CN101342467A - Preparation method for molecular sieve film for water elimination - Google Patents
Preparation method for molecular sieve film for water elimination Download PDFInfo
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- CN101342467A CN101342467A CNA2008101507183A CN200810150718A CN101342467A CN 101342467 A CN101342467 A CN 101342467A CN A2008101507183 A CNA2008101507183 A CN A2008101507183A CN 200810150718 A CN200810150718 A CN 200810150718A CN 101342467 A CN101342467 A CN 101342467A
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Abstract
The invention relates to a preparation method of a molecular sieve membrane used for water-removal, comprising processing steps of preparation of the precursor sol of a molecular sieve, hydrothermal crystallization and preparation of the molecular sieve membrane. The molecular sieve membrane prepared by the invention has good hydrophilicity and can be used for pervaporation separation of an organic substance/water under a pervaporation condition so as to realize effective desorption of the water in an organic solvent. In separating isopropanol and the water, the pervaporation separation is carried out in 75 DEG C; when the mass concentration of the water on a feed side is 10 percent, an average flux is 1 to 3kg/m<2>.h; and a separation coefficient reaches 100 to 2000; thereby the invention can be used for desorbing a little water in the organic solvent and preparing an anhydrous reagent.
Description
Technical field
The invention belongs to the inorganic material film technical field, be specifically related to molecular sieve film for water elimination.
Background technology
Separation process is important key link in the current suitability for industrialized production, has been widely used in the industry such as chemistry, medicine, food, biochemistry.As operating unit important in the industrial production, the quality of separative efficiency and separating effect directly is decided by the height of quality and the industrial production cost and the profit of product quality.Traditional industrial separation process has: filtration, absorption, condensation, recrystallization, distillation and extraction etc.With respect to traditional separation process, be new membrane separation process process, can under temperate condition, realize separating continuously, energy consumption is low, is easy to amplify, and non-secondary pollution has the function of enrichment method in the separation; Simultaneously easy to operate,, used compact equipment, maintenance cost be low, be easy to automation, thereby it is the higher separation means of a kind of efficient in the modern separation technology, can replace traditional isolation technics.It is the most rising that membrane separation technique has been known as mid-term 20 end of the centurys to 21 century in the world, even can cause the great production technology of an industrial revolution, is called cutting edge technology, becomes the focus of countries in the world scientist research.
Infiltration evaporation is under the component steam pressure difference promotes in liquid mixture, to utilize component by the dissolving of film and the different separating process that realize of diffusion rate.Since last century, the eighties infiltration evaporation was realized industrialization, worldwide, existing 320 cover infiltration evaporation commercial plants became one of field, forward position of membrane separation technique in operation.Infiltration evaporation is particularly suitable for that the way of distillation is difficult to separate or indissociable closely boiling or the separation of vapor of mixture liquid; To minor amount of water in the organic solvent remove or waste water in a small amount of organic separation, and the recovery of high value organic component in the aqueous solution, advantage such as have the efficient height, energy consumption is low, equipment is simple, the technology enlarge-effect is little.Compare with the way of distillation, prepare absolute ethyl alcohol with the infiltration evaporation membrane separation technique from industrial alcohol and can save energy 75%; Be used for producing anhydrous isopropyl alcohol and can save energy 65% from moisture 15% isopropyl alcohol; Be used for esterification production ethyl acetate and can save energy 58%.Infiltration evaporation membrane separation technique separating effect is outstanding, has demonstrated application prospects, is thought 21 century chemical field one of the most promising new and high technology by academia.
Zeolite molecular sieve film is a kind of novel inorganic separating film, has advantages such as the aperture is little, uniformity, Heat stability is good.Molecular screen membrane can carry out Selective Separation according to the difference of component bulk of molecule to be separated and/or polarity.The absorption property of molecular sieve is influenced by its framework si-al ratio, and silica alumina ratio is low then to the polar molecule high adsorption capacity, so the molecule of opposed polarity is separated because of selecting to adsorb in the molecule sieve aperture.Owing to have the not available advantage of other inorganic material films, molecular screen membrane has powerful potential advantages.If can on synthetic technology, have than quantum jump, synthesize defective few or zero defect and the big molecular screen membrane of permeation flux, just be expected to obtain can be used for the membrane material of high-temperature gas separation, catalytic film reactor and process of pervaporation equimolecular horizontal separation process.
Since the nineties in 20th century, the development of molecular screen membrane becomes the focus of inoranic membrane research gradually, and the research report quantity of relevant molecular screen membrane also is the trend that rises year by year.Wherein outstanding with the NaA molecular screen membrane, the NaA molecular screen membrane has the pore structure of molecular dimension size and excellent hydrophilicity, demonstrates very high application prospect at organic solvent aspect dewatering.Mitsui Ship-building Company has realized in 1999 that commercially producing of NaA molecular screen membrane and permeability and separation film organic solvent remove the industrial applications of water separation device.Therefore, molecular screen membrane is an important directions of inoranic membrane development, has vast potential for future development.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the molecular sieve film for water elimination that a kind of method is easy, product cost is low, selectivity is good, the permeate water performance is good.
Solving the problems of the technologies described above the technical scheme that is adopted is that it comprises the steps:
1, vehicle treated
With the porous ceramic pipe carrier through sand papering, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined, the two ends of porous ceramic pipe carrier seal with teflin tape.
2, preparation molecular sieve precursor colloidal sol
Under 700 rev/mins rotating speeds stir with Ludox and aluminium hydroxide or sodium metaaluminate, alkali source, hydromassage you than being 1: 0.067～0.2: 0.74～0.81: 16.6～18 fully to mix, obtain the precursor colloidal sol that hydrophilic molecule sieves; Above-mentioned alkali source is the composition of potassium hydroxide and NaOH, and in its composition, the mol ratio of potassium hydroxide and NaOH is 0.449～0.946; The model of above-mentioned Ludox is AS-40, is produced by U.S. Aldrich company.
3, hydrothermal crystallizing
Precursor colloidal sol is poured in the water under high pressure thermal synthesis reactor that the porous ceramic pipe carrier is housed, the sealing of water under high pressure thermal synthesis reactor is placed on static hydrothermal crystallization in the electric heating constant temperature air dry oven, crystallization temperature is 150～190 ℃, and crystallization time is 24～72 hours.
4, preparation molecular screen membrane
Take out water under high pressure thermal synthesis reactor, naturally the cooling or with being water-cooled to room temperature, take out molecular screen membrane, distilled water soaking at room temperature with 30 times of molecular screen membrane volumes is washed 3～5 times, each 5 hours, take out, 60～80 ℃ of dryings of electric heating constant temperature air dry oven 24 hours, take out, be prepared into the molecule sieve membrane.
5, packing
Wrap with toilet paper, be placed in the drier.
In preparation molecular sieve precursor collosol craft step 2 of the present invention, the preferred molar ratio of Ludox and aluminium hydroxide or sodium metaaluminate, alkali source, water is 1: 0.08～0.15: 0.75～0.79: 17～18.In hydrothermal crystallizing processing step 3, preferred crystallization temperature is that 160～180 ℃, crystallization time are 36～60 hours.
In preparation molecular sieve precursor collosol craft step 2 of the present invention, the optimum mole ratio of Ludox and aluminium hydroxide or sodium metaaluminate, alkali source, water is 1: 0.12: 0.77: 17.2.In hydrothermal crystallizing processing step 3, optimum crystallization temperature is that 175 ℃, crystallization time are 48 hours.
Vehicle treated processing step 1 of the present invention also can for: with the porous ceramic pipe carrier through sand papering, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be coated with method or dip coating carries out kind of a crystallization treatment with hand, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined, the two ends of porous ceramic pipe carrier seal with teflin tape.
Porous ceramic pipe of the present invention is mullite pipe or α-Al
2O
3Pipe.
Mullite pipe of the present invention or α-Al
2O
3The average pore size of pipe is that 0.1～10 μ m, porosity are 30～60%, external diameter is that 10～13mm, wall thickness are 1～3mm.
Adopt the molecular screen membrane of the present invention's preparation, have good hydrophily, under the infiltration evaporation condition, the infiltration evaporation that can be used for organic matter/water separates, and water effectively removes in the realization organic solvent.In the separation of isopropanol, 75 ℃ are carried out the infiltration evaporation separation, and the mass concentration of feed side water is 10% o'clock, and average flux is 1～3kg/m
2H, separation reaches 100～2000, can be used for removing of low amounts of water in the organic solvent, the preparation anhydrous reagent.
Description of drawings
Fig. 1 is the X-ray diffraction curve that adopts the molecular screen membrane of the embodiment of the invention 1 preparation.
Fig. 2 is the electron scanning micrograph that adopts the molecular screen membrane surface of the embodiment of the invention 1 preparation.
Fig. 3 is the electron scanning micrograph that adopts the molecular screen membrane section of the embodiment of the invention 1 preparation.
Fig. 4 is the structural representation of infiltration evaporation separation test device.
The specific embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
With the raw materials used total amount of preparation molecular screen membrane is that 220g is an example, and its preparation method is as follows:
1, vehicle treated
It is carrier that the porous ceramic pipe of present embodiment adopts the mullite pipe, and the average pore size of mullite pipe is 5 μ m, and porosity is 45%, and length is 10cm, and external diameter is 11.5mm, and wall thickness is 2mm.With the mullite pipe through 600 purpose sand paperings, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined, the two ends of porous ceramic pipe carrier seal with teflin tape.
2, preparation molecular sieve precursor colloidal sol
Taking by weighing NaOH 0.868g and KOH 21.327g is dissolved in the 113.375mL water, under stirring, 700 rev/mins rotating speeds add the 2.983g sodium metaaluminate, continue to stir after 30 minutes, adding 81.447g mass concentration is 40% silicon sol solution, continue to stir under the room temperature 1 hour, and obtained the precursor colloidal sol of molecular sieve, raw material Ludox and sodium metaaluminate in the above-mentioned precursor colloidal sol, alkali source, hydromassage you than being 1: 0.067: 0.74: 16.6, in alkali source, the mol ratio of KOH and NaOH is 0.946; The model of the Ludox of present embodiment is AS-40, is produced by U.S. Aldrich company.
3, hydrothermal crystallizing
Precursor colloidal sol is poured in the water under high pressure thermal synthesis reactor that the porous ceramic pipe carrier is housed, the sealing of water under high pressure thermal synthesis reactor is placed on static hydrothermal crystallization in the electric heating constant temperature air dry oven, crystallization temperature is 150 ℃, and crystallization time is 72 hours.
4, preparation molecular screen membrane
Take out water under high pressure thermal synthesis reactor, naturally the cooling or with being water-cooled to room temperature, take out molecular screen membrane, distilled water soaking at room temperature with 30 times of molecular screen membrane volumes is washed 3～5 times, each 5 hours, take out, 60～80 ℃ of dryings of electric heating constant temperature air dry oven 24 hours, take out, be prepared into the molecule sieve membrane.
5, packing
Wrap with toilet paper, be placed in the drier.
With the raw materials used total amount of preparation molecular screen membrane is that 220g is an example, and its preparation method is as follows:
In vehicle treated processing step 1, it is carrier that the porous ceramic pipe of present embodiment adopts the mullite pipe, and the average pore size of mullite pipe is 0.1 μ m, and porosity is 30%, and length is 10cm, and external diameter is 10mm, and wall thickness is 1mm.Other step in this processing step is identical with embodiment 1.In preparation molecular sieve precursor collosol craft step 2, taking by weighing NaOH 8.947g and KOH 10.243g is dissolved in the 117.357mL water, under stirring, 700 rev/mins rotating speeds add the 8.225g sodium metaaluminate, continue to stir after 30 minutes, adding 75.228g mass concentration is 40% silicon sol solution, continue under the room temperature to stir 1 hour, obtain the precursor colloidal sol of molecular sieve, raw silicon colloidal sol and sodium metaaluminate in the above-mentioned precursor colloidal sol, alkali source, hydromassage you than being 1: 0.2: 0.81: 18, in alkali source, the mol ratio of KOH and NaOH is 0.449.In hydrothermal crystallizing processing step 3, precursor colloidal sol is poured in the water under high pressure thermal synthesis reactor that the porous ceramic pipe carrier is housed, the sealing of water under high pressure thermal synthesis reactor is placed on static hydrothermal crystallization in the electric heating constant temperature air dry oven, and crystallization temperature is 190 ℃, and crystallization time is 24 hours.Other step is identical with embodiment 1, is prepared into the molecule sieve membrane.
With the raw materials used total amount of preparation molecular screen membrane is that 220g is an example, and its preparation method is as follows:
In vehicle treated processing step 1, it is carrier that the porous ceramic pipe of present embodiment adopts the mullite pipe, and the average pore size of mullite pipe is 10 μ m, and porosity is 60%, and length is 10cm, and external diameter is 13mm, and wall thickness is 3mm.Other step in this processing step is identical with embodiment 1.In preparation molecular sieve precursor collosol craft step 2, taking by weighing NaOH 4.405g and KOH 16.57g is dissolved in the 115.186mL deionized water, under stirring, 700 rev/mins rotating speeds add the 5.161g sodium metaaluminate, continue to stir after 30 minutes, adding 78.678g mass concentration is 40% silicon sol solution, continue under the room temperature to stir 1 hour, obtain the precursor colloidal sol of molecular sieve, raw material Ludox and sodium metaaluminate in the above-mentioned precursor colloidal sol, alkali source, hydromassage you than being 1: 0.12: 0.77: 17.2, in alkali source, the mol ratio of KOH and NaOH is 0.728.In hydrothermal crystallizing processing step 3, precursor colloidal sol is poured in the water under high pressure thermal synthesis reactor that the porous ceramic pipe carrier is housed, the sealing of water under high pressure thermal synthesis reactor is placed on static hydrothermal crystallization in the electric heating constant temperature air dry oven, and crystallization temperature is 175 ℃, and crystallization time is 48 hours.Other step is identical with embodiment 1, is prepared into the molecule sieve membrane.
With the raw materials used total amount of preparation molecular screen membrane is that 220g is an example, and its preparation method is as follows:
In preparing in the molecular sieve precursor collosol craft step 2 of above embodiment 1～3, sodium metaaluminate is replaced with aluminium hydroxide, sodium metaaluminate is identical with the molal quantity of aluminium hydroxide, the molal quantity of other raw material is identical with respective embodiments, and other step in this processing step is identical with respective embodiments.Other processing step is identical with embodiment 1, is prepared into the molecule sieve membrane.
With the raw materials used total amount of preparation molecular screen membrane is that 220g is an example, and its preparation method is as follows:
In the vehicle treated processing step 1 of above embodiment 1～4, used porous ceramic pipe adopts α-Al
2O
3Pipe, α-Al
2O
3Other step and respective embodiments in identical this processing step with the geometry of mullite pipe among the corresponding embodiment of the geometry of pipe are identical.Other processing step is identical with respective embodiments, is prepared into the molecule sieve membrane.
With the raw materials used total amount of preparation molecular screen membrane is that 220g is an example, and its preparation method is as follows:
In the vehicle treated processing step 1 of above embodiment 1～5, with the porous ceramic pipe carrier through sand papering, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be coated with method or dip coating carries out kind of a crystallization treatment with hand, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined, the two ends of porous ceramic pipe carrier seal with teflin tape.Other processing step is identical with respective embodiments, is prepared into the molecule sieve membrane.
In order to verify beneficial effect of the present invention, the inventor adopts the molecular screen membrane of the embodiment of the invention 3 preparations to test, and various tests are as follows:
Test apparatus: X-ray diffractometer, model are Rigaku D/Max2550VB+/PC, and produced by Japanese Rigalcu: Fourier transformation infrared spectrometer, model are EQUINX, are produced by German Brucher company; SEM, model are Quanta 200, are produced by FEI Co..
1, the sign of molecular screen membrane
Adopt the X-ray diffraction curve of the molecular screen membrane of the embodiment of the invention 3 preparations to see Fig. 1, electron scanning micrograph is seen Fig. 2, Fig. 3.
In Fig. 1, curve a is the X-ray diffraction spectrogram of molecular screen membrane, and curve b is the X-ray diffraction spectrogram of the molecular sieve crystal of association, and curve c is the X-ray diffraction spectrogram of mullite pipe carrier.As seen from Figure 1, the characteristic peak 5.55 °, 11.77 °, 15.22 °, 19.30 °, 20.47 °, 22.66 °, 24.32 °, 25.59 °, 27.12 °, 28.00 °, 29.10 ° and 30.71 ° proves that obviously the molecular screen membrane of gained and the powder of association thereof all have the LTL structure.As seen from Figure 2, mullite pipe carrier surface is covered by molecular sieve crystal, forms the crystal layer of a densification, size average out to 1～2 μ m of carrier surface LTL type molecular sieve crystalline substance.As seen from Figure 3, the thickness of molecular screen membrane is 10～20 μ m.
2, separate the alcohol compound aqueous solution and aqueous acetone solution with molecular screen membrane
Solution to be separated is contained in the glass container 4 that has reflux condensing tube 1, is placed on then in the water bath 8 that is fixed on the magnetic stirring apparatus 6.One end of molecular screen membrane 5 and external diameter are 12mm, longly block up for the teflon rod 7 of 2cm is connected, and the other end of molecular screen membrane 5 is that 12mm, length are that glass tube and the vacuum system 3 of 3～4cm links by an external diameter.The outside of molecular screen membrane 5 contacts with solution to be separated, the inboard vacuumizes is 25～45Pa.Infiltration steam is collected in the cold-trap 2 with cooled with liquid nitrogen, also can adopt alternately follow-on test of two cold-traps 2.Each component concentrations is determined by gas chromatographic analysis in solution to be separated and the collection liquid.Total flux is calculated as follows:
Q (kg/m
2H)=collect gross mass/(area of acquisition time * film) of liquid
Q is a total flux in the formula, in the unit interval unit are, by the infiltration evaporation process in the gross mass that sees through the collected organic matter/water of side; The gross mass of collecting liquid obtains by the quality of collecting liquid in the balance weighing cold-trap 2.Acquisition time begins to collected specimens institute elapsed time from cold-trap 2 for the infiltration evaporation process; The area of molecular screen membrane 5 is the area of the film that contacted with solution to be separated in the infiltration evaporation process.The area of used molecular screen membrane 5 is 22.6cm in this experiment
2Separation is calculated as follows
α＝(Y
w/Y
0)/(X
w/X
0)，
α is a separation in the formula, Y
0And Y
wBe the quality percentage composition of organic matter and water in the liquid of collecting in the cold-trap 2, X
0And X
wBe the quality percentage composition of organic matter and water in the solution to be separated, the size of separation is to estimate the major parameter of molecular screen membrane 5 separating property quality.
This test is tested in isopropanol, ethanol/water and three kinds of solution solution of acetone respectively.The infiltration evaporation separation test the results are shown in Table 1.
The Pervaporation Separation of the molecular screen membrane 5 of table 1 embodiment 3 preparations
By table 1 as seen, prepared molecular screen membrane 5 has the penetrated preferably selectivity for the glassware for drinking water of trace in selected three kinds of organic solvents, can be used for removing of minor amount of water in the organic solution.
Compare with the high hydrophilic separating property in the isopropanol system, though the less better (Q=0.87kg/m of separating property of 5 pairs of ethanol/water systems of this molecular screen membrane
2H, α=107), but still have very high hydrophilic separating property.For the acetone system, the separation selectivity of 5 pairs of water of molecular screen membrane is up to 1400, and flux has also reached 1.54kg/m
2H.By the evaluation test of three kinds of organic solvent/aqueous systems, illustrate that prepared molecular screen membrane 5 is the strongly hydrophilic molecular screen membrane, can be used to prepare anhydrous organic solvent, have prospects for commercial application.
Claims (6)
1, a kind of preparation method of molecular sieve film for water elimination is characterized in that it comprises the steps:
(1) vehicle treated
With the porous ceramic pipe carrier through sand papering, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined, the two ends of porous ceramic pipe carrier seal with teflin tape;
(2) preparation molecular sieve precursor colloidal sol
Under 700 rev/mins rotating speeds stir with Ludox and aluminium hydroxide or sodium metaaluminate, alkali source, hydromassage you than being 1: 0.067～0.2: 0.74～0.81: 16.6～18 fully to mix, obtain the precursor colloidal sol that hydrophilic molecule sieves; Above-mentioned alkali source is the composition of potassium hydroxide and NaOH, and in its composition, the mol ratio of potassium hydroxide and NaOH is 0.449～0.946;
(3) hydrothermal crystallizing
Precursor colloidal sol is poured in the water under high pressure thermal synthesis reactor that the porous ceramic pipe carrier is housed, the sealing of water under high pressure thermal synthesis reactor is placed on static hydrothermal crystallization in the electric heating constant temperature air dry oven, crystallization temperature is 150～190 ℃, and crystallization time is 24～72 hours;
(4) preparation molecular screen membrane
Take out water under high pressure thermal synthesis reactor, naturally the cooling or with being water-cooled to room temperature, take out molecular screen membrane, distilled water soaking at room temperature with 30 times of molecular screen membrane volumes is washed 3～5 times, each 5 hours, take out, 60～80 ℃ of dryings of electric heating constant temperature air dry oven 24 hours, take out, be prepared into the molecule sieve membrane.
2, dewater with the preparation method of zirconium-silicon molecular sieve film according to claim 1 is said, it is characterized in that: in preparation molecular sieve precursor collosol craft step (2), said Ludox and aluminium hydroxide or sodium metaaluminate, alkali source, hydromassage you than being 1: 0.08～0.15: 0.75～0.79: 17～18; In hydrothermal crystallizing processing step (3), said crystallization temperature is that 160～180 ℃, crystallization time are 36～60 hours.
3, according to the preparation method of the said molecular sieve film for water elimination of claim 1, it is characterized in that: in preparation molecular sieve precursor collosol craft step (2), said Ludox and aluminium hydroxide or sodium metaaluminate, alkali source, hydromassage you than being 1: 0.12: 0.77: 17.2; In hydrothermal crystallizing processing step (3), said crystallization temperature is that 175 ℃, crystallization time are 48 hours.
4, according to the preparation method of the said molecular sieve film for water elimination of claim 1, it is characterized in that said vehicle treated processing step (1) is: with the porous ceramic pipe carrier through sand papering, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be coated with method or dip coating carries out kind of a crystallization treatment with hand, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined, the two ends of porous ceramic pipe carrier seal with teflin tape.
5, according to the preparation method of the said molecular sieve film for water elimination of claim 1, it is characterized in that: said porous ceramic pipe is mullite pipe or α-Al
2O
3Pipe.
6, according to the preparation method of the said molecular sieve film for water elimination of claim 5, it is characterized in that: said mullite pipe or α-Al
2O
3The average pore size of pipe is that 0.1～10 μ m, porosity are 30～60%, external diameter is that 10～13mm, wall thickness are 1～3mm.
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Cited By (5)
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| CN105727757A (en) * | 2016-03-18 | 2016-07-06 | 宁夏大学 | Preparation method of orientation LTL type molecular sieving membrane for gas separation |
| CN103816815B (en) * | 2012-11-15 | 2017-09-05 | 日立造船株式会社 | The device and method of alkene is separated, reclaimed from the mixture of alkane and alkene |
| CN109081356A (en) * | 2018-10-12 | 2018-12-25 | 安徽工程大学 | A method of fine and close zero defect molecular screen membrane is grown in tubular porous support inner wall |
| CN109956852A (en) * | 2018-12-20 | 2019-07-02 | 湖南东搏科技有限公司 | The method of energy-efficient preparing benzenediol from hydroxylating phenol |
| CN113265493A (en) * | 2021-06-04 | 2021-08-17 | 四川大学 | Tanning method without tanning agent |
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| CN104815566B (en) | 2015-04-28 | 2017-03-08 | 南京工业大学 | Preparation method of antibacterial dust removal film |
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| CN103816815B (en) * | 2012-11-15 | 2017-09-05 | 日立造船株式会社 | The device and method of alkene is separated, reclaimed from the mixture of alkane and alkene |
| CN105727757A (en) * | 2016-03-18 | 2016-07-06 | 宁夏大学 | Preparation method of orientation LTL type molecular sieving membrane for gas separation |
| CN105727757B (en) * | 2016-03-18 | 2019-12-24 | 宁夏大学 | Preparation method of oriented LTL type molecular sieve membrane for gas separation |
| CN109081356A (en) * | 2018-10-12 | 2018-12-25 | 安徽工程大学 | A method of fine and close zero defect molecular screen membrane is grown in tubular porous support inner wall |
| CN109081356B (en) * | 2018-10-12 | 2021-04-20 | 安徽工程大学 | Method for growing compact defect-free molecular sieve membrane on inner wall of tubular porous carrier |
| CN109956852A (en) * | 2018-12-20 | 2019-07-02 | 湖南东搏科技有限公司 | The method of energy-efficient preparing benzenediol from hydroxylating phenol |
| CN113265493A (en) * | 2021-06-04 | 2021-08-17 | 四川大学 | Tanning method without tanning agent |
| CN113265493B (en) * | 2021-06-04 | 2022-03-01 | 四川大学 | Tanning method without tanning agent |
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| CN101342467B (en) | 2011-11-16 |
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