CN116553496A - Helium refining method and device - Google Patents
Helium refining method and device Download PDFInfo
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- CN116553496A CN116553496A CN202310362520.6A CN202310362520A CN116553496A CN 116553496 A CN116553496 A CN 116553496A CN 202310362520 A CN202310362520 A CN 202310362520A CN 116553496 A CN116553496 A CN 116553496A
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- 239000001307 helium Substances 0.000 title claims abstract description 259
- 229910052734 helium Inorganic materials 0.000 title claims abstract description 259
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 title claims abstract description 259
- 238000007670 refining Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 84
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 59
- 230000003197 catalytic effect Effects 0.000 claims abstract description 56
- 238000001179 sorption measurement Methods 0.000 claims abstract description 51
- 238000000605 extraction Methods 0.000 claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000012528 membrane Substances 0.000 claims abstract description 29
- 238000011049 filling Methods 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003345 natural gas Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000010168 coupling process Methods 0.000 claims abstract description 5
- 230000008878 coupling Effects 0.000 claims abstract description 4
- 238000005859 coupling reaction Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000003463 adsorbent Substances 0.000 claims description 17
- 239000002808 molecular sieve Substances 0.000 claims description 14
- 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 14
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 239000012466 permeate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000002737 fuel gas Substances 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 239000003949 liquefied natural gas Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0094—Combined chemical and physical processing
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention discloses a helium refining method and a helium refining device, and relates to the technical field of natural gas treatment and helium recovery. The device comprises a coarse helium extraction unit, a catalytic dehydrogenation unit, a helium refining unit and a filling unit. The BOG raw material gas is subjected to coarse helium extraction unit to obtain hydrogen and helium mixed gas with the content of more than 95%, the hydrogen content is reduced to be less than 1ppm through the catalytic dehydrogenation unit, and the hydrogen is purified to high-purity helium meeting the requirements through the helium refining unit. The helium extraction unit adopts a room temperature pressure swing adsorption coupling membrane separation method to extract helium, and solves the problems of high energy consumption, small operation elasticity, unstable operation and high investment in a low-temperature process. And meanwhile, the resolved gas and the forward-bleed gas generated by the room temperature pressure swing adsorption assembly are recycled, a dirty gas repurification pipeline interface is arranged, and the low-purity helium gas is depressurized and then returned to the helium refining unit for repurification, so that the secondary recovery of methane-rich gas is realized, and the recovery rate of helium gas is improved.
Description
Technical Field
The invention relates to the technical field of natural gas treatment and helium recovery, in particular to a helium refining method and a helium refining device.
Background
Helium is taken as a rare strategic resource and has important application in the fields of semiconductors, medical treatment, petrochemical industry, aerospace, navigation and the like, and the helium which is currently used for business is mainly from byproducts in the natural gas processing or liquefied natural gas (liquified natural gas, LNG) process, wherein the helium content of liquefied natural gas evaporation gas (LNG-BOG) is high, and the helium extraction raw gas requirement can be met, so that the BOG can be utilized for helium extraction.
The existing helium extraction technology is a low Wen Dihai technology, the international main stream helium extraction device adopts a cryogenic separation technology to extract helium, a refrigerator or liquid nitrogen is adopted as a cold source, the separation of helium is realized by utilizing the difference of critical temperatures of all components in natural gas, and the helium extraction technology is suitable for the working conditions of high helium content and high treatment capacity in natural gas, but when the device scale is not large, the cryogenic separation technology has the problems of high energy consumption, small operation elasticity, unstable operation and poor economic benefit in the low-temperature technology.
Disclosure of Invention
In view of the foregoing problems of the prior art, a first technical problem to be solved by the present invention is to provide a helium refining apparatus; the second technical problem to be solved by the invention is to provide a method for refining helium by using the device.
The technical scheme adopted by the invention is as follows:
a crude helium refining device comprises a crude helium extraction unit, a catalytic dehydrogenation unit, a helium refining unit and a filling unit; the crude helium extraction unit, the catalytic dehydrogenation unit, the helium refining unit and the filling unit are sequentially connected through pipelines.
The crude helium extraction unit comprises a room temperature pressure swing adsorption assembly and a membrane separation assembly which are connected in sequence.
The room temperature pressure swing adsorption component performs pressure adsorption, normal pressure or reduced pressure analysis under room temperature conditions through the equilibrium adsorption amount of the adsorbent.
The membrane separation assembly is used for separating through the transmission of different components and the difference of permeation rates of the gases to obtain permeation gas of the membrane separation assembly and non-permeation gas of the membrane separation assembly.
The crude helium extraction unit separates helium, hydrogen, methane and nitrogen by utilizing the characteristics of different components of the mixed gas, such as different molecular polarities and different particle sizes.
The catalytic dehydrogenation unit comprises a catalytic dehydrogenation reactor, a water cooler, a gas-liquid separator, an adsorption dryer, a circulating compressor, a flowmeter and a hydrogen analyzer; the flowmeter and the hydrogen analyzer are respectively arranged on an air inlet pipeline and an air outlet pipeline of the catalytic dehydrogenation unit.
The helium refining unit comprises a crude helium compressor and a helium purifier which are connected in sequence.
Wherein, the permeate gas outlet of membrane separation subassembly is connected catalytic dehydrogenation reactor, and the export of adsorption dryer is connected the import of coarse helium compressor, and the export of helium purifier is connected filling unit.
The room temperature pressure swing adsorption component is also connected with a natural gas compressor and a BOG compressor, so that the recovery and the utilization of the resolved gas and the forward-bleed gas generated by the room temperature pressure swing adsorption component are realized.
Further, a cut-off valve is arranged between the coarse helium extraction unit, the catalytic dehydrogenation unit, the helium refining unit and the filling unit for isolation, and a safety discharge pipeline is also arranged for emptying treatment.
Further, the helium purifier has at least 2 helium purifiers, one helium purifier performs purification work, and one helium purifier performs activation regeneration.
A method of refining crude helium comprising the steps of:
s1, feeding BOG raw material gas into a coarse helium extraction unit through an air inlet pipeline, and separating by a room temperature pressure swing adsorption coupling film to obtain coarse helium treated by the coarse helium extraction unit;
s2, inputting the crude helium processed by the crude helium extraction unit into a catalytic dehydrogenation unit for dehydrogenation treatment to obtain dehydrogenated crude helium;
s3, inputting the dehydrogenated crude helium into a helium refining unit, pressurizing the crude helium by a crude helium compressor, entering a helium purifier, finishing refining, and feeding the crude helium into a filling unit for filling.
Further, the method for refining the coarse helium specifically comprises the following steps:
s1.1, BOG raw gas enters a coarse helium extraction unit through an air inlet pipeline, and coarse helium, analysis gas and forward bleed gas are produced through a room temperature pressure swing adsorption component; the resolved gas is returned to the natural gas compressor and is sent to a fuel gas pipe network, the sequential bleed gas is recycled and liquefied through the BOG compressor, and crude helium product is subjected to membrane separation assembly to obtain crude helium treated by the crude helium extraction unit;
s2.1, inputting the crude helium processed by the crude helium extraction unit into a catalytic dehydrogenation unit, removing hydrogen in permeation gas of a membrane separation assembly to be less than 1ppm through a catalytic dehydrogenation reactor of the catalytic dehydrogenation unit, cooling through a water cooler to obtain condensed liquid water, separating the condensed liquid water through a gas-liquid separator, and then entering an adsorption dryer to remove water in permeation gas of the membrane separation assembly to be less than 3ppm to obtain dehydrogenated crude helium;
s3.1, inputting the dehydrogenated crude helium into a helium refining unit, pressurizing to 20MPa by a crude helium compressor, entering a helium purifier to finish refining, and sending the refined helium with the purity of more than 99.999 percent into a filling unit, and returning the helium with the purity of less than 99.999 percent to the crude helium compressor through decompression to perform secondary purification.
Further, in step S1.1, the room temperature pressure swing adsorption module is filled with an adsorbent.
Further, the adsorbent is a molecular sieve adsorbent.
Further, molecular sieve adsorbents include, but are not limited to, silica molecular sieve adsorbents, carbon molecular sieve adsorbents, zeolite molecular sieve adsorbents.
Further, in step S2.1, the catalytic dehydrogenation reactor is filled with a catalyst; the adsorption dryer is filled with molecular sieve adsorbent.
Further, the catalyst includes, but is not limited to, palladium catalyst, platinum catalyst.
Further, molecular sieve adsorbents include, but are not limited to, silica molecular sieve adsorbents, carbon molecular sieve adsorbents, zeolite molecular sieve adsorbents.
The beneficial effects of the invention are as follows:
(1) The invention obtains more than 95% of hydrogen and helium mixed gas through a coarse helium extraction unit, reduces the hydrogen content to be less than 1ppm through a catalytic dehydrogenation unit, and further purifies helium to high-purity helium meeting the requirements of GB/T4844 through a helium refining unit.
(2) The coarse helium extraction unit adopts room temperature pressure swing adsorption and membrane separation coupling method to extract helium, can realize coarse extraction of helium at normal temperature, does not need to be provided with a refrigerator, and has low energy consumption, stability, reliability and simple operation.
(3) The invention effectively recycles the analysis gas and the forward-bleed gas generated by the room temperature pressure swing adsorption component, realizes the secondary recycling of the methane-rich gas and improves the recycling rate of helium.
(4) According to the invention, the dirty gas repurification pipeline interface is arranged, low-purity helium is depressurized and then returned to the inlet of the helium compressor of the helium refining unit for repurification, so that the recovery purity of helium is improved.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a block diagram of the process flow of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments of the present invention and corresponding drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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. The following describes in detail the technical solutions provided by the embodiments of the present invention with reference to the accompanying drawings.
Example 1
As shown in fig. 1, a crude helium refining apparatus is divided according to functional unit modules, and may be divided into a crude helium extraction unit, a catalytic dehydrogenation unit, a helium refining unit, and a filling unit in this order; in consideration of equipment failure, unit shutdown, interlocking shutdown and the like of the system during operation, a shut-off valve is arranged among the crude helium extraction unit, the catalytic dehydrogenation unit, the helium refining unit and the filling unit for isolation, and a safety discharge pipeline is arranged for emptying treatment.
1. Coarse helium extraction unit
The crude helium extraction unit comprises a room temperature pressure swing adsorption assembly and a membrane separation assembly which are sequentially connected; and performing pressure swing adsorption coupling multistage membrane separation at room temperature to obtain the crude helium treated by the crude helium extraction unit.
The crude helium extraction unit separates helium, hydrogen, methane and nitrogen by utilizing the characteristics of different components of the mixed gas, such as different molecular polarities and different particle sizes, so as to obtain the gas with the required purity.
The full-automatic control system applies a circulation process of pressurized adsorption, normal pressure or reduced pressure analysis under the condition of room temperature according to a specific programmable program, and the separation and discharge of impurities are completed through the membrane separation assembly, so that the discharged tail gas with the required purity is obtained.
The room temperature pressure swing adsorption assembly is also connected with a natural gas compressor and a BOG compressor, and crude helium, analysis gas and forward bleed gas are produced by the room temperature pressure swing adsorption assembly; the resolved gas is returned to the natural gas compressor and is sent to a fuel gas pipe network, the sequential bleed gas is recycled and liquefied through the BOG compressor, and crude helium product is subjected to membrane separation assembly to obtain crude helium treated by the crude helium extraction unit;
2. catalytic dehydrogenation unit
The catalytic dehydrogenation unit comprises a catalytic dehydrogenation reactor, a water cooler, a gas-liquid separator, an adsorption dryer, a circulating compressor, a flowmeter and a hydrogen analyzer; the catalytic dehydrogenation unit comprises a shell and a circulating compressor, wherein the circulating compressor is positioned outside the shell, the catalytic dehydrogenation reactor, the water cooler, the gas-liquid separator and the adsorption dryer are positioned in the shell, and the flowmeter and the hydrogen analyzer are respectively arranged on an air inlet pipeline and an air outlet pipeline of the catalytic dehydrogenation unit. The recycle compressor increases the gas pressure to form a recycle gas flow in the system, which is controlled by the control system and metered by the flowmeter.
The permeable gas outlet of the membrane separation component is connected with a catalytic dehydrogenation reactor, a catalyst is filled in the catalytic dehydrogenation reactor and used for removing hydrogen in crude helium, the reaction temperature of the catalytic reactor is accurately controlled, crude helium treated by a crude helium extraction unit is input into the catalytic dehydrogenation unit and is subjected to oxygen-adding catalytic dehydrogenation with oxygen from a liquid oxygen storage tank, the crude helium coming out of the catalytic dehydrogenation reactor contains a large amount of reaction water, the reaction water is firstly cooled by a water cooler and then separated by a gas-liquid separator, condensed liquid is then separated and enters a switching type adsorption dryer, and as the molecular sieve adsorbent is filled in the adsorption dryer, water in raw material gas can be removed, the molecular sieve adsorbent is heated and regenerated after being adsorbed and saturated, so that the adsorption activity is recovered, and the two adsorption dryers alternately adsorb and regenerate, thereby realizing continuous drying of crude helium coming out of the catalytic dehydrogenation reactor, and obtaining the crude helium after dehydrogenation.
3. Helium refining unit
The helium refining unit comprises a crude helium compressor and a helium purifier which are sequentially connected; and an outlet of the adsorption dryer of the catalytic dehydrogenation unit is connected with an inlet of the coarse helium compressor.
The dehydrogenated coarse helium is increased to a preset pressure by a coarse helium compressor, enters a helium purifier, and is subjected to low-temperature condensation separation and adsorption to obtain high-purity helium with the purity of more than 99.999%, and is sent to a filling unit for filling; the helium with purity less than 99.999% is decompressed and returned to the inlet of the crude helium compressor for further purification.
At least 2 helium purifiers are provided, and 2 helium purifiers (1 is used) are configured in the embodiment, wherein one helium purifier is used for purifying, and the other helium purifier is used for activating and regenerating, and the single continuous working capacity is more than 20 hours.
The helium purifier is a Dewar type purifier, the working principle is to adopt high-pressure and low-temperature condensation separation and adsorption for purification, the working process is to carry out the purification under the temperature of liquid nitrogen of 77K (-196 ℃), and unpurified helium entering the helium purifier and helium purified from the helium purifier are subjected to countercurrent heat exchange in a high-pressure double-pipe heat exchanger so as to reduce the loss of liquid nitrogen in the working process of the device. The temperature of the high-pressure unpurified gas discharged from the high-pressure double-pipe heat exchanger is slightly higher than the temperature of liquid nitrogen, and generally has a temperature difference of about 10-13K, so that the gas is further cooled by the supercooling heat exchanger soaked in the liquid nitrogen, and the temperature is closer to the temperature of the liquid nitrogen, thereby separating out part of impurities. Under high pressure and low temperature, when the unpurified helium enters a liquid separating cylinder in a helium purifier, the impurity components mixed in the liquid separating cylinder are supercooled and saturated to be separated out because the boiling point is higher than the liquid nitrogen temperature, the impurity components are accumulated at the bottom of the liquid separating cylinder, and the impurity components are discharged into the atmosphere through a discharge valve of a high pressure and low temperature pneumatic valve. Finally, the residual impurity components are adsorbed by the adsorption characteristics of the activated carbon and the molecular sieve in a low-temperature (liquid nitrogen 77K) environment, so that the purity of the helium is increased to 99.999 percent, and then the helium is stored under high pressure.
The middle part of the Dewar of the helium purifier is provided with a differential pressure liquid level meter, and in the precooling stage of the helium purifier, when the liquid level meter monitors that the liquid level is more than or equal to L+0.1m, the liquid nitrogen filling valve is automatically closed, and when the pressure is reduced to Lm, the liquid nitrogen filling valve is automatically opened to start filling liquid nitrogen.
During the operation of the helium purifier, if the purity is detected to be less than 99.999%, the pure air valve is closed, the dirty air valve is opened, and the dirty air is returned to the dirty air storage tank.
When the helium purifier performs purification work, when the purity of the gas outlet of the helium purifier reaches more than 99.999 percent and is stable for 15S, the pure gas valve is opened, the dirty gas valve is closed, and the high-purity helium is output by the purifier.
When the electric heating activation regeneration is started, if the temperature detected by the thermometer in the middle of the purifier reaches the set temperature, the electric heating is automatically turned off, and after the temperature is reduced, the electric heating is automatically turned on.
When the helium purifier stably operates, the opening of the proportional valve at the inlet of the vacuum pump is controlled by adopting the vacuum degree of liquid nitrogen, and the vacuum degree of the Dewar is controlled to be stable. The nitrogen is directly emptied through the bypass valve when the helium purifier is precooled, and meanwhile, the Dewar is provided with safety accessories such as a safety valve and the like, so that overpressure relief of the Dewar is ensured.
When the helium purifier is activated and regenerated, a treatment mode of hot nitrogen purging and vacuumizing is adopted, after the pressure of the purifier is relieved to normal pressure, hot nitrogen is used for purging the helium purifier, and after purging is completed, a nitrogen purging valve is closed. And (3) starting the vacuum pump to evacuate and replace when the purifier reaches normal pressure, wherein the equipment shares an activated vacuum pump, and the evacuation time is about 3 times, wherein a small amount of high-purity helium gas is used for backfilling the purifier to micro-positive pressure after each evacuation is completed. The equipment is provided with a nitrogen heater, and the temperature of the inner wall of the nitrogen heater is controlled to be less than 120 ℃.
4. Filling unit
The highest gas outlet pressure of the helium refining unit is 20MPa, high-purity helium obtained through a helium purifier firstly enters a site high-pressure cache steel cylinder group, after a helium container tube bundle vehicle enters a factory, the high-pressure cache steel cylinder group firstly inflates the helium container tube bundle vehicle, and then the helium refining unit pressurizes the helium until the pressure of the helium container tube bundle vehicle is reached.
The high-purity helium filling unit is provided with a filling port of the bulk gas cylinder, so that the bulk gas cylinder can be conveniently pressurized. In addition, a vacuum pump is arranged, so that when the helium container tube bundle vehicle is polluted, the helium container tube bundle vehicle is conveniently subjected to vacuumizing gas replacement. When the product gas is transported, the oxygen content and the water content in the product gas are required to be monitored on line according to industry practice so as to ensure that the product meets the national standard requirement.
Example 2
In this example, BOG raw material gas (in terms of V/V, composition: HE3.50%, H) 2 1.70％，N 2 15.30％，CH 4 79.50％，O 2 0％，H 2 O0%) was exemplified as helium refining, and the refining procedure was as follows:
(1) BOG raw gas enters a coarse helium extraction unit through an air inlet pipeline, and coarse helium, analysis gas and forward bleed gas are produced through a room temperature pressure swing adsorption component; the resolved gas is returned to the natural gas compressor and is sent to a fuel gas pipe network, the sequential bleed gas is recycled and liquefied through the BOG compressor, and crude helium product is obtained through the membrane separation assembly, so that crude helium treated by the crude helium extraction unit is obtained.
Equilibrium adsorption capacity of room temperature pressure swing adsorption component through adsorbentPerforming pressure adsorption, normal pressure or reduced pressure analysis under room temperature; the membrane separation assembly separates by different transfer and permeation rates of different components of the gas. The purity of helium and hydrogen in the crude helium treated by the crude helium extraction unit is 95 percent (in terms of V/V, the composition is HE63.94 percent, H) 2 31.06％，N 2 0.81％，CH 4 4.19％，O 2 0％，H 2 O0％)。
(2) The catalytic dehydrogenation reactor of the catalytic dehydrogenation unit is filled with a catalyst, the crude helium treated by the crude helium extraction unit is input into the catalytic dehydrogenation unit, hydrogen in the crude helium is removed to be less than 1ppm, condensed liquid water is obtained through cooling by a water cooler, then the condensed liquid water is separated by a gas-liquid separator and then enters an adsorption dryer, water in the permeation gas of the membrane separation assembly is removed to be less than 3ppm, and the crude helium after dehydrogenation is obtained;
(3) The dehydrogenated coarse helium is input into a helium refining unit, is pressurized to 20MPa by a coarse helium compressor, enters a helium purifier to finish refining, and the refined helium with the purity of more than 99.999% is sent into a filling unit to be filled.
Comparative example 1
In this example, BOG raw material gas (in terms of V/V, composition: HE3.50%, H) 2 1.70％，N 2 15.30％，CH 4 79.50％，O 2 0％，H 2 O0%) was exemplified as helium refining, and the refining procedure was as follows:
(1) BOG raw gas enters a coarse helium extraction unit through an air inlet pipeline, coarse helium, analysis gas and forward gassing gas are produced through a room temperature pressure swing adsorption component, the coarse helium directly enters a catalytic dehydrogenation unit, the purity of helium and hydrogen in the coarse helium is 51% (in terms of V/V, the composition is HE34.04%, H 2 16.53％，N 2 7.98％，CH 4 41.45％，O 2 0％，H 2 O0％)。
(2) The catalytic dehydrogenation reactor of the catalytic dehydrogenation unit is filled with a catalyst, the crude helium treated by the crude helium extraction unit is input into the catalytic dehydrogenation unit, hydrogen in the crude helium is dehydrogenated, condensed liquid water is obtained by cooling by a water cooler, then the condensed liquid water is separated by a gas-liquid separator and then enters an adsorption dryer, and water in the permeation gas of the membrane separation assembly is removed to below 3ppm to obtain dehydrogenated crude helium;
(3) The dehydrogenated coarse helium is input into a helium refining unit, is pressurized to 20MPa by a coarse helium compressor, enters a helium purifier to finish refining, and the purity after refining does not meet the requirements of GB/T4844.
Comparative example 2
In this example, BOG raw material gas (in terms of V/V, composition: HE3.50%, H) 2 1.70％，N 2 15.30％，CH 4 79.50％，O 2 0％，H 2 O0%) was exemplified as helium refining, and the refining procedure was as follows:
(1) BOG raw gas enters a crude helium extraction unit through an air inlet pipeline, directly enters a membrane separation assembly without passing through a room temperature pressure swing adsorption assembly, and permeate gas after membrane separation enters a catalytic dehydrogenation unit, wherein the purity of helium and hydrogen in the crude helium is 51% (in terms of V/V, the composition is HE29.90%, H 2 14.53％，N 2 0.09％，CH 4 55.48％，O 2 0％，H 2 O0％)。
(2) The catalytic dehydrogenation reactor of the catalytic dehydrogenation unit is filled with a catalyst, the crude helium treated by the crude helium extraction unit is input into the catalytic dehydrogenation unit, hydrogen in the crude helium is removed, condensed liquid water is obtained through cooling by a water cooler, then the condensed liquid water is separated by a gas-liquid separator and then enters an adsorption dryer, and water in the permeation gas of the membrane separation assembly is removed to below 3ppm to obtain the dehydrogenated crude helium;
(3) The dehydrogenated coarse helium is input into a helium refining unit, is pressurized to 20MPa by a coarse helium compressor, enters a helium purifier to finish refining, and the purity after refining does not meet the requirements of GB/T4844.
Claims (10)
1. The crude helium refining device is characterized by comprising a crude helium extraction unit, a catalytic dehydrogenation unit, a helium refining unit and a filling unit; the crude helium extraction unit, the catalytic dehydrogenation unit, the helium refining unit and the filling unit are sequentially connected through pipelines; the crude helium extraction unit is also connected with a natural gas compressor and a BOG compressor.
2. A crude helium refining apparatus according to claim 1, wherein,
the crude helium extraction unit comprises a room temperature pressure swing adsorption assembly and a membrane separation assembly which are sequentially connected;
the catalytic dehydrogenation unit comprises a catalytic dehydrogenation reactor, a water cooler, a gas-liquid separator, an adsorption dryer, a circulating compressor, a flowmeter and a hydrogen analyzer; the flowmeter and the hydrogen analyzer are respectively arranged on an air inlet pipeline and an air outlet pipeline of the catalytic dehydrogenation unit;
the helium refining unit comprises a crude helium compressor and a helium purifier which are sequentially connected;
wherein, the permeate gas outlet of the membrane separation assembly is connected with the catalytic dehydrogenation reactor, the outlet of the adsorption dryer is connected with the inlet of the coarse helium compressor, and the outlet of the helium purifier is connected with the filling unit;
the room temperature pressure swing adsorption assembly is also connected with a natural gas compressor and a BOG compressor.
3. A crude helium refining apparatus according to claim 1 or claim 2, wherein a shut-off valve is provided between the crude helium extraction unit, the catalytic dehydrogenation unit, the helium refining unit and the filling unit for isolation, and a safety discharge line is provided for emptying.
4. A method for refining crude helium, comprising the steps of:
s1, feeding BOG raw material gas into a coarse helium extraction unit through an air inlet pipeline, and separating by a room temperature pressure swing adsorption coupling film to obtain coarse helium treated by the coarse helium extraction unit;
s2, inputting the crude helium processed by the crude helium extraction unit into a catalytic dehydrogenation unit for dehydrogenation treatment to obtain dehydrogenated crude helium;
s3, inputting the dehydrogenated crude helium into a helium refining unit, pressurizing the crude helium by a crude helium compressor, entering a helium purifier, finishing refining, and feeding the crude helium into a filling unit for filling.
5. The method for refining crude helium according to claim 4, comprising the steps of:
s1.1, BOG raw gas enters a coarse helium extraction unit through an air inlet pipeline, and coarse helium, analysis gas and forward bleed gas are produced through a room temperature pressure swing adsorption component; the resolved gas is returned to the natural gas compressor and is sent to a fuel gas pipe network, the sequential bleed gas is recycled and liquefied through the BOG compressor, and crude helium product is obtained through a membrane separation assembly to obtain crude helium treated by a crude helium extraction unit;
s2.1, inputting the crude helium processed by the crude helium extraction unit into a catalytic dehydrogenation unit, removing hydrogen in permeation gas of a membrane separation assembly to a preset concentration through a catalytic dehydrogenation reactor of the catalytic dehydrogenation unit, cooling by a water cooler to obtain condensed liquid water, separating the condensed liquid water through a gas-liquid separator, and then entering an adsorption dryer to remove water in permeation gas of the membrane separation assembly to a specified concentration to obtain dehydrogenated crude helium;
s3.1, inputting the dehydrogenated crude helium into a helium refining unit, pressurizing by a crude helium compressor, then entering a helium purifier to finish refining, sending the refined helium with the purity of more than 99.999% into a filling unit, and returning the helium with the purity of less than 99.999% to the crude helium compressor through decompression for re-purification.
6. The method of refining raw helium according to claim 5, wherein in step S1.1, the purity of helium gas and hydrogen gas in the raw helium gas after the treatment of the raw helium extraction unit is 95% or more.
7. The method for purifying raw helium according to claim 5, wherein hydrogen in the permeate gas of the membrane separation module is removed to 1ppm or less in step S2.1 by passing the permeate gas through a catalytic dehydrogenation reactor of a catalytic dehydrogenation unit.
8. A process for purifying raw helium according to claim 5, wherein in step S2.1, water in the permeate gas of the membrane separation module is removed to 3ppm or less by passing the product to an adsorption dryer.
9. A method of refining crude helium according to claim 5, wherein in step S3.1, the crude helium is pressurized to 20MPa by a compressor and enters a helium purifier to complete the refining.
10. The method for purifying crude helium according to claim 5, wherein the room temperature pressure swing adsorption unit, the catalytic dehydrogenation reactor and the adsorption dryer are filled with an adsorbent, a catalyst and a molecular sieve adsorbent, respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310362520.6A CN116553496A (en) | 2023-04-06 | 2023-04-06 | Helium refining method and device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310362520.6A CN116553496A (en) | 2023-04-06 | 2023-04-06 | Helium refining method and device |
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| Publication Number | Publication Date |
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| CN116553496A true CN116553496A (en) | 2023-08-08 |
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| CN202310362520.6A Pending CN116553496A (en) | 2023-04-06 | 2023-04-06 | Helium refining method and device |
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| Country | Link |
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| CN (1) | CN116553496A (en) |
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