CN111533095A - Equipment and process for purifying helium from BOG gas - Google Patents
Equipment and process for purifying helium from BOG gas Download PDFInfo
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- CN111533095A CN111533095A CN202010347519.2A CN202010347519A CN111533095A CN 111533095 A CN111533095 A CN 111533095A CN 202010347519 A CN202010347519 A CN 202010347519A CN 111533095 A CN111533095 A CN 111533095A
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Abstract
The invention discloses a device and a process for purifying helium from BOG gas, which relate to the field of purifying helium from BOG gas, and comprise a first-stage catalytic dehydrogenation reactor, a cooler, a molecular sieve dryer, a feed gas compressor, a heat exchanger, a membrane separator and a vacuum pump, wherein hydrogen in the process of purifying helium is reduced by adopting three-stage catalytic dehydrogenation reaction, because the physical properties of hydrogen and helium are very close, hydrogen in pure helium cannot be removed by using a pressure swing adsorption or cryogenic process, and the purity of helium is ensured by multistage catalytic dehydrogenation and dehydrogenation, the invention adopts the process of membrane separation, the BOG gas of a raw material is concentrated to 30 times, the treatment capacity in the subsequent process of purifying helium is reduced, the invention adopts the modes of pressurizing before a membrane and vacuumizing after the membrane to increase the permeability coefficient of gas molecules, uses less membrane area to enable the helium to achieve higher yield and purity, and the analytic gas of the helium purifier returns to the front of the feed gas compressor, the recovery rate of helium is increased, and the helium yield of the whole set of device is as high as 99%.
Description
Technical Field
The invention relates to the field of purifying helium from BOG gas, in particular to equipment and a process for purifying helium from BOG gas.
Background
Helium is widely applied to the fields of aerospace, refrigeration, medical treatment, optical fiber, leak detection, deep sea diving, high-precision welding production and the like due to the properties of low density, low boiling point and inertia of helium. Particularly in the launching engineering of space launch vehicles which adopt liquid hydrogen/liquid oxygen as fuel in the space launch field, the helium is widely used for safe replacement of pipelines, safe replacement of rocket storage tanks, pressurization and gas supplement of rocket storage tanks in the flying process and safe blowing off of partial low-temperature components due to the low boiling point and safety of helium, and at present, no other product has the function of replacing helium.
Helium is a product of radioactive decay and is present in relatively high concentrations in only a small portion of natural gas. Natural gas stripping helium is currently the only source of commercial use for helium.
For natural gas processing, cryogenic processing of natural gas is, in order of processing temperature from high to low, ethane recovery (-100 ℃), natural gas liquefaction (-160 ℃), and natural gas denitrification (-190 ℃). In the process of liquefying LNG, the non-condensable gas such as helium, hydrogen and the like in the LNG are continuously concentrated and enriched and exist in BOG gas. The helium extraction process in natural gas is divided into a cryogenic process and a non-cryogenic process, and the cryogenic process is still the main industrial selection method.
However, in BOG helium extraction cryogenic work, along with the continuous reduction of the refrigeration temperature, the energy consumption of unit refrigeration capacity is increased sharply, the design, manufacture and operation of equipment both put forward higher and more rigorous requirements, natural gas is a multi-component mixture, low-temperature phase equilibrium is the basis of natural gas cryogenic helium extraction, due to the limitation of the freezing point and solubility of substances, more substances can cause low-temperature blockage along with the reduction of the refrigeration temperature, and the enrichment and concentration of trace hydrogen in the natural gas limit the high purity of the helium.
Disclosure of Invention
In order to solve the problems in the prior art, the invention discloses equipment and a process for purifying helium from BOG gas, wherein the equipment comprises the following contents:
in a first aspect, the invention provides equipment for purifying helium from BOG gas, which comprises a primary catalytic dehydrogenation reactor, a cooler, a molecular sieve dryer, a feed gas compressor, a heat exchanger, a membrane separator, a vacuum pump, a secondary catalytic dehydrogenation reactor, a helium purifier, a tertiary catalytic dehydrogenation reactor, a helium supercharger, a digital display type gas supply busbar device and a helium bottle, and is characterized in that the output end of the primary catalytic dehydrogenation reactor is connected with the input end of the cooler, the output end of the cooler is connected with the input end of the molecular sieve dryer, the output end of the molecular sieve dryer is connected with the input end of the feed gas compressor, the output end of the feed gas compressor is connected with the input end of the heat exchanger, the output end of the heat exchanger is connected with the input end of the membrane separator, the permeation gas end of the membrane separator is connected with the input end of the vacuum pump, the output end of the secondary catalytic dehydrogenation reactor is connected with the input end of a helium purifier, the purified gas output end of the helium purifier is connected with the input end of a tertiary catalytic dehydrogenation reactor, the output end of the tertiary catalytic dehydrogenation reactor is connected with the input end of a helium supercharger, the output end of the helium supercharger is connected with the input end of a digital display type gas supply busbar device, and the output end of the digital display type gas supply busbar device is connected with a helium bottle.
Preferably, a BOG raw gas removing helium extraction device hand valve is installed at the input end of the primary catalytic dehydrogenation reactor, a BOG raw gas removing fuel gas pipe network hand valve is installed at one side, located at the BOG raw gas removing helium extraction device hand valve, of the input end of the primary catalytic dehydrogenation reactor, a membrane separator non-permeation gas removing BOG fuel gas hand valve is installed at the non-permeation gas output end of the membrane separator, and the helium purifier desorption gas output end is connected with the input end of the raw gas compressor.
Preferably, the cooler is one of a water cooler and an air cooler, and the heat exchanger is one of a steam heater and an electric heater.
Preferably, the membrane separator is one of a single-stage membrane separation device or a two-stage membrane separation device or a multi-stage membrane separation device.
Preferably, the helium purifier is a pressure swing adsorption purifier or a cryogenic condensation purifier.
Preferably, the helium tank has a volume of one of 40L and 50L.
In a second aspect, the present invention provides a process for purifying helium from BOG gas, comprising the following steps:
step 1: mixing BOG raw material gas from an original BOG fuel gas pipe network with air, then feeding the mixture into a primary catalytic dehydrogenation reactor for dehydrogenation, cooling the dehydrogenated gas to below 40 ℃ through a cooler, and then cooling the cooled gas to below-60 ℃ through a molecular sieve dryer;
step 2: conveying the gas dried in the step 1 into a feed gas compressor for compression, conveying the compressed gas to a heat exchanger for heating to 65 ℃, conveying the heated gas into a membrane separator for separation, merging non-permeable gas generated at a non-permeable gas outlet of the membrane separator into an original BOG fuel gas pipe network for discharging and supplying to combustion, and separating crude helium from a permeable gas outlet of the membrane separator;
and step 3: conveying the crude helium in the step 2 to a vacuum pump, and conveying the crude helium to a secondary catalytic dehydrogenation reactor through the vacuum pump for secondary dehydrogenation;
and 4, step 4: conveying the crude helium subjected to secondary dehydrogenation in the step 3 into a helium purifier for purification, refluxing desorption gas generated during purification of the helium purifier into the raw material gas compressor in the step 2 for mixing with the dried gas for re-separation, and generating purified gas helium at a purified gas end of the helium purifier;
and 5: and (4) conveying the purified gas helium in the step (4) into the three-stage catalytic dehydrogenation reactor for concentration and enrichment, pressurizing the concentrated and enriched helium through a helium supercharger, and filling the helium cylinder through a digital display type gas supply busbar device.
Preferably, the BOG feed gas pressure from the raw BOG fuel gas grid in step 1 is 0.02 MPaG.
Preferably, the inlet pressure of the vacuum pump in the step 3 is-0.09 MPaG, and the outlet pressure of the vacuum pump is 0.05 MPaG.
Preferably, the second-stage catalytic dehydrogenation reactor and the third-stage catalytic dehydrogenation reactor in steps 3 and 5 remove hydrogen by using metal oxide as an oxidant.
Advantageous effects
The equipment and the process for purifying helium by using the BOG gas manufactured by the technical scheme of the invention;
1. the hydrogen in the helium purification process is reduced by adopting three-stage catalytic dehydrogenation reaction, and the hydrogen and the helium have very close physical properties, so that the hydrogen in the pure helium cannot be removed by using a pressure swing adsorption or cryogenic process, and the purity of the helium is ensured by multi-stage catalytic dehydrogenation.
2. The invention adopts the membrane separation process, the BOG gas of the raw material is concentrated to 30 times, and the treatment capacity of the subsequent helium purification process is reduced.
3. The invention adopts the mode of pressurizing before the membrane and vacuumizing after the membrane to increase the permeability coefficient of gas molecules and uses less membrane area to ensure that helium gas achieves higher yield and purity.
4. The desorption gas of the helium purifier is returned to the raw material gas compressor, so that the recovery rate of helium is increased, and the helium yield of the whole device is as high as 99%.
5. The invention adds a new interface on the original BOG fuel gas pipeline to concentrate helium in BOG raw material gas, and the loss of non-permeable gas after passing through a membrane separator is less than 5 percent.
6. The process is reasonable, and the effective components of the raw material gas are recycled to the maximum extent.
Drawings
FIG. 1 is a flow chart of the present invention;
in the figure, 1-a first-stage catalytic dehydrogenation reactor; 2-a cooler; 3-a molecular sieve dryer; 4-a feed gas compressor; 5-a heat exchanger; 6-membrane separator; 7-a vacuum pump; 8-a secondary catalytic dehydrogenation reactor; 9-a helium purifier; 10-three-stage catalytic dehydrogenation reactor; 11-helium booster; 12-digital display type gas supply bus device; 13-helium tank; 14-BOG raw material gas helium extraction device hand valve; 15-BOG raw material gas is sent to a fuel gas pipe network hand valve; the 16-membrane separator non-permeate gas goes to BOG fuel gas hand valve.
Detailed Description
The present invention will be described in further detail with reference to examples.
The embodiment is characterized by comprising a BOG gas helium purification device, which comprises a primary catalytic dehydrogenation reactor 1, a cooler 2, a molecular sieve dryer 3, a raw material gas compressor 4, a heat exchanger 5, a membrane separator 6, a vacuum pump 7, a secondary catalytic dehydrogenation reactor 8, a helium purifier 9, a tertiary catalytic dehydrogenation reactor 10, a helium supercharger 11, a digital display type gas supply busbar device 12 and a helium bottle 13, and is characterized in that the output end of the primary catalytic dehydrogenation reactor 1 is connected with the input end of the cooler 2, the output end of the cooler 2 is connected with the input end of the molecular sieve dryer 3, the output end of the molecular sieve dryer 3 is connected with the input end of the raw material gas compressor 4, the output end of the raw material gas compressor 4 is connected with the input end of the heat exchanger 5, the output end of the heat exchanger 5 is connected with the input end of the membrane separator, the membrane separator 6 is connected with the input end of a vacuum pump 7 at the permeation gas end, the output end of the vacuum pump 7 is connected with the input end of a secondary catalytic dehydrogenation reactor 8, the output end of the secondary catalytic dehydrogenation reactor 8 is connected with the input end of a helium purifier 9, the output end of the helium purifier 9 is connected with the input end of a tertiary catalytic dehydrogenation reactor 10, the output end of the tertiary catalytic dehydrogenation reactor 10 is connected with the input end of a helium booster 11, the output end of the helium booster 11 is connected with the input end of a digital display type gas supply busbar device 12, the output end of the digital display type gas supply busbar device 12 is connected with a helium gas bottle 13, a BOG raw material gas removing helium removing device hand valve 14 is installed at the input end of a primary catalytic dehydrogenation reactor 1, a BOG raw material gas removing fuel gas pipe network hand valve 15 is installed at one side of the BO, membrane separator 6 non-permeate gas output end mountain is installed membrane separator non-permeate gas and is removed BOG fuel gas hand valve 16, helium purifier 9 is analyzed the gas output and is connected with 4 input of feed gas compressor, one kind in cooler 2 adopts water chiller or the air-cooled ware, one kind in heat exchanger 5 adopted steam heater or the electric heater, membrane separator 6 is one kind among single-stage membrane separator or second grade membrane separator or the multistage membrane separator, helium purifier 9 is pressure swing adsorption purifier or cryrogenic condensation purifier, 13 volumes of helium gas bottle are 40L or in the 50L.
Example (b): as can be seen from the attached figure 1 in the specification, when the BOG helium extraction device is put into use, the BOG feed gas is closed to the fuel gas pipe network hand valve 15, the BOG feed gas to the helium extraction device hand valve 14 is opened, the membrane separator non-permeate gas to the BOG fuel gas hand valve 16 is opened, and the BOG helium purification system is put into use. When the BOG purification helium system is overhauled, the BOG raw material gas is opened to the fuel gas pipe network hand valve 15, the BOG raw material gas is closed to the helium extraction device hand valve 14, the non-permeable gas of the membrane separator is closed to the BOG fuel gas hand valve 16, the BOG fuel gas pipe network can normally supply gas, and the use of subsequent users is not influenced.
As can be seen from the attached figure 1 of the specification, when in use, raw material gas and air are mixed and then enter a primary catalytic dehydrogenation reactor 1, hydrogen in the raw material gas is combusted, the combusted gas is cooled by a cooler 2, the cooled gas enters a molecular sieve dryer 3 for drying and dehydration, the molecular sieve dryer 3 adopts porous aluminosilicate crystals, the dried and dehydrated gas enters a raw material gas compressor 4 for compression, the gas is heated by a heat exchanger 5 and then is sent to a membrane separator 6, a non-permeable gas outlet of the membrane separator 6 is merged into an original BOG fuel gas pipe network for combustion, permeable gas of the membrane separator 6 is enriched crude helium and is led into an inlet connected with a vacuum pump 7, the vacuum pump 7 increases the pressure difference and pressure ratio of the membrane separator 6 and increases the separation coefficient of the gas, the enriched crude helium enters a secondary catalytic dehydrogenation reactor 8, the secondary catalytic dehydrogenation reactor 8 adopts metal oxide as an oxidant for hydrogen removal, and (3) without adding any impurity gas, sending the crude helium subjected to hydrogen removal by the secondary catalytic dehydrogenation reactor 8 to a helium purifier 9, selecting the helium purifier 9 according to the handling capacity of the BOG raw material gas, if the amount of the pure helium is small, selecting a pressure swing adsorption device for the helium purifier 9, if the amount of the pure helium is large, selecting a cryogenic condensing device for the helium purifier 9, sending the analysis gas of the helium purifier 9 to a raw material gas compressor 4, mixing with the dehydrogenated BOG gas, and separating again to increase the recovery rate of the helium. Hydrogen in purified gas helium purified by the helium purifier 10 is sent to the tertiary catalytic dehydrogenation reactor 10 to be concentrated and enriched again, the tertiary catalytic dehydrogenation reactor 10 removes hydrogen by using metal oxide as an oxidant, no impurity gas is added, helium after the tertiary catalytic dehydrogenation reactor 10 is pressurized by a helium supercharger 11, and then is filled into a helium tank 13 by a digital display type gas supply busbar device 12.
As can be seen from the attached figure 1 in the specification, the process for purifying helium by BOG gas is characterized by comprising the following steps:
step 1: mixing a BOG raw material gas with the pressure of 0.02MPaG from an original BOG fuel gas pipe network with air, then entering a primary catalytic dehydrogenation reactor 1 for dehydrogenation, controlling the reaction temperature of the primary catalytic dehydrogenation reactor 1 to be 200 ℃, ensuring that hydrogen in the BOG raw material gas is combusted, and methane is not combusted, wherein the components in the gas comprise methane, helium, oxygen, water and nitrogen at the moment, cooling the dehydrogenated gas to below 40 ℃ through a cooler 2, and then reducing the dew point of the cooled gas to below-60 ℃ through a molecular sieve dryer 3;
step 2: conveying the gas dried in the step 1 into a feed gas compressor 4 for compression, wherein the pressure of the compressed gas is 0.8MPaG, conveying the compressed gas to a heat exchanger 5 for heating to 65 ℃, conveying the heated gas into a membrane separator 6 for separation, merging non-permeable gas generated at a non-permeable gas outlet of the membrane separator 6 into an original BOG fuel gas pipe network for discharging and supplying for combustion, wherein hydrogen and helium belong to fast gas and are concentrated and enriched in the membrane separator 6, crude helium is separated at a permeable gas outlet of the membrane separator 6, and the content of the helium is 75% of the total gas volume;
and step 3: and (3) conveying the crude helium in the step (2) to a vacuum pump (7), wherein the inlet pressure of the vacuum pump (7) is-0.09 MPaG, increasing the pressure difference and pressure ratio of the membrane separator (6), and increasing the separation coefficient of the gas. The outlet pressure of the vacuum pump 7 is 0.05MPaG, the gas is conveyed into the secondary catalytic dehydrogenation reactor 8 through the vacuum pump 7 for secondary dehydrogenation, and the secondary catalytic dehydrogenation reactor 8 adopts metal oxide as an oxidant for removing hydrogen without adding impurity gas;
and 4, step 4: conveying the crude helium subjected to secondary dehydrogenation in the step 3 into a helium purifier 9 for purification, selecting the helium purifier 9 according to the treatment capacity of BOG raw material gas, if the amount of pure helium is small, selecting a pressure swing adsorption device for the helium purifier 9, and if the amount of pure helium is large, selecting a cryogenic condensing device for the helium purifier 9, wherein desorption gas generated during purification of the helium purifier 9 flows back into the raw material gas compressor 4 in the step 2 for mixing with the dried gas for re-separation, so that the recovery rate of helium is increased, and purified gas helium is generated at the purified gas end of the helium purifier 9;
and 5: and (3) conveying the purified gas helium in the step (4) into a three-stage catalytic dehydrogenation reactor 10 for concentration and enrichment, wherein the three-stage catalytic dehydrogenation reactor 10 adopts metal oxide as an oxidant to remove hydrogen, no impurity gas is newly added, the helium concentration after passing through the three-stage catalytic dehydrogenation reactor 10 reaches more than 99.999%, the concentrated and enriched helium is pressurized by a helium supercharger 11 to enable the gas pressure to reach 16.0MPaG, and then a helium bottle 13 is filled by a digital display type gas supply busbar device 12.
The technical solutions described above only represent the preferred technical solutions of the present invention, and some possible modifications to some parts of the technical solutions by those skilled in the art all represent the principles of the present invention, and fall within the protection scope of the present invention.
Claims (10)
1. A BOG gas helium purification device comprises a primary catalytic dehydrogenation reactor (1), a cooler (2), a molecular sieve dryer (3), a raw material gas compressor (4), a heat exchanger (5), a membrane separator (6), a vacuum pump (7), a secondary catalytic dehydrogenation reactor (8), a helium purifier (9), a tertiary catalytic dehydrogenation reactor (10), a helium supercharger (11), a digital display type gas supply busbar device (12) and a helium bottle (13), and is characterized in that the output end of the primary catalytic dehydrogenation reactor (1) is connected with the input end of the cooler (2), the output end of the cooler (2) is connected with the input end of the molecular sieve dryer (3), the output end of the molecular sieve dryer (3) is connected with the input end of the raw material gas compressor (4), the output end of the raw material gas compressor (4) is connected with the input end of the heat exchanger (5), the output of heat exchanger (5) is connected with membrane separator (6) input, membrane separator (6) infiltration gas end is connected with vacuum pump (7) input, vacuum pump (7) output is connected with second grade catalytic dehydrogenation reactor (8) input, second grade catalytic dehydrogenation reactor (8) output is connected with helium purifier (9) input, helium purifier (9) purify the gas output and be connected with tertiary catalytic dehydrogenation reactor (10) input, tertiary catalytic dehydrogenation reactor (10) output is connected with helium booster compressor (11) input, helium booster compressor (11) output is connected with digital display formula air feed busbar device (12) input, digital display formula air feed busbar device (12) output is connected with helium bottle (13).
2. The equipment for purifying helium from BOG gas according to claim 1, wherein a BOG raw material gas and helium extraction device hand valve (14) is installed at the input end of the primary catalytic dehydrogenation reactor (1), a BOG raw material gas and fuel gas pipe network hand valve (15) is installed at one side, located at the BOG raw material gas and helium extraction device hand valve (14), of the input end of the primary catalytic dehydrogenation reactor (1), a membrane separator non-permeable gas and BOG fuel gas hand valve (16) is installed at the non-permeable gas output end of the membrane separator (6), and the desorption gas output end of the helium purifier (9) is connected with the input end of the raw material gas compressor (4).
3. The apparatus for purifying helium from BOG gas according to claim 1, wherein the cooler (2) is one of a water cooler and an air cooler, and the heat exchanger (5) is one of a steam heater and an electric heater.
4. An apparatus for BOG gas purification of helium according to claim 1, wherein the membrane separator (6) is one of a single stage membrane separation device or a two-stage membrane separation device or a multi-stage membrane separation device.
5. The plant for purifying helium from BOG gas according to claim 1, wherein the helium purifier (9) is a pressure swing adsorption purifier or a cryocondensation purifier.
6. An apparatus for BOG gas purification of helium according to claim 1, wherein the helium tank (13) has a volume of one of 40L or 50L.
7. A process for purifying helium from BOG gas is characterized by comprising the following steps:
step 1: mixing BOG raw material gas from an original BOG fuel gas pipe network with air, then entering a primary catalytic dehydrogenation reactor (1) for dehydrogenation, cooling the dehydrogenated gas to below 40 ℃ through a cooler (2), and then reducing the dew point of the cooled gas to below-60 ℃ through a molecular sieve dryer (3);
step 2: conveying the gas dried in the step 1 into a raw gas compressor (4) for compression, conveying the compressed gas to a heat exchanger (5) for heating to 65 ℃, conveying the heated gas into a membrane separator (6) for separation, merging non-permeable gas generated at a non-permeable gas outlet of the membrane separator (6) into an original BOG fuel gas pipe network for discharging and supplying for combustion, and separating crude helium from a permeable gas outlet of the membrane separator (6);
and step 3: conveying the crude helium in the step 2 to a vacuum pump (7), and conveying the crude helium to a secondary catalytic dehydrogenation reactor (8) through the vacuum pump (7) for secondary dehydrogenation;
and 4, step 4: conveying the crude helium subjected to secondary dehydrogenation in the step 3 into a helium purifier (9) for purification, refluxing desorption gas generated during purification of the helium purifier (9) into the raw material gas compressor (4) in the step 2 for mixing with the dried gas for re-separation, and generating purified gas helium at a purified gas end of the helium purifier (9);
and 5: and (4) conveying the purified gas helium in the step (4) into a three-stage catalytic dehydrogenation reactor (10) for concentration and enrichment, pressurizing the concentrated and enriched helium through a helium supercharger (11), and filling a helium bottle (13) through a digital display type gas supply busbar device (12).
8. The process of claim 7, wherein the BOG feed gas pressure from the raw BOG fuel gas grid in step 1 is 0.02 MPaG.
9. The process for purifying helium from BOG gas as claimed in claim 7, wherein the inlet pressure of the vacuum pump (7) in the step 3 is-0.09 MPaG, and the outlet pressure of the vacuum pump (7) is 0.05 MPaG.
10. The process for purifying helium from BOG gas according to claim 7, wherein the secondary catalytic dehydrogenation reactor (8) and the tertiary catalytic dehydrogenation reactor (10) in the steps 3 and 5 use metal oxide as oxidant to remove hydrogen.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174102A (en) * | 2020-09-24 | 2021-01-05 | 四川省达科特能源科技股份有限公司 | Device and method for multistage separation and extraction of high-purity helium from BOG gas |
| CN112919437A (en) * | 2021-03-24 | 2021-06-08 | 北京中科富海低温科技有限公司 | Refining method and system for crude helium with high hydrogen content |
| CN113108551A (en) * | 2021-05-17 | 2021-07-13 | 中石化中原石油工程设计有限公司 | Process and device for extracting high-purity helium in liquefied natural gas production process |
| CN113501508A (en) * | 2021-07-08 | 2021-10-15 | 北京中科富海低温科技有限公司 | System and method for extracting helium from natural gas or BOG |
| CN113731170A (en) * | 2021-09-27 | 2021-12-03 | 四川远丰森泰能源集团股份有限公司 | Integrated system for bog helium extraction process |
| CN113735079A (en) * | 2020-12-31 | 2021-12-03 | 李保军 | Method for extracting ultra-high purity helium gas at normal temperature and production device |
| CN115872371A (en) * | 2021-09-26 | 2023-03-31 | 中国石油化工股份有限公司 | Method and system for purifying ultrapure helium |
| CN116281896A (en) * | 2022-12-01 | 2023-06-23 | 煤炭科学技术研究院有限公司 | Helium extraction method for helium-containing coal bed gas concentration at low temperature |
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