CN1453063A - Application of zeolite molecular sieve film in the separation of ethylidene dichloride-nitrogen mixture - Google Patents
Application of zeolite molecular sieve film in the separation of ethylidene dichloride-nitrogen mixture Download PDFInfo
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- CN1453063A CN1453063A CN 03111690 CN03111690A CN1453063A CN 1453063 A CN1453063 A CN 1453063A CN 03111690 CN03111690 CN 03111690 CN 03111690 A CN03111690 A CN 03111690A CN 1453063 A CN1453063 A CN 1453063A
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- molecular sieve
- dichloroethanes
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to the separation of organic macromolecular gas(es) and inorganic small molecular gas. The present invention features the sol compounded with Na2O, SiO2, Al2O3 and H2O in the molar ratio of 15-25 to 6.4-25.6 to 1 to 300-1500; the alpha-Al2O3 carrier tube, which is surface activated with organic acid or alcohol solvent before synthesis and then low temperature crystallized in hydrothermal condition for 20-36 hr to synthesize NaY zeolite molecular sieve film; the ion exchange of the NaY zeolite film in alkali or alkali earth solution at 60 deg.c for 4 hr to obtain KY, LiY, CaY, BaY and other zeolite film; and the film tube set inside film separator with pressure difference on two sides controlled in 10-100 KPa to result in the separating factor between dichloroethane and nitrogen of 20-80. The present invention has the features of simple apparatus and low power consumption.
Description
Technical field
The invention belongs to technical field of chemical engineering, relate to organic macromolecule gas and inorganic molecules separation of gaseous mixture, specially refer to the separation method of dichloroethanes and nitrogen in the chlorine industry.
Technical background
In the chlor-alkali plant of petroleum chemical industry, produce in the process of PVC at present, the storage and the transmission that have a large amount of intermediate product dichloroethanes are used.Therefore all be to seal dichloroethanes on the technology, can produce a large amount of by the saturated nitrogen of dichloroethanes with nitrogen.Industrially do not do recycling, therefore caused the waste of atmosphere pollution and resource usually with its direct emptying.
Reclaim the adoptable technology of dichloroethanes from separating of dichloroethanes and nitrogen mixture and mainly contain condensation separation method, absorption process, absorption method.
The condensation separation method is with the gaseous mixture condensation liquefaction that pressurizes, and utilizes rectifying that nitrogen is separated with dichloroethanes again.Because the boiling point of nitrogen is-195.8 ℃, the boiling point of dichloroethanes is 83.4 ℃, need high pressure and low temperature as if the mixture liquefaction with both, so its energy consumption is very high, and equipment investment is big, and economic benefit is low.
Absorption process is that employing tetrachloroization two carbon or trichloropropane are absorbent, absorbs dichloroethanes at low temperatures, resolves through high temperature and reclaims dichloroethanes.The absorbent of this technology source difficulty, energy waste is also very serious, and the nitrogen in the tail gas also takes away certain solvent, thereby causes new pollution.Therefore this The Application of Technology also is restricted.
Absorption method is that employing is an adsorbent to active carbon or the NACF that dichloroethanes has very high selection absorption property, adsorbs dichloroethanes at low temperatures, inhales the residual air nitrogen purge.When adsorbent bed reaches capacity, reclaim dichloroethanes through the high temperature desorb.Environment measuring center, Nanjing is an adsorbent with active carbon, micro-dichloroethanes in the enriched air By, and tetrachloro-ethylene, organic pollutions such as bromic ether have been obtained good effect.But because the concentration of dichloroethanes is about 20% (mol) in the dichloroethanes storage tank breathing gas of vinyl chloride workshop, adopt absorption method to reclaim dichloroethanes, certainly will need a large amount of adsorbents, cause equipment volume huge, high temperature desorption energy consumption height, the cooling difficulty has restricted industrial applications.
Summary of the invention
The purpose of this invention is to provide a kind of membrane separating method that just can separate dichloroethanes and nitrogen at normal temperatures, utilize this method to prepare a kind of zeolite molecular sieve film with special pore size distribution, this zeolite membrane has selective absorption to polar gas, make organic macromolecule gas in its hole, capillary condensation take place simultaneously, and then stop inorganic molecules gas to pass through, realize the separation of mist.
Key of the present invention is to synthesize the NaY zeolite molecular sieve film.Realize that technical scheme of the present invention is, according to Na
2O: SiO
2: Al
2O
3: H
2O=(15～25): (6.4～25.6): 1: the mole proportioning preparation colloidal sol of (300～1500), wherein aluminum contained compound can use gibbsite, aluminum sulfate, alchlor or old metal aluminium etc., raw silicon oxide material can be waterglass, silicic acid, Ludox halogenated silanes and the unformed silica of various activity etc., and NaOH and water is raw material, is made into colloidal sol through stirring.Adopt α-Al
2O
3Earthenware (aperture 3～5 μ m, porosity 30～50%) is carrier, support tube is through organic acid (citric acid, EDTA, acetate etc.) or organic alcohols solvent (ethanol, n-butanol, isopropyl alcohol, glycerine etc.) surface activation process, low temperature crystallized synthetic NaY zeolite molecular sieve film under hydrothermal condition then before synthetic.
The present invention also can carry out cation exchange with synthetic film, obtains Modified Membrane such as KY, LiY, CaY and BaY.The structure of zeolite membrane and outward appearance are confirmed through X-ray diffraction and stereoscan photograph analysis.
Effect of the present invention is to have realized under the normal temperature separating of dichloroethanes and nitrogen that equipment is simple with benefit, and energy savings can be avoided environmental pollution again simultaneously, has reclaimed valuable resource, has improved existent environment of people.
Description of drawings
Accompanying drawing is the apparatus structure schematic diagram that the y-type zeolite film separates dichloroethanes and nitrogen.
(1) vavuum pump among the figure; (2) gaseous mixture; (3) needle valve; (4) Pressure gauge; (5) osmotic cell; (6) film pipe; (7) gas-chromatography; (8) soap film flowmeter.
The specific embodiment
Be described in detail the specific embodiment of the present invention and most preferred embodiment below in conjunction with accompanying drawing
Embodiment:
Colloidal sol preparation: in the beaker of 400ml, add 32g NaOH and 100ml water, fully dissolving back adding 44.8ml Ludox under brute force stirs obtains solution (a), then 16.7g aluminum sulfate is dissolved in and gets solution (b) in the 110ml water, slowly solution (b) is added drop-wise in the solution (a) again, forms leucosol.
The carrier preliminary treatment: before synthesizing that carrier surface is smooth with 400#, 600#, 800# sand papering, use ultrasonic oscillation again, flush away surface and hole inner suspension particle soak 1～2d with acid or alkali then, and ultrasonic wave is washed to neutrality, dry for standby.
Film preparation: the pretreated support tube of learning from else's experience, with citric acid immersion treatment support tube surface, to manage two ends after the processing shuts with poly tetrafluoroethylene, vertically put into the stainless steel crystallizing kettle, slowly add still in along tube wall colloidal sol, be put into after sealing in 100 ℃ the baking oven, crystallization 24h takes out, and cools off naturally and is washed till neutrality with deionized water.Air drying 1～2d, again at 100 ℃ of drying 1～2d, before roasting through N
2If test still ventilative, then repeats crystallization to airtight.
The film roasting: in air atmosphere according to certain heating and cooling program roasting film pipe, to remove the crystallization water in the fenestra.Heating rate is: 0.5～1K/min, rate of temperature fall is: 1～2K/min.
The cation exchange modification: with the NaY zeolite membrane under 60 ℃, at 0.4mol/l
-1KNO
3Effects of ion exchange 4h.After the ion-exchange treatment, the film pipe is at room temperature used rinsed with deionized water 12h, then 150 ℃ of dry 1d.
The NaY zeolite membrane that will make according to the method described above then and install in the membrane separation device shown in the accompanying drawing with the film after the cation exchange, the pressure reduction at film two ends is controlled at 40kPa.The air inlet side concentration of dichloroethanes is 13%, air inlet effluent speed 180ml/min; Tail gas concentration is 4.5%, flow velocity 160ml/min.The branch factor of the two is 30.
Claims (1)
1. a zeolite molecular sieve film is used for the separation method of dichloroethanes and nitrogen mixture, it is characterized in that according to Na
2O: SiO
2: Al
2O
3: H
2O=(15～25): (6.4～25.6): 1: the mole proportioning preparation colloidal sol of (300～1500), wherein aluminum contained compound can use gibbsite, aluminum sulfate, alchlor or old metal aluminium etc., but raw silicon oxide material waterglass, silicic acid, Ludox halogenated silanes and the unformed silica of various activity etc., and NaOH and water is raw material, is made into colloidal sol through stirring; Adopt α-Al
2O
3Earthenware, pore directly is 3～5 μ m, porosity 30～50% is a carrier, support tube is through organic acid before synthetic, as surface activation process such as citric acid, EDTA, acetate etc. or organic alcohols solvent such as ethanol, n-butanol, isopropyl alcohol, glycerine, 80 ℃～100 ℃ of low temperature under hydrothermal condition then, crystallization 20～36h synthesizes the NaY zeolite molecular sieve film, before roasting through N
2If test still ventilative, then repeats crystallization to airtight; Then with the NaY zeolite membrane under 60 ℃, at 0.1～0.4mol/l
-1Alkali and alkaline earth effects of ion exchange 4h; After the ion-exchange treatment, the film pipe is at room temperature used rinsed with deionized water 12h, then 150 ℃ of dry 1d; At last the film pipe is placed membrane separation device, control both sides differential pressure of membrane 10～100kpa, the separation factor of dichloroethanes and nitrogen is between 20～80.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031116906A CN1195578C (en) | 2003-05-15 | 2003-05-15 | Application of zeolite molecular sieve film in the separation of ethylidene dichloride-nitrogen mixture |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031116906A CN1195578C (en) | 2003-05-15 | 2003-05-15 | Application of zeolite molecular sieve film in the separation of ethylidene dichloride-nitrogen mixture |
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| Publication Number | Publication Date |
|---|---|
| CN1453063A true CN1453063A (en) | 2003-11-05 |
| CN1195578C CN1195578C (en) | 2005-04-06 |
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|---|---|---|---|
| CNB031116906A Expired - Fee Related CN1195578C (en) | 2003-05-15 | 2003-05-15 | Application of zeolite molecular sieve film in the separation of ethylidene dichloride-nitrogen mixture |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344352C (en) * | 2005-06-03 | 2007-10-24 | 大连理工大学 | Process for separating mixture of benzene and nitrogen gas by X-type fluorite film |
| CN101279208B (en) * | 2008-05-20 | 2010-06-09 | 吉林大学 | Method for preparing Y type molecular sieve film |
| CN1946658B (en) * | 2004-04-26 | 2010-06-23 | 昭和电工株式会社 | Method for purification of 1,1-dichloroethane and process for production of 1,1-difluoroethane using this method |
| CN101099924B (en) * | 2006-07-06 | 2010-12-01 | 中国科学院大连化学物理研究所 | Method for preparing chitosan/ZSM-5 molecular compound film |
| CN105363352A (en) * | 2015-11-14 | 2016-03-02 | 大连理工大学 | Method for synthesizing high acid resistant MOR zeolite molecular sieve membrane from fluorine-containing dilute solution |
| CN105531020A (en) * | 2013-05-07 | 2016-04-27 | 陶氏环球技术有限责任公司 | Vacuum-assisted process for preparing an ion-exchanged zeolite membrane |
| CN109110782A (en) * | 2018-10-09 | 2019-01-01 | 山东国瓷功能材料股份有限公司 | A kind of preparation method of SSZ-13 molecular sieve |
| CN112118902A (en) * | 2019-05-09 | 2020-12-22 | 三井易艾斯机械有限公司 | Method for treating fluid to be treated supplied to zeolite membrane |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653715B (en) * | 2008-08-20 | 2012-01-04 | 中国科学院大连化学物理研究所 | Process for improving chemical reaction conversion rate by utilizing FAU-type molecular sieve membrane |
-
2003
- 2003-05-15 CN CNB031116906A patent/CN1195578C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1946658B (en) * | 2004-04-26 | 2010-06-23 | 昭和电工株式会社 | Method for purification of 1,1-dichloroethane and process for production of 1,1-difluoroethane using this method |
| CN100344352C (en) * | 2005-06-03 | 2007-10-24 | 大连理工大学 | Process for separating mixture of benzene and nitrogen gas by X-type fluorite film |
| CN101099924B (en) * | 2006-07-06 | 2010-12-01 | 中国科学院大连化学物理研究所 | Method for preparing chitosan/ZSM-5 molecular compound film |
| CN101279208B (en) * | 2008-05-20 | 2010-06-09 | 吉林大学 | Method for preparing Y type molecular sieve film |
| CN105531020A (en) * | 2013-05-07 | 2016-04-27 | 陶氏环球技术有限责任公司 | Vacuum-assisted process for preparing an ion-exchanged zeolite membrane |
| CN105363352A (en) * | 2015-11-14 | 2016-03-02 | 大连理工大学 | Method for synthesizing high acid resistant MOR zeolite molecular sieve membrane from fluorine-containing dilute solution |
| CN109110782A (en) * | 2018-10-09 | 2019-01-01 | 山东国瓷功能材料股份有限公司 | A kind of preparation method of SSZ-13 molecular sieve |
| CN112118902A (en) * | 2019-05-09 | 2020-12-22 | 三井易艾斯机械有限公司 | Method for treating fluid to be treated supplied to zeolite membrane |
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| Publication number | Publication date |
|---|---|
| CN1195578C (en) | 2005-04-06 |
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