CN112263895A - Palladium/palladium alloy membrane purifier and using method thereof - Google Patents
Palladium/palladium alloy membrane purifier and using method thereof Download PDFInfo
- Publication number
- CN112263895A CN112263895A CN202011063225.3A CN202011063225A CN112263895A CN 112263895 A CN112263895 A CN 112263895A CN 202011063225 A CN202011063225 A CN 202011063225A CN 112263895 A CN112263895 A CN 112263895A
- Authority
- CN
- China
- Prior art keywords
- palladium
- alloy membrane
- palladium alloy
- hydrogen
- sleeve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- 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
- C01B3/505—Membranes containing palladium
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention discloses a palladium/palladium alloy membrane purifier, which comprises an outer shell, a heat exchanger, a membrane tube bundle, a sleeve integration disc and a membrane tube bundle integration disc, wherein the membrane tube bundle consists of a plurality of palladium/palladium alloy membrane tubes in the outer shell; one end of each palladium/palladium alloy membrane tube is closed, and the other end of each palladium/palladium alloy membrane tube is fixedly connected to the membrane tube bundle integrated disc; one end of each sleeve is fixedly connected to the sleeve bundle integrated disc, and the other end of each sleeve is parallelly inserted outside the palladium/palladium alloy membrane tube. The application method comprises the steps of purging, heating the purifier, preparing pure hydrogen and the like. The invention has wide application range, strong pressure resistance, high hydrogen permeation efficiency and high energy utilization rate; the application method has the characteristics of simple flow, good reliability, various auxiliary heat source sources, wide application field and the like.
Description
Technical Field
The invention belongs to the technical field of hydrogen purification, and relates to a palladium/palladium alloy membrane purifier and an application method thereof.
Background
Hydrogen is one of the basic raw materials in the modern chemical industry, and in the refining industry, the hydrogen has huge demand in the fields of ammonia synthesis, methanol synthesis, hydrogenation in the petroleum refining process and the like. In the metallurgical industry, hydrogen is used as a reducing gas to reduce metal oxides to metals, and in high temperature forging of some metal devices, hydrogen is often used as a shielding gas to protect the metals from oxidation. In the optoelectronic and semiconductor industries, high-purity hydrogen is used as a reaction gas, a reducing gas or a protective gas in the growth of some electronic materials and the preparation of substrates, oxidation processes, epitaxial processes and Chemical Vapor Deposition (CVD) technologies. Hydrogen is used as energy, is fuel of fuel cells for future power generation and electric vehicles, and the product is water, so that the hydrogen has no pollution to the environment, and is known as clean fuel for human beings in the future.
In recent years, with the rapid development of industries such as hydrogen energy and the like, the demand of high-purity hydrogen is rapidly increased, and the research on the production and separation technology of high-purity hydrogen is promoted. The hydrogen purification technology mainly comprises pressure swing adsorption, selective oxidation, palladium membrane separation, low-temperature deep cooling and the like. The palladium membrane separation technology is characterized in that palladium or palladium alloy is prepared into a membrane shape or a tubular shape by a physical or chemical method, and effective separation of hydrogen molecules and other impurity gas molecules is realized by utilizing the unique selective permeability of palladium to hydrogen at a certain temperature (350-450 ℃). The hydrogen purification technology based on palladium membrane separation has the advantages of small volume of a purification device, simple structure, high separation efficiency and the like, and is suitable for preparing medium and small-scale high-purity hydrogen and ultrahigh-purity hydrogen. At present, palladium membrane hydrogen purification devices have been implemented in small-scale applications in the fields of high-purity hydrogen/ultra-high-purity hydrogen production, hydrogen fuel cells, optical fiber manufacturing, and the like.
The palladium/palladium alloy membrane purifier is generally composed of a palladium membrane tube, a protective shell, a mouthpiece and the like, wherein the palladium membrane tube is a core component of the purifier. There are two types of palladium membrane tubes, one is an unsupported palladium membrane tube prepared by a conventional roll-to-roll process. The traditional roll-rolling method can realize continuous production of the palladium membrane tube, and has the defects of low yield, and in addition, in order to keep certain mechanical strength of the palladium membrane tube, the wall thickness and the tube diameter of the membrane tube are large, so the hydrogen permeation efficiency of the palladium membrane tube is seriously influenced. The other is a supported palladium membrane tube obtained by loading palladium/palladium alloy on the surface of a porous tubular support material such as porous ceramic, porous stainless steel and the like by adopting physical and chemical methods such as chemical plating, electroplating, composite plating, chemical/physical vapor deposition and the like, for example, Chinese patent (CN 103721576B) provides a chemical plating method for preparing a palladium membrane and a composite membrane thereof, and Chinese patent (CN 102162094A) provides a cyclic chemical plating process for preparing the palladium/palladium alloy membrane.
Because the support materials such as porous ceramics, porous stainless steel and the like have higher compressive strength, the thickness of the film layer of the palladium film tube is usually thinner (10-50 um), the hydrogen permeation efficiency is higher, and the main defects are that: on one hand, when a thin palladium membrane layer is deposited on a porous carrier material, the defects of pinholes, inconsistent membrane thickness and the like are easily generated; on the other hand, the adhesion between the palladium or palladium alloy membrane and the tubular support material is poor, the thermal expansion coefficients of the two materials are different, and the two materials are easy to fall off in the using process, so that the whole hydrogen purification device fails. In addition, a large amount of sewage containing heavy metal ions is generated in the traditional palladium membrane preparation processes such as chemical plating, electroplating and the like, so that the problem of serious sewage and waste treatment is brought.
In order to solve the above problems, the inventor of the present invention provides a palladium/palladium alloy membrane purifier and a method for using the same in chinese patent (CN 105967145B), wherein the purifier has a compact structure and a high hydrogen permeation efficiency, and has disadvantages that the air tightness of the purifier is poor, and when the crude hydrogen inlet pressure is high, a palladium membrane tube is easily broken and fails.
Therefore, there is a need for further development of a novel hydrogen purifier having a wide application range, a high pressure resistance, and a high hydrogen permeation efficiency.
Disclosure of Invention
One of the purposes of the invention is to provide a novel hydrogen purifier with wide application range, strong pressure resistance and high hydrogen permeation efficiency aiming at the defects of the existing palladium/palladium alloy membrane purifier.
The technical scheme adopted by the invention for solving the technical problems is as follows: a palladium/palladium alloy membrane purifier comprises a cylindrical outer shell with two elliptical seal heads at two ends and a heat exchanger connected with the outer shell; the shell is internally provided with a membrane tube bundle integrated disc, a sleeve integrated disc and a membrane tube bundle consisting of a plurality of palladium/palladium alloy membrane tubes, and the palladium/palladium alloy membrane tubes are externally provided with sleeves; one end of each palladium/palladium alloy membrane tube is closed, the other end of each palladium/palladium alloy membrane tube is fixedly connected to the membrane tube bundle integrated disc, one end of each sleeve is fixedly connected to the sleeve tube bundle integrated disc, and the other end of each sleeve is parallelly inserted outside the palladium/palladium alloy membrane tube; one end of the outer shell is communicated with a crude hydrogen input pipe provided with a crude hydrogen inlet valve, the other end of the outer shell is communicated with a pure hydrogen output pipe provided with a pure hydrogen outlet valve, and the outer side surface of the outer shell, which is close to the pure hydrogen outlet, is communicated with a tail gas output pipe provided with a tail gas outlet valve; the raw material gas of the crude hydrogen in the crude hydrogen input pipe is used as a cold medium, the tail gas in the tail gas output pipe is used as a heat medium, and the two media carry out heat exchange through a heat exchanger; the crude hydrogen input pipe is spirally wound outside the outer shell, crude hydrogen feed gas in the crude hydrogen input pipe is further preheated by the spiral coil pipe, and hydrogen molecules in the crude hydrogen input pipe permeate and diffuse to the inner side through the outer side of the palladium/palladium alloy membrane pipe.
The outer shell, the sleeve, the membrane tube bundle integrated disc and the sleeve integrated disc of the palladium/palladium alloy membrane purifier are all made of 316 or 316L stainless steel with the same thermal expansion coefficient.
According to the palladium/palladium alloy membrane purifier, the center distance between palladium/palladium alloy membrane tubes is 1.2-2.5 times of the outer diameter of the palladium/palladium alloy membrane tubes, and the distance between the outer wall of each palladium/palladium alloy membrane tube and the inner wall of a sleeve is 60-600 microns.
According to the palladium/palladium alloy membrane purifier, the distance between the opening end of the sleeve and the near end face of the membrane tube bundle integrated disc is 1-8 mm.
According to the palladium/palladium alloy membrane purifier, one end of a palladium/palladium alloy membrane tube is fixedly connected with a membrane tube bundle integrated disc, and a sleeve is connected with a sleeve integrated disc through welding by a laser welding method.
The invention also aims to provide a using method of the palladium/palladium alloy membrane purifier.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method of using a palladium/palladium alloy membrane purifier comprising the steps of:
a) purging the palladium/palladium alloy membrane purifier chamber: closing a crude hydrogen inlet valve, a tail gas outlet valve and a pure hydrogen outlet valve, connecting a purging gas source on a port of a crude hydrogen input pipe, sequentially opening the crude hydrogen inlet valve and the tail gas outlet valve, purging a cavity of the purifier by adopting inert gases such as high-purity nitrogen, and sequentially closing the tail gas outlet valve and the crude hydrogen inlet valve after the purging process is completed;
b) heating the palladium/palladium alloy membrane purifier to a predetermined temperature: after a crude hydrogen raw material gas is connected to a port of a crude hydrogen input pipe, starting an auxiliary heating source of a palladium/palladium alloy membrane purifier, heating the purifier to 380-450 ℃, and preparing to input the crude hydrogen raw material gas after the temperature is stable;
c) and preparing pure hydrogen by a palladium/palladium alloy membrane purifier: opening a crude hydrogen inlet valve and a tail gas outlet valve in sequence, opening a pure hydrogen outlet valve after the gas pressure of crude hydrogen raw material gas is stable, allowing hydrogen molecules to flow through an annular gap formed between a palladium/palladium alloy membrane tube and a sleeve, permeating and diffusing from the outer side of the palladium/palladium alloy membrane tube to the inner side of the membrane tube, and outputting outwards through a pure hydrogen output tube; and the impurity gas molecules and a small amount of non-permeated hydrogen molecules are output through a tail gas output pipe.
The use method of the palladium/palladium alloy membrane purifier has the purging flow of purging gas pressure of 0.2 MPa-2.0 MPa and purging time of 0.5 min-2 min.
The application method of the palladium/palladium alloy membrane purifier is characterized in that the auxiliary heating source is one of a direct current or alternating current power supply and high-temperature flue gas.
According to the using method of the palladium/palladium alloy membrane purifier, the high-temperature flue gas is one of methanol catalytic combustion flue gas, ethanol catalytic combustion flue gas, natural gas catalytic combustion flue gas and diesel oil catalytic combustion flue gas, and the temperature of the flue gas is 500-800 ℃.
The invention has the beneficial effects that:
the invention overcomes the defects of poor air tightness and reliability and small application range of the existing palladium/palladium alloy membrane purifier, and has the advantages of wide application range, strong pressure resistance, high hydrogen permeation efficiency and energy utilization rate and the like.
2, the use method of the palladium/palladium alloy membrane purifier has the characteristics of simple flow, good reliability, various auxiliary heat source sources, wide application field and the like.
Drawings
Fig. 1 is a schematic structural composition diagram of a palladium/palladium alloy membrane purifier of the present invention.
The notation in the figure is: the device comprises a shell, 2-palladium/palladium alloy membrane tubes, 2' -membrane tube bundles, 3-sleeves, 4-crude hydrogen input tubes, 5-heat exchangers, 6-crude hydrogen inlet valves, 7-tail gas outlet valves, 8-tail gas output tubes, 9-pure hydrogen outlet valves, 10-pure hydrogen output tubes, 11-membrane tube bundle integrated discs and 12-sleeve tube bundle integrated discs.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1
A basic embodiment of the palladium/palladium alloy membrane purifier of the present invention, as shown in fig. 1, comprises a cylindrical outer shell 1 with elliptical end sockets at both ends, a heat exchanger 5, a membrane tube bundle 2' consisting of a plurality of palladium/palladium alloy membrane tubes 2 in the outer shell 1, a sleeve 3 outside the palladium/palladium alloy membrane tubes 2, a sleeve integrated tray 12, and a membrane tube bundle integrated tray 11; one end of each palladium/palladium alloy membrane tube 2 is closed, and the other end is fixedly connected to the membrane tube bundle integration disc 11; one end of each sleeve 3 is fixedly connected to the sleeve bundle integration disc 12, and the other end of each sleeve is parallelly inserted outside the palladium/palladium alloy membrane tube 2; one end of the outer shell 1 is communicated with a crude hydrogen input pipe 4 provided with a crude hydrogen inlet valve 6, and the other end is communicated with a pure hydrogen output pipe 10 provided with a pure hydrogen outlet valve 9; the outer side surface of the outer shell 1 close to the pure hydrogen outlet is communicated with a tail gas output pipe 8 provided with a tail gas outlet valve 7. The raw hydrogen gas in the raw hydrogen input pipe 4 is used as a cold medium, the tail gas in the tail gas output pipe 8 is used as a heat medium, and the two media carry out heat exchange through the heat exchanger 5; the crude hydrogen input pipe 4 is spirally wound outside the outer shell 1, crude hydrogen feed gas in the crude hydrogen input pipe 4 is further preheated by the spiral coil, and hydrogen molecules in the crude hydrogen input pipe 4 are permeated and diffused from the outer side to the inner side of the palladium/palladium alloy membrane pipe 2.
Example 2
Further examples on the basis of example 1: the outer shell 1, the sleeve 3, the membrane tube bundle integration disc 11 and the sleeve integration disc 12 of the palladium/palladium alloy membrane purifier are all made of 316 or 316L stainless steel with the same thermal expansion coefficient. The center distance between the palladium/palladium alloy membrane tubes 2 is 1.2-2.5 times of the outer diameter of the palladium/palladium alloy membrane tubes, and the distance between the outer wall of the palladium/palladium alloy membrane tubes 2 and the inner wall of the sleeve 3 is 60-600 um. The distance between the open end of the sleeve 3 and the proximal end face of the membrane tube bundle integrated disc 11 is 1-8 mm. The fixed connection of one end of the palladium/palladium alloy membrane tube 2 and the membrane tube bundle integrated disc 11 and the connection of the sleeve 3 and the sleeve integrated disc 12 are welded by a laser welding method.
Example 3
Is a further example on the basis of example 2. The difference from example 2 is: the center distance between the palladium/palladium alloy membrane tubes 2 is 1.5 times of the outer diameter of the palladium/palladium alloy membrane tubes, and the distance between the outer wall of the palladium/palladium alloy membrane tubes 2 and the inner wall of the sleeve 3 is 60 um. The distance between the open end of the sleeve 3 and the proximal end face of the membrane tube bundle integrated disc 11 is 1 mm.
Example 4
Is a further example on the basis of example 2. The difference from example 2 is: the center distance between the palladium/palladium alloy membrane tubes 2 is 2.5 times of the outer diameter of the palladium/palladium alloy membrane tubes, and the distance between the outer wall of the palladium/palladium alloy membrane tubes 2 and the inner wall of the sleeve 3 is 600 mu m. The distance between the open end of the sleeve 3 and the proximal end face of the membrane tube bundle integrated disc 11 is 8 mm.
Example 5
The application method of the palladium/palladium alloy membrane purifier disclosed by the invention comprises the following steps:
a) purging the palladium/palladium alloy membrane purifier chamber: closing a crude hydrogen inlet valve 6, a tail gas outlet valve 7 and a pure hydrogen outlet valve 9, connecting a purging gas source on the port of a crude hydrogen input pipe 4, sequentially opening the crude hydrogen inlet valve 6 and the tail gas outlet valve 7, purging the cavity of the purifier by adopting inert gases such as high-purity nitrogen, and sequentially closing the tail gas outlet valve 7 and the crude hydrogen inlet valve 6 after the purging process is completed;
b) heating the palladium/palladium alloy membrane purifier to a predetermined temperature: after the crude hydrogen raw material gas is connected to the port of the crude hydrogen input pipe 4, starting an auxiliary heating source of the palladium/palladium alloy membrane purifier, heating the purifier to 380-450 ℃, and preparing to input the crude hydrogen raw material gas after the temperature is stable;
c) preparing pure hydrogen by a palladium/palladium alloy membrane purifier: sequentially opening a crude hydrogen inlet valve 6 and a tail gas outlet valve 7, after the gas pressure of crude hydrogen raw material gas is stable, opening a pure hydrogen outlet valve 9, allowing hydrogen molecules to flow through an annular gap formed by the palladium/palladium alloy membrane tube 2 and the sleeve 3, to permeate and diffuse from the outer side of the palladium/palladium alloy membrane tube 2 to the inner side of the membrane tube, and to be output outwards through a pure hydrogen output tube 10; the impurity gas molecules and a small amount of non-permeated hydrogen molecules are output through a tail gas output pipe 8.
The purging process in the step a) is that the pressure of the purging gas is 0.2 MPa-2.0 MPa, the purging time is 0.5 min-2 min, the auxiliary heating source in the step b) is one of a direct current or alternating current power supply and high-temperature flue gas, the high-temperature flue gas is one of methanol catalytic combustion flue gas, ethanol catalytic combustion flue gas, natural gas catalytic combustion flue gas and diesel oil catalytic combustion flue gas, and the temperature of the flue gas is 500-800 ℃.
Example 6
Is a further example on the basis of example 5. The difference from example 5 is: the application method of the palladium/palladium alloy membrane purifier comprises the steps that the purging flow in the step a) is that the pressure of the purging gas is 0.2MPa, the purging time is 2min, the auxiliary heating source in the step b) is methanol catalytic combustion flue gas, and the temperature of the flue gas is 600 ℃.
The scope of protection of the claims of the invention is not limited to the embodiments described above.
Claims (9)
1. A palladium/palladium alloy membrane purifier, characterized in that: comprises a cylindrical outer shell (1) with two elliptical end sockets at two ends and a heat exchanger (5) connected with the outer shell (1); the device is characterized in that a membrane tube bundle integrated disc (11), a sleeve integrated disc (12) and a membrane tube bundle (2') consisting of a plurality of palladium/palladium alloy membrane tubes (2) are arranged in the outer shell (1), and sleeves (3) are arranged outside the palladium/palladium alloy membrane tubes (2); one end of each palladium/palladium alloy membrane tube (2) is closed, the other end of each palladium/palladium alloy membrane tube is fixedly connected to the membrane tube bundle integrated disc (11), one end of each sleeve (3) is fixedly connected to the sleeve tube bundle integrated disc (12), and the other end of each sleeve is parallelly inserted outside the palladium/palladium alloy membrane tube (2); one end of the outer shell (1) is communicated with a crude hydrogen input pipe (4) provided with a crude hydrogen inlet valve (6), the other end of the outer shell is communicated with a pure hydrogen output pipe (10) provided with a pure hydrogen outlet valve (9), and the outer side surface of the outer shell (1) close to a pure hydrogen outlet is communicated with a tail gas output pipe (8) provided with a tail gas outlet valve (7); raw hydrogen raw material gas in the raw hydrogen input pipe (4) is used as a cold medium, tail gas in the tail gas output pipe (8) is used as a heat medium, and the two media carry out heat exchange through the heat exchanger (5); the crude hydrogen input pipe (4) is spirally wound outside the outer shell (1), crude hydrogen raw gas in the crude hydrogen input pipe (4) is further preheated through the spiral coil pipe, and hydrogen molecules in the crude hydrogen input pipe (4) permeate and diffuse towards the inner side through the outer side of the palladium/palladium alloy membrane pipe (2).
2. The palladium/palladium alloy membrane purifier according to claim 1, wherein the outer shell (1), the sleeve (3), the membrane bundle integrated disk (11) and the sleeve integrated disk (12) are all made of 316 or 316L stainless steel with the same thermal expansion coefficient.
3. The palladium/palladium alloy membrane purifier according to claim 1, wherein the center-to-center distance between the palladium/palladium alloy membrane tubes (2) is 1.2 to 2.5 times of the outer diameter thereof, and the distance between the outer wall of the palladium/palladium alloy membrane tubes (2) and the inner wall of the sleeve (3) is 60 to 600 um.
4. A palladium/palladium alloy membrane purifier according to claim 1, wherein the distance between the open end of the sleeve (3) and the proximal end face of the membrane bundle integrated disk (11) is 1-8 mm.
5. A palladium/palladium alloy membrane purifier according to claim 1, wherein the connection of the palladium/palladium alloy membrane tubes (2) to the membrane tube bundle integrated tray (11) and the connection of the sleeve (3) to the sleeve integrated tray (12) are laser welded.
6. A method of using a palladium/palladium alloy membrane purifier as claimed in claim 1 comprising the steps of:
a) purging the palladium/palladium alloy membrane purifier chamber: closing a crude hydrogen inlet valve (6), a tail gas outlet valve (7) and a pure hydrogen outlet valve (9), connecting a purging gas source on a port of a crude hydrogen input pipe (4), then opening the crude hydrogen inlet valve (6) and the tail gas outlet valve (7) in sequence, purging a purifier chamber by adopting inert gas, and closing the tail gas outlet valve (7) and the crude hydrogen inlet valve (6) in sequence after the purging process is finished;
b) heating the palladium/palladium alloy membrane purifier to a predetermined temperature: after the raw hydrogen feed gas is connected to the port of the raw hydrogen input pipe (4), starting an auxiliary heating source of a palladium/palladium alloy membrane purifier, heating the purifier to 380-450 ℃, and preparing to input the raw hydrogen feed gas after the temperature is stable;
c) and preparing pure hydrogen by a palladium/palladium alloy membrane purifier: sequentially opening a crude hydrogen inlet valve (6) and a tail gas outlet valve (7), after the gas pressure of crude hydrogen feed gas is stable, opening a pure hydrogen outlet valve (9), allowing hydrogen molecules to flow through an annular gap formed between a palladium/palladium alloy membrane tube (2) and a sleeve (3), to permeate and diffuse from the outer side of the palladium/palladium alloy membrane tube (2) to the inner side of the membrane tube, and to be output outwards through a pure hydrogen output tube (10); the impurity gas molecules and a small amount of non-permeated hydrogen molecules are output through a tail gas output pipe (8).
7. The method of using a palladium/palladium alloy membrane purifier according to claim 6, wherein the purge gas pressure is 0.2 to 2.0MPa and the purge time is 0.5 to 2 min.
8. The use method of the palladium/palladium alloy membrane purifier according to claim 6, wherein the auxiliary heating source is one of a DC or AC power source and high temperature flue gas.
9. The use method of the palladium/palladium alloy membrane purifier as recited in claim 8, wherein the high temperature flue gas is one of methanol catalytic combustion flue gas, ethanol catalytic combustion flue gas, natural gas catalytic combustion flue gas and diesel oil catalytic combustion flue gas, and the flue gas temperature is 500 ℃ to 800 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011063225.3A CN112263895B (en) | 2020-09-30 | 2020-09-30 | Palladium/palladium alloy membrane purifier and using method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011063225.3A CN112263895B (en) | 2020-09-30 | 2020-09-30 | Palladium/palladium alloy membrane purifier and using method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112263895A true CN112263895A (en) | 2021-01-26 |
| CN112263895B CN112263895B (en) | 2022-05-31 |
Family
ID=74338738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011063225.3A Active CN112263895B (en) | 2020-09-30 | 2020-09-30 | Palladium/palladium alloy membrane purifier and using method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112263895B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113252591A (en) * | 2021-06-15 | 2021-08-13 | 佛山绿色发展创新研究院 | Detection system and detection method applied to hydrogen distribution station |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2685218A1 (en) * | 1991-12-19 | 1993-06-25 | Inst Francais Du Petrole | HYDROGEN PURIFIER COMPRISING AN ALLOY BASE OF THE SAME COMPOSITION AS THAT OF THE TUBES. |
| JPH11200817A (en) * | 1998-01-05 | 1999-07-27 | Central Res Inst Of Electric Power Ind | Hydrogen separation type thermal power generation system |
| JP2003146610A (en) * | 2001-11-09 | 2003-05-21 | Mitsubishi Heavy Ind Ltd | Apparatus for manufacturing hydrogen |
| CN101177240A (en) * | 2007-11-09 | 2008-05-14 | 清华大学 | Integrated device for preparing hydrogen by the recapitalization of dimethyl ether aqueous vapor and method |
| US7396385B1 (en) * | 2005-03-31 | 2008-07-08 | Bossard Peter R | System and method for efficiently separating hydrogen gas from a mixed gas source |
| JP2009226403A (en) * | 2008-03-21 | 2009-10-08 | Peter R Bossard | Hydrogen gas separation system having microchannel structure for effectively separating hydrogen gas from source of mixed gas |
| US8002875B1 (en) * | 2004-02-02 | 2011-08-23 | Bossard Peter R | System and method for separating hydrogen gas from a mixed gas source using composite structure tubes |
| US20150196871A1 (en) * | 2014-01-16 | 2015-07-16 | Japan Pionics Co., Ltd. | Palladium alloy membrane unit, storage structure thereof, and method of purifying hydrogen by using the same |
| US9169118B1 (en) * | 2011-05-04 | 2015-10-27 | Saes Pure Gas, Inc. | Hydrogen gas separator system having a micro-channel construction with a tubular wire insert for retaining catalyst material |
| CN105169896A (en) * | 2015-09-06 | 2015-12-23 | 中国船舶重工集团公司第七一二研究所 | Tube bundle palladium or palladium alloy membrane purifier and making method thereof |
| CN204938972U (en) * | 2015-08-20 | 2016-01-06 | 吴东 | A kind of hydrogen separation device |
| CN105967145A (en) * | 2016-05-09 | 2016-09-28 | 中国船舶重工集团公司第七〇二研究所 | Purifier with palladium/palladium alloy membrane and usage method thereof |
| CN111689469A (en) * | 2019-03-15 | 2020-09-22 | 中石化南京化工研究院有限公司 | Process for preparing high-purity hydrogen by adopting palladium alloy membrane purification |
-
2020
- 2020-09-30 CN CN202011063225.3A patent/CN112263895B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2685218A1 (en) * | 1991-12-19 | 1993-06-25 | Inst Francais Du Petrole | HYDROGEN PURIFIER COMPRISING AN ALLOY BASE OF THE SAME COMPOSITION AS THAT OF THE TUBES. |
| JPH11200817A (en) * | 1998-01-05 | 1999-07-27 | Central Res Inst Of Electric Power Ind | Hydrogen separation type thermal power generation system |
| JP2003146610A (en) * | 2001-11-09 | 2003-05-21 | Mitsubishi Heavy Ind Ltd | Apparatus for manufacturing hydrogen |
| US8002875B1 (en) * | 2004-02-02 | 2011-08-23 | Bossard Peter R | System and method for separating hydrogen gas from a mixed gas source using composite structure tubes |
| US7396385B1 (en) * | 2005-03-31 | 2008-07-08 | Bossard Peter R | System and method for efficiently separating hydrogen gas from a mixed gas source |
| CN101177240A (en) * | 2007-11-09 | 2008-05-14 | 清华大学 | Integrated device for preparing hydrogen by the recapitalization of dimethyl ether aqueous vapor and method |
| JP2009226403A (en) * | 2008-03-21 | 2009-10-08 | Peter R Bossard | Hydrogen gas separation system having microchannel structure for effectively separating hydrogen gas from source of mixed gas |
| US9169118B1 (en) * | 2011-05-04 | 2015-10-27 | Saes Pure Gas, Inc. | Hydrogen gas separator system having a micro-channel construction with a tubular wire insert for retaining catalyst material |
| US20150196871A1 (en) * | 2014-01-16 | 2015-07-16 | Japan Pionics Co., Ltd. | Palladium alloy membrane unit, storage structure thereof, and method of purifying hydrogen by using the same |
| CN204938972U (en) * | 2015-08-20 | 2016-01-06 | 吴东 | A kind of hydrogen separation device |
| CN105169896A (en) * | 2015-09-06 | 2015-12-23 | 中国船舶重工集团公司第七一二研究所 | Tube bundle palladium or palladium alloy membrane purifier and making method thereof |
| CN105967145A (en) * | 2016-05-09 | 2016-09-28 | 中国船舶重工集团公司第七〇二研究所 | Purifier with palladium/palladium alloy membrane and usage method thereof |
| CN111689469A (en) * | 2019-03-15 | 2020-09-22 | 中石化南京化工研究院有限公司 | Process for preparing high-purity hydrogen by adopting palladium alloy membrane purification |
Non-Patent Citations (1)
| Title |
|---|
| 贾志华等: "管状钯膜的研究进展", 《稀有金属》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113252591A (en) * | 2021-06-15 | 2021-08-13 | 佛山绿色发展创新研究院 | Detection system and detection method applied to hydrogen distribution station |
| CN113252591B (en) * | 2021-06-15 | 2021-10-15 | 佛山绿色发展创新研究院 | Detection system and detection method applied to hydrogen distribution station |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112263895B (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8518151B2 (en) | Porous hollow fiber supported dense membrane for hydrogen production, separation, or purification | |
| WO2013137720A1 (en) | Method and system for the production of hydrogen | |
| TWI635893B (en) | Membrane modules for hydrogen separation and fuel processors and fuel cell systems including the same | |
| CN104098071A (en) | Tubular metallic membrane reactor and application thereof | |
| CN112263895B (en) | Palladium/palladium alloy membrane purifier and using method thereof | |
| CN105967145B (en) | A kind of palladium/palladium alloy membrane purifier and its application method | |
| JP5757243B2 (en) | Silica-based hydrogen separation material and method for producing the same, and hydrogen separation module and hydrogen production apparatus including the same | |
| CN105169896A (en) | Tube bundle palladium or palladium alloy membrane purifier and making method thereof | |
| CN111632557A (en) | Novel sulfuric acid decomposition device and method for thermochemical sulfur-iodine cycle hydrogen production | |
| CN213193140U (en) | Purifier | |
| CN115650160A (en) | Device for preparing high-purity hydrogen by integrating ammonia decomposition hydrogen production and plate-type membrane reactor | |
| CN112723308B (en) | Method for preparing hydrogen by catalyzing chain with carbon hydrocarbon fuel plasma | |
| CN212328238U (en) | Novel sulfuric acid decomposition device for thermochemical sulfur-iodine cycle hydrogen production | |
| JPS62216634A (en) | Reformer for fuel | |
| JP4443968B2 (en) | Hydrogen production equipment | |
| JPH06171904A (en) | Gaseous hydrogen refiner | |
| CN213356957U (en) | High-efficient thermal utilization methanol-water reforming hydrogen production device | |
| CN111359543A (en) | Metal ceramic membrane reactor for natural gas conversion | |
| JP5757186B2 (en) | Fluid separation material and manufacturing method thereof | |
| CN116332129B (en) | Green hydrogen preparation system and technology | |
| CN114031038B (en) | Self-heating palladium membrane purification device and purification method | |
| CN220703247U (en) | Green hydrogen preparation system | |
| CN112919411B (en) | Membrane separator with heating and hydrogen separation functions | |
| Iaquaniello et al. | Palladium-based selective membranes for hydrogen production | |
| TWI473760B (en) | Membrane tube composite and apparatus for generating high purity hydrogen gas using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |