CN116462159A - Hydrogen purification system and method - Google Patents
Hydrogen purification system and method Download PDFInfo
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- CN116462159A CN116462159A CN202310531781.6A CN202310531781A CN116462159A CN 116462159 A CN116462159 A CN 116462159A CN 202310531781 A CN202310531781 A CN 202310531781A CN 116462159 A CN116462159 A CN 116462159A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 248
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 248
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 241
- 238000000746 purification Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 163
- 239000007789 gas Substances 0.000 claims abstract description 110
- 238000010521 absorption reaction Methods 0.000 claims abstract description 91
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 58
- 238000010926 purge Methods 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 33
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000005086 pumping Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- BLRHMMGNCXNXJL-UHFFFAOYSA-N 1-methylindole Chemical compound C1=CC=C2N(C)C=CC2=C1 BLRHMMGNCXNXJL-UHFFFAOYSA-N 0.000 claims description 14
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 239000002808 molecular sieve Substances 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000002028 Biomass Substances 0.000 claims description 10
- 230000002950 deficient Effects 0.000 claims description 10
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000004891 communication Methods 0.000 claims description 6
- 229910002840 Pt-MoS2 Inorganic materials 0.000 claims description 5
- 230000003139 buffering effect Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- -1 azaethylcarbazole Chemical compound 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 229910052961 molybdenite Inorganic materials 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 9
- 239000000571 coke Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
- C01B3/54—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids including a catalytic reaction
-
- 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
- C01B2203/0415—Purification by absorption in liquids
-
- 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
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- 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
- C01B2203/048—Composition of the impurity the impurity being an organic compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a hydrogen purification system and a method, wherein the hydrogen purification system comprises: the absorption device is provided with an absorption cavity, a gas inlet to be purified and a hydrogen-containing carrier liquid outlet, wherein the gas inlet to be purified is used for introducing gas to be purified, the absorption cavity is used for containing a hydrogen-poor carrier liquid, and the hydrogen-poor carrier liquid can absorb hydrogen in the gas to be purified and generate the hydrogen-containing carrier liquid; the decomposing device is provided with a decomposing inner cavity, a hydrogen-containing carrying liquid inlet and a purified hydrogen outlet, wherein the hydrogen-containing carrying liquid inlet is communicated with the decomposing inner cavity, the decomposing inner cavity is used for carrying out decomposition reaction on the hydrogen-containing carrying liquid, and the purified hydrogen outlet is used for outputting hydrogen generated by decomposing the hydrogen-containing carrying liquid. The method and the device have the advantages that the hydrogen in the gas to be purified is absorbed, various impurity gases are remained, then the hydrogen is released independently, the difficulty caused by impurity removal is avoided, and the difficulty of hydrogen purification is reduced.
Description
Technical Field
The invention relates to the technical fields of chemical industry and new energy, in particular to a hydrogen purification system and method.
Background
Hydrogen is an important synthetic raw material in the chemical industry field, and can also be used as a clean and efficient energy carrier for the fields of power generation, transportation and the like.
Most of the existing hydrogen is from chemical production, and the hydrogen-containing gas must be purified and separated in the hydrogen production process to obtain pure hydrogen. The existing hydrogen purification technology mainly comprises a low-temperature methanol washing method, an active MDEA (methyldiethanolamine) absorption method, a Selexol (polyethylene glycol dimethyl ether method), pressure swing adsorption and the like. The principle of each technology is to absorb/adsorb impurity gas in the mixed gas, and leave clean hydrogen. In the process of chemical hydrogen production, the hydrogen-containing raw gas is generally very complex, so that the impurity gas is required to be removed in multiple stages, the purification process is relatively complicated, and the purification equipment investment is high. In addition, many industrial by-product gases and purge gases contain hydrogen. Because the content of hydrogen in the hydrogen-containing gas is relatively low, the impurity is removed by the prior art, the technology is difficult and the cost is high, so a large amount of industrial hydrogen-containing gas is directly ignited, no recycling is performed, and energy waste and a large amount of carbon emission are caused.
Therefore, how to reduce the difficulty of hydrogen purification is a technical problem to be solved by the person skilled in the art.
Disclosure of Invention
In view of the above, a first object of the present invention is to provide a hydrogen purification system, which aims to reduce the difficulty of hydrogen purification.
A second object of the present invention is to provide a hydrogen purification method.
In order to achieve the first object, the present invention provides the following solutions:
a hydrogen purification system comprising:
the absorption device is provided with an absorption inner cavity, a gas inlet to be purified and a hydrogen-containing carrier liquid outlet, wherein the gas inlet to be purified is used for introducing gas to be purified, the absorption inner cavity is used for containing a hydrogen-poor carrier liquid, and the hydrogen-poor carrier liquid can absorb hydrogen in the gas to be purified and generate the hydrogen-containing carrier liquid;
the decomposing device is provided with a decomposing inner cavity, a hydrogen-containing carrying liquid inlet and a purified hydrogen outlet, wherein the hydrogen-containing carrying liquid inlet is communicated with the hydrogen-containing carrying liquid outlet, the decomposing inner cavity is used for the hydrogen-containing carrying liquid to perform decomposition reaction, and the purified hydrogen outlet is used for outputting hydrogen generated by the decomposition of the hydrogen-containing carrying liquid.
In a specific embodiment, the absorption lumen is filled with an absorption catalyst;
and/or
The decomposition cavity is filled with a decomposition catalyst.
In another specific embodiment, the absorption catalyst is a Pd-Zn-I r three-way catalyst, wherein the content of Pd is not less than 1wt%, the content of effective catalytic components of Pd, zn and I r is not less than 3wt%, and the mass ratio of Zn to I r is not higher than 5:3;
the decomposition catalyst is a Pt-MoS2 binary catalyst, wherein the content of Pt is not less than 1wt%, and the content of effective catalytic components of Pt and MoS2 is not less than 5wt%.
In another specific embodiment, the absorption lumen is provided with a first carrier carrying the first catalyst;
the decomposition cavity is provided with a second carrier carrying the second catalyst.
In another specific embodiment, both the first support and the second support are biomass carbon molecular sieves;
and/or
The hydrogen-deficient carrier liquid comprises azaindole methyl formate, azaethylcarbazole, toluene, 1-methylindole and 2-methylindole, wherein the volume ratio of toluene is not higher than 5%, the content of 1-methylindole is not lower than 15%, and the content of azaindole methyl formate is not lower than 20%;
or alternatively
The hydrogen-deficient carrier liquid comprises azaindole methyl formate, azaethylcarbazole and 1-methylindole, wherein the volume ratio of the azaindole methyl formate to the azaethylcarbazole to the 1-methylindole is 3:2:1.
In another specific embodiment, the absorption device further has a residual gas outlet in communication with the absorption lumen for discharging residual gas after the hydrogen gas is absorbed by the hydrogen-lean carrier liquid from the gas to be purified;
the decomposing device is also provided with a hydrogen-lean carrying liquid outlet communicated with the decomposing cavity, and the hydrogen-lean carrying liquid outlet is used for outputting the hydrogen-lean carrying liquid generated by decomposing the hydrogen-containing carrying liquid in the decomposing cavity.
In another specific embodiment, the hydrogen purification system further comprises a pressure reducer, an inlet of the pressure reducer being in communication with the hydrogen-containing carrier liquid outlet of the absorber device, an outlet being in communication with the hydrogen-containing carrier liquid inlet of the decomposer device;
and/or
The hydrogen purification system further comprises a booster, wherein an outlet of the booster is communicated with the gas inlet to be purified, and an inlet of the booster is used for inputting the gas to be purified.
In another specific embodiment, the hydrogen purification system further comprises a purge device;
one end of the purging device is communicated with the outlet of the pressure reducer, and the other end of the purging device is communicated with the hydrogen-containing carrier liquid inlet of the decomposing device.
In another specific embodiment, the hydrogen purification system further comprises a buffer device and a power pumping device;
the inlet of the buffer device is communicated with the lean hydrogen carrying liquid outlet of the decomposing device, the outlet of the buffer device is communicated with the inlet of the power pumping device, and the outlet of the power pumping device is communicated with the liquid inlet of the absorbing device.
In another specific embodiment, the hydrogen purification system further comprises a heating device and a heat exchange device;
the heat exchange device is arranged between the absorption device and the decomposition device and is used for exchanging heat between the absorption device and the decomposition device;
the heating device is used for heating the decomposing device.
The various embodiments according to the invention may be combined as desired and the resulting embodiments after such combination are also within the scope of the invention and are part of specific embodiments of the invention.
In order to achieve the second object, the present invention provides the following solutions:
a hydrogen purification method comprising:
providing a hydrogen purification system as claimed in any one of the preceding claims;
introducing gas to be purified into the absorption device, absorbing hydrogen in the gas to be purified by the hydrogen-poor carrying liquid contained in the absorption device to generate hydrogen-containing carrying liquid, and conveying the hydrogen-containing carrying liquid into the decomposition device;
the hydrogen-containing carrier liquid is subjected to decomposition reaction in the decomposition device, and generated hydrogen is discharged from a purified hydrogen outlet of the decomposition device so as to obtain pure hydrogen.
In a specific embodiment, after the gas to be purified reacts with the hydrogen-depleted carrier liquid to generate the hydrogen-containing carrier liquid in the absorption device, residual gas is discharged from a residual gas outlet of the absorption device;
and/or
In the decomposing device, the hydrogen-containing carrier liquid generated after the decomposition of the hydrogen-containing carrier liquid is output to a buffer device of the hydrogen purification system for buffering, and is pumped into the absorbing device through a power pumping device of the hydrogen purification system;
and/or
The method further comprises pressurizing the gas to be purified by a pressurizer of the hydrogen purification system before delivering the gas to be purified to the absorption device;
and/or
The hydrogen-containing carrier liquid generated in the absorption device is conveyed to the decomposition device, and specifically comprises: and outputting the hydrogen-containing carrier liquid to a pressure reducer of the hydrogen purification system for pressure reduction, conveying the depressurized hydrogen-containing carrier liquid to a purging device of the hydrogen purification system, and purging the hydrogen-containing carrier liquid in the purging device to the decomposing device.
When the hydrogen purification system provided by the invention is used, the gas to be purified is input into the absorption cavity of the absorption device through the gas inlet to be purified of the absorption device, the temperature of the absorption cavity of the absorption device reaches the temperature required by the absorption reaction, and at the moment, the hydrogen-containing carrier liquid is generated by absorbing the hydrogen in the gas to be purified by the hydrogen-poor carrier liquid contained in the absorption cavity; the hydrogen-containing carrier liquid enters a decomposition cavity of the decomposition device from a hydrogen-containing carrier liquid inlet of the decomposition device, the temperature of the decomposition cavity reaches the temperature required by the decomposition reaction, and at the moment, hydrogen generated by the decomposition of the hydrogen-containing carrier liquid in the decomposition cavity is discharged from a purified hydrogen outlet, so that pure hydrogen is obtained. The method and the device have the advantages that the hydrogen in the gas to be purified is absorbed, various impurity gases are remained, then the hydrogen is released independently, the difficulty caused by impurity removal is avoided, and the difficulty of hydrogen purification is reduced.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a hydrogen purification system according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "top surface", "bottom surface", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the indicated positions or elements must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limitations of the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Referring to fig. 1, a first aspect of the present invention provides a hydrogen purification system to reduce the difficulty of hydrogen purification.
The invention discloses a hydrogen purification system, which comprises an absorption device and a decomposition device, and particularly discloses that the absorption device and the decomposition device are three-phase reactors, and the hydrogen purification system is not limited to the three-phase reactors, but can also be other devices with inner cavities.
As shown in fig. 1, the absorption device is provided with an absorption cavity, a gas inlet to be purified and a hydrogen-containing carrier liquid outlet, wherein the gas inlet to be purified is respectively communicated with the absorption cavity, the gas inlet to be purified is used for introducing gas to be purified, the absorption cavity is used for containing a hydrogen-lean carrier liquid, and the hydrogen-lean carrier liquid can absorb hydrogen in the gas to be purified and generate the hydrogen-containing carrier liquid.
In order to facilitate the discharge of the residual gas in the gas to be purified, the invention discloses that the absorption device is also provided with a residual gas outlet communicated with the absorption cavity, and the residual gas outlet is used for discharging the residual gas of the gas to be purified after the hydrogen is absorbed by the hydrogen-lean carrier liquid.
In order to facilitate the discharge of the hydrogen-containing carrier liquid, the invention discloses a hydrogen-containing carrier liquid outlet which is arranged at the bottommost end of an absorption device. The gas inlet to be purified is arranged on the side wall of the absorption device, the absorption device is also provided with a liquid inlet communicated with the absorption cavity, and the liquid inlet is arranged at the topmost end of the absorption device.
The decomposing device is provided with a decomposing cavity, a hydrogen-containing carrying liquid inlet and a purified hydrogen outlet, wherein the hydrogen-containing carrying liquid inlet is communicated with the decomposing cavity, the hydrogen-containing carrying liquid inlet is communicated with the hydrogen-containing carrying liquid outlet, the decomposing cavity is used for carrying out decomposition reaction on the hydrogen-containing carrying liquid, and the purified hydrogen outlet is used for outputting hydrogen generated by decomposition of the hydrogen-containing carrying liquid.
In order to facilitate the discharge of the hydrogen-lean carrier liquid, the invention discloses a decomposing device which is also provided with a hydrogen-lean carrier liquid outlet communicated with the decomposing cavity, wherein the hydrogen-lean carrier liquid outlet is used for outputting the hydrogen-lean carrier liquid generated by decomposing the hydrogen-containing carrier liquid in the decomposing cavity.
In order to facilitate clean discharge of the lean hydrogen carrying liquid, the invention discloses a lean hydrogen carrying liquid outlet which is arranged at the bottommost end of a decomposing device. The hydrogen-containing carrier liquid inlet is arranged at the topmost end of the decomposing device, and the purified hydrogen outlet is arranged on the side wall of the decomposing device.
It should be noted that the absorption cavity of the absorption device can reach the temperature required by the reaction of the hydrogen-lean carrier liquid and the hydrogen in the gas to be purified. The decomposing cavity of the decomposing device can reach the temperature required by decomposing the hydrogen-containing carrier liquid.
Furthermore, the invention discloses a hydrogen purification system which also comprises a heating device and a heat exchange device, wherein the heating device can be a combustion chamber and the like, and the heating device can be an electric heating sleeve sleeved outside the decomposing device.
The heat exchange device is specifically a heat exchanger and the like, is arranged between the absorption device and the decomposition device and is used for exchanging heat between the absorption device and the decomposition device, and the heat exchange device can transfer heat released by absorption reaction of the absorption device to the decomposition device, so that the energy is recycled, and the cost is reduced.
The heating device is used for heating the decomposing device, and when the energy required by the absorbing device for supplying the decomposing device is insufficient, the heating device is started to supply heat to the decomposing device.
In some embodiments, the hydrogen purification system further comprises a booster, an outlet of the booster being in communication with the gas to be purified inlet, the booster inlet being for inputting the gas to be purified. The arrangement of the pressurizer realizes the pressurization of the gas to be purified which is input into the absorption device, and is convenient for the absorption reaction with the hydrogen-lean carrier liquid in the absorption device.
It should be noted that, when the pressure of the gas to be purified itself can reach the temperature required for the absorption reaction to occur in the absorption device, the pressurizing function of the pressurizing unit may not be started, and at this time, the pressurizing unit only functions as a passage through which the gas to be purified flows.
In some embodiments, the hydrogen purification system further comprises a pressure reducer, an inlet of the pressure reducer is communicated with a hydrogen-containing carrier liquid outlet of the absorption device, and an outlet of the pressure reducer is communicated with a hydrogen-containing carrier liquid inlet of the decomposition device for reducing the pressure of the hydrogen-containing carrier liquid so as to facilitate overflow of various impurity gases directly dissolved in the hydrogen-containing carrier liquid.
Further, the invention discloses a hydrogen purification system which also comprises a purging device, wherein one end of the purging device is communicated with the outlet of the pressure reducer, and the other end of the purging device is communicated with the hydrogen-containing carrier liquid inlet of the decomposition device.
Specifically, the purging device is a purging tank, and a stirring device is arranged in the purging tank so as to stir the hydrogen-containing carrier liquid in the purging tank. An air inlet is formed in the bottom end of the purging tank and used for introducing purging gas. The top end opening of the purging tank is used for discharging purge gas, and the bottom end of the purging tank is provided with a discharge port for discharging hydrogen-containing carrier liquid, wherein the discharge port is communicated with the hydrogen-containing carrier liquid inlet of the decomposing device.
The sweeping device can speed up the overflow speed of various gases directly dissolved in the hydrogen-containing carrier liquid through sweeping, so that the purity of the prepared hydrogen is improved.
In some embodiments, the hydrogen purification system further includes a buffer device and a power pumping device, where, specifically, the buffer device is a buffer tank, the power pumping device is a liquid pump, it should be noted that setting the buffer device as the buffer tank, setting the power pumping device as the liquid pump is only one specific embodiment of the present invention, and in practical application, the buffer device may be another container, and setting the power pumping device as another power device.
The inlet of the buffer device is communicated with the lean hydrogen carrying liquid outlet of the decomposing device, the outlet of the buffer device is communicated with the inlet of the power pumping device, and the outlet of the power pumping device is communicated with the liquid inlet of the absorbing device. The buffer device and the power pumping device are arranged, so that the recycling of the hydrogen-poor carrier liquid is realized.
In some embodiments, the absorption lumen is filled with an absorption catalyst, and the placement of the absorption catalyst accelerates the rate at which the hydrogen-depleted carrier liquid of the absorption lumen absorbs hydrogen from the gas to be purified.
Specifically, the invention discloses an absorption catalyst which is a Pd-Zn-I r ternary catalyst, wherein the content of Pd is not less than 1wt%, the content of effective catalytic components of Pd, zn and I r is not less than 3wt%, and the mass ratio of Zn to I r is not higher than 5:3. It should be noted that the component of the absorbent catalyst disclosed above is only one specific embodiment of the present invention, and other components may be selected according to specific requirements in practical applications.
Further, the absorption cavity is provided with a first carrier for carrying a first catalyst, specifically, the first carrier is a biomass carbon molecular sieve, and the aperture of the biomass carbon molecular sieve is 0.9nm. The first carrier is not limited to the biomass carbon molecular sieve, and may be other carriers.
In some embodiments, the decomposition lumen is filled with a decomposition catalyst, the placement of which accelerates the rate of decomposition of the hydrogen-containing carrier liquid in the decomposition lumen.
Specifically, the invention discloses a decomposition catalyst which is a Pt-MoS2 binary catalyst, wherein the content of Pt is not less than 1wt%, and the content of effective catalytic components of Pt and MoS2 is not less than 5wt%. It should be noted that the above-disclosed component of the decomposition catalyst is only one embodiment of the present invention, and other components may be selected according to specific requirements in practical applications.
Further, the invention discloses a second carrier for bearing a second catalyst in the decomposition cavity, specifically, the second carrier is a biomass carbon molecular sieve, and the aperture of the biomass carbon molecular sieve is 0.9nm. The second carrier is not limited to the biomass carbon molecular sieve, and may be other carriers.
In some embodiments, the invention discloses a hydrogen-depleted carrier liquid comprising azaindole methyl formate, azaethylcarbazole, toluene, 1-methylindole and 2-methylindole, wherein the volume ratio of toluene is not higher than 5%, the content of 1-methylindole is not lower than 15%, and the content of azaindole methyl formate is not lower than 20%.
It should be noted that the specific components of the hydrogen-deficient carrier liquid disclosed above are only one specific embodiment of the present invention, and in practical applications, the components of the hydrogen-deficient carrier liquid may be set to be other components, for example, the hydrogen-deficient carrier liquid includes azaindole methyl formate, azaethylcarbazole and 1-methylindole, where the volume ratio of the azaindole methyl formate, the azaethylcarbazole and the 1-methylindole is 3:2:1.
The second aspect of the present invention provides a hydrogen purification method comprising:
step S1: a hydrogen purification system as in any one of the embodiments above is provided.
Step S2: and introducing the gas to be purified into an absorption device, absorbing the hydrogen in the gas to be purified by the hydrogen-poor carrying liquid contained in the absorption device to generate the hydrogen-containing carrying liquid, and conveying the hydrogen-containing carrying liquid into a decomposition device.
Specifically, in the absorption device, after the purified gas reacts with the hydrogen-poor carrier liquid to generate the hydrogen-containing carrier liquid, the residual gas is discharged from a residual gas outlet of the absorption device.
Further, the invention discloses that the method further comprises pressurizing the gas to be purified by a pressurizer of the hydrogen purification system before conveying the gas to be purified to the absorption device, so that the gas to be purified input into the absorption device can reach the pressure of the hydrogen-lean carrier liquid for absorbing the hydrogen.
Step S3: the hydrogen-containing carrier liquid undergoes decomposition reaction in the decomposing device, and the generated hydrogen is discharged from a purified hydrogen outlet of the decomposing device to obtain pure hydrogen.
Specifically, in the decomposing device, the hydrogen-poor carrying liquid generated after the decomposition of the hydrogen-containing carrying liquid is output to a buffer device of the hydrogen purification system for buffering, and is pumped into the absorbing device through a power pumping device of the hydrogen purification system.
Further, the present invention discloses that the transportation of the hydrogen-containing carrier liquid generated in the absorption device to the decomposition device specifically includes: and outputting the hydrogen-containing carrier liquid to a pressure reducer of the hydrogen purification system for pressure reduction, conveying the hydrogen-containing carrier liquid after pressure reduction to a purging device of the hydrogen purification system, and purging the hydrogen-containing carrier liquid in the purging device to the decomposition device.
Example 1
Taking a hydrogen purification system for purifying hydrogen as an example, after raw coke oven gas is subjected to various chemical product recovery procedures, the main components of the residual coke oven gas are H2 and CH4, and the residual coke oven gas contains a small amount of other gases such as N2, CO, O2 and the like. The absorption device is filled with a Pd-Zn-I r ternary catalyst, wherein the content of Pd, zn and I r in the ternary catalyst is 2wt%, 1wt% and 2wt% respectively, a biomass carbon molecular sieve is adopted as a first carrier, and the pore diameter of the molecular sieve is 2nm. The decomposing device is filled with Pt-MoS2 binary catalyst, and the content is 2.5wt% and 2.5wt% respectively. The hydrogen-deficient carrier liquid comprises the components of azaindole methyl formate, azaethylcarbazole and 1-methylindole in a volume ratio of 3:2:1.
When H2 in coke oven gas is purified, the pressure of the coke oven gas is controlled to be 3MPa
3.5MPa, and then, utilizing the waste heat of the raw gas to raise the temperature of the coke oven gas to 250 ℃, and preheating the hydrogen-lean carrier liquid in the buffer device to 250 ℃; the coke oven gas enters an absorption device, and meanwhile, the hydrogen-poor carrier liquid is introduced into the absorption device; the hydrogen in the coke oven gas is absorbed, and the residual gas flows out from a residual gas outlet of the absorbing device, so that the residual gas can be further treated or utilized. The hydrogen-containing carrier liquid flows into a pressure reducer, the pressure is reduced to normal pressure, and then the hydrogen-containing carrier liquid flows into a purging device; continuously introducing nitrogen into the purging device for purging, enabling the hydrogen-containing carrier liquid to stay in the purging tank for at least 60 seconds, and enabling the carrier liquid to enter the decomposing device after flowing out; the temperature in the decomposing device is 200 ℃ which is lower than the temperature of the absorbing device, a part of heat required in the decomposing process is exchanged heat from the absorbing device, a part of heat is supplied from the heating device (fuel in the heating device can be selected at will), the hydrogen-containing carrier liquid is decomposed into high-purity hydrogen and a lean hydrogen carrier liquid, the high-purity hydrogen flows out from a purified hydrogen outlet of the decomposing device, the lean hydrogen carrier liquid flows out from a lean hydrogen carrier liquid outlet and enters the buffering device, and the liquid in the buffering device is continuously pumped into the absorbing device by the power pumping device for the next circulation process.
The purity of the hydrogen purified by the method can reach more than 99.999 percent, and the net energy consumption in the decomposition process is lower.
Example two
Taking the example of preparing high-purity hydrogen from the byproduct gas of chlorine-alkali hydrogen enrichment, the vast majority of the residual gas is hydrogen after dechlorination, desulfurization and deoxidization of the flowing gas of the chlorine-alkali main pipe, the purity can reach more than 99 percent, and the residual gas contains a small amount of N2, water vapor, O2 and other impurities. The absorption device is filled with a Pd-Zn-I r ternary catalyst, wherein the content of Pd, zn and I r in the ternary catalyst is 2wt%, 0.5wt% and 1wt% respectively, a biomass carbon molecular sieve is adopted as a carrier, and the pore diameter of the molecular sieve is 0.9nm. The decomposing device is filled with Pt-MoS2 binary catalyst, and the content is 3wt% and 2wt% respectively. The hydrogen-deficient carrier liquid comprises the components of azaindole methyl formate, azaethylcarbazole, 1-methylindole, toluene and 2-methylindole in a volume ratio of 5:1:2:1:1.
The chlor-alkali byproduct gas may be pressurized before deoxidization, and when the pressure of the deoxidized gas is less than 2MPa, the pressure of the gas to be purified is higher than 2MPa by using a booster; preheating the lean hydrogen carrying liquid in the buffer device to more than 220 ℃ to enable byproduct gas (raw material gas) to enter the absorption device, and simultaneously, introducing the lean hydrogen carrying liquid into the absorption device; the raw material gas is heated in the absorption device, hydrogen in the raw material gas is absorbed, and the gas which is not completely absorbed is injected into the raw material gas again by the booster; the hydrogen-rich carrier liquid generated by the reaction flows into a pressure reducer, the pressure is reduced to normal pressure, and then the hydrogen-rich carrier liquid flows into a purging device; continuously introducing air into the purging device for purging, enabling the hydrogen-rich carrier liquid to stay in the purging device for at least 30s, and enabling the carrier liquid to enter the decomposing device after flowing out; the temperature in the decomposing device is 180 ℃ which is lower than the temperature of the absorbing device, a part of heat required in the decomposing process is exchanged heat from the absorbing device, a part of heat is supplied from the heating device, the hydrogen-rich carrying liquid is decomposed into high-purity hydrogen and a hydrogen-poor carrying liquid, the high-purity hydrogen flows out from a purified hydrogen outlet of the decomposing device, the hydrogen-poor carrying liquid flows out from a hydrogen-poor carrying liquid outlet, and the hydrogen-poor carrying liquid enters the buffer device; the liquid in the buffer device is continuously pumped into the absorption device by the power pumping device, and the next circulation process is carried out. The purity of the hydrogen purified by the method can reach more than 99.9998 percent, and the hydrogen recovery rate is not lower than 78 percent.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (12)
1. A hydrogen purification system, comprising:
the absorption device is provided with an absorption inner cavity, a gas inlet to be purified and a hydrogen-containing carrier liquid outlet, wherein the gas inlet to be purified is used for introducing gas to be purified, the absorption inner cavity is used for containing a hydrogen-poor carrier liquid, and the hydrogen-poor carrier liquid can absorb hydrogen in the gas to be purified and generate the hydrogen-containing carrier liquid;
the decomposing device is provided with a decomposing inner cavity, a hydrogen-containing carrying liquid inlet and a purified hydrogen outlet, wherein the hydrogen-containing carrying liquid inlet is communicated with the hydrogen-containing carrying liquid outlet, the decomposing inner cavity is used for the hydrogen-containing carrying liquid to perform decomposition reaction, and the purified hydrogen outlet is used for outputting hydrogen generated by the decomposition of the hydrogen-containing carrying liquid.
2. The hydrogen purification system of claim 1, wherein the absorption lumen is filled with an absorption catalyst;
and/or
The decomposition cavity is filled with a decomposition catalyst.
3. The hydrogen purification system according to claim 2, wherein the absorption catalyst is a Pd-Zn-Ir three-way catalyst, wherein the content of Pd is not less than 1wt%, the content of effective catalytic components of Pd, zn and Ir is not less than 3wt%, and the mass ratio of Zn to Ir is not higher than 5:3;
the decomposition catalyst is a Pt-MoS2 binary catalyst, wherein the content of Pt is not less than 1wt%, and the content of effective catalytic components of Pt and MoS2 is not less than 5wt%.
4. The hydrogen purification system of claim 2, wherein the absorption lumen is provided with a first carrier carrying the first catalyst;
the decomposition cavity is provided with a second carrier carrying the second catalyst.
5. The hydrogen purification system of claim 4, wherein the first carrier and the second carrier are both biomass carbon molecular sieves;
and/or
The hydrogen-deficient carrier liquid comprises azaindole methyl formate, azaethylcarbazole, toluene, 1-methylindole and 2-methylindole, wherein the volume ratio of toluene is not higher than 5%, the content of 1-methylindole is not lower than 15%, and the content of azaindole methyl formate is not lower than 20%;
or alternatively
The hydrogen-deficient carrier liquid comprises azaindole methyl formate, azaethylcarbazole and 1-methylindole, wherein the volume ratio of the azaindole methyl formate to the azaethylcarbazole to the 1-methylindole is 3:2:1.
6. The hydrogen purification system according to any one of claims 1 to 5, wherein the absorption device further has a surplus gas outlet communicating with the absorption chamber, the surplus gas outlet being for discharging a surplus gas after the gas to be purified has absorbed hydrogen gas through the hydrogen-deficient carrier liquid;
the decomposing device is also provided with a hydrogen-lean carrying liquid outlet communicated with the decomposing cavity, and the hydrogen-lean carrying liquid outlet is used for outputting the hydrogen-lean carrying liquid generated by decomposing the hydrogen-containing carrying liquid in the decomposing cavity.
7. The hydrogen purification system of claim 6, further comprising a pressure reducer having an inlet in communication with the hydrogen-containing carrier liquid outlet of the absorber device and an outlet in communication with the hydrogen-containing carrier liquid inlet of the decomposer device;
and/or
The hydrogen purification system further comprises a booster, wherein an outlet of the booster is communicated with the gas inlet to be purified, and an inlet of the booster is used for inputting the gas to be purified.
8. The hydrogen purification system of claim 7, further comprising a purge device;
one end of the purging device is communicated with the outlet of the pressure reducer, and the other end of the purging device is communicated with the hydrogen-containing carrier liquid inlet of the decomposing device.
9. The hydrogen purification system of claim 6, further comprising a buffer device and a power pumping device;
the inlet of the buffer device is communicated with the lean hydrogen carrying liquid outlet of the decomposing device, the outlet of the buffer device is communicated with the inlet of the power pumping device, and the outlet of the power pumping device is communicated with the liquid inlet of the absorbing device.
10. The hydrogen purification system of claim 6, further comprising a heating device and a heat exchange device;
the heat exchange device is arranged between the absorption device and the decomposition device and is used for exchanging heat between the absorption device and the decomposition device;
the heating device is used for heating the decomposing device.
11. A method for purifying hydrogen, comprising:
providing a hydrogen purification system as claimed in any one of claims 1 to 10;
introducing gas to be purified into the absorption device, absorbing hydrogen in the gas to be purified by the hydrogen-poor carrying liquid contained in the absorption device to generate hydrogen-containing carrying liquid, and conveying the hydrogen-containing carrying liquid into the decomposition device;
the hydrogen-containing carrier liquid is subjected to decomposition reaction in the decomposition device, and generated hydrogen is discharged from a purified hydrogen outlet of the decomposition device so as to obtain pure hydrogen.
12. The method for purifying hydrogen as claimed in claim 11, wherein in the absorption device, after the gas to be purified reacts with the hydrogen-depleted carrier liquid to produce the hydrogen-containing carrier liquid, a surplus gas is discharged from a surplus gas outlet of the absorption device;
and/or
In the decomposing device, the hydrogen-containing carrier liquid generated after the decomposition of the hydrogen-containing carrier liquid is output to a buffer device of the hydrogen purification system for buffering, and is pumped into the absorbing device through a power pumping device of the hydrogen purification system;
and/or
The method further comprises pressurizing the gas to be purified by a pressurizer of the hydrogen purification system before delivering the gas to be purified to the absorption device;
and/or
The hydrogen-containing carrier liquid generated in the absorption device is conveyed to the decomposition device, and specifically comprises: and outputting the hydrogen-containing carrier liquid to a pressure reducer of the hydrogen purification system for pressure reduction, conveying the depressurized hydrogen-containing carrier liquid to a purging device of the hydrogen purification system, and purging the hydrogen-containing carrier liquid in the purging device to the decomposing device.
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