CN112744789B - Oxygen generation method and device based on coupling separation technology - Google Patents
Oxygen generation method and device based on coupling separation technology Download PDFInfo
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- 238000000926 separation method Methods 0.000 title claims abstract description 82
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000001301 oxygen Substances 0.000 title claims abstract description 75
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005516 engineering process Methods 0.000 title claims abstract description 24
- 238000010168 coupling process Methods 0.000 title claims abstract description 9
- 230000008878 coupling Effects 0.000 title claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 109
- 239000012528 membrane Substances 0.000 claims abstract description 94
- 238000001179 sorption measurement Methods 0.000 claims abstract description 89
- 239000010457 zeolite Substances 0.000 claims abstract description 76
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 64
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 7
- 238000011069 regeneration method Methods 0.000 claims abstract description 7
- 239000002912 waste gas Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 20
- 239000000872 buffer Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000012466 permeate Substances 0.000 claims description 11
- 230000006835 compression Effects 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 230000000717 retained effect Effects 0.000 claims description 6
- 230000000149 penetrating effect Effects 0.000 claims description 5
- 239000012536 storage buffer Substances 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 59
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 31
- 229910052786 argon Inorganic materials 0.000 abstract description 17
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000003570 air Substances 0.000 description 36
- 239000002808 molecular sieve Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- -1 for example Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 3
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BERHMLRNWCQBPU-UHFFFAOYSA-N [O].[N].[Ar].[O] Chemical compound [O].[N].[Ar].[O] BERHMLRNWCQBPU-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910000154 gallium phosphate Inorganic materials 0.000 description 1
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0259—Physical processing only by adsorption on solids
- C01B13/0262—Physical processing only by adsorption on solids characterised by the adsorbent
- C01B13/0274—Other molecular sieve materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0259—Physical processing only by adsorption on solids
- C01B13/0262—Physical processing only by adsorption on solids characterised by the adsorbent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Separation Of Gases By Adsorption (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of gas separation, and particularly relates to an oxygen generation method and device based on a coupling separation technology. The invention couples the pressure swing adsorption drying technology with the zeolite membrane separation technology, namely, the oxygen production process comprises a pre-stage pressure swing adsorption drying process and a secondary zeolite membrane separation process; the pressure swing adsorption drying technology adopts a single adsorption tower to remove the moisture in the air and compress the air; the zeolite membrane separation technology is to adopt a zeolite membrane separator to separate oxygen and nitrogen and separate oxygen and argon, so as to remove nitrogen and argon in the dry compressed air from which the moisture is removed by an adsorption drying bed layer, and obtain high-purity oxygen with purity of 90% or even more than 99.5%. Wherein, a part of the waste gas generated in the zeolite membrane separation process flows back to the pre-stage variable pressure adsorption drying process and is utilized as the cleaning gas in the regeneration stage. The invention simultaneously reduces the gas consumption of the system, saves the consumption of compressed air and improves the overall recovery rate of the system.
Description
Technical Field
The invention belongs to the technical field of gas separation, and particularly relates to a method and a device for preparing high-purity oxygen from air, which can separate oxygen with purity of 90% or even more than 99.5%.
Background
Pressure Swing Adsorption (PSA) is an important and widely used gas separation process, such as pressure swing adsorption drying, pressure swing adsorption oxygen production, nitrogen production, etc., where adsorption drying is typically used to remove moisture contained in compressed air to obtain dry compressed air with a low dew point.
Conventional PSA processes for producing oxygen from an air stream typically use nitrogen adsorbents such as type CaA, caX, naX, liX to produce oxygen based on equilibrium adsorption theory, but even if all of the nitrogen in the air is adsorbed, it is difficult to produce a product gas having a concentration greater than 95% and containing about 5% argon. Therefore, in order to obtain high purity oxygen, a more complicated multi-stage pressure swing adsorption system has to be adopted, and domestic patent CN1226142a discloses a pressure swing adsorption method for obtaining 98.4% purity by multi-stage pressure swing adsorption, a zeolite nitrogen adsorbent is used for removing a large amount of nitrogen, a carbon molecular sieve based on kinetic separation characteristics is used for separating oxygen and argon, although a single power device is used for realizing the separation process, the purity still has difficulty in meeting the requirement of more than 99.5%, and the oxygen recovery rate of 15% greatly limits the application.
The membrane separation technology is a high new technology developed in the middle of the 20 th century, in industrialized practice applied to purifying oxygen, so far, representative organic membrane separation materials capable of being applied to air separation have an alpha (alpha) value of oxygen-nitrogen separation of between 2 and 7, the selectivity of oxygen-argon separation is not more than 3.5, and separation materials with oxygen-nitrogen-oxygen-argon separation characteristics are less common, namely, the selectivity of alpha, namely, oxygen-nitrogen or oxygen-argon, namely, the ratio of membrane separation materials to the permeation of oxygen/nitrogen and oxygen/argon, and simulation process calculation shows that the membrane separation materials with the oxygen-nitrogen separation selectivity of about 7 can directly obtain oxygen with the purity of about 60 percent or less from air, and a system adopting a multistage membrane separation process can obtain oxygen with the purity of even more than 90 percent, for example, U.S. patent No. 626559 discloses a method and a system for separating pure component gas from gaseous mixture, can effectively obtain oxygen (with the purity of between 60 and 90 percent) from ambient air, the required by providing a method of at least three-stage permeation of pure oxygen separation system is not more than a complicated method, but a pressure swing adsorption system is not required, but a pressure swing adsorption system is obviously reduced, compared with a three-stage separation method is required, and a pressure swing adsorption system is not required.
There are also methods for producing 99% pure oxygen by using an organic membrane separation technology, such as a Continuous Membrane Column (CMC), and various methods for purifying oxygen by using 95% oxygen produced by PSA as a raw material and using a general organic membrane separation method or a Continuous Membrane Column (CMC), particularly, a membrane circulation separation system of a 4-outlet membrane module is preferable, and oxygen with purity of 99% or more can be produced, but the additional compression power of the separation system is very high, the special membrane separator required by CMC circulation is very expensive, the industrial application of the special membrane separator is restricted, and the separation efficiency of the separation system of oxygen-argon separation of the membrane separator which is commercialized at present is not more than 3.5 is difficult to apply to the aspect of purifying high purity oxygen with purity of 99% or more, and moreover, the organic hollow fiber membrane is basically not suitable for industrial application because of the excessive energy consumption.
Therefore, in order to obtain high purity oxygen, a separation process with simple process, low system cost and low failure rate is needed, and the coupling process generally needs a larger number of control valves and storage tanks needed for recycling the middle process gas, which not only greatly increases the complexity of the equipment, but also greatly increases the volume of the equipment, and the failure rate of the equipment is also outstanding because of the complex process system.
Disclosure of Invention
In view of the above, the present invention provides a method and apparatus for producing high purity oxygen gas, which has a purity of 90% or even as high as 99.5% or more, by coupling an adsorption separation oxygen production technology with a zeolite membrane separation technology, in order to obtain high purity oxygen gas having a purity of 90% or even as high as 99.5% or more by a non-cryogenic air separation technology.
The invention provides a method for preparing high-purity oxygen from air, which couples a pressure swing adsorption drying technology with a zeolite membrane separation technology, namely an oxygen preparation process comprises a pre-stage pressure swing adsorption drying process and a secondary zeolite membrane separation process. Wherein:
the pressure swing adsorption drying technology adopts an adsorption tower (single tower) drying bed layer to remove moisture in air and compress the moisture, so that the subsequent zeolite membrane separation material is not polluted, the gas consumption of the system is reduced, and the waste gas in the primary membrane separation process is used as cleaning gas, thereby saving the consumption of compressed air and improving the overall recovery rate of the system.
The zeolite membrane separation technology adopts a zeolite membrane separator to separate oxygen and nitrogen and separate oxygen and argon, and removes nitrogen and argon in dry compressed air from which moisture is removed by an adsorption drying bed layer, so that high-purity oxygen with purity of 90% or even more than 99.5% is obtained, and the high-purity oxygen is obtained by adopting a multi-stage pressure swing adsorption process, a well-known organic membrane separator or a multi-stage organic membrane separation process.
In the present invention, at least a part of the exhaust gas generated in the zeolite membrane separation process is returned to the pre-stage pressure-swing adsorption drying process and used as the purge gas in the regeneration stage.
Also, in the present invention, if higher purity oxygen is desired, at least a portion of the gas produced by the secondary membrane separation process may be vented out of the system.
Based on the principle, the device for preparing high-purity oxygen based on the coupling separation technology provided by the invention comprises the following components:
(1) At least one compression device providing feed air at the necessary pressure, including the equipment required for air pretreatment (not shown in the drawings);
(2) A set of pressure swing adsorption device, which comprises an adsorption tower, wherein one or more combinations of nitrogen adsorbents such as CaA, caX, naX, liX type are arranged in the adsorption tower and are used for removing water in raw material air; the device also comprises an air inlet valve and a necessary connecting pipeline thereof, an air outlet valve and a necessary connecting pipeline thereof, and a gas production valve and a necessary connecting pipeline thereof;
(3) At least one zeolite membrane separator containing zeolite membrane separation material and coupled after the adsorption separator; for separating and producing high-purity oxygen; each zeolite membrane separator has three interfaces: the device comprises a raw material gas interface, a penetrating gas outlet and a detention gas outlet, wherein the raw material gas inlet is connected in series with the product end of an adsorption tower, the penetrating gas outlet is connected in series with a control valve at the product end of an adsorption separator, and the detention gas outlet is communicated with the product end of another group of adsorption drying towers to be used as regeneration cleaning gas of the towers;
(4) A group of loops consisting of valves and pipelines are matched at the detention gas end of the zeolite membrane separator; on the one hand, the retained gas is sent to a gas temporary storage buffer tank of a pre-stage adsorption separation system, and a valve capable of adjusting flow is arranged on the passage; in addition, a pipeline and a valve for exhausting the retained gas are also arranged, and the retained gas can be also sent to an inlet (not shown in the figure) of a raw material gas inlet valve;
(5) Preferably, but not necessarily, a product gas buffer tank is provided in communication with the permeate gas outlet end of the zeolite membrane separator for receiving permeate components enriched from the zeolite membrane separator, and even a gas buffer tank is provided for receiving the valve-vented exhaust gas and for feeding the gas to the feed air inlet or to the adsorbent regeneration process of the pre-stage adsorption column;
(6) A complete set of control components for the necessary operational control of the valve elements in the circuit and the necessary operation of the compression device.
In the invention, the membrane separator can be provided with a plurality of stages of membrane separators connected in series for separating the components of the permeation gas with higher purity.
In the present invention, when the pressure of the raw material gas is insufficient, an additional raw material gas compression device (not shown) can be used to send the raw material gas into the zeolite membrane separator, and the gas can be simply sent into more stages of zeolite membrane separators by arranging necessary additional pipelines and switching valves and using a compressor.
The product gas buffer tank, as described in the prior art, may be provided with the necessary packing in the container to achieve a more economical buffer volume.
In the invention, necessary gas detection equipment is arranged at the inlet and outlet ends of the zeolite membrane separator, and necessary pressure detection, dew point detection and purity detection are arranged on the zeolite membrane separator and the buffer tank, so that a system which completely operates according to the required pressure and purity is designed, and the system is easy to realize for a person skilled in the art. In addition, the debugging process of the system is almost a process of self-adapting the system to be stable, and on the basis of fault judgment, the control program gives more sufficient information to maintenance staff and even directly designates a fault point.
Typically, the structure of the device for preparing high-purity oxygen based on the coupling separation technology provided by the invention is shown in fig. 2. In fig. 2, V represents an automatic control valve, and the numbers of V01, V02, …, V08, etc. represent the valve numbers, which can be opened or closed according to preset logic, and of course, the valves can also be automatic control valves with flow control adjustment performance, and the valves can also be pneumatic control valves or electric or hydraulic control valves; a01 is an adsorption tower filled with adsorbent; m01 represents a zeolite membrane separator; AB01 represents a compressor; PV101, PV102, etc. represent buffer tanks; JV01, JV02 represent manual valves that can regulate flow.
The device structure is as follows: the adsorption tower A01 is filled with an adsorbent, the zeolite membrane separator M01, the compressor AB01 and the buffer tanks PV101 and PV102; wherein:
the raw material gas pipeline is connected with a compressor AB01 and then connected with an air inlet of an adsorption tower A01; the front pipeline and the rear pipeline of the compressor AB01 are respectively provided with an automatic control valve V01 and a valve V02, the automatic control valve V01 is used for controlling air inlet flow, and the automatic control valve V02 is used for controlling waste gas emission; bypass lines are respectively arranged on front and rear pipelines of the compressor AB01 and are connected with an air inlet of the adsorption tower A01, and automatic control valves V04 and V03 are respectively arranged on the front and rear bypass lines;
the product end of the adsorption tower A01 is connected with a raw material gas inlet pipeline of the zeolite membrane separator M01, and an automatic control valve V05 is arranged on the connecting pipeline; the product end of the adsorption tower A01 is connected with a buffer tank PV101 through a pipeline, and an automatic control valve V06 and a manual valve JV01 are sequentially arranged on the connecting pipeline; in addition, a pipeline is connected between the buffer tank PV101 and a retention gas interface of the zeolite membrane separator M01, and an automatic control valve V07 and a manual valve JV02 are sequentially arranged on the connecting pipeline; thereby forming a loop;
an automatic control valve V08 is arranged at the connecting pipeline of the detention gas interface of the zeolite membrane separator M01 and the manual valve JV02 and is used for emptying control.
In the above described device, various modifications may be made without departing from the gist of the present invention. Thus, although it is preferred to use 1 or more zeolite membrane separators of fixed volume, or fixed pressure, coupled to the pre-stage adsorptive separation oxygen generation system, and subsequent stages 1 or more and forming a complete coupled separation process system with the product gas buffer tank and the necessary power plant; more than two zeolite membrane separators and multiple storage tanks, multiple power plants may be utilized.
Based on the above-described exemplary configuration, a standard operating sequence is as follows:
1) Opening V01, V03, V05 and A01 to adsorb the produced gas; at the same time, the post-separation system opens V07, adjusts JV02, opens V08 as needed for purity
2) Opening V02, V04, V06, A01, decompressing in parallel flow and countercurrent, recycling part of valuable gas into the PV101 buffer tank, and simultaneously evacuating most of waste gas to the atmosphere;
3) Opening V02, V04, A01 for countercurrent depressurization, and evacuating most of the waste gas to atmosphere
4) Opening V02, V04, V07, A01, continuously reducing the pressure in countercurrent, simultaneously introducing product gas into an adsorption tower for gas-phase purging and evacuating the atmosphere, and strengthening the regeneration of the adsorption tower
5) Opening V02, V04, V06 and A01 to continuously maintain countercurrent depressurization, simultaneously introducing valuable gas recovered and temporarily stored in PV101 into an adsorption tower to carry out gas-phase purging and atmospheric evacuation, and reducing product gas consumption
6) Opening the inlet gas of V01, V03, V06 and A01, and simultaneously introducing valuable gas which is recovered and temporarily stored in the PV101 to pre-charge the adsorption tower; at the same time, the post-separation system opens V07, adjusts JV02, and opens V08 as needed for purity.
All valves except the appointed open valve are in a closed state, and the purging or recycling flow can be controlled by adjusting JV01 and JV02; according to the steps, the steps are repeated in a circulating way, so that oxygen with the purity of 90 percent or even more than 99.5 percent can be generated, and the rest is nitrogen and argon.
In the present invention, the gas flow form of the zeolite membrane separator may be axial flow, radial flow, lateral flow or other forms.
In the present invention, for a single zeolite membrane separator, each may comprise a plurality of primary membrane separation layers, or one or more pretreatment layers may be provided to remove other components (non-oxygen components such as water vapor). And each membrane separation layer may comprise a single variety of membrane separation materials or a mixture of two or more membrane separation materials.
In the present invention, a gas which is easily adsorbed can be separated from a gas which is difficult to adsorb/permeate by an adsorbent, and either the easily adsorbed/permeated component or the hardly adsorbed/permeated component can be used alone or simultaneously as a desired product gas.
The present invention is preferably used in PSA processes based on equilibrium adsorption theory rather than kinetic separation theory, but does not exclude PSA processes based on kinetic separation theory, and may be employed to achieve the objects of the invention. The disclosed principles are applicable to many other separation applications.
Typical examples of separations that can be achieved by the method of the present invention include:
by selectively penetrating N 2 Is used for recovering N from air 2 ；
By permselective O 2 Is used for recovering O from air 2 ；
Enriching CO from gasified coal with a CO-permselective zeolite membrane material;
by selective permeation of CO 2 Is used for removing CO from gasified coal 2 ；
CO 2 /CH 4 Separation of CO 2 /N 2 Separation, H of 2 /N 2 And olefin/alkane separation. From O-containing 2 Separation of O from a gas mixture obtained by separating air from Ar gas such as pressure swing adsorption coupled membrane 2 Or Ar, may also be separated using any combination of one or more suitable adsorbent-zeolite membrane materials, such as, but not limited to, the use of CaA zeolite, liX zeolite, or any other specific separation material to recover oxygen or nitrogen, with the difficult to adsorb/permeate gas enriched from the non-feed end and the more easily selectively adsorbed/permeate component enriched from the other end.
Some words in the present invention are defined as follows:
the product gas refers to gas which is difficult to be adsorbed by the adsorbent, for example, nitrogen is easy to be adsorbed by the nitrogen adsorbent, and oxygen and argon are difficult to be adsorbed by the nitrogen adsorbent;
exhaust gas refers to gas that is more easily adsorbed by the adsorbent than product gas, such as nitrogen, moisture, and other oxygen that is more easily adsorbed by the nitrogen adsorbent;
adsorbents, also known as molecular sieves, are commonly employed in conventional PSA processes for producing oxygen from an air stream to produce oxygen based on equilibrium adsorption theory using nitrogen adsorbents such as type CaA, caX, naX, liX;
an adsorption column, which may also be referred to as an adsorber, an adsorbent bed, a separator, refers to a vessel filled with at least one adsorbent such as the one described above, the adsorbent having a strong adsorption capacity for components of the mixed gas that are more easily adsorbed;
the terms pressure swing adsorption, adsorption separation, PSA, and the like, refer not only to PSA processes, but also to processes similar thereto, such as vacuum pressure swing adsorption (Vacuum Swing Adsorption-VSA) or mixed pressure swing adsorption (Mixed Pressure Swing Adsorption-MPSA) processes, and the like, are to be understood in a broader sense, that is, for the adsorption pressure of the periodic cycle, a higher pressure is a higher pressure relative to the desorption step, and may include greater than or equal to atmospheric pressure, while the desorption pressure of the periodic cycle, a lower pressure is a lower pressure relative to the adsorption step, and then less than or equal to atmospheric pressure;
the zeolite membrane separator M01 is a 3-port zeolite membrane separator, each zeolite membrane separator consists of 1 raw material gas inlet, 1 detention gas outlet and 1 permeate gas outlet, and has the separation function of oxygen, nitrogen and argon, wherein the oxygen is easy to permeate and the nitrogen and the argon are difficult to pass through;
zeolite materials generally refer to aluminosilicate molecular sieves, but zeolite is sometimes referred to generally as crystalline molecular sieves, zeolite in this specification generally refers to general molecular sieves, including, for example, aluminosilicates, aluminophosphates, gallium phosphate, and metal substituted varieties of these materials, and zeolite materials are often referred to as molecular sieve materials; in practice, however, by controlling their composition and manufacture, the structure may be made to contain a number of holes or cavities of a particular size so that atoms or molecules of the desired maximum size are effectively filtered and/or adsorbed. In addition, the zeolite material can be made to have desired electrical polarization characteristics, polar molecules or atoms or molecules that are easily polarized can be selectively attracted to the zeolite material, and thus, by combining dimensional selectivity (which is due to the fact that the pores and grooves of the zeolite material are similar to the size of the molecules) with control over the electrical characteristics of the zeolite material, the kind of gas attracted to and adsorbed on the zeolite membrane can be controlled, and thus, the zeolite material can be used as a membrane separation material having selectivity for a specific component, so that its crystalline structure enables the atoms or molecules of the gas desired to be separated to be adsorbed therein and to be diffused through the material. Typically, such as membranes made from easily polarizable zeolite materials, examples of such zeolite materials are chabazite, as one of the components to be separated in the mixed gas is drawn towards the polarizable zeolite material. In this way, the rate at which the relative component is initially adsorbed onto the zeolite membrane material can be increased, and once the component to be separated is drawn into the membrane, the pore channel size of the zeolite material is such that only molecules of oxygen pass therethrough and nitrogen and argon cannot diffuse therethrough, whereby the separation efficiency can be significantly increased by such a control method that the rate at which oxygen is adsorbed onto the membrane is greater than the adsorption rate of other gases in the gas mixture (such as nitrogen and argon).
For zeolite membrane separators, the zeolite membrane may comprise a porous substrate such as sintered metal or ceramic and a layer of zeolite membrane formed thereon, the important feature being that the zeolite membrane is substantially defect-free so that there are no "pinholes" or small cavities throughout the thickness of the membrane that are similar or larger to the size of the zeolite material itself, such as the membrane described in International patent WO 94/01209.
The retentate gas of the zeolite membrane separator is enriched in nitrogen, argon, also known as off-gas, and the permeate gas of the zeolite membrane separator is enriched in oxygen, also known as product gas, in terms of the feed gas being a mixed component of oxygen, nitrogen and argon.
The pressure referred to in the present invention is gauge pressure.
Drawings
FIG. 1 shows an oxygen generator for a single column adsorptive separation process.
FIG. 2 shows an apparatus for producing high purity oxygen based on a coupling separation technique according to the present invention.
Detailed Description
As shown in figure 1, an oxygen generating device of a single tower adsorption separation process is provided, nitrogen adsorbent is filled in an adsorber, and basic oxygen generating method and device based on equilibrium adsorption mechanism are schematically shown, in general, the system boosts raw material air through matched compression equipment and then enters an adsorption separator, wherein nitrogen is adsorbed, oxygen is enriched and conveyed into a buffer tank, after the adsorption of the adsorbent in the adsorption tower is saturated, the booster equipment is adopted to desorb and discharge the nitrogen adsorbed in the tower to the atmosphere, and thus the cyclic reciprocation is carried out, so that oxygen enriched air with purity of more than 90% can be obtained; typically, air is boosted by a compression device and then is matched with an air pretreatment facility (not shown in the figure), typically, a pretreatment system formed by a matched filter, a freeze dryer, an adsorption dryer or the like is used for removing moisture, solid particle impurities and oil components carried in the compressed air singly or in various combinations and then enters an adsorption tower, and as known technology, a water removal adsorbent can be arranged in the adsorption tower to be used as a mixed bed to synchronously adsorb oxygen to remove the moisture and carbon dioxide contained in the air; the post-system can also be matched with a necessary storage tank according to the prior art, and a person skilled in the art can flexibly grasp the components and the design requirements contained in the pretreatment system according to the common design requirements.
As described above, the treated raw air enters the pressure swing adsorption separation system of the known technology described in FIG. 1, then nitrogen, moisture, carbon dioxide and other components are removed from V02, and oxygen with a purity of about 93% is output from V5 and PV102, and the pressure swing adsorption oxygen production system is a typical single tower adsorption system, and oxygen enriched air is produced by the pressure swing adsorption oxygen production process based on the equilibrium adsorption mechanism, and typical basic steps are shown in the following table:
all valves except the appointed open valve are closed, and the purging or recycling flow can be controlled by adjusting JV01 and JV 02.
According to the steps, the steps are repeated in a circulating way, so that oxygen with the purity of about 93 percent can be generated, and the rest is nitrogen and argon.
Obviously, only oxygen enriched air with a purity of about 93% can be produced by pressure swing adsorption of the above technology.
As shown in figure 2, the invention is based on a single tower pressure swing adsorption oxygen production process, and the zeolite membrane separator is coupled with the outlet of the oxygen output end of the product after the adsorption separator in series, the necessary matched valve of the adsorption system is fully utilized, in the separation process of M01, concentrated oxygen is enriched at the permeate gas outlet to supply gas to users, typically, a storage tank, a metering facility and the like (not shown in the figure) can be matched, while waste gas is enriched at the outlet of the retention side, is introduced into the process gas temporary storage buffer tank of the front stage separation system, and is recycled in the recovery process of the adsorption separation system, thereby saving the consumption of raw material air and improving the recovery rate of the system.
Referring to fig. 2, further, if oxygen is concentrated to a higher purity, the V08 valve can be controlled to remove at least a portion of the gas from the system, and the removed exhaust gas can be continuously introduced into the feed air inlet via the pipeline and the valve to further increase the oxygen content of the feed gas, so that the pressure swing adsorption cycle is followed to form a coupled separation process, the system is simple, the number of valves is small, and the operation steps of the coupled separation system are as follows:
all valves except the appointed open valve are closed, and the purging or recycling flow can be controlled by adjusting JV01 and JV 02.
According to the steps, the steps are repeated in a circulating way, so that oxygen with the purity of 90 percent or even more than 99.5 percent can be generated, and the rest is nitrogen and argon.
While the foregoing disclosure of the present invention has been described in some detail by way of illustration, it should be understood that the scope of the subject matter of the present invention is not limited to the foregoing examples, and that the techniques implemented based on the foregoing disclosure fall within the scope of the invention.
Claims (2)
1. An oxygen generating device based on a coupling separation technology, which is characterized by comprising:
(1) At least one compression device providing the necessary pressurized feed air; including the devices required for air pretreatment;
(2) The set of pressure swing adsorption device comprises an adsorption tower, wherein an adsorbent is arranged in the adsorption tower and is used for removing moisture in raw material air; the device also comprises an air inlet valve and a necessary connecting pipeline thereof, an air outlet valve and a necessary connecting pipeline thereof, and a gas production valve and a necessary connecting pipeline thereof;
(3) At least one zeolite membrane separator containing zeolite membrane separation material and coupled after the adsorption column; for separating and producing high-purity oxygen; each zeolite membrane separator has three interfaces: the device comprises a raw material gas interface, a penetrating gas outlet and a detention gas outlet, wherein the raw material gas interface is connected in series with the product end of an adsorption tower, the penetrating gas outlet is connected in series with a control valve of the product end of an adsorption separator, and the detention gas outlet is communicated with the product end of another group of adsorption drying towers and is used as regeneration cleaning gas of the towers; in addition, the device also comprises necessary cleaning gas connecting pipelines and regulating valves;
(4) A group of loops consisting of valves and pipelines are matched at the detention gas end of the zeolite membrane separator; on the one hand, the retained gas is sent into a gas temporary storage buffer tank of a pre-stage variable pressure adsorption device; and a valve capable of adjusting flow rate is arranged on the loop; in addition, a pipeline and a valve for exhausting the retained gas are also arranged, and the retained gas can be sent to an inlet of a raw material gas inlet valve;
(5) A product gas buffer tank in communication with the permeate gas outlet end of the zeolite membrane separator for receiving permeate components enriched from the zeolite membrane separator; a gas buffer tank which can accept the exhaust gas discharged by the valve is also arranged, and the gas can be sent to a raw material air inlet or sent to the adsorbent regeneration process of the pre-stage adsorption tower;
(6) A complete set of control components for performing the necessary operational control of the valve elements on the circuit and the necessary operation of the compression device;
the membrane separator is provided with a plurality of stages of membrane separators which are connected in series and are used for separating and obtaining high-purity oxygen with the purity of more than 99.5 percent; wherein, the single zeolite membrane separator comprises a plurality of main membrane separation layers and is provided with a pretreatment layer for removing non-oxygen components;
the inlet and outlet ends of the zeolite membrane separator are provided with gas detection equipment, and the zeolite membrane separator and the buffer tank are provided with pressure detection, dew point detection and purity detection, so that a system which operates completely according to the required pressure and purity is designed;
the concrete structure comprises: the adsorption tower A01 is filled with an adsorbent, the zeolite membrane separator M01, the compressor AB01 and the buffer tanks PV101 and PV102; wherein:
the raw material gas pipeline is connected with a compressor AB01 and then connected with an air inlet of an adsorption tower A01; the front pipeline and the rear pipeline of the compressor AB01 are respectively provided with an automatic control valve V01 and a valve V02, the automatic control valve V01 is used for controlling air inlet flow, and the automatic control valve V02 is used for controlling waste gas emission; bypass lines are respectively arranged on the front pipeline and the rear pipeline of the compressor AB01 and are connected with an air inlet of the adsorption tower A01, and automatic control valves V04 and V03 are respectively arranged on the bypass lines;
the product end of the adsorption tower A01 is connected with a raw material gas inlet pipeline of the zeolite membrane separator M01, and an automatic control valve V05 is arranged on the connecting pipeline; the product end of the adsorption tower A01 is connected with a pipeline of the buffer tank PV101, and an automatic control valve V06 and a manual valve JV01 are sequentially arranged on the connecting pipeline, in addition, the buffer tank PV101 is connected with a detention gas interface of the zeolite membrane separator M01 through a pipeline, and the automatic control valve V07 and the manual valve JV02 are sequentially arranged on the connecting pipeline, so that a loop is formed;
an automatic control valve V08 is arranged at the connecting pipeline of the detention gas interface of the zeolite membrane separator M01 and the manual valve JV02 and is used for emptying control.
2. The oxygen plant based on a coupled separation technology according to claim 1, characterized in that the gas flow of the zeolite membrane separator is in the form of axial flow, radial flow or lateral flow.
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