CN210237128U - System for purifying helium from natural gas liquefied helium-containing tail gas - Google Patents
System for purifying helium from natural gas liquefied helium-containing tail gas Download PDFInfo
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- CN210237128U CN210237128U CN201920423931.0U CN201920423931U CN210237128U CN 210237128 U CN210237128 U CN 210237128U CN 201920423931 U CN201920423931 U CN 201920423931U CN 210237128 U CN210237128 U CN 210237128U
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Abstract
The utility model discloses a system for helium is purified to natural gas liquefaction helium-containing tail gas, it mainly includes compression, membrane separation, pressure swing adsorption, deoxidation unit, multistage dehydrogenation unit. The method comprises the steps that natural gas liquefaction helium-containing tail gas (BOG) is compressed to a certain pressure through a compression unit I and enters a membrane separation unit I to improve helium concentration, the membrane separation unit I is single-section or multi-section membrane separation, non-permeate gas out of the membrane separation unit I is sent back to a natural gas liquefaction system, the permeate gas determines whether to enter the membrane separation unit again according to the helium concentration to further improve the helium concentration, the permeate gas with high helium concentration is mixed with oxygen-containing helium from a pressure swing adsorption unit 2, and the permeate gas is compressed to a certain pressure through a compression unit II and enters a deoxidation unit. Adopt the utility model discloses a system of helium tail gas purification helium is contained in natural gas liquefaction is retrieved the helium in the liquefied natural gas tail gas for high-purity helium product, has simple process, invests in low, with low costs, advantage that helium rate of recovery is high.
Description
Technical Field
The utility model belongs to natural gas liquefaction field of handling, especially contain helium natural gas liquefaction tail gas.
Background
The natural gas contains a small amount of helium, after the LNG product is prepared by taking the natural gas as a raw material, the helium concentration in tail gas is greatly improved, and in order to further obtain helium with higher purity, the helium is usually purified by adopting a low-temperature separation method or an adsorption method or membrane separation method. The tail gas usually contains hydrogen, although the low-temperature separation can separate helium from hydrogen, the investment and the energy consumption are large, and the process is not economical; at present, the method is suitable for the condition of high hydrogen concentration, and when the hydrogen concentration is not too high, the method also adopts the supplementary carbon monoxide or carbon dioxide or the mixture of the carbon monoxide and the carbon dioxide to react with the hydrogen to generate methane, so that the operation is complex and the cost is higher.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a: to prior art's problem, the utility model discloses earlier adopt membrane separation and adsorption method combined technology to separate out containing helium and a small amount of hydrogen from natural gas liquefaction tail gas, then adopt the catalytic oxidation method to remove hydrogen with hydrogen and oxygen reaction formation water, reuse adsorption method purification helium obtains high-purity helium product. The method removes hydrogen by reacting hydrogen in tail gas with pure oxygen or oxygen-enriched air or air to generate water, and then purifies helium to obtain a helium product with high purity, high helium recovery rate, low investment and low energy consumption.
The purpose of the utility model is realized through the following technical scheme:
a system for purifying helium from natural gas liquefied helium-containing tail gas comprises the following steps: the natural gas liquefaction contains helium tail gas (BOG) and is connected with one section entry of I unit of compression, and I unit export of compression and I unit access connection of membrane separation. The non-permeate gas of the unit outlet of the membrane separation I is connected with a natural gas liquefaction system, and the permeate gas of the unit outlet of the membrane separation I is connected with the inlet of the unit of the compression II. An outlet of the compression II unit is connected with a deoxidizing unit, the deoxidizing unit is connected with an inlet of the pressure swing adsorption I unit, and a desorbed gas at an outlet of the pressure swing adsorption I unit and a liquefied natural gas (BOG) helium-containing tail gas are connected with a section of inlet pipeline of the compression I unit; high-concentration helium at the outlet of the pressure swing adsorption unit I is connected with the inlet of one section of the multi-section dehydrogenation unit. The outlet of the final stage of the multi-stage dehydrogenation is connected with the inlet of the pressure swing adsorption 2 unit, the high-purity helium gas at the outlet of the pressure swing adsorption 2 unit is connected with the inlet of the compression III unit, the outlet of the compression III unit is connected with the high-purity helium gas package, the gas analyzed at the outlet of the pressure swing adsorption 2 unit is divided into two parts, one part of the gas analyzed is connected with the inlet of the compression IV unit, and the outlet of the compression IV unit and the outlet of the pressure swing adsorption 1 unit are connected with the inlet pipeline of the; and a part of the analysis gas and the permeation gas at the outlet of the membrane separation unit I are connected with the inlet pipeline of the compression unit II.
Alternatively, the membrane separation unit I is single-stage or multi-stage membrane separation, the number of membrane separation stages is determined according to the helium concentration and the helium recovery rate in the natural gas liquefied helium-containing tail gas, the liquefied helium-containing concentration and the helium recovery rate are high, the number of membrane separation stages is large, and vice versa.
Alternatively, the final stage of compression of the compression II unit is not cooled.
Alternatively, the deoxidation unit consists of a reactor filled with a catalyst and a cooler, wherein oxygen and hydrogen react in the reactor under the action of the catalyst to generate water, the water is cooled to normal temperature by the cooler, the hydrogen entering the deoxidation unit is excessive, and the gas leaving the deoxidation unit does not contain oxygen components.
Alternatively, the pressure swing adsorption unit I is a single-stage or two-stage pressure swing adsorption process, the number of pressure swing adsorption stages is determined according to the helium-containing concentration and the helium recovery rate of the pressure swing adsorption gas, the helium-containing concentration is low, the helium recovery rate is high, and the pressure swing adsorption process adopts two-stage adsorption process. The helium separated by the pressure swing adsorption unit I does not contain combustible components except hydrogen, and the desorption gas separated by the pressure swing adsorption unit I is connected with a natural gas liquefied helium-containing tail gas pipeline at the inlet of the compression unit I.
Optionally, the number of the multiple dehydrogenation units is determined according to the hydrogen content and the highest tolerance temperature of the catalyst, each dehydrogenation unit is provided with a heat exchanger, a reactor filled with the catalyst and a cooler, a certain amount of oxygen or oxygen-enriched air or air is added to each dehydrogenation unit to be mixed with helium containing hydrogen, then the mixture is subjected to heat exchange through the heat exchanger, the temperature is raised to about 60 ℃ and enters the reactor, the oxygen and the hydrogen react under the action of the catalyst in the reactor to generate water, meanwhile, the temperature is raised, the water is separated after the mixture is cooled to normal temperature through the heat exchanger and the cooler, and finally, excessive oxygen is added to the dehydrogenation unit, so that the water is generated by the whole reaction of the hydrogen.
Optionally, the desorption gas separated by the pressure swing adsorption 2 unit is divided into two parts, one part of the desorption gas is compressed by the compression IV unit and then returns to the first section of inlet of the multi-section dehydrogenation unit for circulation, and the other part of the desorption gas and the permeation gas at the outlet of the membrane separation I unit are connected with the inlet of the compression II unit through a pipeline.
Aforementioned the utility model discloses main scheme and each further alternative can the independent assortment in order to form a plurality of schemes, are the utility model discloses can adopt and claim the scheme of protection: if the utility model discloses, each selection can with other selection arbitrary combinations, and the technical field personnel can understand according to prior art and common general knowledge after understanding the utility model discloses the scheme back has multiple combination, is the utility model discloses the technical scheme that will protect does not do the exhaustion here.
The utility model has the advantages that:
and (I) concentrating the liquefied tail gas helium by adopting membrane separation and returning methane to a liquefaction system for recycling.
And (II) combustible components except hydrogen are removed by adopting pressure swing adsorption, so that the addition of oxygen is saved, and the yield of methane is improved.
And (III) removing the reaction water by adopting pure oxygen or oxygen-enriched oxygen and hydrogen to obtain a high-purity helium product.
Drawings
FIG. 1 is a schematic flow chart of an apparatus according to embodiment 1 of the present invention;
fig. 2 is a schematic flow chart of the apparatus according to embodiment 2 of the present invention;
reference numerals:
Detailed Description
The following non-limiting examples serve to illustrate the invention.
Example 1:
the process flow of the system for purifying helium from natural gas liquefied helium-containing tail gas in the embodiment is as follows:
the flow is shown in FIG. 1. In the embodiment, the natural gas is used for liquefying the helium-containing tail gas with 300Nm3For example,/h, the pressure of the liquefied helium-containing tail gas is about 0.11MPa (G), and the temperature: -40 ℃, tail gas composition: HE: 8.07%, H2: 1.0%, N2: 13.87%, CH 4: 77.06%, mixing with the gas from pressure swing adsorption unit I, compressing to 2.7Mpa (G) through three stages, and separating in membrane unit I. The membrane separation I unit is two-stage membrane separation, the pressure of the non-permeation gas of the membrane separation I unit is about 2.6Mpa (G), the main component is methane, and the methane returns to a methane liquefaction system; the two sections of permeation gases of the membrane separation unit I are merged, the pressure is about 0.01Mpa (G), and the composition is as follows: HE: 52.8%, H2: 6.5%, N2: 6.2%, CH 4: 34.4% and a flow rate of about 58.4Nm3And h, mixing the gas with the desorption gas from the pressure swing adsorption unit 2, compressing the gas to about 2.7Mpa (G) through a compression unit II in three sections, entering a deoxidation unit to remove oxygen, and taking out helium-containing gas from the deoxidation unit and entering a pressure swing adsorption unit 1. The desorption gas pressure from the pressure swing adsorption 1 unit is about 0.01mpa (g) and comprises the following components: HE: 28.4%, H2: 2.4%, N2: 22.4%, CH 4: 46.1 percent of the tail gas containing helium is mixed with the liquefied tail gas; high concentration helium from pressure swing adsorption 1 unit at a pressure of about 2.6mpa (g) and consisting of HE: 92.05%, H2: 7.92%, N2: 0.03%, and a flow rate of about 31.4Nm3And h, mixing with the desorption gas which comes from the pressure swing adsorption 2 unit and is pressurized by the compression IV unit, and then entering the first section of the dehydrogenation unit. Totally 3 sections of dehydrogenation units are arranged, each section is provided with a heat exchanger, a reactor and a cooler, and about 2Nm is added into each section of the previous two sections3Air, pressure about 2.8MPa (G), composition: o2: 21%, N2: 79% of helium gas, and then mixing with a high concentration of helium gasHeating to about 60 deg.C by heat exchanger, reacting oxygen with hydrogen in the reactor under the action of catalyst to produce water, raising the temperature to about 220 deg.C, cooling to normal temperature by heat exchanger and cooler, separating water, reducing the hydrogen concentration in the gas to about 1.4% after two-stage reaction, adding 3.1Nm3The air is mixed with the gas, and the gas passes through the last dehydrogenation unit, the pressure of the gas is about 2.5Mpa (G), and the composition is as follows: HE: 72.3%, H2: none, O2: 0.4%, N2: 27.0 percent and 0.3 percent of H2O. The gas from the oxidative dehydrogenation enters a pressure swing adsorption II unit, and the high-purity helium gas from the pressure swing adsorption II unit has the pressure of about 2.4Mpa (G) and the flow of about 21.3Nm3H, helium-containing gas in the deoxygenation unit with the helium concentration of more than 99.999 percent is compressed to 15Mpa (G) through a second stage of a compression unit III and is bottled; the desorption gas from the pressure swing adsorption II unit, with a pressure of about 0.01mpa (G), is composed of HE: 56.6%, O2: 0.7%, N2: 42.2%, H2O: 0.5%, and a flow rate of about 37.6Nm3In which 24.1Nm3The analytic gas is compressed to 2.6Mpa (G) through a 3-stage compression IV unit, returned to the inlet of the dehydrogenation unit, and the rest 13.5Nm3And/h, mixing the inlet of the decompression unit II with the permeate gas at the outlet of the membrane separation unit I.
Example 2:
the process flow of the system for purifying helium from natural gas liquefied helium-containing tail gas in the embodiment is as follows:
the flow is shown in fig. 2. In this embodiment, the natural gas is used to liquefy the helium-containing tail gas with 800Nm3For example,/h, the pressure of the liquefied helium-containing tail gas is about 0.11MPa (G), and the temperature: -40 ℃, tail gas composition: HE: 3.0%, H2: 0.38%, N2: 15.62%, CH 4: 81.0 percent of the gas is mixed with the gas which is generated from the pressure swing adsorption unit I and then enters a compression unit I, and the gas is compressed to about 2.7Mpa (G) through three sections and then enters a membrane separation unit I. The pressure of the non-permeable gas discharged from the membrane separation unit I is about 2.6Mpa (G), and the main component is methane which returns to a methane liquefaction system; the pressure of the permeation gas from the membrane separation unit I is about 0.01Mpa (G), and the composition is as follows: HE: 33.3%, H2: 4.1%, N2: 10.1%, CH 4: 52.5% and a flow rate of about 92.9Nm3Then mixing with desorption gas from a pressure swing adsorption 2 unit, compressing to about 2.7Mpa (G) in three stages through a compression II unit,the helium enters a deoxidation unit to remove oxygen, and the helium-containing gas out of the deoxidation unit enters a pressure swing adsorption 1 unit. The desorption gas pressure from the pressure swing adsorption 1 unit is about 0.01mpa (g) and comprises the following components: HE: 13.9%, H2: 1.7%, N2: 13.6%, CH 4: 70.7 percent of the mixture is mixed with the liquefied helium-containing tail gas; high concentration helium from pressure swing adsorption 1 unit at a pressure of about 2.6mpa (g) and consisting of HE: 89.36%, H2: 10.61%, N2: 0.04% and a flow rate of about 25Nm3And h, mixing with the desorption gas which comes from the pressure swing adsorption 2 unit and is pressurized by the compression IV unit, and then entering the first section of the dehydrogenation unit. 4 dehydrogenation units are arranged in total, each section is provided with a heat exchanger, a reactor and a cooler, and about 0.4Nm is added into each section of the first three sections3Air, pressure about 2.8MPa (G), composition: o2: 99.6%, N2: 0.4 percent of the nitrogen-containing gas is mixed with high-concentration helium, then the mixture is heated by a heat exchanger to about 60 ℃ and enters a reactor, oxygen and hydrogen react under the action of a catalyst in the reactor to generate water, meanwhile, the temperature is raised to about 300 ℃, the mixture is cooled by the heat exchanger and a cooler to normal temperature and then separated from water, the hydrogen concentration in the gas is reduced to about 0.7 percent after three-stage reaction, 0.45Nm is added3The pure oxygen is mixed with the gas, and the gas passes through the last dehydrogenation unit, the pressure of the gas is about 2.5Mpa (G), and the composition is as follows: HE: 98.2%, H2: none, O2: 0.9%, N2: 0.6 percent and 0.3 percent of H2O. The gas from the oxidative dehydrogenation enters a pressure swing adsorption II unit, and the high-purity helium gas from the pressure swing adsorption II unit has the pressure of about 2.4Mpa (G) and the flow of about 21.3Nm3H, helium-containing gas in the deoxygenation unit with the helium concentration of more than 99.999 percent is compressed to 15Mpa (G) through a second stage of a compression unit III and is bottled; the desorption gas from the pressure swing adsorption II unit, with a pressure of about 0.01mpa (G), is composed of HE: 95.6%, O2: 2.2%, N2: 1.4%, H2O: 0.8%, and a flow rate of about 14.9Nm3In which 13.8Nm3The analytic gas is compressed to 2.6Mpa (G) through a 3-stage compression IV unit, returned to the inlet of the dehydrogenation unit, and the rest 1.1Nm3And/h, mixing the inlet of the decompression unit II with the permeate gas at the outlet of the membrane separation unit I.
Claims (3)
1. The system for purifying the helium gas from the natural gas liquefied helium-containing tail gas comprises the following units of a compression unit, a membrane separation unit, a pressure swing adsorption unit, a deoxidation unit and a multi-section dehydrogenation unit, and is characterized by comprising the following units: the method comprises the following steps that natural gas liquefied helium-containing tail gas is connected with a section of inlet of a compression I unit, an outlet of the compression I unit is connected with an inlet of a membrane separation I unit, non-permeable gas at an outlet of the membrane separation I unit is connected with a natural gas liquefaction system, permeable gas at an outlet of the membrane separation I unit is connected with an inlet of a compression II unit, an outlet of the compression II unit is connected with a deoxidizing unit, the deoxidizing unit is connected with an inlet of a pressure swing adsorption I unit, and desorbed gas at an outlet of the pressure swing adsorption I unit and the natural gas liquefied helium-containing tail gas are connected with a section of inlet; high-concentration helium at the outlet of the pressure swing adsorption unit I is connected with a section of inlet of a multi-section dehydrogenation unit, the outlet of the last section of multi-section dehydrogenation is connected with the inlet of a pressure swing adsorption unit II, high-purity helium at the outlet of the pressure swing adsorption unit II is connected with the inlet of a compression unit III, the outlet of the compression unit III is connected with a high-purity helium package, the gas desorbed at the outlet of the pressure swing adsorption unit II is divided into two parts, one part of the desorbed gas is connected with the inlet of a compression unit IV, and the outlet of the compression unit IV and the outlet of the pressure swing adsorption unit; and a part of the analysis gas and the permeation gas at the outlet of the membrane separation unit I are connected with the inlet pipeline of the compression unit II.
2. The system for purifying helium from natural gas liquefied helium-containing tail gas as claimed in claim 1, wherein the membrane separation I unit is single-stage or multi-stage membrane separation, the number of membrane separation stages depends on the concentration of helium in the natural gas liquefied helium-containing tail gas and the recovery rate of helium, the concentration of liquefied helium-containing gas and the recovery rate of helium are low, the number of membrane separation stages is large, and vice versa.
3. The system for purifying helium from natural gas liquefied helium-containing tail gas as claimed in claim 1, wherein the final stage of compression of the compression II unit is not cooled.
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| CN111646438A (en) * | 2020-06-09 | 2020-09-11 | 重庆瑞信气体有限公司 | Hydrogen-rich helium tail gas catalytic oxidation dehydrogenation process and system thereof |
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| CN113144821A (en) * | 2021-04-27 | 2021-07-23 | 大连理工大学 | Multi-technology integrated separation process for producing high-purity helium gas from helium-rich natural gas liquefaction tail gas |
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Address after: 215011 room 7b, Jinshi building, Shishan Road, high tech Zone, Suzhou, Jiangsu 006 Patentee after: Jiangsu baoelo Environmental Protection Technology Co.,Ltd. Patentee after: Chengdu zejiahuafei Technology Co., Ltd Address before: 710000 room 20302, building 6, coal aviation family courtyard, No. 3, Jianxi street, Beilin District, Xi'an City, Shaanxi Province Patentee before: XI'AN BAOAILUO ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Patentee before: Chengdu zejiahuafei Technology Co., Ltd |