is different from example 1 in that: crystallizing at 220 deg.C for 2.5 hr to obtain the final product. The rest of the procedure was the same as in example 1.
The surface and the section of the obtained DDR molecular sieve membrane are shown in FIG. 4, and it can be seen from the figure that the surface of the carrier is completely covered by the rhombic DDR crystals, and the cross-linking among the crystals is good (see a picture); the thickness of the film was relatively uniform, about 1.6 microns (see panel b).
CO of the DDR molecular sieve membrane tube2/CH4The results of the gas separation test are shown below, at 0.2MPa, for their CO2Has an average value of 4.3X 10-7mol/(m2·s·Pa)，CO2/CH4The separation selectivity of (a) was 122 on average.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A method for synthesizing a DDR molecular sieve membrane is characterized by comprising
Ball-milling the DDR molecular sieve powder to obtain submicron DDR molecular sieve crystal seeds;
mixing a silicon source, amantadine, tetraethyl ammonium hydroxide and water to obtain a DDR molecular sieve membrane synthesis mother liquor;
coating DDR molecular sieve seed crystals on a porous carrier tube;
placing DDR molecular sieve membrane synthetic mother liquor and a porous carrier tube in a crystallization kettle;
placing the crystallization kettle in an oven for hydro-thermal synthesis, and washing and drying the obtained membrane tube after the synthesis is finished;
roasting and removing tetraethyl ammonium hydroxide under the ozone atmosphere to obtain the activated DDR molecular sieve membrane.
2. The method for synthesizing the DDR molecular sieve membrane of claim 1, wherein the silicon source is selected from one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, sodium silicate, sodium metasilicate, silica sol and white carbon black.
3. The method for synthesizing the DDR molecular sieve membrane of claim 1 or 2, wherein the SiO of the silicon source2The molar ratio of amantadine to tetraethylammonium hydroxide to water is 1: (0.005-0.5): (0.01-0.2): (0.05-100).
4. The method for synthesizing the DDR molecular sieve membrane as claimed in claim 1, wherein the DDR molecular sieve seed crystal is coated by brushing, dipping, spraying or spin coating.
5. The method for synthesizing the DDR molecular sieve membrane as claimed in claim 4, wherein the DDR molecular sieve is formed by dip coating, and the concentration of DDR molecular sieve seed crystals is 0.01-1 wt%.
6. The method for synthesizing the DDR molecular sieve membrane of claim 1, wherein the shape of the porous carrier tube comprises a single-channel tubular shape, a multi-channel tubular shape, a flat plate shape or a hollow fiber tubular shape, the material comprises ceramic, stainless steel, alumina, titanium dioxide, zirconium dioxide, silicon carbide or silicon nitride, and the pore diameter is 2-2000 nm.
7. The method for synthesizing the DDR molecular sieve membrane as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 160-240 ℃ and the time is 1-12 hours.
8. The method for synthesizing the DDR molecular sieve membrane as claimed in claim 1, wherein the temperature is controlled to be 100-300 ℃ during the calcination, the calcination time is 1-10 days, the calcination atmosphere is an ozone atmosphere, and the ozone concentration is 1-200 mg/L.
9. The method for synthesizing the DDR molecular sieve membrane of claim 1, wherein DDR molecular sieve powder is ball milled and crushed into seed crystals with a particle size of less than 300 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910779384.4A CN110605029A (en) | 2019-08-22 | 2019-08-22 | Method for synthesizing DDR molecular sieve membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910779384.4A CN110605029A (en) | 2019-08-22 | 2019-08-22 | Method for synthesizing DDR molecular sieve membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110605029A true CN110605029A (en) | 2019-12-24 |
Family
ID=68889832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910779384.4A Pending CN110605029A (en) | 2019-08-22 | 2019-08-22 | Method for synthesizing DDR molecular sieve membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110605029A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111375314A (en) * | 2020-04-08 | 2020-07-07 | 福州大学 | Molecular sieve membrane and preparation method and application thereof |
| CN114832645A (en) * | 2022-05-26 | 2022-08-02 | 江西师范大学 | Preparation method and application of SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel |
| CN115057452A (en) * | 2022-07-10 | 2022-09-16 | 苏州科技大学 | Method for rapidly preparing molecular sieve and molecular sieve membrane by using 'clean' crystal seeds |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050229779A1 (en) * | 2001-09-17 | 2005-10-20 | Ngk Insulators, Ltd. | Method for preparing ddr type zeolite membrane, ddr type zeolite membrane, and composite ddr type zeolite membrane, and method for preparation thereof |
| US20090011926A1 (en) * | 2006-03-14 | 2009-01-08 | Ngk Insulators,Ltd. | Process for producing ddr type zeolite membrane |
| CN103449475A (en) * | 2012-05-29 | 2013-12-18 | 上海中科高等研究院 | Preparation method of AlPO-18 molecular sieve membrane |
| CN104925826A (en) * | 2015-06-02 | 2015-09-23 | 中国科学院上海高等研究院 | Method for preparing DD3R molecular sieve |
| CN104986783A (en) * | 2015-07-03 | 2015-10-21 | 中国科学院上海高等研究院 | Method for preparing all-silicon DD3R molecular sieve |
| CN105016354A (en) * | 2015-07-03 | 2015-11-04 | 中国科学院上海高等研究院 | Method for preparing submicron all-silicon DD3R molecular sieve |
| CN105460943A (en) * | 2015-11-25 | 2016-04-06 | 中国科学院上海高等研究院 | Full-silicon DD3R molecular sieve synthesis method |
| CN105668578A (en) * | 2016-04-13 | 2016-06-15 | 中国科学院上海高等研究院 | Method for quickly synthesizing DD3R molecular sieve |
| CN106745026A (en) * | 2016-12-16 | 2017-05-31 | 南京工业大学 | A kind of preparation method of zero defect DDR molecular screen membranes |
| CN109694083A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The preparation method of DDR zeolite molecular sieve |
| CN110104659A (en) * | 2019-05-27 | 2019-08-09 | 上海工程技术大学 | A kind of method that low temperature removes template in molecular screen membrane |
-
2019
- 2019-08-22 CN CN201910779384.4A patent/CN110605029A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050229779A1 (en) * | 2001-09-17 | 2005-10-20 | Ngk Insulators, Ltd. | Method for preparing ddr type zeolite membrane, ddr type zeolite membrane, and composite ddr type zeolite membrane, and method for preparation thereof |
| US20090011926A1 (en) * | 2006-03-14 | 2009-01-08 | Ngk Insulators,Ltd. | Process for producing ddr type zeolite membrane |
| CN103449475A (en) * | 2012-05-29 | 2013-12-18 | 上海中科高等研究院 | Preparation method of AlPO-18 molecular sieve membrane |
| CN104925826A (en) * | 2015-06-02 | 2015-09-23 | 中国科学院上海高等研究院 | Method for preparing DD3R molecular sieve |
| CN104986783A (en) * | 2015-07-03 | 2015-10-21 | 中国科学院上海高等研究院 | Method for preparing all-silicon DD3R molecular sieve |
| CN105016354A (en) * | 2015-07-03 | 2015-11-04 | 中国科学院上海高等研究院 | Method for preparing submicron all-silicon DD3R molecular sieve |
| CN105460943A (en) * | 2015-11-25 | 2016-04-06 | 中国科学院上海高等研究院 | Full-silicon DD3R molecular sieve synthesis method |
| CN105668578A (en) * | 2016-04-13 | 2016-06-15 | 中国科学院上海高等研究院 | Method for quickly synthesizing DD3R molecular sieve |
| CN106745026A (en) * | 2016-12-16 | 2017-05-31 | 南京工业大学 | A kind of preparation method of zero defect DDR molecular screen membranes |
| CN109694083A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The preparation method of DDR zeolite molecular sieve |
| CN110104659A (en) * | 2019-05-27 | 2019-08-09 | 上海工程技术大学 | A kind of method that low temperature removes template in molecular screen membrane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111375314A (en) * | 2020-04-08 | 2020-07-07 | 福州大学 | Molecular sieve membrane and preparation method and application thereof |
| CN114832645A (en) * | 2022-05-26 | 2022-08-02 | 江西师范大学 | Preparation method and application of SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel |
| CN114832645B (en) * | 2022-05-26 | 2023-10-20 | 江西师范大学 | Preparation method and application of SSZ-13 molecular sieve membrane in fluorine-free and aluminum-free gel |
| CN115057452A (en) * | 2022-07-10 | 2022-09-16 | 苏州科技大学 | Method for rapidly preparing molecular sieve and molecular sieve membrane by using 'clean' crystal seeds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7416135B2 (en) | Manufacturing method of RHO type zeolite | |
| CN109224879B (en) | Preparation method of CHA molecular sieve membrane | |
| JP5690325B2 (en) | Zeolite membrane and method for producing zeolite membrane | |
| CN110605029A (en) | Method for synthesizing DDR molecular sieve membrane | |
| CN110683559A (en) | Green synthesis method of ultrathin SSZ-13 molecular sieve membrane | |
| CN111056560B (en) | Economic synthesis method of ultrathin SSZ-13 molecular sieve membrane | |
| CN103933871B (en) | A kind of preparation method of high stability all-silica MFI type molecular screen membrane | |
| JP2009539592A (en) | Method for producing composite membrane | |
| JP4751996B2 (en) | Method for producing ZSM-5 type zeolite membrane | |
| JP2010131600A (en) | Method of manufacturing zsm-5 type zeolite membrane | |
| CN112744828B (en) | Ultrathin molecular sieve membrane and preparation method thereof | |
| CN105727757A (en) | Preparation method of orientation LTL type molecular sieving membrane for gas separation | |
| CN101259383A (en) | Acidproof zeolite molecular sieve membrane for separating liquid mixture and preparation thereof | |
| CN101837989B (en) | Preparation method of fluorine-containing T-type zeolite membrane | |
| JP5481075B2 (en) | Method for producing zeolite membrane | |
| CN111530302B (en) | Controllable synthesis method of all-silicon and high-silicon CHA molecular sieve membrane | |
| CN101219346A (en) | High temperature enclosed type synthesized high-performance water permeability zeolite molecular sieve film and method for producing the same | |
| CN110508158B (en) | Method for preparing ultrathin SAPO-34 molecular sieve membrane | |
| CN109970075B (en) | Method for synthesizing A-type molecular sieve membrane at low temperature | |
| CN112645344A (en) | Method for preparing SSZ-13 molecular sieve membrane by steam-assisted conversion | |
| CN109663509B (en) | Preparation method of hierarchical pore SAPO-34 molecular sieve membrane | |
| CN114804139B (en) | Preparation method of multi-channel MFI type molecular sieve membrane | |
| JP2002249313A (en) | Method for coating with zeolite crystal, substrate coated with the same, method for manufacturing zeolite film, zeolite film and method of separation | |
| CN111013404B (en) | Rapid and economical synthesis method of ultrathin MFI molecular sieve membrane | |
| CN105366689B (en) | A kind of method of weak solution Microwave-assisted synthesis MOR zeolite molecular sieve films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191224 |
|
| RJ01 | Rejection of invention patent application after publication |