CN105883719A - Device for separating hydrogen and helium through PET film - Google Patents
Device for separating hydrogen and helium through PET film Download PDFInfo
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- CN105883719A CN105883719A CN201610188831.5A CN201610188831A CN105883719A CN 105883719 A CN105883719 A CN 105883719A CN 201610188831 A CN201610188831 A CN 201610188831A CN 105883719 A CN105883719 A CN 105883719A
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- helium
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- semipermeable membrane
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- hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0042—Physical processing only by making use of membranes
- C01B23/0047—Physical processing only by making use of membranes characterised by the membrane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
Abstract
The invention discloses a device for separating hydrogen and helium through a PET film, and aims at solving the problems that a method of liquid air separation or natural gas cryogenic separation is mainly adopted in industrial helium preparation at present, the requirement for equipment is high, and energy consumption is large. The device for separating helium in natural gas and comprehensively utilizing hydrogen in mixed gas through the PET (the main raw material for common mineral water bottles) film is designed. Several embodiments for increasing the film superficial area include a branch tubule scheme (hydrogen and helium in raw material gas can be separated most thoroughly), a bi-layer thin-wall clamping tubule array scheme (leaked gas is minimal when the device is broken mechanically), a three-dimensional orthogonal stacking double-layered tube scheme (cost is minimal for acquiring unit volume of hydrogen or helium) and a zigzag foldable multi-layer thin film scheme (the manufacturing cost of the device is minimal), separation can be achieved at a low temperature and low pressure, the device has the advantages that separation is easy, convenient and quick, the energy consumption and cost are low and the product purity is high, and prospects are good.
Description
Technical field
The present invention relates to the use of hydrogen in PET semipermeable membrane separation mixed gas, the method for helium and accelerate to separate
The method of the rate of departure of the semipermeable membrane that coefficient is less, with the equipment using these methods.
Background technology
Domestic current industrial making pure helium mainly uses separation liquid air or the side of natural gas cryogenic separation
Method, high to equipment requirements, energy consumption is bigger.From the point of view of world wide, helium ratio in atmosphere is relatively low,
Skewness in natural gas.At present, multinational " helium storehouse " supply falls short of demand, helium, liquid helium, helium air-making
Product are expensive.How to reduce the cost obtaining helium, become problem demanding prompt solution.
From the point of view of molecular structure, organic polymeric plastic is usually present bigger molecular gap, as poly-to benzene
The molecular gap radius of dioctyl phthalate second diester (Poly Ethylene Terephthalate, hereinafter referred to as PET)
More than hydrogen, the molecular radius (order of magnitude is about 0.1nm) of helium, determine hydrogen molecule, helium gas molecules
The molecule less Deng radius can pass through.
Laboratory observation finds, when the cylindrical pet container smooth with a constant volume (0.5L) inside and outside wall is airtight
Certain pressure intensity (2atm) pure hydrogen or helium, then gas under constant room temperature (298K) through same shape,
Size, surfaces externally and internally amasss, and container wall thickness (1mm) PET semipermeable membrane container, in bottle, pressure becomes 1atm institute
Take time about 10h.After about 5d, if keeping container volume constant, then in PET bottle, pressure can be down to 0.1atm
Below.And this phenomenon can repeat more than 70 times.
It is simple and efficient that semi-transparent embrane method has separation, and energy consumption is low, low cost, the advantage that product purity is high, prospect
Preferably.Meanwhile, PET is cheap, and conventional plastic beverage bottle i.e. uses this kind of material to make.Therefore, profit
The gas fractionation unit manufactured and designed with the selective penetrated property of PET film, can be under relatively low cost with energy consumption
Obtain the helium that present price is expensive, but currently have no relevant other patent that can be retrieved.
Summary of the invention
Present invention aim at providing hydrogen in separation mixed gas, helium simple and efficient, energy consumption is low, low cost,
Hydrogen, helium separation method and the segregation apparatus that product purity is high.Meanwhile, the object of the invention lies also in and passes through
The improvement of membrane structure makes the raising of the filter efficiency of semipermeable membrane, and expands to for separation less by application
And the raising of the filter efficiency of the semipermeable membranes that separation factor is higher, especially PET film.
For achieving the above object, it is provided that a kind of utilize PET film separation hydrogen and the device of helium, its feature exists
In, comprising: gas washing equipment, removing the oxygen in unstripped gas, hydrogen sulfide, ammonia, steam etc. successively has
Evil component is to volume fraction less than 0.05%；Compression device, pressurization gas washing after unstripped gas to more than 4atm,
Below 150atm, to increase the dividing potential drop of hydrogen, helium；Air-extractor, decompression forms parital vacuum, and can
It is filled with and extracts the delivery gas (such as carbon dioxide) easily washed away again and transport and diffuse to the hydrogen of low-voltage space, helium
Gas；Air filtration equipment, use increase surface area PET semipermeable membrane from unstripped gas filter out hydrogen, helium or its
Gaseous mixture, if desired, unstripped gas will be through multistage air filtration equipment；Reclaimer, with molecular sieve or hydrogen storage material
Hydrogen in material, or alkali metal recovery hydrogen, helium gas mixture；Off-the-shelf hardware, stores, processes enrichment after filtration
Hydrogen, the gas of helium, make gas with various product, such as pure helium, pure hydrogen, helium air (helium
Mixed gas with oxygen volume ratio 78: 22), other is hydrogeneous or containing gaseous mixture etc. of helium.
Monofilm prism close paving scheme, for a kind of semipermeable membrane area that increases to improve the side of semipermeable membrane filter efficiency
Method, it is characterised in that: the semipermeable membrane that separation factor is higher for separation is less, especially such as PET
The semipermeable membrane of film one class, uses honey comb like monolayer semipermeable membrane prism structure, and its cross section is positive six limits of Mi Pu
Shape, is divided into low concentration cylindrical cavity and the mixing of logical raw material of logical vehicle medium fluid (such as solution or delivery gas)
The high concentration cylindrical cavity of fluid, during filtration, low concentration cylindrical cavity surrounds high concentration cylindrical cavity, it is achieved mesh
Mark product spreads to vehicle medium fluid (such as solution or delivery gas) from raw material.
Three-dimensional orthogonal stacking bimetallic tube scheme, improves semipermeable membrane for one increase semipermeable membrane area and selects to pass through
Efficiency, simultaneously improves the method that when structure ensures pressurization, semipermeable membrane does not ruptures, it is characterised in that: pin
To semipermeable membrane, especially as less in PET film one class separation and semipermeable membrane that separation factor is higher, use
The prismatic semipermeable membrane pipe box semi-transparent membrane tube of inside cylindrical shape in outside, makes semipermeable membrane bimetallic tube；Bimetallic tube is indirect
Tactile relation is inscribe and the cross section of adhesion, i.e. cylindrical tube is just the inscribed circle of external contact zone；Will be with
Transversely, longitudinally, vertical semipermeable membrane bimetallic tube is unit, the alternate stacking of three-dimensional orthogonal, is placed in heavy wall empty
Intracavity；The frustum cone side shape tubule that each units terminal number is identical with prismatic pipe rib number connects evacuation
Gap between cylindrical tube and prismatic pipe is also inserted in region, simultaneously works as fixing and will filter product guiding container
Outer effect.
Preferably, above-mentioned three-dimensional orthogonal stacking bimetallic tube scheme, it is characterised in that: perform to select through gas
Or during the operation of solute, be sandwiched in outside cylindrical tube and inside prismatic pipe between gap be low-voltage space,
It is passed through delivery gas or evacuation；Inside cylindrical tube and it is high-pressure space outside prismatic pipe, is passed through pressurization
Unstripped gas；When occurring damaging, only with the bimetallic tube changing single damage.
Double-layer thin wall folder tubule battle array scheme, for a kind of reduce semipermeable membrane by mechanical damage time the scheme that leaks, its
It is characterised by: described double-layer thin wall folder tubule battle array scheme, is the rhombus cancellate semipermeable membrane of close paving by cross section
Inscribe and the tubular semipermeable membrane of adhesion, according to the concentration difference of fluid target product component be divided into high concentration chamber with
Low concentration chamber, when pressurization passes through, high concentration chamber, low concentration chamber distribute alternately, and tubular semipermeable membrane is high concentration
Chamber, and arrange one without tube layer every 7-16 layer grid.
Tortuous folding multilayer thin film scheme, for a kind of scheme increasing semipermeable membrane chamber specific surface area, its feature exists
In: it is continuous folding shape that described scheme tortuous folding multilayer thin film folds semipermeable membrane, and surface tool is shaped as radius
Recessed or the protruding sunsidiary fold of first-order fold axial plane separation it is less than or equal to, according to fluid target more than thickness
The concentration difference of product component is divided into high concentration chamber and low concentration chamber, carries out through high concentration chamber during operation, low
Concentration chamber distributes alternately, and fluid flows the most round about.
Branch's tubule scheme, for a kind of scheme increasing semipermeable membrane chamber specific surface area, it is characterised in that: described
Semipermeable membrane is made branch-like tubulose by scheme, and branch is less than 8 times, and most will to segment Zhi Huihe be pencil；
Carry out flowing in opposite directions through high concentration fluid, low-concentration fluid during operation, contain high concentration fluid, low concentration
The segmentation of fluid is wrapped in splendid attire low-concentration fluid, the trunk branch of high concentration fluid respectively.Especially
Ground, when tubule materials is PET, when the tube wall thickness of branch is less than 0.07mm, converges all end branches,
If gaseous mixture kept in by air bag, until its volume no longer reduces.Or with capillary quartz glass tube by hydrogen, helium
Gas one step proposes.Thus the hydrogen being completely separated in unstripped gas most and helium.
Extraly, according to the principle separating hydrogen with PET film, helium device is identical, design is a kind of with PET
Film is the sampler that shell collects helium isotope, it is characterised in that: described sampler is shaped as spherical, shell
0.025mm, no thicker than 0.581mm it is not thinner than for be made up of PET film, the uniform spherical shell of thickness, spherical shell
Included chabasie interlayer, the attached ceramic spherical shell without glaze of inwall, internal backing material of filling is chabasie granule；
Implant volume is not less than the 43.59% of sampler volume, no more than the 78.53% of spherical shell volume；Take out before using
Become vacuum immersion to be stored in distilled water and be enclosed within container, place at least 4h at sampling site during use, use
Rear immersion is stored in distilled water and is enclosed within container temporary storage time less than 15h.
Matingly, it is provided that a kind of PET film-zeolite molecular sieve composite for filtering micro-molecular gas,
It is characterized in that: described PET film-zeolite molecular sieve composite exceptionally layer, middle level, internal layer, outer layer is adopted
Use mould plastics sucking moulding；Middle level uses filter paper infiltration to be mixed with chabasie powder aqueous not being coarser than 200 mesh
Silica dioxide gel through attach, be dried operation invest outer membrane inwall, infiltrate gel solid phase contain Pedicellus et Pericarpium Trapae boiling
Stone is not less than 58%, and the silica dioxide gel water content before mixing is not less than 31%；It is dried former two
The container of one-step forming is mould blow molding.
The PET film separation hydrogen of present invention offer, helium device, the architectural feature of its air filtration equipment is:
The separation scheme of described air filtration equipment can be selected for monofilm prism close paving scheme, three-dimensional orthogonal stacking bimetallic tube side
Case, double-layer thin wall folder tubule battle array scheme, tortuous folding multilayer thin film scheme, any in branch's tubule scheme
A kind of scheme, single air filtration equipment can only select a kind of scheme；The most selected PET film can use thickness common
PET film, or the PET film-zeolite molecular sieve composite of aforementioned supporting present invention design, thickness is little
In 1mm, not less than 0.07mm, operating temperature not higher than 65 DEG C is not less than 30 DEG C.
Following experimental program, experimentation and data record, can be as some foundations of preceding feature.
Prepared by unstripped gas
Helium ratio in atmosphere is relatively low, about 5.24ppm.But the volume fraction in part gas reservoir up to
4%～7%, i.e. in air about 10,000 times of volume fraction.Therefore, this experiment selects natural gas as extraction
The unstripped gas of helium.With reference to the gas componant preparation raw material gas in certain natural gas gas reservoir.Mixed gas composition is shown in Table-1.
Table-1 mixed gas composition
PET film test experiments material selects
Choosing multiple identical special PET bottle of certain brand beverage, volume is about 0.5L, and after air filtration, experiment cuts
The position bottle wall thickness about 0.7mm of 1 × 10cmPET strip.
Mixed gas separation is tested
Mixed gas is prepared, by the mixed gas of 1atm appearance shown in figure-1 according to table-1 mixed gas composition
Device seals, and often five identical containers of group, test the most at different temperatures.Make gas in atmosphere freely
Residual gas volume is recorded the most after a period of time, it is considered to temperature by the method arranging saturated sodium sulfite solution
Affecting gas volume, preferable final stationary value is 92.5%.Experimental result such as table-2:
Table-2 different temperatures measures mixed gas residual volume percent/% in container
From experimental result, the timing of initial pressure one, in certain temperature range, along with temperature promotes,
Hydrogen, helium transmission rates in mixed gas are accelerated, and finally tend towards stability.But when temperature is too high, mixing
Other composition in gas also can pass through, and when temperature is too low, the rate of departure is slower.Therefore actual production
Cheng Zhong, operating temperature is it is not recommended that more than 65 DEG C, it is not recommended that less than 30 DEG C.Unstripped gas pressure can be increased simultaneously,
Use CO2The gas that be cannot easily penetrate semipermeable membrane Deng easily washing away makees delivery gas, increases film both sides helium
Edema caused by disorder of QI pressure reduction, reduces mixed gas pressure intensity poor, it is ensured that separation process is continual and steady, reduces the load of film.
The inspection that hydrogen embrittlement, helium are crisp
When hydrogen and helium gas molecules are through solid material molecule gap, may result in the physics of material, chemical
Matter changes, thus changes material internal structure, has affected the intensity of material, and this phenomenon often claims
Hydrogen embrittlement or helium for material are crisp.Whether PET semipermeable membrane can occur significant hydrogen embrittlement during filtering hydrogen or helium
Or helium is crisp, it is necessary to pass through experimental verification.
Owing to, during actual air filtration, the stress state being apparent from PET film is tensile stress, a kind of material Young mould
Size and the tensile strength of amount are proportionate, the Young's modulus of PET after therefore plan uses dynamic method survey air filtration,
Determine PET film change of intensity before and after air filtration.
Often group takes ten identical PET bottle, five pure hydrogens containing 2atm, and another five contain the pure of 2atm
Helium, and set and be subjected only to air filtration group relevant temperature, identical time and the blank experiment group of non-air filtration, altogether 22
Group.Filling the CO of 1atm2The container of saturated sodium bicarbonate solution fluid-tight makes gas permeation in bottle, to bottle
Till interior pressure (25 DEG C) is 1atm.Experimental temperature selects to be shown in Table-3, and the most front four temperature values are at temperature
Lower realization, rear three temperature realize under the sal glauberi heat-retaining condition of fusing.After air filtration completes, use
The Young's modulus of PET after dynamic method survey air filtration, often group 5 is averaged, the property of material before and after observation air filtration
Can change, test result such as table-3.
Table-3 different temperatures, air filtration number of times PET film are through Young's modulus/10 after equivalent pure hydrogen, helium9N·m-2
From data above, time within through pure hydrogen or helium 50 times, same operating temperature, pressure
PET film Young's modulus not with through number of times increase and be remarkably decreased, it is believed that through pure hydrogen
Or PET does not occur significant hydrogen embrittlement, helium crisp time within helium 50 times.Notice PET when temperature raises
Young's modulus decline notable, this also illustrates operating temperature should not be higher than 65 DEG C.
Consider in the presence of hydrogen, O2、NH3、H2S etc. are harmful constituent, and PET has hydrophilic,
Wet gaseous mixture knows from experience its permeability of reduction, so should first remove O before being passed through gas2、NH3、H2S etc. are harmful to
Composition is also dried.Therefore, in actual production process, mixed gas must carry out gas washing, be dried etc. pre-place
Reason, removes its harmful components.
In conjunction with to same thickness, temperature, pressure difference, the PET film of different air filtration times measures Young's modulus
Experiment, has no that PET film occurs significant hydrogen embrittlement crisp with helium within air filtration 50 times, but in view of pressure-bearing filtration
Safety, it is proposed that air filter produce before by experiment test confirm used PET film quality the most reliable.
From above-mentioned about invention: knowable to PET film separation hydrogen, the description of helium device, practice content, this
Compared with prior art, it has the beneficial effects that: PET for the PET film separation hydrogen of application offer, helium device
Cheap, conventional plastic beverage bottle i.e. uses this kind of material to make.Currently with vacuum thermoplastic mould once
Film technique is ripe, natural gas gas washing technology maturation, and gas pressurized is ripe with vacuum technique, therefore expands film
Area also is unlikely to make equipment cost too high, the gas washing of unstripped gas and the molding of container, pressurization, vacuum
To implement on prior art basis.Therefore, the gas utilizing the selective penetrated property of PET film to manufacture and design separates
Device, can be at purifying hydrogen of hydrogen under relatively low cost and energy consumption, or from natural gas, cryogenic separation liquid nitrogen tail
Gas etc. obtain, containing separating in helium unstripped gas, the helium that present price is expensive.A series of examinations according to 2014-2015
Test, at embodiment " thin film-molecular sieves compound material scheme " the single acquisition-271 DEG C that the present invention is relatively costly
The helium of 1L liquid helium equivalent (about 20g) the most only needs about 30.2 yuan of (equivalent people of the U.S. in 2014 liquid helium quotation
About 305 yuan/L of people's coin, is about 331 yuan/L in 2015), cost is only about 1/10th of nearly 2 years prices,
Therefore the present invention can be greatly reduced the cost producing helium, in new forms of energy market, helium and helium air market,
Gas industry good market prospect.Present invention can apply to research and teaching, hydrogen energy source, the construction of natural gas fields,
Chemical industry, diving apparatus, dirigible manufacture, nuclear industry, aerospace industry etc. have hydrogen and the field of helium demand.
It addition, collect the sampler of helium isotope with PET film for shell, more existing cellulose nitrate is sampled
For device, not evacuation before existing sampler samples, it is easily caused sample contamination, and cellulose nitrate
Character is unstable, inflammable and explosive, the sampler stable chemical nature that the application provides, evacuation before sampling,
Can preferably preserve helium isotope gas sample.
Accompanying drawing explanation
Fig. 1 be one of them embodiment of the present invention relate to PET film separation hydrogen, helium device workflow
Schematic diagram.
Fig. 2 is that the air filtration equipment of one of them embodiment of the monofilm prism close paving scheme that the present invention relates to is horizontal
Schematic cross-section.
Fig. 3 is that the air filtration of one of them embodiment of the three-dimensional orthogonal stacking bimetallic tube scheme that the present invention relates to sets
Standby cross sectional representation.
Fig. 4 is the air filtration equipment of one of them embodiment of the double-layer thin wall folder tubule battle array scheme that the present invention relates to
Cross sectional representation.
Fig. 5 is one of them enforcement of a kind of sampler collecting helium isotope with PET film that the present invention relates to
Example cross sectional representation.
Reference: 1: high partial pressures chamber；2: low dividing potential drop chamber；3: without tube layer；4: shell；5: chabasie
Interlayer；6: ceramic spherical shell；7: implant.
Detailed description of the invention
In order to make the purpose of the present invention, feature, advantage become apparent from understandable, below in conjunction with the accompanying drawings in relate to
Embodiments of the invention are clearly and completely described by detailed description of the invention.Obviously, described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiment.Based on embodiments of the invention, this
All other embodiments that skilled person obtains under not carrying out creative work premise, broadly fall into this
The scope of bright protection.
A kind of utilize PET film separation hydrogen and the device of helium, it is characterised in that comprising: gas washing equipment,
Remove successively the harmful constituents such as the oxygen in unstripped gas, hydrogen sulfide, ammonia, steam to volume fraction 0.05% with
Under；Compression device, the unstripped gas after pressurization gas washing to more than 4atm, below 150atm, with increase hydrogen,
The dividing potential drop of helium；Air-extractor, decompression forms parital vacuum, and can be filled with and extract the delivery gas easily washed away again
(such as carbon dioxide) transports and diffuses to the hydrogen of low-voltage space, helium；Air filtration equipment, uses and increases table
The PET semipermeable membrane of area filters out hydrogen, helium or its gaseous mixture from unstripped gas, and if desired, unstripped gas is wanted
Through multistage air filtration equipment；Reclaimer, with molecular sieve or hydrogen storage material, or alkali metal reclaims hydrogen, helium mixes
Close the hydrogen in gas；Off-the-shelf hardware, store, process filtration after be enriched the gas of hydrogen, helium, make
Gas with various product, such as pure helium, pure hydrogen, helium air (helium and the gaseous mixture of oxygen volume ratio 78: 22
Body), other is hydrogeneous or containing gaseous mixture etc. of helium.
Monofilm prism close paving scheme, for a kind of semipermeable membrane area that increases to improve the side of semipermeable membrane filter efficiency
Method, it is characterised in that: the semipermeable membrane that separation factor is higher for separation is less, especially such as PET
The semipermeable membrane of film one class, uses honey comb like monolayer semipermeable membrane prism structure, and its cross section is positive six limits of Mi Pu
Shape, is divided into the low concentration cylindrical cavity (2: low dividing potential drop chamber) of logical vehicle medium fluid (such as solution or delivery gas)
With the high concentration cylindrical cavity (1: high partial pressures chamber) of logical raw material fluid-mixing, low concentration cylindrical cavity during filtration
(2: low dividing potential drop chamber) surround high concentration cylindrical cavity (1: high partial pressures chamber), it is achieved target product from raw material to
Vehicle medium fluid (such as solution or delivery gas) diffusion.
Three-dimensional orthogonal stacking bimetallic tube scheme, improves semipermeable membrane for one increase semipermeable membrane area and selects to pass through
Efficiency, simultaneously improves the method that when structure ensures pressurization, semipermeable membrane does not ruptures, it is characterised in that: pin
To semipermeable membrane, especially as less in PET film one class separation and semipermeable membrane that separation factor is higher, use
The prismatic semipermeable membrane pipe box semi-transparent membrane tube of inside cylindrical shape in outside, makes semipermeable membrane bimetallic tube；Bimetallic tube is indirect
Tactile relation is inscribe and the cross section of adhesion, i.e. cylindrical tube is just the inscribed circle of external contact zone；Will be with
Transversely, longitudinally, vertical semipermeable membrane bimetallic tube is unit, the alternate stacking of three-dimensional orthogonal, is placed in heavy wall empty
Intracavity；The frustum cone side shape tubule that each units terminal number is identical with prismatic pipe rib number connects evacuation
Gap between cylindrical tube and prismatic pipe is also inserted in region, simultaneously works as fixing and will filter product guiding container
Outer effect.
Preferably, above-mentioned three-dimensional orthogonal stacking bimetallic tube scheme, it is characterised in that: perform to select through gas
Or during the operation of solute, be sandwiched in outside cylindrical tube and inside prismatic pipe between gap be low-voltage space (2:
Low dividing potential drop chamber), it is passed through delivery gas or evacuation；Inside cylindrical tube and it is high-pressure space outside prismatic pipe
(1: high partial pressures chamber), is passed through pressurized feedstock gas；When occurring damaging, only with the bimetallic tube changing single damage.
Double-layer thin wall folder tubule battle array scheme, for a kind of reduce semipermeable membrane by mechanical damage time the scheme that leaks, its
It is characterised by: described double-layer thin wall folder tubule battle array scheme, is the rhombus cancellate semipermeable membrane of close paving by cross section
Inscribe and the tubular semipermeable membrane of adhesion, be divided into 1 according to the concentration difference of fluid target product component: high partial pressures chamber,
2: low dividing potential drop chamber, pressurization is when passing through 1: high partial pressures chamber, 2: low dividing potential drop chamber distributes alternately, and tubular semipermeable membrane is equal
For high concentration chamber, and arrange one 3 every 7-16 layer grid: without tube layer.
Tortuous folding multilayer thin film scheme, for a kind of scheme increasing semipermeable membrane chamber specific surface area, its feature exists
In: it is continuous folding shape that described scheme tortuous folding multilayer thin film folds semipermeable membrane, and surface tool is shaped as radius
Recessed or the protruding sunsidiary fold of first-order fold axial plane separation it is less than or equal to, according to fluid target more than thickness
The concentration difference of product component is divided into high concentration chamber and low concentration chamber, carries out through high concentration chamber during operation, low
Concentration chamber distributes alternately, and fluid flows the most round about.
Branch's tubule scheme, for a kind of scheme increasing semipermeable membrane chamber specific surface area, it is characterised in that: described
Semipermeable membrane is made branch-like tubulose by scheme, and branch is less than 8 times, and most will to segment Zhi Huihe be pencil；
Carry out flowing in opposite directions through high concentration fluid, low-concentration fluid during operation, contain high concentration fluid, low concentration
The segmentation of fluid is wrapped in splendid attire low-concentration fluid, the trunk branch of high concentration fluid respectively.
Extraly, according to the sampler of with PET film collecting helium isotope a kind of with principle, it is characterised in that:
Described sampler is shaped as spherical, and 4: shell is not to be thinner than 0.025mm by what PET film was made, no thicker than
0.581mm, the uniform spherical shell of thickness, spherical shell included 5: chabasie interlayer, inwall is attached without the 6 of glaze: ceramic
Spherical shell, internal 7: implant is chabasie granule；7: implant volume is not less than the 43.59% of sampler volume,
It is not more than the 78.53% of spherical shell volume；It is evacuated before using and soaks and be stored in distilled water and be enclosed within container,
Placing at least 4h at sampling site during use, after using, immersion is stored in distilled water and is enclosed within temporary storage time in container
Less than 15h.
Matingly, it is provided that a kind of PET film-zeolite molecular sieve composite for filtering micro-molecular gas,
It is characterized in that: described PET film-zeolite molecular sieve composite exceptionally layer, middle level, internal layer, outer layer is adopted
Use mould plastics sucking moulding；Middle level uses filter paper infiltration to be mixed with chabasie powder aqueous not being coarser than 200 mesh
Silica dioxide gel through attach, be dried operation invest outer membrane inwall, infiltrate gel solid phase contain Pedicellus et Pericarpium Trapae boiling
Stone is not less than 58%, and the silica dioxide gel water content before mixing is not less than 31%；It is dried former two
The container of one-step forming is mould blow molding.
Preferably, the architectural feature of its air filtration equipment is: the separation scheme of described air filtration equipment can be selected for list
Tunic prism close paving scheme, three-dimensional orthogonal stacking bimetallic tube scheme, double-layer thin wall folder tubule battle array scheme, tortuous
Folding multilayer thin film scheme, any one scheme in branch's tubule scheme, single air filtration equipment can only select one
The scheme of kind；The most selected PET film can use thickness common PET thin film, or aforementioned supporting present invention design
PET film-zeolite molecular sieve composite, thickness is not more than 1mm, not less than 0.07mm, work temperature
Degree not higher than 65 DEG C is not less than 30 DEG C.
From above-mentioned about description of the invention, practice content knowable to, the present invention provide PET film separation hydrogen,
Compared with prior art, it has the beneficial effects that the various embodiments scheme of helium device: PET is cheap,
Conventional plastic beverage bottle i.e. uses this kind of material to make.Current with vacuum thermoplastic mould one-pass film-forming technology one-tenth
Ripe, natural gas gas washing technology maturation, gas pressurized and vacuum technique are ripe, therefore expand membrane area unlikely
In making equipment cost too high, the gas washing of unstripped gas and the molding of container, pressurization, vacuum all can be in existing skills
Art basis is implemented.Therefore, utilize the gas fractionation unit that the selective penetrated property of PET film manufactures and designs, permissible
Purifying hydrogen of hydrogen under relatively low cost with energy consumption, or former containing helium from natural gas, cryogenic separation liquid nitrogen tail gas etc.
Material gas separates and obtains the helium that present price is expensive.
The description of the most several embodiment of such scheme, only the application, but the protection domain of the application
Being not limited only to this, according to claims, the improvement project of membrane structure is not limited only to use PET by the present invention
Semipermeable membrane, the raw material filtered is not limited only to the natural gas of hydrogen, helium.Therefore, any it is familiar with this skill
The people of art can realize in scope described herein easily, or does not change the change of claim ultimate principle
Or replace, such as: only the material of semipermeable membrane is completely or partially replaced with physicochemical properties close with PET film
Material, and do not change the embodiment of the shape of film, structure, compound mode, only replace by filter stock
Or the embodiment of product component, it is only used as one or several parts of above-mentioned design and uses claims
The product of described air filtration equipment separation scheme, all should contain within the protection domain of the application, i.e. the application
Protection domain should be as the criterion with claims.
Claims (10)
1. a membrane separation device, mainly by PET film separation hydrogen and the device of helium, it is characterised in that
Comprising:
Gas washing equipment, removes the harmful constituents such as the oxygen in unstripped gas, hydrogen sulfide, ammonia, steam successively to volume
Mark less than 0.05%；
Compression device, the unstripped gas after pressurization gas washing is to more than 4atm, below 150atm, to increase hydrogen, helium
Dividing potential drop；
Air-extractor, decompression forms parital vacuum, and can be filled with and extract the delivery gas (such as carbon dioxide) easily washed away again
Transport and diffuse to the hydrogen of low-voltage space, helium；
Air filtration equipment, uses the semipermeable membrane increasing surface area, mainly PET semipermeable membrane, filters out hydrogen from unstripped gas
Gas, helium or its gaseous mixture, if desired, unstripped gas will be through multistage air filtration equipment；
Reclaimer, with the hydrogen in molecular sieve or hydrogen storage material, or alkali metal recovery hydrogen, helium gas mixture；
Off-the-shelf hardware, store, process filtration after be enriched the gas of hydrogen, helium, make gas with various product,
Such as pure helium, pure hydrogen, the helium air mixed gas of oxygen volume ratio 78: 22 (helium with), other is hydrogeneous
Or the gaseous mixture etc. containing helium.
The most as claimed in claim 1 a kind of mainly utilizing PET film separation hydrogen and the device of helium, its air filtration sets
Standby it is characterised by:
The separation scheme of described air filtration equipment can be selected for monofilm prism close paving scheme, three-dimensional orthogonal stacking bilayer
Pipe scheme, double-layer thin wall folder tubule battle array scheme, tortuous folding multilayer thin film scheme, in branch's tubule scheme
Any one scheme, single air filtration equipment can only select a kind of scheme；When selecting PET as membrane material, selected
Thickness common PET thin film, or a kind of PET film-zeolite molecular sieve composite can be used with PET film,
Thickness is not more than 1mm, and not less than 0.07mm, operating temperature is not higher than 65 DEG C, is not less than 30 DEG C.
3. monofilm prism close paving scheme as claimed in claim 2, increases semipermeable membrane area for one and improves half
The method of permeable membrane filter efficiency, it is characterised in that:
The semipermeable membrane that separation factor is higher for separation is less, uses honey comb like monolayer semipermeable membrane prism,
Its cross section is the regular hexagon that the length of side of Mi Pu is not more than 14mm, is divided into logical vehicle medium fluid (such as solution
Or delivery gas) low concentration cylindrical cavity and the high concentration cylindrical cavity of logical raw material fluid-mixing, low during filtration
Concentration cylindrical cavity surround high concentration cylindrical cavity, it is achieved target product from raw material to vehicle medium fluid (as
Solution or delivery gas) diffusion.
4. three-dimensional orthogonal stacking bimetallic tube scheme as claimed in claim 2, increases semipermeable membrane area for one and carries
High semipermeable membrane selects, through efficiency, to simultaneously improve the method that when structure ensures pressurization, semipermeable membrane does not ruptures,
It is characterized in that:
For permselective membrane, especially separation is less and semipermeable membrane that separation factor is higher, outside employing
The incline cylindricality semipermeable membrane pipe box semi-transparent membrane tube of inside cylindrical shape, makes semipermeable membrane bimetallic tube；Contact between bimetallic tube
Relation is inscribe and the cross section of adhesion, i.e. cylindrical tube is just the inscribed circle of external contact zone；Will be with edge
Laterally, longitudinally, vertical semipermeable membrane bimetallic tube is unit, and the alternate stacking of three-dimensional orthogonal is placed in heavy wall cavity
In；The frustum cone side shape tubule that each units terminal number is identical with prismatic pipe rib number connects evacuation district
Gap between cylindrical tube and prismatic pipe is also inserted in territory, simultaneously works as fixing and will filter outside product guiding container
Effect.
5. the three-dimensional orthogonal stacking bimetallic tube scheme as described in claim 2 or 4, it is characterised in that:
When performing to select the operation through gas or solute, be sandwiched in outside cylindrical tube and inside prismatic pipe it
Between gap be low-voltage space, be passed through delivery gas or evacuation；Inside cylindrical tube and outside prismatic pipe all
For high-pressure space, it is passed through pressurized feedstock gas；When occurring damaging, only with the bimetallic tube changing single damage.
6. double-layer thin wall folder tubule battle array scheme as claimed in claim 2, comes for a kind of increase semipermeable membrane area
Improve semipermeable membrane to select through efficiency, the scheme leaked when reducing semipermeable membrane by mechanical damage, its feature simultaneously
It is:
Described double-layer thin wall folder tubule battle array scheme, cross section be rhombus close paving cancellate semipermeable membrane inscribe and
The tubular semipermeable membrane of adhesion, is divided into high concentration chamber and low concentration according to the concentration difference of fluid target product component
Chamber, when pressurization passes through, high concentration chamber, low concentration chamber distribute alternately, and tubular semipermeable membrane is high concentration chamber, and
One is arranged without tube layer every 7-16 layer grid.
Tortuous folding multilayer thin film scheme the most as claimed in claim 2, increases semipermeable membrane area for one and improves
Semipermeable membrane selects the scheme through efficiency, it is characterised in that:
It is continuous folding shape that described scheme tortuous folding multilayer thin film folds semipermeable membrane, and surface tool is shaped as radius
Recessed or the protruding sunsidiary fold of first-order fold axial plane separation it is less than or equal to, according to fluid target more than thickness
The concentration difference of product component is divided into high concentration chamber and low concentration chamber, carries out through high concentration chamber during operation, low
Concentration chamber distributes alternately, and fluid flows the most round about.
8. branch as claimed in claim 2 tubule scheme, for a kind of scheme increasing semipermeable membrane chamber specific surface area,
It is characterized in that:
Semipermeable membrane is made branch-like tubulose by described scheme, and branch is less than 8 times, and most will segment Zhi Huihe
In pencil；Carry out flowing in opposite directions through high concentration fluid, low-concentration fluid during operation, splendid attire high concentration fluid,
The segmentation of low-concentration fluid is wrapped in splendid attire low-concentration fluid, the trunk branch of high concentration fluid respectively.
A kind of PET film-zeolite molecular sieve for filtering micro-molecular gas is combined
Material, it is characterised in that:
Described PET film-zeolite molecular sieve composite exceptionally layer, middle level, internal layer, outer layer uses mould
Plastics sucking moulding；Middle level uses filter paper infiltration to be mixed with the aqueous dioxy of the chabasie powder not being coarser than 200 mesh
The operation through attaching, be dried of the SiClx gel invests outer membrane inwall, and infiltrated gel solid phase is the lowest containing chabasie
In 58%, the silica dioxide gel water content before mixing is not less than 31%；Two one-step formings before after being dried
Container be mould blow molding.
10. one kind with PET film as outer wall, for collecting the sampler of helium isotope, it is characterised in that:
Described sampler is shaped as spherical, and shell is not to be thinner than 0.025mm by what PET film was made, no thicker than
0.581mm, the uniform spherical shell of thickness, spherical shell included chabasie interlayer, the attached ceramic spherical shell without glaze of inwall, interior
It is chabasie granule that backing material is filled in portion；Implant volume is not less than the 43.59% of sampler volume, not quite
In spherical shell volume 78.53%；It is evacuated before using and soaks and be stored in distilled water and be enclosed within container, make
Used time places at least 4h at sampling site, soaks and be stored in distilled water and be enclosed within container temporary storage time not after using
More than 15h.
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| CN201610188831.5A CN105883719B (en) | 2016-03-30 | 2016-03-30 | PET film separates hydrogen, helium device |
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| CN110921625A (en) * | 2019-11-19 | 2020-03-27 | 安徽中科皖能科技有限公司 | Separation and recovery device for hydrogen and helium in purge gas of synthetic ammonia |
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| CN105883719B (en) | 2019-04-19 |
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