CN117682488A - Equipment and process for purifying helium from helium-depleted natural gas - Google Patents
Equipment and process for purifying helium from helium-depleted natural gas Download PDFInfo
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- CN117682488A CN117682488A CN202211107271.8A CN202211107271A CN117682488A CN 117682488 A CN117682488 A CN 117682488A CN 202211107271 A CN202211107271 A CN 202211107271A CN 117682488 A CN117682488 A CN 117682488A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052734 helium Inorganic materials 0.000 title claims abstract description 134
- 239000001307 helium Substances 0.000 title claims abstract description 133
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000003345 natural gas Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000012528 membrane Substances 0.000 claims abstract description 169
- 239000007789 gas Substances 0.000 claims abstract description 128
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 50
- 238000000746 purification Methods 0.000 claims abstract description 46
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 30
- 230000023556 desulfurization Effects 0.000 claims abstract description 30
- 239000012535 impurity Substances 0.000 claims abstract description 27
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000008929 regeneration Effects 0.000 claims description 29
- 238000011069 regeneration method Methods 0.000 claims description 29
- 238000000926 separation method Methods 0.000 claims description 29
- 239000012466 permeate Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims description 19
- 230000003009 desulfurizing effect Effects 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 17
- 238000011144 upstream manufacturing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052945 inorganic sulfide Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005371 permeation separation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005262 decarbonization Methods 0.000 abstract description 3
- 229910052754 neon Inorganic materials 0.000 abstract description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- -1 alcohol amine Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 125000001741 organic sulfur group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LOMOKCTVHZMXMP-UHFFFAOYSA-N [S].[He] Chemical compound [S].[He] LOMOKCTVHZMXMP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a device and a process for purifying helium from helium-depleted natural gas. According to the current situation of resources, the invention is mainly used for solving the problems of helium purification in natural gas lean in helium and ultra-lean in helium, and all CO in raw material gas is removed by pre-purification 2 The method has the advantages that the quick gas component of the membrane separator is greatly reduced, helium concentration is facilitated, the multi-stage membrane separator is adopted for helium concentration, the method is suitable for treating helium-poor and ultra-helium-poor natural gas, sulfide is thoroughly removed by adopting a catalytic hydrogenation process and dry desulfurization in the process, and the method plays a very key role in helium purification; the invention solves the problems of decarbonization, desulfurization, dehydrogenation, drying and removal of trace impurities, especially neon, of natural gas, thereby improving the purity of helium.
Description
Technical Field
The invention relates to the technical field of helium production, in particular to equipment and a process for purifying helium from helium-depleted natural gas.
Background
Helium is an essential strategic material for the military and aerospace industries.
Chinese patent No. CN214087729U, a normal temperature natural gas helium gas extraction and purification system, and chinese patent No. CN215113528U, a device for extracting helium from natural gas to obtain liquid helium, respectively disclose a technology for extracting helium from natural gas. The CN214087729U adopts pressure swing adsorption as a final means of decarburization and helium purification, so that impurities are not thoroughly removed, the impurities are easy to accumulate in the process production process, the purity of the helium does not reach the standard, drying and dehydration are not considered, and the dew point of a product is difficult to ensure; CN215113528U adopts MDEA for decarbonization, and is not considered to volatilize alcohol amine or entrain the influence to tolerance and performance index of the subsequent separation membrane, and there is higher back pressure downstream of the membrane separator, and the pressure difference of membrane separation operation is small, so that the separation effect is poor, the investment of membrane equipment is greatly increased, and economy is not realized.
For the technology disclosed in the prior art for extracting helium from natural gas, the following problems are also common:
1) The natural gas of the gas field contains trace sulfur, and the sulfur content of the natural gas is required to be not more than 100mg/cm by the national standard 3 In the prior art, no proposal for removing organic sulfur and inorganic sulfur is considered, and neither PSA nor MDEA can thoroughly remove the organic sulfur to meet the catalyst requirement of subsequent catalytic dehydrogenation, thus easily causing catalyst poisoning, simultaneously hydrogen impurities cannot be separated from helium, and finally the purity of the helium is unqualified;
2) The prior art does not consider reasonable organization of heat exchange in the process, and cold and hot diseases exist; if the heat generated by the compressor is cooled to decarbonize, the dehydrogenation reaction needs to be heated, the subsequent process needs to be cooled, and if the dehydrogenation is performed at normal temperature, H is difficult to ensure 2 The removal rate of (2) directly affects the purity of helium;
3) The content of the natural gas He suitable for the prior art is about 0.1%, and the current state of the gas field is lean helium or even ultra-lean helium natural gas, and the effective separation and purification can not be obtained by contrast.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a method for purifying helium from helium-depleted and ultra-helium-depleted natural gas, which can directly extract helium from natural gas pretreated from a helium-depleted and ultra-helium-depleted gas field (0.03-0.1% He) and purify the helium into high purity helium (99.999%) aiming at the current state of the art.
The second technical problem to be solved by the invention is to provide a device for purifying helium from helium-lean and ultra-helium-lean natural gas, which can solve the problems of decarbonization, desulfurization, dehydrogenation, drying and trace impurity removal, especially neon, of natural gas so as to improve the purity of the product.
The third technical problem to be solved by the invention is to provide a process for purifying helium from helium-depleted and ultra-helium-depleted natural gas, which is aimed at the current state of the artThe purification process is arranged at the front end of the process so as to solve the problem of CO 2 Incomplete removal, adverse effect on the subsequent membrane separation effect and corrosion to a subsequent system, and solves the existing cold and hot disease problem by optimizing process heat exchange.
The invention solves at least one of the technical problems by adopting the following technical proposal:
an apparatus for purifying helium from helium-depleted, ultra-helium-depleted natural gas comprising:
pre-clean system with inlet for helium lean natural gas input for CO in the feed gas 2 Removing water, heavy hydrocarbon and partial sulfide;
the membrane separation system is arranged at the downstream of the pre-purification system and comprises at least more than two groups of membrane separators which are connected in series or in parallel and is used for carrying out permeation separation on materials to obtain non-permeation gas which is sent to a natural pipe network and permeation gas which is concentrated by helium;
the desulfurization unit is connected to the membrane separation system and is used for removing sulfide in the process gas;
the dehydrogenation unit is connected to the membrane separation system and positioned at the downstream of the desulfurization unit and is used for removing residual hydrogen in the process gas; and
a low-temperature impurity removing unit which is arranged at the downstream of the membrane separation system and the dehydrogenation unit and is used for removing CH contained in the process gas 4 、N 2 、Ar、O 2 At least one of Ne.
The facilities for desulfurizing, dehydrogenating and removing impurities can be further changed into the facilities for carrying out the desulfurization, the dehydrogenation and the impurity removal, and the facilities can also be implemented in a distributed and graded manner or can be implemented in a mutually coupled and integrated manner.
Preferably, the desulfurization unit is connected in series between two adjacent membrane separators and comprises a hydrogenation reactor positioned at the upstream and a desulfurization tower positioned at the downstream, wherein the hydrogenation reactor is used for reacting hydrogen in natural gas with organic sulfide so as to convert organic sulfur into inorganic sulfur sulfide, and the desulfurization tower is used for removing inorganic sulfur sulfide.
Preferably, a 2# compressor is arranged between two adjacent membrane separators, a primary inlet of the 2# compressor is communicated with a permeate air side of the membrane separator at the upstream of the two adjacent membrane separators, a final outlet of the 2# compressor is communicated with a top inlet of the desulfurizing tower, a middle outlet of the 2# compressor is communicated with a top inlet of a hydrogenation reactor, and a bottom outlet of the hydrogenation reactor is communicated with a final inlet of the 2# compressor.
Preferably, the dehydrogenation units are connected in series between two adjacent membrane separators and comprise a catalytic dehydrogenation reactor positioned at the upstream and a dehydrogenation cooler positioned at the downstream, wherein the catalytic dehydrogenation reactor is used for removing residual hydrogen in the process gas, and the dehydrogenation cooler is used for cooling the process gas after the residual hydrogen is removed and preparing for entering the downstream membrane separator.
Preferably, the low-temperature impurity removing unit comprises a crude helium precooler and a low-temperature adsorber which are sequentially connected in series at the downstream of the membrane separation system, wherein the crude helium precooler is used for reducing the dew point of water, and the low-temperature adsorber is used for reducing CH contained in the process gas 4 、N 2 、Ar、O 2 At least one of Ne.
Preferably, the membrane separation system comprises a 1# membrane separator, a 2# membrane separator, a 3# membrane separator and a 4# membrane separator which are sequentially connected in series, a 1# compressor for boosting the process gas is arranged between the 1# membrane separator and the 2# membrane separator, a 2# compressor for boosting the process gas is arranged between the 2# membrane separator and the 3# membrane separator, a 3# compressor for boosting the process gas is arranged between the 3# membrane separator and the 4# membrane separator, and a 4# compressor for boosting the process gas is arranged between the 4# membrane separator and the low-temperature impurity removal unit.
Preferably, the invention can be based on H in the feed gas 2 The content sets the dehydrogenation and desulfurization positions, and the feed gas contains H 2 In a high-pressure state, the desulfurization unit is arranged between the No. 2 membrane separator and the No. 3 membrane separator and is connected with the No. 2 compressor in a matched manner, and the dehydrogenation unit is arranged between the No. 3 membrane separator and the No. 4 membrane separator; in the feed gas containing H 2 In a low-volume state (preferably, the concentration of hydrogen entering the dehydrogenation reactor is not more than 2%), the dehydrogenation unit is arranged on the No. 4 membraneThe downstream of the separator, the desulfurization unit is arranged between the 3# membrane separator and the 4# membrane separator and is connected with the 3# compressor in a matching way.
Preferably, the top of the No. 1 membrane separator is connected with a first pipeline for connecting the non-permeation side of the No. 1 membrane separator with a natural gas pipeline network, the top of the No. 2 membrane separator is connected with a second pipeline for connecting the non-permeation side of the No. 2 membrane separator with the first pipeline, a natural gas buffer tank and a natural gas booster connected in series along the air flow direction are arranged on the second pipeline, the top of the No. 3 membrane separator is connected with a third pipeline for connecting the non-permeation side of the No. 3 membrane separator with the second pipeline at the upstream of the natural gas buffer tank, and the top of the No. 4 membrane separator is connected with a fourth pipeline for connecting the non-permeation side of the No. 4 membrane separator with pipelines at the downstream of the desulfurization unit and at the upstream of the No. 3 membrane separator.
Preferably, the pre-purification system is a TSA purification system, the TSA purification system is temperature swing adsorption and comprises an adsorption unit and a regeneration unit, and the adsorption unit is filled with a catalyst for adsorbing CO 2 The regeneration unit comprises a fifth pipeline, a regeneration gas heater, a sixth pipeline and a regeneration gas cooler, wherein the fifth pipeline is connected between the vicinity of an inlet of the first pipeline and a bottom inlet of the TSA purification system, the regeneration gas heater is arranged on the fifth pipeline and used for heating part of non-permeate gas in the first pipeline and then inputting the heated non-permeate gas into the TSA purification system to blow out impurities adsorbed in the adsorbent, the sixth pipeline is connected between a top outlet of the TSA purification system and the first pipeline and is positioned behind the fifth pipeline and before a natural gas booster, and the regeneration gas cooler is arranged on the sixth pipeline and used for cooling the heated non-permeate gas.
Preferably, the number of stages of the membrane separation and the pressure difference of the membrane separation operation in the invention are comprehensively determined according to the helium content of the raw material gas, the project scale and the technical economy, and are not particularly limited.
In the invention, the desulfurizing tower is a dry desulfurizing process, namely, an active desulfurizing agent (such as ZnO) is adopted to thoroughly remove inorganic sulfur. The coarse helium precooler is based on compression refrigeration drying principle, and can be replaced by molecular sieve adsorption drying structure or triethylene glycol dehydration principle. The osmotic pressure (back pressure) of the membrane separator is automatically controlled by the compressor at the outlet of the membrane separator, and no negative pressure is generated for safety.
The TSA purification system can be replaced by an MEA (generalized alcohol amine method) +water washing system, so that alcohol amine entrainment is effectively eliminated, and the influence of volatile solvents on membrane separation is fundamentally avoided.
A process for purifying helium from ultra-helium-depleted natural gas comprising the steps of:
lean helium and sulfur-containing natural gas from a gas field treatment plant firstly enters a TSA purification device to remove all CO 2 Water, heavy hydrocarbon and partial sulfide enter a No. 1 membrane separator;
after the permeation treatment of the No. 1 membrane separator, obtaining non-permeation gas without helium and permeation gas with helium, wherein the non-permeation gas is almost not decompressed and directly sent to a natural gas pipe network; the permeation air is pressureless, helium in the permeation air is concentrated, and the helium is sent to a No. 2 membrane separator after being boosted by a No. 1 compressor;
after the permeation treatment by a No. 2 membrane separator, the helium concentration in the obtained permeation gas is increased, and the permeation gas is firstly boosted and heated by a No. 2 compressor and then enters a hydrogenation reactor;
in a hydrogenation reactor, utilizing a catalyst (such as cobalt molybdenum) to react hydrogen in natural gas with organic sulfide, converting the organic sulfide into inorganic sulfide, then re-entering a final stage of a No. 2 compressor for boosting and cooling, and entering a desulfurizing tower;
in a desulfurizing tower, inorganic sulfide is removed to be less than 0.1ppm, and the inorganic sulfide enters a 3# membrane separator;
after permeation treatment by a 3# membrane separator, the helium concentration in the obtained permeation gas is further concentrated, and the permeation gas is boosted by a 3# compressor and then is sent into a catalytic dehydrogenation reactor and a dehydrogenation cooler in sequence after being heated; after passing through a catalytic dehydrogenation reactor and a dehydrogenation cooler, residual hydrogen in the process gas is thoroughly removed and cooled, and enters a No. 4 membrane separator;
after the permeation treatment of the No. 4 membrane separator, crude helium meeting the low-temperature adsorption requirement is obtained at an outlet, and the crude helium enters a crude helium precooler to reduce the dew point of water after being compressed by a No. 4 compressorLow and almost completely removing residual CH by low-temperature adsorber 4 、N 2 、Ar、O 2 Ne impurity to obtain helium with purity not lower than 99.999%;
the non-permeate gas of the No. 2 membrane separator and the No. 3 membrane separator firstly enters a natural gas buffer tank, is boosted by a natural gas booster and then is merged into a pipe network, and a large amount of helium gas contained in the non-permeate gas of the No. 4 membrane separator is returned to an inlet of the No. 3 membrane separator for recovery; in the regeneration step of the pre-purification system, non-permeate gas from the No. 1 membrane separator is heated by a regeneration gas heater, impurities adsorbed in the adsorbent are blown off from the bottom of an adsorption tower of the pre-purification system, and then the non-permeate gas is cooled to normal temperature by a regeneration gas cooler and is merged into a natural gas pipe network.
Compared with the prior art, the invention has the advantages that: according to the current situation of resources, the invention is mainly used for solving the problems of helium purification in natural gas lean in helium and ultra-lean in helium, and all CO in raw material gas is removed by pre-purification 2 The method has the advantages that the quick gas component of the membrane separator is greatly reduced, helium concentration is facilitated, the multi-stage membrane separator is adopted for helium concentration, the method is suitable for treating helium-poor and ultra-helium-poor natural gas, sulfide is thoroughly removed by adopting a catalytic hydrogenation process and dry desulfurization in the process, and the method plays a very key role in helium purification;
specifically, the invention sets pre-purification at the front end of the process, solves the problem of CO 2 Incomplete removal, adverse effect on the subsequent membrane separation effect and corrosion problem on the subsequent system; the compression heat is adopted for hydrogenation and dehydrogenation reactions, so that the heat exchange of the system is optimized, and the problem of cold and hot diseases in the prior art is solved; the invention adopts low-temperature adsorption lower than the liquid nitrogen temperature zone to carry out residual purification, greatly improves the selectivity and efficiency, can thoroughly remove impurities such as neon, argon and the like which are difficult to adsorb by a normal temperature method, and effectively ensures the purity of the product; a helium precooling unit is arranged for cooling and dehydration before purification, and a molecular sieve dehydration flow is arranged, so that the dew point requirement of a product is effectively met; CO purification System Using TSA 2 The non-permeable gas is adopted as the regeneration medium without nitrogen, and no redundant impurities enter the process after the removal to below 20ppmIn the air; the outlet of the membrane separator is provided with a compressor control pressure, so that the membrane operation is ensured under reasonable pressure difference and lower back pressure, and the concentration and recovery rate of the membrane separator are effectively ensured under reasonable investment.
The invention is suitable for purifying the helium in the natural gas treatment plants of various large gas fields, and the treatment scale of the natural gas with the helium content of 0.03-0.1% is more than or equal to 200 square/day.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention;
FIG. 2 is a schematic structural diagram of embodiment 2 of the present invention;
fig. 3 is another structural schematic diagram of embodiment 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Example 1:
as shown in fig. 1, the apparatus for purifying helium from helium-depleted natural gas according to the present embodiment comprises:
pre-clean system 1 with inlet for helium lean natural gas input for CO in the feed gas 2 Removing water, heavy hydrocarbon and partial sulfide;
the membrane separation system A is arranged at the downstream of the pre-purification system 1 and comprises at least two groups of membrane separators connected in series, and is used for carrying out permeation separation on materials to obtain non-permeation gas for sending a natural gas pipe network and permeation gas after helium concentration;
the desulfurization unit B is connected to the membrane separation system A and is used for removing sulfide in the process gas;
the dehydrogenation unit C is connected to the membrane separation system A and positioned at the downstream of the desulfurization unit B and is used for removing residual hydrogen in the process gas; and
a low-temperature impurity removing unit D arranged at the downstream of the membrane separation system A and the dehydrogenation unit C and used for removing CH contained in the process gas 4 、N 2 、Ar、O 2 Ne, etc.
Specifically, the membrane separation system A is a multistage series membrane separator group, and can be specifically set according to the needs. The membrane separation system A of the embodiment comprises a 1# membrane separator 2, a 2# membrane separator 4, a 3# membrane separator 8 and a 4# membrane separator 12 which are sequentially connected in series, a 1# compressor 3 for boosting the process gas is arranged between the 1# membrane separator 2 and the 2# membrane separator 4, a 2# compressor 5 for boosting the process gas is arranged between the 2# membrane separator 4 and the 3# membrane separator 8, a 3# compressor 9 for boosting the process gas is arranged between the 3# membrane separator 8 and the 4# membrane separator 12, and a 4# compressor 13 for boosting the process gas is arranged between the 4# membrane separator 12 and the low-temperature impurity removal unit D.
Can be based on H in the raw material gas 2 The content sets the dehydrogenation and desulfurization positions, and the feed gas contains H 2 In the high state, the desulfurization unit B is arranged between the 2# membrane separator 4 and the 3# membrane separator 8 and is connected with the 2# compressor 5 in a matched manner, and the dehydrogenation unit C is arranged between the 3# membrane separator 8 and the 4# membrane separator 12; in the feed gas containing H 2 In a low-volume state (preferably, the concentration of hydrogen entering the dehydrogenation reactor is not more than 2%), the dehydrogenation unit C is arranged at the downstream of the No. 4 membrane separator, and the desulfurization unit B is arranged between the No. 3 membrane separator 8 and the No. 4 membrane separator 12 and is connected with the No. 3 compressor 9 in a matched manner.
The desulfurization unit B of this embodiment includes a hydrogenation reactor 6 located at the upstream and a desulfurization tower 7 located at the downstream, where the hydrogenation reactor 6 is used to react hydrogen and organic sulfide in natural gas to convert organic sulfur into inorganic sulfur sulfide, and the desulfurization tower 7 is used to remove inorganic sulfur sulfide. The primary inlet of the No. 2 compressor 5 is communicated with the permeate gas side of the No. 2 membrane separator 4 at the upstream thereof, the final outlet is communicated with the top inlet of the desulfurizing tower 7, the middle outlet of the No. 2 compressor 5 is communicated with the top inlet of the hydrogenation reactor 6, and the bottom outlet of the hydrogenation reactor 6 is communicated with the final inlet of the No. 2 compressor 5.
The dehydrogenation unit C of this embodiment includes a catalytic dehydrogenation reactor 10 located at the upstream and a dehydrogenation cooler 11 located at the downstream, where the catalytic dehydrogenation reactor 10 is used for removing residual hydrogen in the process gas, and the dehydrogenation cooler 11 is used for cooling the process gas after removing residual hydrogen and preparing for entering a downstream No. 4 membrane separator 12.
The low-temperature impurity removal unit D of the embodiment comprises a coarse helium precooler 14 and a low-temperature absorber 15 which are sequentially connected in series at the downstream of the membrane separation system A, wherein the coarse helium precooler 14 is used for reducing the dew point of water, and the low-temperature absorber 15 is used for reducing CH contained in process gas 4 、N 2 、Ar、O 2 Ne, etc.
In the present embodiment, the top of the 1# membrane separator 2 is connected to the first pipe 01,2# membrane separator 4, the top of which connects the non-permeate side thereof to the natural gas pipe network, the second pipe 02, the natural gas buffer tank 18 and the natural gas booster 19 connected in series in the gas flow direction are provided on the second pipe 02, the top of the 3# membrane separator 8 is connected to the third pipe 03,4# membrane separator 12, the top of which connects the non-permeate side thereof to the second pipe 02 upstream of the natural gas buffer tank 18, and the fourth pipe 04, which connects the non-permeate side thereof to the pipe downstream of the desulfurization unit B and upstream of the 3# membrane separator 8.
The pre-purification system 1 of the embodiment is a TSA purification system, and the TSA purification system is temperature swing adsorption and comprises an adsorption unit and a regeneration unit, wherein the adsorption unit is filled with a catalyst for adsorbing CO 2 The regeneration unit comprises a fifth pipeline 05, a regeneration gas heater 16, a sixth pipeline 06 and a regeneration gas cooler 17, wherein the fifth pipeline 05 is connected between the vicinity of an inlet of the first pipeline 01 and the bottom inlet of the TSA purification system, the regeneration gas heater 16 is arranged on the fifth pipeline 05 and is used for heating part of non-permeate gas in the first pipeline 01 and then inputting the heated non-permeate gas into the TSA purification system to blow out impurities adsorbed in the adsorbent, the sixth pipeline 06 is connected between the top outlet of the TSA purification system and the first pipeline 01 and is positioned behind the fifth pipeline 05 and in front of the natural gas booster 19 at the joint of the sixth pipeline 06 and the first pipeline 01, and the regeneration gas cooler 17 is arranged on the sixth pipeline 06 and is used for cooling the heated non-permeate gas.
In this embodiment, the desulfurizing tower 7 is a dry desulfurizing process, i.e., an active desulfurizing agent (e.g., znO) is used to thoroughly remove inorganic sulfur. The coarse helium precooler 14 includes a compression refrigeration and molecular sieve drying structure. The osmotic pressure (back pressure) of the membrane separator is automatically controlled by a compressor at the outlet of the membrane separator, preferably 0-10 kPa, and no negative pressure is generated for safety. The TSA purification system of this embodiment may also be replaced with an MEA (generalized alcohol amine process) +water washing system, which is to effectively eliminate alcohol amine entrainment, and fundamentally avoid the influence of the volatile solvent on the membrane separation.
The process for purifying helium from helium-depleted ultra-helium-depleted natural gas of this embodiment comprises the steps of:
lean helium sulfur-containing natural gas with the pressure of about 3.5MPa and the helium concentration of 0.05% from a gas field treatment plant enters a TSA purification device to remove all CO first 2 Water, heavy hydrocarbon and partial sulfide enter a No. 1 membrane separator 2;
after the permeation treatment of the No. 1 membrane separator 2, obtaining non-permeation gas without helium and permeation gas with helium, wherein the non-permeation gas is almost directly sent to a natural gas pipe network without decompression; the permeation air is pressureless, the volume concentration of helium in the permeation air is 0.35% -0.4%, the pressure is increased to 2.0MPa through a No. 1 compressor 3, and the helium is sent to a No. 2 membrane separator 4;
after the permeation treatment by a No. 2 membrane separator 4, the helium concentration in the obtained permeation gas is changed to 1.58-1.8%, the concentration is firstly boosted to 1.0MPa by a No. 2 compressor 5, and the permeation gas is heated to 180 ℃ and then enters a hydrogenation reactor 6;
in a hydrogenation reactor 6, utilizing a catalyst (such as cobalt molybdenum) to react hydrogen in natural gas with organic sulfide, converting the organic sulfide into inorganic sulfide, then re-entering a No. 2 compressor 5 to boost pressure to 2.0MPa at the final stage, cooling to 40 ℃, and entering a desulfurizing tower 7;
in the desulfurizing tower 7, thoroughly removing inorganic sulfide to below 0.1ppm, and entering a 3# membrane separator 8;
after the permeation treatment by a 3# membrane separator 8, the helium concentration in the obtained permeation gas is concentrated to 9.0% -10.3%, the concentration is boosted to 2.0MPa by a 3# compressor 9, and the permeation gas is heated to 180 ℃ and then sequentially sent into a catalytic dehydrogenation reactor 10 and a dehydrogenation cooler 11; after passing through a catalytic dehydrogenation reactor 10 and a dehydrogenation cooler 11, residual hydrogen in the process gas is thoroughly removed and cooled, and enters a No. 4 membrane separator 12;
permeation through No. 4 membrane separator 12After the permeation treatment, crude helium with the concentration of 53.9% -61.2% is obtained at an outlet, compressed to 2.0MPa by a No. 4 compressor 13, enters a crude helium precooler 14 to reduce the dew point of water to 2-5 ℃, and then the residual CH is removed by a low-temperature adsorber 15 4 、N 2 、Ar、O 2 Ne impurity to obtain helium with purity not lower than 99.999%;
in the process, the non-permeate gas of the No. 2 membrane separator 4 and the No. 3 membrane separator 8 firstly enters a natural gas buffer tank 18, is boosted to 3.5MPa by a natural gas booster 19 and is integrated into a pipe network, and the non-permeate gas of the No. 4 membrane separator 12 contains a large amount of helium gas and is returned to the inlet of the No. 3 membrane separator 8 for recovery; the TSA purification system adopts a temperature swing adsorption process, and comprises two adsorbers filled with molecular sieves, one for adsorption, the other for regeneration, sequential control and continuous operation, wherein non-permeate gas from a No. 1 membrane separator 2 is heated to 190 ℃ through a regeneration gas heater 16 in the regeneration step, impurities adsorbed in the adsorbent are blown off from the bottom of an adsorption tower of the TSA purification system, and then the gas is cooled to normal temperature through a regeneration gas cooler 17 and is integrated into a natural gas pipe network. The recovery rate of helium in the whole process is more than 93%.
Example 2:
as shown in fig. 2 to 3, the apparatus for purifying helium from helium-depleted natural gas in this embodiment may also employ structural modifications, and of course, the operation principle and basic process steps remain the same as those of embodiment 1.
Claims (10)
1. An apparatus for purifying helium from helium-depleted natural gas, comprising:
pre-clean system with inlet for helium lean natural gas input for CO in the feed gas 2 Removing water, heavy hydrocarbon and partial sulfide;
the membrane separation system is arranged at the downstream of the pre-purification system and comprises at least two groups of membrane separators connected in series, and is used for carrying out permeation separation on materials to obtain non-permeation gas for sending a natural gas pipe network and permeation gas after helium concentration;
the desulfurization unit is connected to the membrane separation system and is used for removing sulfide in the process gas;
the dehydrogenation unit is connected to the membrane separation system and positioned at the downstream of the desulfurization unit and is used for removing residual hydrogen in the process gas; and
a low-temperature impurity removing unit which is arranged at the downstream of the membrane separation system and the dehydrogenation unit and is used for removing CH contained in the process gas 4 、N 2 、Ar、O 2 At least one of Ne.
2. The apparatus for purifying helium from helium-depleted natural gas of claim 1, wherein: the desulfurization unit is connected in series between two adjacent membrane separators and comprises a hydrogenation reactor positioned at the upstream and a desulfurization tower positioned at the downstream, wherein the hydrogenation reactor is used for converting H in natural gas 2 And an organic sulfide to convert the organic sulfide into an inorganic sulfide, and the desulfurizing tower is used for removing the inorganic sulfide.
3. The apparatus for purifying helium from helium-depleted natural gas of claim 2, wherein: a 2# compressor is arranged between two adjacent membrane separators, a primary inlet of the 2# compressor is communicated with a permeate air side of the membrane separator at the upstream of the two adjacent membrane separators, a final outlet of the 2# compressor is communicated with a top inlet of the desulfurizing tower, a middle outlet of the 2# compressor is communicated with a top inlet of a hydrogenation reactor, and a bottom outlet of the hydrogenation reactor is communicated with a final inlet of the 2# compressor.
4. An apparatus for purifying helium from helium-depleted natural gas according to claim 1 or 2 or 3, wherein: the dehydrogenation unit is connected in series between two adjacent membrane separators and comprises a catalytic dehydrogenation reactor positioned at the upstream and a dehydrogenation cooler positioned at the downstream, wherein the catalytic dehydrogenation reactor is used for removing residual hydrogen in the process gas, and the dehydrogenation cooler is used for cooling the process gas after the residual hydrogen is removed and preparing for entering the downstream membrane separator.
5. According to the weightsAn apparatus for purifying helium from helium-depleted natural gas as in claim 1 or 2 or 3, wherein: the low-temperature impurity removal unit comprises a crude helium precooler and a low-temperature adsorber which are sequentially connected in series at the downstream of the membrane separation system, wherein the crude helium precooler is used for reducing the dew point of water, and the low-temperature adsorber is used for reducing CH contained in process gas 4 、N 2 、Ar、O 2 At least one of Ne.
6. An apparatus for purifying helium from helium-depleted natural gas according to claim 1 or 2 or 3, wherein: the membrane separation system comprises a 1# membrane separator, a 2# membrane separator, a 3# membrane separator and a 4# membrane separator which are sequentially connected in series, a 1# compressor for boosting process gas is arranged between the 1# membrane separator and the 2# membrane separator, a 2# compressor for boosting process gas is arranged between the 2# membrane separator and the 3# membrane separator, a 3# compressor for boosting process gas is arranged between the 3# membrane separator and the 4# membrane separator, and a 4# compressor for boosting process gas is arranged between the 4# membrane separator and the low-temperature impurity removal unit.
7. The apparatus for purifying helium from helium-depleted natural gas of claim 6, wherein: the desulfurization unit is arranged between the No. 2 membrane separator and the No. 3 membrane separator and is connected with the No. 2 compressor in a matched manner, and the dehydrogenation unit is arranged between the No. 3 membrane separator and the No. 4 membrane separator; in the feed gas containing H 2 In a low-volume state, the dehydrogenation unit is arranged at the downstream of the No. 4 membrane separator, and the desulfurization unit is arranged between the No. 3 membrane separator and the No. 4 membrane separator and is connected with the No. 3 compressor in a matched manner.
8. The apparatus for purifying helium from helium-depleted natural gas of claim 6, wherein: the top of the No. 1 membrane separator is connected with a first pipeline which connects the non-seepage side with a natural gas pipeline network, the top of the No. 2 membrane separator is connected with a second pipeline which connects the non-seepage side with the first pipeline, the second pipeline is provided with a natural gas buffer tank and a natural gas booster which are connected in series along the airflow direction, the top of the No. 3 membrane separator is connected with a third pipeline which connects the non-seepage side with the second pipeline at the upstream of the natural gas buffer tank, and the top of the No. 4 membrane separator is connected with a fourth pipeline which connects the non-seepage side with the pipeline at the downstream of the desulfurization unit and the upstream of the No. 3 membrane separator.
9. The apparatus for purifying helium from helium-depleted natural gas of claim 8, wherein: the pre-purification system is a TSA purification system, the TSA purification system comprises an adsorption unit and a regeneration unit, and the adsorption unit is filled with a catalyst for adsorbing CO 2 The regeneration unit comprises a fifth pipeline, a regeneration gas heater, a sixth pipeline and a regeneration gas cooler, wherein the fifth pipeline is connected between the vicinity of an inlet of the first pipeline and a bottom inlet of the TSA purification system, the regeneration gas heater is arranged on the fifth pipeline and used for heating part of non-permeate gas in the first pipeline and then inputting the heated non-permeate gas into the TSA purification system to blow out impurities adsorbed in the adsorbent, the sixth pipeline is connected between a top outlet of the TSA purification system and the first pipeline and is positioned behind the fifth pipeline and before a natural gas booster, and the regeneration gas cooler is arranged on the sixth pipeline and used for cooling the heated non-permeate gas.
10. A process for purifying helium from helium-depleted natural gas comprising the steps of:
lean helium and sulfur-containing natural gas from a gas field treatment plant firstly enters a TSA purification device to remove all CO 2 Water, heavy hydrocarbon and partial sulfide enter a No. 1 membrane separator;
after the permeation treatment of the No. 1 membrane separator, obtaining non-permeation gas without helium and permeation gas with helium, wherein the non-permeation gas is almost not decompressed and directly sent to a natural gas pipe network; the permeation air is pressureless, the volume concentration of helium in the permeation air is 0.35% -0.4%, and the helium is sent to a No. 2 membrane separator after being boosted by a No. 1 compressor;
after the permeation treatment by a No. 2 membrane separator, the concentration of helium in the obtained permeation gas is changed into 1.58-1.8%, and the permeation gas is firstly boosted and heated by a No. 2 compressor and then enters a hydrogenation reactor;
in a hydrogenation reactor, utilizing a cobalt-molybdenum catalyst to react hydrogen in natural gas with organic sulfide, converting the organic sulfide into inorganic sulfide, then re-entering a final stage of a No. 2 compressor for boosting and cooling, and entering a desulfurizing tower;
in a desulfurizing tower, thoroughly removing inorganic sulfide to below 0.1ppm, and entering a 3# membrane separator;
after permeation treatment by a 3# membrane separator, the concentration of helium in the obtained permeation gas is concentrated to 9.0% -10.3%, and the obtained permeation gas is boosted by a 3# compressor and then is heated, and then is sequentially sent into a catalytic dehydrogenation reactor and a dehydrogenation cooler; after passing through a catalytic dehydrogenation reactor and a dehydrogenation cooler, residual hydrogen in the process gas is thoroughly removed and cooled, and enters a No. 4 membrane separator;
after the permeation treatment of the No. 4 membrane separator, crude helium with the concentration of 53.9% -61.2% is obtained at an outlet, the crude helium enters a crude helium precooler after being compressed by a No. 4 compressor to reduce the dew point of water to 2-5 ℃, and then the residual CH is removed by a low-temperature adsorber 4 、N 2 、Ar、O 2 Ne impurity to obtain helium with purity not lower than 99.999%;
the non-permeate gas of the No. 2 membrane separator and the No. 3 membrane separator firstly enters a natural gas buffer tank, is boosted by a natural gas booster and then is merged into a pipe network, and a large amount of helium gas contained in the non-permeate gas of the No. 4 membrane separator is returned to an inlet of the No. 3 membrane separator for recovery; in the regeneration step of the pre-purification system, non-permeate gas from the No. 1 membrane separator is heated by a regeneration gas heater, impurities adsorbed in the adsorbent are blown off from the top of an adsorption tower of the pre-purification system, and then the non-permeate gas is cooled to normal temperature by a regeneration gas cooler and is merged into a natural gas pipe network.
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