CN114890397A - Method and device system for concentrating helium at normal temperature - Google Patents
Method and device system for concentrating helium at normal temperature Download PDFInfo
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- CN114890397A CN114890397A CN202210609157.9A CN202210609157A CN114890397A CN 114890397 A CN114890397 A CN 114890397A CN 202210609157 A CN202210609157 A CN 202210609157A CN 114890397 A CN114890397 A CN 114890397A
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- 239000001307 helium Substances 0.000 title claims abstract description 119
- 229910052734 helium Inorganic materials 0.000 title claims abstract description 119
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000000926 separation method Methods 0.000 claims abstract description 180
- 239000012528 membrane Substances 0.000 claims abstract description 177
- 239000007789 gas Substances 0.000 claims abstract description 116
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000003345 natural gas Substances 0.000 claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims description 36
- 238000005516 engineering process Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000012141 concentrate Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003949 liquefied natural gas Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- C01B23/0036—Physical processing only
-
- 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
- C01B23/0036—Physical processing only
- C01B23/0042—Physical processing only by making use of membranes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0029—Obtaining noble gases
- C01B2210/0031—Helium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0046—Nitrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0062—Water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0068—Organic compounds
- C01B2210/007—Hydrocarbons
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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
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0098—Other impurities
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- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method and a device system for concentrating helium at normal temperature, wherein the device system comprises a pretreatment unit, a first pressurizing assembly, a membrane separation unit and a gas collection unit which are sequentially connected according to the flowing direction of natural gas; the membrane separation unit comprises a first membrane separation unit and a second membrane separation unit which are sequentially connected; and a second pressurizing assembly is arranged between the first membrane separation unit and the second membrane separation unit. The device system for concentrating helium gas at normal temperature provided by the invention is based on a membrane separation technology and a proper hydrogen doping method, and can directly concentrate helium gas from 100ppmv of raw material natural gas to helium gas and/or hydrogen gas concentration of more than 98% at normal temperature, thereby realizing the effects of stable technology, low cost and high yield of concentrated helium gas.
Description
Technical Field
The invention belongs to the technical field of chemical industry and resource recycling, and relates to a method for concentrating and recycling helium, in particular to a method and a device system for concentrating helium at normal temperature.
Background
Helium is a colorless and tasteless inert gas, is widely applied to the fields of optical fibers, semiconductors, medical treatment, national defense and the like, and is a non-renewable scarce strategic resource. Helium has wide application and large dosage, but has limited acquisition sources. Conventionally, helium is mainly associated with natural gas, but due to the natural resource differences of all parts of the world, the helium content in the natural gas is very different, the high helium content is even more than 10% vol, the general helium content with higher industrial extraction value is more than 0.5% vol, while the low helium content in China is less than or even less than 50ppmv, and the industrial development difficulty and cost are very high. At present, the helium content of the common natural gas field in China is mostly not more than 0.1% vol (1000ppmv), and the average content of the common natural gas field is 200-500 ppmv.
One of the most mainstream solutions to solve the problems of high development technical difficulty and high cost due to low helium content in raw natural gas is to extract helium from flash gas (BOG) of liquefied natural gas. That is, methane is almost completely liquefied, and gases having a boiling point lower than that of methane, such as nitrogen, hydrogen, helium, and the like, are not yet liquefied. Through one or more flash evaporation, the concentration of the non-condensable gas is greatly improved relative to the respective proportion of the non-condensable gas in the raw material natural gas, the non-condensable gas which is not liquefied basically, particularly hydrogen and helium are concentrated by 10-20 times (even can be concentrated by tens of thousands of times, but the yield is sacrificed), and the helium is barely in line with the concentration with industrial development value.
In addition, there are other possible schemes for extracting helium from BOG, and some of them have already been implemented industrially, for example: any one of cryogenic process, liquefaction process, Pressure Swing Adsorption (PSA) process, membrane separation, or a combination of two or more thereof.
The technical key point of the deep cooling scheme is that the balance between refrigerating capacity and consumed refrigerating capacity is controlled through strict calculation, when the refrigerating capacity in the system is not matched, the system can generate the problem of sudden temperature rise and drop, and when the temperature is too high, helium cannot be extracted; when the temperature is too low, the energy consumption is greatly increased, and even liquid enters the compressor to cause damage to the compressor. Therefore, the cryogenic scheme has poor system stability except over-high energy consumption. Since helium and hydrogen cannot be liquefied by pressurization at normal temperature, liquid hydrogen and liquid helium can be obtained only by the aid of a low-temperature or cryogenic process at the front end, but since the liquefaction points of helium and hydrogen are close to each other, helium and hydrogen cannot be thoroughly separated, and energy consumption is very high. PSA processes are well established but suffer from low yields or even complete ineffectiveness for low concentration helium purification. The membrane separation method is a relatively new scheme compared with the scheme, and has been applied industrially primarily because of the great advantages of the specific modularization and energy conservation.
CN 110207461a discloses a method and an apparatus for concentrating helium gas from natural gas, the apparatus includes an air expander, a cooler, a cold box, a main heat exchanger, an air reboiler, an LNG reboiler, a rectifying tower, a subcooler, a condensing evaporator, a crude helium gas subcooler, and a gas-liquid separator. The patent provides a method and a device for simultaneously concentrating helium and hydrogen from natural gas in a low-temperature rectification environment by adopting an air expansion process and secondary concentration of a gas-liquid separator aiming at the characteristic that a feed gas containing helium is rich in hydrogen. The device and the method provided by the patent need to be concentrated under low temperature condition (-120 ℃ below) to obtain helium, the operating temperature of the method is too low, a large amount of energy is consumed, and the operating condition is harsh.
CN 113148967a discloses a method and a device for recovering helium from pipeline natural gas, wherein the recovery method comprises the following steps: the pipeline natural gas is sent into a first-stage membrane separation component for first-stage separation under pressure regulation, and then sent into at least two-stage membrane separation components for at least two-stage membrane separation after pressurization, wherein the at least two-stage membrane separation components at least comprise a second-stage membrane separation component and a third-stage membrane separation component which are connected in series; a compressor is arranged or not arranged between the secondary membrane separation component and the tertiary membrane separation component; the pressure ratio of the gas inlet pressure to the permeate gas outlet side of the first-stage membrane separation assembly, the second-stage membrane separation assembly and the third-stage membrane separation assembly is not less than 5; the concentration process also comprises the step of carrying out primary separation after carrying out heavy hydrocarbon removal treatment on the pipeline natural gas. The method provided by the patent firstly concentrates natural gas to the helium content of more than 20% through at least two stages of membrane separation assemblies, and then directly obtains high-purity helium gas from pipeline natural gas through a pressure swing adsorption purification device, a hydrogen-helium separation device, a temperature swing adsorption purification device and the like. The method has complex device and complex operation, and is not beneficial to industrial development.
In summary, it is one of the problems to be solved in the art to provide a recycling apparatus and method that have low energy consumption and simple operation, and can achieve the effects of stable technology, low cost and high yield of helium extraction and purification.
Disclosure of Invention
The invention aims to provide a method and a device system for concentrating helium at normal temperature, wherein the device system is based on a membrane separation technology and a proper hydrogen doping method, can realize the concentration of helium at normal temperature, and achieves the effects of technically stable concentrated helium, low cost and high yield.
The method and the device system for concentrating helium at normal temperature provided by the invention are also suitable for the chemical industry based on hydrogen produced by natural gas as a raw material, such as: synthetic ammonia, methanol preparation, acetylene preparation and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
according to a first aspect, the invention provides a device system for concentrating helium at normal temperature, which comprises a pretreatment unit, a first pressurizing assembly, a membrane separation unit and a gas collection unit which are sequentially connected and arranged according to the flowing direction of natural gas;
the membrane separation unit comprises a first membrane separation unit and a second membrane separation unit which are sequentially connected;
and a second pressurizing assembly is arranged between the first membrane separation unit and the second membrane separation unit.
The device system for concentrating helium gas at normal temperature provided by the invention is based on a membrane separation technology and a proper hydrogen doping method, and can directly concentrate helium gas from 100ppmv of raw material natural gas to helium gas and/or hydrogen gas concentration of more than 98% at normal temperature, thereby realizing the effects of stable technology, low cost and high yield of concentrated helium gas.
The pretreatment unit is used for removing impurities such as particles, oil water and the like in the natural gas raw material; in addition, when the temperature of natural gas is lower than 20 ℃, the natural gas can also be heated to 30-70 ℃.
The raw material gas used in the device system for condensing helium at normal temperature provided by the invention can be natural gas or liquefied natural gas purge gas (BOG) in the using process.
Preferably, the gas collection unit includes an impurity collection tank and a gas collection tank.
Preferably, the first membrane separation unit comprises a membrane separation device.
Preferably, the impurity outlet of the membrane separation device is connected to the impurity collection tank through a first back pressure valve.
Preferably, the gas outlet of the membrane separation device is connected to the second pressure boosting assembly through a second backpressure valve.
Preferably, the second membrane separation unit comprises a primary membrane separation assembly, a secondary membrane separation assembly and a tertiary membrane separation assembly.
Preferably, the secondary membrane separation assembly is connected to the impurity collection tank through a third back pressure valve.
Preferably, the tertiary membrane separation assembly is arranged in parallel with the primary membrane separation assembly or the secondary membrane separation assembly.
When the three-stage membrane separation assembly provided by the invention is used in parallel with the first-stage membrane separation assembly, the penetrating gas of the first-stage membrane separation assembly is used as the inlet gas of the second-stage membrane separation assembly, and the penetrating gas of the first-stage membrane separation assembly is used as the inlet gas of the third-stage membrane separation assembly.
When the three-stage membrane separation assembly and the two-stage membrane separation assembly are used in parallel, the permeation gas of the two-stage membrane separation assembly is used as the inlet gas of the three-stage membrane separation assembly.
Preferably, the impurity outlet of the three-stage membrane separation assembly is connected with the second pressurizing assembly through a first one-way valve.
And a gas outlet of the third-stage membrane separation assembly is connected with the gas collection tank through a fourth backpressure valve.
Preferably, a fifth backpressure valve is arranged between the first one-way valve and the second pressurization assembly.
Preferably, the gas outlet of the primary membrane separation assembly or the secondary membrane separation assembly is connected with the second pressurizing assembly through a second one-way valve.
Preferably, a seventh backpressure valve is arranged between the second one-way valve and the second pressurization assembly.
The back pressure valve in the device system provided by the invention is used for adjusting the pressure of gas in the system, and further controlling the flow direction of the gas so as to obtain mixed gas of helium and hydrogen with higher concentration.
The membrane separation module provided by the invention comprises a plurality of separation membranes, and the number of the separation membranes in the membrane separation module is not further limited. The separation membrane in the membrane separation assembly provided by the invention can be an organic membrane or an inorganic membrane, wherein the organic membrane comprises any one or a combination of at least two of PI, PVDF, PTFE or PEEK, and preferably PI; the inorganic film comprises an alumina or zirconia base and the coating is a MOFs, preferably alumina + MOFs.
In a second aspect, the present invention provides a method for concentrating helium at room temperature, which is performed by using the apparatus system for concentrating helium at room temperature provided in the first aspect.
The method comprises the following steps:
(1) pretreating natural gas, primary pressurizing and primary membrane separation in sequence to obtain impurity gas and mixed gas;
(2) performing secondary pressurization and at least two-stage membrane separation on the mixed gas obtained in the step (1) to obtain impurity gas and concentrated helium;
the invention can concentrate in the natural gas with low helium concentration content to obtain more helium at normal temperature by simple membrane separation technology, and the method is simple, low in cost and environment-friendly.
In the membrane separation process, the outlet pressure after membrane separation is not higher than the inlet pressure.
In the primary membrane separation process in the step (1), only one membrane separation assembly is adopted, but one or more membranes are connected in parallel in the membrane separation assembly, or the sizes of the membranes are different; the amount is determined according to the total flow rate of the incoming membrane.
Preferably, the at least two-stage membrane separation of step (2) is as follows:
(a) sequentially passing the mixed gas obtained in the step (1) through a primary membrane separation component and a secondary membrane separation component to obtain impurity gas;
(b) and (b) passing the helium-containing gas obtained by the separation of the first-stage membrane separation assembly or the second-stage membrane separation assembly in the step (a) through a third-stage membrane separation assembly to obtain the concentrated helium gas.
Preferably, the temperature of the natural gas after the pretreatment in step (1) is 20 to 70 ℃, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the gas pressure after said first pressurisation in step (1) is in the range 16 to 45bara, and may for example be 16bara, 20bara, 25bara, 30bara, 35bara, 40bara or 45bara, but is not limited to the values recited, and other values not recited within the ranges are equally applicable.
Preferably, the contaminant gas outlet pressure after said primary membrane separation of step (1) is in the range of from 20 to 45bara, for example 20bara, 25bara, 30bara, 35bara, 40bara or 45bara, but not limited to the values recited, and other values not recited within the ranges are equally applicable.
Preferably, the mixed gas outlet pressure after the primary membrane separation in step (1) is in the range of from 1 to 2bara, and may for example be 1bara, 1.2bara, 1.4bara, 1.6bara, 1.8bara or 2bara, but is not limited to the values recited, and other values not recited within the ranges are equally applicable.
Preferably, the pressure of the second pressurised gas in step (2) is in the range 16 to 25bara, for example 16bara, 17bara, 18bara, 19bara, 20bara, 21bara, 22bara, 23bara, 24bara or 25bara, but not limited to the values recited, and other values not recited within the ranges are equally applicable.
Preferably, the impurity gas outlet pressure after the at least two-stage membrane separation in step (2) is in the range 16 to 25bara, and may for example be 16bara, 17bara, 18bara, 19bara, 20bara, 21bara, 22bara, 23bara, 24bara or 25bara, but is not limited to the recited values, and other values not recited within the range of values are equally applicable. Preferably, the concentrated helium outlet pressure after the at least two stage membrane separation of step (2) is in the range 1 to 10bara, for example 1bara, 2bara, 3bara, 4bara, 5bara, 6bara, 7bara, 8bara, 9bara or 10bara, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the impurity gas separated by the three-stage membrane separation assembly in the step (b) is returned to the first-stage separation assembly through two-stage pressurization.
Preferably, the impurity gas outlet pressure of the tertiary membrane separation module is in the range of from 1 to 3bar, and may for example be 1bara, 1.3bara, 1.6bara, 1.9bara, 2.1bara, 2.4bara, 2.7bara or 3bara, but is not limited to the values recited, and other values not recited within the ranges are equally applicable. Preferably, the natural gas of step (1) has a pressure in the range 1 to 100bara, and may for example be 1bara, 10bara, 20bara, 30bara, 40bara, 50bara, 60bara, 70bara, 80bara, 90bara or 100bara, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the natural gas of step (1) has a helium content of 0.01-2% vol, such as 0.01% vol, 0.1% vol, 0.3% vol, 0.5% vol, 0.8% vol, 1% vol, 1.3% vol, 1.5% vol, 1.8% vol or 2% vol, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the natural gas of step (1) has a hydrogen content of 0.003-1% vol, such as 0.003-vol, 0.03-vol, 0.1-vol, 0.3-vol, 0.5-vol, 0.7-vol, 0.9-vol or 1-vol, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The natural gas raw material adopted by the invention only comprises non-condensable gas such as methane, nitrogen, other small molecular hydrocarbons and the like, a small amount of water and particles besides hydrogen and helium.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the following beneficial effects:
(1) the device system for concentrating helium gas at normal temperature provided by the invention is based on a membrane separation technology and a proper hydrogen doping method, and can directly concentrate helium gas from 100ppmv of raw material natural gas to helium gas and/or hydrogen gas concentration of more than 98% at normal temperature;
(2) the method for concentrating helium at normal temperature provided by the invention realizes the effects of stable technology, low cost and high yield of concentrated helium.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus system for concentrating helium at room temperature according to embodiment 1 of the present invention;
fig. 2 is a schematic structural diagram of an apparatus system for concentrating helium at room temperature according to embodiment 2 of the present invention;
wherein 101 is a pretreatment unit, 201 is a first pressurizing assembly, 202 is a second pressurizing assembly, 301 is a membrane separation device, 302 is a primary membrane separation assembly, 303 is a secondary membrane separation assembly, 304 is a tertiary membrane separation assembly, 401 is a first backpressure valve, 402 is a second backpressure valve, 403 is a third backpressure valve, 404 is a fourth backpressure valve, 405 is a fifth backpressure valve, 501 is a first check valve, 502 is a second check valve, 601 is an impurity collecting tank, and 602 is a gas collecting tank.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an apparatus system for concentrating helium at normal temperature as shown in fig. 1, which includes a pretreatment unit 101, a first pressurizing assembly 201, a membrane separation unit and a gas collection unit, which are connected in sequence according to the flowing direction of natural gas;
the membrane separation unit comprises a first membrane separation unit and a second membrane separation unit which are sequentially connected; a second pressurizing assembly 202 is arranged between the first membrane separation unit and the second membrane separation unit.
The gas collection unit comprises an impurity collection tank 601 and a gas collection tank 602;
the first membrane separation unit comprises a membrane separation device 301; an impurity outlet of the membrane separation device 301 is connected with the impurity collection tank 601 through a first backpressure valve 401; the gas outlet of the membrane separation device 301 is connected to the second pressure increasing assembly 202 via a second backpressure valve 402.
The second membrane separation unit comprises a primary membrane separation assembly 302, a secondary membrane separation assembly 303 and a tertiary membrane separation assembly 304; the primary membrane separation component 302 and the secondary membrane separation component 303 are arranged in series; the secondary membrane separation assembly 303 is connected with the impurity collection tank 601 through a third backpressure valve 403; the tertiary membrane separation assembly 304 is arranged in parallel with the primary membrane separation assembly 302;
the impurity outlet of the three-stage membrane separation module 304 is connected with the second pressurizing module 202 through a first one-way valve 501; the gas outlet of the tertiary membrane separation module 304 is connected to the gas collection tank 602 through a fourth backpressure valve 404; a fifth backpressure valve 405 is arranged between the first check valve 501 and the second pressurization assembly 202.
The gas outlet of the secondary membrane separation module 303 is connected with the second pressurizing module 202 through a second check valve 502.
In this embodiment, a back pressure valve is disposed on a connection pipeline between the primary membrane separation assembly 302 and the secondary membrane separation assembly 303.
Example 2
This example provides an apparatus system for ambient temperature concentration of helium gas as shown in fig. 2, which differs from example 1 only in that: in this embodiment, the third-stage separation element 304 and the second-stage separation element 303 are arranged in parallel, and a back pressure valve is arranged on a connection pipeline between a permeate gas outlet of the first-stage separation element 302 and the second pressurizing element 202; and a back pressure valve arranged on a connecting pipeline of the primary membrane separation component 302 and the secondary membrane separation component 303 is omitted.
Example 3
This example provides an apparatus system for concentrating helium at room temperature, which only differs from example 1 in that: the present embodiment omits the three-stage membrane separation module 304 arranged in parallel.
Example 4
This example provides an apparatus system for concentrating helium at room temperature, which only differs from example 1 in that: this example replaces the organic membrane used in the membrane separation unit with an inorganic membrane.
Application example 1
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 1.
The method for concentrating helium at normal temperature comprises the following steps:
(1) pretreating and heating natural gas with the pressure of 10-50bara, the helium content of 0.2-2% vol and the hydrogen content of 0.05-1% vol to 60 ℃, pressurizing to 20bara for one time, and separating by a first-stage membrane to obtain impurity gas and mixed gas; the outlet pressure of the impurity gas after the primary membrane separation is 20bara, and the outlet pressure of the mixed gas after the primary membrane separation is 1-2 bara;
(2) carrying out secondary pressurization on the mixed gas obtained in the step (1) to 16-45bara and at least two-stage membrane separation to obtain impurity gas and concentrated helium; the outlet pressure of the impurity gas after the at least two stages of membrane separation is 16-45bara, and the outlet pressure of the concentrated helium gas after the at least two stages of membrane separation is 1-10 bara.
The at least two-stage membrane separation of step (2) is as follows:
(a) sequentially passing the mixed gas obtained in the step (1) through a primary membrane separation component and a secondary membrane separation component to obtain impurity gas;
(b) passing the helium-containing gas obtained by the separation of the first-stage membrane separation assembly in the step (a) through a third-stage membrane separation assembly to obtain the concentrated helium gas; and the outlet pressure of the impurity gas of the three-stage membrane separation assembly is 1-3 bar.
Application example 2
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 1.
The method for concentrating helium at normal temperature is only different from the application example 1 in that: in the application example, the pressure of the natural gas in the step (1) is changed to 10-100bara, the helium content is changed to 100-.
Application example 3
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 1.
The method for concentrating helium at normal temperature is only different from the application example 1 in that: the application example changes the temperature after the pretreatment in the step (1) to 18 ℃.
Application example 4
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 1.
The method for concentrating helium at normal temperature is only different from the application example 1 in that: the application example changes the temperature after the pretreatment in the step (1) to 75 ℃.
Application example 5
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 1.
The method for concentrating helium at normal temperature is only different from the application example 1 in that: in the application example, the outlet pressure of the mixed gas after the primary membrane separation in the step (1) is changed into 5 bara.
Application example 6
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 1.
The method for concentrating helium at normal temperature is only different from the application example 1 in that: the application example changes the concentrated helium outlet pressure after the at least two-stage membrane separation in the step (2) to 12 bara.
Application example 7
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 1.
The method for concentrating helium at normal temperature is only different from the application example 1 in that: in the application example, the outlet pressure of the concentrated helium gas after the at least two-stage membrane separation in the step (2) is changed into 1 bara.
Application example 8
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 2.
The method for concentrating helium at normal temperature is only different from the application example 1 in that: in the application example, the step (b) is changed into the step (a), the helium-containing gas obtained by separation of the secondary membrane separation assembly passes through the three-stage membrane separation assembly, and then the concentrated helium gas is obtained.
Application example 9
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 3.
The method for concentrating helium at normal temperature is the same as that of application example 1.
Application example 10
The application example provides a method for concentrating helium at normal temperature, and the method is carried out by adopting the device system provided by the embodiment 4.
The method for concentrating helium at normal temperature is only different from the application example 1 in that: in the application example, the pressure after the primary pressurization in the step (1) is changed into 5-10 bara.
The concentrated helium gas obtained in application examples 1 to 10 of the present invention was a mixed gas of helium gas and hydrogen gas, and the purity and content of the concentrated gas obtained in application examples 1 to 10 were measured, respectively, and the results are shown in table 1.
TABLE 1
In summary, the device system for concentrating helium gas at normal temperature provided by the invention is based on the membrane separation technology and a proper hydrogen doping method, and can directly concentrate helium gas from 100ppmv of raw material natural gas to helium gas and/or hydrogen gas concentration of more than 98% at normal temperature, thereby realizing the effects of stable technology, low cost and high yield of concentrated helium gas.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The device system for concentrating helium at normal temperature is characterized by comprising a pretreatment unit, a first pressurizing assembly, a membrane separation unit and a gas collection unit which are sequentially connected according to the circulation direction of natural gas;
the membrane separation unit comprises a first membrane separation unit and a second membrane separation unit which are sequentially connected;
and a second pressurizing assembly is arranged between the first membrane separation unit and the second membrane separation unit.
2. The ambient temperature helium concentrator system of claim 1, wherein the gas collection unit comprises an impurity collection tank and a gas collection tank.
3. The ambient temperature concentrated helium gas apparatus system according to claim 1 or 2, wherein the first membrane separation unit comprises a membrane separation device;
preferably, an impurity outlet of the membrane separation device is connected with the impurity collecting tank through a first backpressure valve;
preferably, the gas outlet of the membrane separation device is connected to the second pressure boosting assembly through a second backpressure valve.
4. The ambient temperature concentrated helium gas apparatus system according to claim 2 or 3, wherein the second membrane separation unit comprises a primary membrane separation assembly, a secondary membrane separation assembly and a tertiary membrane separation assembly;
preferably, the primary membrane separation assembly is arranged in series with the secondary membrane separation assembly;
preferably, the secondary membrane separation assembly is connected with the impurity collecting tank through a third backpressure valve;
preferably, the tertiary membrane separation assembly is arranged in parallel with the primary membrane separation assembly or the secondary membrane separation assembly;
preferably, the impurity outlet of the tertiary membrane separation assembly is connected with the second pressurizing assembly through a first one-way valve;
a gas outlet of the third-stage membrane separation assembly is connected with the gas collection tank through a fourth backpressure valve;
preferably, a fifth backpressure valve is arranged between the first one-way valve and the second pressurization assembly.
5. The apparatus system for condensing helium at normal temperature according to claim 4, wherein a gas outlet of said primary or secondary membrane separation module is connected to said second pressurizing module through a second check valve.
6. A method for concentrating helium at normal temperature is characterized in that the method adopts the device system for concentrating helium at normal temperature of any one of claims 1 to 5;
the method comprises the following steps:
(1) pretreating natural gas, primary pressurizing and primary membrane separation in sequence to obtain impurity gas and mixed gas;
(2) and (2) carrying out secondary pressurization and at least two-stage membrane separation on the mixed gas obtained in the step (1) to obtain impurity gas and concentrated helium.
7. The method of claim 6, wherein the at least two-stage membrane separation of step (2) is as follows:
(a) sequentially passing the mixed gas obtained in the step (1) through a primary membrane separation component and a secondary membrane separation component to obtain impurity gas;
(b) and (b) passing the helium-containing gas obtained by the separation of the first-stage membrane separation assembly or the second-stage membrane separation assembly in the step (a) through a third-stage membrane separation assembly to obtain the concentrated helium gas.
8. The method according to claim 6 or 7, wherein the temperature of the natural gas after the pretreatment in step (1) is 20-70 ℃;
preferably, the gas pressure after the primary pressurization in step (1) is 16 to 45 bara;
preferably, the impurity gas outlet pressure after said primary membrane separation of step (1) is in the range of from 20 to 45 bara;
preferably, the mixed gas outlet pressure after the primary membrane separation in step (1) is 1-2 bara;
preferably, the gas pressure after the secondary pressurization in step (2) is 16 to 25 bara;
preferably, the impurity gas outlet pressure after said at least two stages of membrane separation of step (2) is in the range of from 16 to 25 bara;
preferably, the concentrated helium outlet pressure after the at least two stages of membrane separation of step (2) is in the range of from 1 to 10 bara.
9. The method of claim 7, wherein the impurity gas separated in the third membrane separation module in the step (b) is returned to the first separation module by two-stage pressurization;
preferably, the impurity gas outlet pressure of the three-stage membrane separation assembly is 1-3 bar.
10. A process according to any one of claims 6 to 9 wherein the natural gas of step (1) is at a pressure of from 1 to 100 bara;
preferably, the content of helium in the natural gas in the step (1) is 0.01-2% vol;
preferably, the content of hydrogen in the natural gas in the step (1) is 0.003-1% vol.
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| CN104001409A (en) * | 2014-05-22 | 2014-08-27 | 上海精腾新能源科技有限公司 | Membrane-method helium purifying device system and process |
| CN104023821A (en) * | 2011-12-27 | 2014-09-03 | 赢创纤维有限公司 | Method for separating gases |
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| CN104023821A (en) * | 2011-12-27 | 2014-09-03 | 赢创纤维有限公司 | Method for separating gases |
| CN104001409A (en) * | 2014-05-22 | 2014-08-27 | 上海精腾新能源科技有限公司 | Membrane-method helium purifying device system and process |
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