CN218841717U - Equipment for directly obtaining high-purity helium from natural gas - Google Patents
Equipment for directly obtaining high-purity helium from natural gas Download PDFInfo
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- CN218841717U CN218841717U CN202222439860.8U CN202222439860U CN218841717U CN 218841717 U CN218841717 U CN 218841717U CN 202222439860 U CN202222439860 U CN 202222439860U CN 218841717 U CN218841717 U CN 218841717U
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000001307 helium Substances 0.000 title claims abstract description 78
- 229910052734 helium Inorganic materials 0.000 title claims abstract description 78
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003345 natural gas Substances 0.000 title claims abstract description 61
- 239000012528 membrane Substances 0.000 claims abstract description 136
- 239000007789 gas Substances 0.000 claims abstract description 135
- 238000000034 method Methods 0.000 claims abstract description 66
- 230000008569 process Effects 0.000 claims abstract description 60
- 238000000746 purification Methods 0.000 claims abstract description 48
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 41
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 32
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- 238000000926 separation method Methods 0.000 claims abstract description 29
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 230000007062 hydrolysis Effects 0.000 claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 230000008929 regeneration Effects 0.000 claims description 14
- 238000011069 regeneration method Methods 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005371 permeation separation Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000003795 desorption Methods 0.000 abstract description 4
- 201000010099 disease Diseases 0.000 abstract description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 239000012466 permeate Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000005261 decarburization Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000011084 recovery Methods 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000003054 catalyst Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
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- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The utility model relates to an equipment of high-purity helium is directly obtained from the natural gas, and the equipment that directly obtains high-purity helium from the natural gas includes accurate oil filter, membrane separation system, sour gas desorption unit, fine desulfurization unit, dehydrogenation unit, clean system and low temperature impurity desorption unit again. The utility model discloses according to domestic resource current situation, mainly used solves the helium purification in poor helium, the special poor helium natural gas, adopts multistage membrane separation + cryosorption technology to realize that poor helium natural gas draws and obtains high-purity helium or liquid helium, can directly draw the helium and purify to high-purity helium (99.999%) from the purification natural gas in poor helium, the special poor helium field (0.03-0.1%); before low-temperature purification, a purification unit is arranged to purify CO 2 、H 2 Thoroughly removing O and regenerating by non-permeable tail gas without N 2 Impurities enter the process gas, the problem of cold and hot diseases in the process flow is avoided by reasonably arranging the COS hydrolysis and dehydrogenation reaction positions, and the impurities Ar and Ne and the like can be thoroughly removed, so that the purity of helium is effectively ensured.
Description
Technical Field
The utility model relates to a helium production technical field specifically indicates a directly acquire equipment of high-purity helium from the natural gas.
Background
Helium is a scarce non-renewable resource in China, and plays an irreplaceable role in national defense progress and scientific and technological development. The traditional helium extraction technology cryogenic method is used for poor helium and even ultra-poor helium fields which are ubiquitous in China, the unit product cost is high, and no industrial application value exists.
The Chinese patent with the publication number of CN214087729U, namely a normal-temperature natural gas helium extraction and purification system, and the Chinese patent with the publication number of CN215113528U, namely a device for extracting helium from natural gas to prepare liquid helium respectively disclose technology for extracting helium from natural gas. Wherein CN214087729U is final means for helium purification by pure pressure swing adsorption, CH 4 、N 2 Ar, particularly Ne impurities are not thoroughly removed, and the impurities are accumulated along with the circulating gas in the process production process, so that the purity of helium does not reach the standard; secondly, drying and dehydration are not considered, and the dew point of the product is difficult to ensure; thirdly, the removal of sulfur is not considered, and the dehydrogenation unit is difficult to operate for a long time. CN215113528U adopts MDEA decarburization, firstly, the influence of alcohol amine volatilization or entrainment on subsequent separation membrane tolerance and performance index is not considered, secondly, higher back pressure exists at the downstream of a membrane separator, and the pressure difference of membrane separation operation is small, so that the separation effect is poor, the membrane equipment investment is greatly increased, and the technical economy is unreasonable.
With the technology for extracting helium from natural gas disclosed in the prior art, the following problems are also common:
1) Natural gas in domestic gas fields generally contains sulfur, even if the sulfur content of treated export products is generally 20-100 mg/cm 3 The prior published technology does not consider the sulfur removal scheme, and neither PSA nor MDEA can effectively remove the organic sulfur so as to remove the sulfurThe hydrogen unit cannot operate for a long time;
2) In the prior art, the operation conditions of catalytic dehydrogenation and decarburization are not considered, and the conversion rate of hydrogen cannot be ensured when dehydrogenation is carried out at normal temperature, so that the purity of helium does not reach the standard;
3) The oil-gas industry mostly adopts piston compressors with oil lubrication, natural gas products contain trace lubricating oil, the long-term operation can affect the membrane separation effect and the service life, and the prior art is provided with a pre-membrane filtration treatment facility.
4) The prior art does not consider the source of dehydrogenation oxygen and trace N in the oxygen 2 Impurities such as Ar, etc. may adversely affect the product purity.
5) The prior art considers the dehydration process, but does not clearly indicate the regeneration mode of a drying system and the source problem of regeneration gas.
Therefore, there is still much room for improvement in the current technology for obtaining a single helium product based on domestic natural gas conditions.
SUMMERY OF THE UTILITY MODEL
The utility model discloses the first technical problem that will solve is based on internal resource current situation, provides one kind and can directly draw the helium and purify the equipment for high-purity helium (99.999%) and production liquid helium from poor helium, the defeated natural gas of extra poor helium pipe.
The utility model discloses the second technical problem that will solve is the current situation to prior art, provides a filtration treatment device before the membrane, solves the influence that the remaining lubricating grease that comes from the compressor caused to membrane separation long-term operation.
The third technical problem to be solved in the utility model is to provide a method for removing acid gas to the current situation of prior art, avoid absorbing the solvent and bring into process gas and cause adverse effect to the separation membrane.
The utility model discloses the fourth technical problem that will solve is to prior art's current situation, provides one kind and effectively deviates from organic sulphur and inorganic sulphur method through COS medium temperature hydrolysis tower, smart desulfurizing tower combined process, has guaranteed the long steady operation of catalytic dehydrogenation unit.
The fifth technical problem to be solved by the utility model is to the current situation of prior art, provide the specific position of the required oxygenating of hydrogenation and organic sulphur oxidation and adopt the electrolysis water to obtain the accumulation of high purity oxygen in order to reduce impurity, can effectively guarantee helium purity.
The sixth technical problem to be solved in the utility model is to prior art's current situation, proposes to adopt TSA to carry out thorough drying and utilize tail gas as the regeneration air supply, reduces useful gas loss.
The utility model discloses the seventh technical problem that will solve is to prior art's current situation, proposes to utilize the compressor segmentation to satisfy COS hydrolysis, fine desulfurization, the best operating temperature's of dehydrogenation reaction requirement to "cold and hot disease" problem of process flow has been avoided, makes the energy utilization more reasonable.
The utility model provides a technical scheme that at least one above-mentioned technical problem adopted is:
an apparatus for obtaining high purity helium gas directly from natural gas comprising:
the precise oil filter is provided with an air inlet for inputting the helium-poor sulfur-containing natural gas and is used for removing suspended oil drops in the natural gas;
the membrane separation system is arranged at the downstream of the precision oil filter, comprises at least 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 and permeation gas after helium gas concentration which are sent to a natural gas pipeline network;
an acid gas removal unit connected to the membrane separation system for removing CO from the process gas 2 、H 2 S, removing the volatilized amine liquid;
the fine desulfurization unit is connected to the membrane separation system, is positioned at the downstream of the acid gas removal unit and is used for removing sulfur-containing substances in the process gas;
a dehydrogenation unit connected in the membrane separation system and located downstream of the fine desulfurization unit for removing residual H in the process gas 2 Removing;
a re-purification system arranged at the downstream of the membrane separation system and the dehydrogenation unit for removing CO contained in the process gas 2 、H 2 At least one of O and sulfideRemoving; and
a low-temperature impurity removal unit arranged at the downstream of the re-purification system and used for removing CH contained in the process gas 4 、N 2 、Ar、O 2 And Ne is removed.
Preferably, the acid gas removal unit is connected in series between two adjacent membrane separators and comprises an amine scrubber and an amine scrubber which are connected in series in the gas flow direction in sequence, wherein the amine scrubber is used for removing a large amount of CO in the process gas 2 、H 2 And S, the amine washing tower is used for removing the amine liquid entrained in the process gas. Preferably, when the scale of raw material treatment is small, CO 2 When the content is high, the acid gas removal unit can be replaced by a VPSA process.
Preferably, the fine desulfurization unit is connected in series between two adjacent membrane separators and comprises a COS medium-temperature hydrolysis tower, a water cooler and a fine desulfurization tower which are sequentially connected in series, wherein the COS medium-temperature hydrolysis tower is used for converting COS into H 2 And S, the water cooler is used for cooling the process gas, and the fine desulfurization tower is used for removing all sulfides. Preferably, the desulfurization unit can adopt multi-stage COS hydrolysis towers and fine desulfurization for series or parallel combination as required.
Preferably, the device also comprises an electrolytic water device for providing high purity oxygen, and an oxygen output end of the electrolytic water device is connected with an inlet of the fine desulfurization tower and is used for providing oxygen required by an organic sulfur oxidation and dehydrogenation unit of the fine desulfurization tower.
Preferably, the dehydrogenation unit is connected in series between two adjacent membrane separators and comprises an upstream catalytic dehydrogenation reactor and a downstream dehydrogenation cooler, wherein the catalytic dehydrogenation reactor is used for removing residual H in the process gas 2 Removing the residual H in the dehydrogenation cooler 2 The latter process gas is cooled in preparation for entering the downstream membrane separator. Preferably, multiple dehydrogenation reactors may be employed in series or in parallel combinations as desired.
Preferably, the membrane separation system comprises a 1# membrane separator, a 2# membrane separator and a 3# membrane separator which are connected in series in sequence, a 1# compressor for boosting the process gas is arranged between the 1# membrane separator and the 2# membrane separator, a 2# compressor and a 2# supercharger for boosting the process gas are arranged between the 2# membrane separator and the 3# membrane separator, and a 3# compressor for boosting the process gas is arranged between the 3# membrane separator and the re-purification system.
Preferably, the acid gas removal unit is arranged between the No. 1 membrane separator and the No. 2 membrane separator and is positioned at the downstream of the No. 1 compressor; the fine desulfurization unit is arranged between the 2# membrane separator and the 3# membrane separator and is positioned between the 2# compressor and the 2# supercharger; the dehydrogenation unit is arranged between the No. 2 membrane separator and the No. 3 membrane separator and is positioned at the downstream of the No. 2 booster. Preferably, for best effect, no after cooler is provided for the 2# compressor and the 2# supercharger.
Preferably, the top of the # 1 membrane separator is connected with a first pipe connecting the non-permeate gas side thereof with a natural gas pipe network, the top of the # 2 membrane separator is connected with a second pipe connecting the non-permeate gas side thereof with the first pipe, and the top of the # 3 membrane separator is connected with a third pipe connecting the non-permeate gas side thereof with a pipe between the # 1 compressor and the inlet of the # 2 membrane separator.
Preferably, the re-purification system is a TSA purification system, which comprises an adsorption unit and a regeneration unit, wherein the adsorption unit is filled with a material for adsorbing CO 2 The regeneration unit comprises a fourth pipeline and a fifth pipeline, the fourth pipeline is connected between the position near the inlet of the first pipeline and the top inlet of the TSA purification system and used for inputting part of non-permeable gas in the first pipeline into the TSA purification system to blow off impurities adsorbed in the adsorbent, and the fifth pipeline is connected between the top outlet of the TSA purification system and the second pipeline.
The utility model discloses in, low temperature impurity desorption unit also can be PSA process equipment, and PSA's tail gas can circulate to 1# compressor entry or 2# compressor entry to improve the helium yield, TSA clean system can replace considering desorption system moisture with the refrigeration dryer this moment. The non-permeable gas of the 3# membrane separator directly returns to the inlet of the 2# membrane separator, and can also return to the 1# compressor, thereby achieving the same purpose. The amine scrubber and the amine scrubber can also be arranged at proper positions between the 2# compressor and the 2# supercharger according to requirements. According to the processing parameters, the 2# compressor and the 2# supercharger can be two sections of one compressor, so that the investment can be reduced, and the occupied area can be saved.
A process for obtaining high purity helium directly from natural gas comprising the steps of:
purified natural gas from a natural gas treatment plant firstly enters a precision oil filter to remove oil drops suspended in the natural gas brought by an upstream oil injection lubrication piston type compressor and enters a No. 1 membrane separator;
obtaining non-permeable gas without helium and permeable gas with helium after the permeation treatment of a # 1 membrane separator, wherein the non-permeable gas is almost not decompressed and is directly sent to a natural gas pipe network; the permeation gas is at normal pressure, the helium concentration in the permeation gas is increased, the flow is greatly reduced, the pressure is increased to the pressure of the raw material gas through a 1# compressor, and the raw material gas is sent to an amine washing tower;
amine scrubber for removing large amounts of CO 2 、H 2 S, removing amine liquid carried in the process gas through an amine washing tower, and entering a No. 2 membrane separator;
after the permeation treatment of a 2# membrane separator, the helium concentration in the obtained permeation gas is further concentrated, and the gas is firstly pressurized to a certain pressure by a 2# compressor and directly enters a COS medium temperature hydrolysis tower without being cooled;
in a COS medium temperature hydrolysis tower, COS is converted into H by using compression heat and a hydrolysis catalyst 2 S, cooling the product by a water cooler, feeding the product into a fine desulfurization tower to remove all sulfides, feeding the product into a 2# supercharger to boost the pressure to be close to the pressure of the raw natural gas, and directly feeding the product into a catalytic dehydrogenation reactor without cooling to remove all H 2 Cooling the mixture by a dehydrogenation cooler and then feeding the cooled mixture into a 3# membrane separator;
after the permeation treatment by the 3# membrane separator, the helium concentration in the obtained permeation gas is concentrated to the concentration required by the low-temperature purification unit, and is boosted to the required pressure by the 2# supercharger and sent to a TSA purification system;
removal of residual CO in a TSA purification system 2 、H 2 O and sulfide enter a low-temperature purification unit;
removal of residual CH in a cryogenic purification unit 4 、N 2 、Ar、O 2 Ne impurity to obtain helium with purity of 99.999%;
the non-permeable gas of the No. 1 membrane separator and the non-permeable gas of the No. 2 membrane separator are directly merged into a natural gas exhaust pipe network, and the non-permeable gas of the No. 3 membrane separator contains a large amount of helium and returns to the inlet of the No. 2 membrane separator for recovery; the regeneration medium of the TSA purification system adopts non-permeable gas of a No. 1 membrane separator, and the regeneration tail gas is merged into a natural gas tail gas pipe network.
Compared with the prior art, the utility model has the advantages of: the utility model is mainly used for purifying and preparing helium in the helium-poor natural gas and the ultra-low helium-poor natural gas according to the current situation of domestic resources, realizes the extraction of the helium-poor natural gas and obtains high-purity helium or liquid helium by adopting a multistage membrane separation and low-temperature adsorption process;
specifically, the utility model provides a set up accurate oil filter at the natural gas entry, get rid of come from the oil droplet that comes into the suspension in the natural gas of the oil spout lubrication piston compressor in the upper reaches, can avoid producing the influence to the efficiency of membrane separator; the combination of the amine washing tower and the amine washing tower is adopted for desulfurization and decarburization, the operation flexibility is high, and the method is particularly suitable for H-containing oil fields 2 S、CO 2 Under the condition of high natural gas, the amine washing tower is arranged, so that the adverse effect of solvent entrainment on a subsequent membrane separator is effectively avoided; COS hydrolysis and dehydrogenation reaction are carried out by utilizing the compression heat, so that the defect of cold and heat diseases in the process flow is avoided, and meanwhile, separate heating equipment and cooling water consumption are avoided; the 2# membrane separator and the 3# membrane separator are directly operated by adopting the pressure close to the pressure of the raw material gas, the yield and the separation performance of the membranes are high, the area required by the membrane separator can be greatly reduced, and the investment and the energy consumption are further reduced along with the reduction of the prior art; the utility model adopts the three-stage membrane separator to concentrate helium, the 3# membrane separator is not segmented, and the non-permeation gas directly circulates to the inlet of the 2# membrane separator, thereby reducing the equipment quantity, reducing the membrane investment and greatly reducing the compression power; setting TSA purification unit to purify CO before low-temperature purification 2 、H 2 The O is thoroughly removed, non-permeable tail gas is adopted for regeneration, the helium yield is high, and no N is generated 2 Impurities enter the process gas(ii) a The purification is carried out by adopting low-temperature adsorption below a liquid nitrogen temperature region, the selectivity is good, the efficiency is high, impurities Ar, ne and the like which are difficult to adsorb by a normal-temperature method can be thoroughly removed, and the product purity is effectively ensured; oxygen required by oxidative dehydrogenation is provided by adopting electrolyzed water for oxygen production, the purity is higher, and the influence of impurities such as Ar, ne and the like is avoided.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention;
FIG. 2 is a first process flow diagram of example 2 of the present invention;
FIG. 3 is a second process flow diagram of example 2 of the present invention;
FIG. 4 is a third process flow diagram of example 2 of the present invention;
fig. 5 is a fourth process flow diagram of embodiment 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
Example 1:
as shown in fig. 1, the apparatus for obtaining high purity helium gas directly from natural gas of this embodiment comprises:
the precise oil filter 1 is provided with an air inlet for inputting the helium-poor and sulfur-containing natural gas and is used for removing suspended oil drops in the natural gas;
the membrane separation system A is arranged at the downstream of the precision oil filter 1 and comprises a plurality of groups of membrane separators which are connected in series and used for carrying out permeation separation on materials to obtain non-permeation gas and permeation gas after helium gas concentration which are sent to a natural gas exhaust pipe network;
an acid gas removal unit B connected to the membrane separation system A and used for removing CO in the process gas 2 、H 2 S, removing and preventing the volatile amine liquid from being brought in;
the fine desulfurization unit C is connected to the membrane separation system A, is positioned at the downstream of the acid gas removal unit B and is used for removing sulfur-containing substances in the process gas;
a dehydrogenation unit D connected in the membrane separation system A and positioned at the downstream of the fine desulfurization unit C and used for removing residual H in the process gas 2 Removing;
a re-purification system 16 arranged at the downstream of the membrane separation system A and the dehydrogenation unit D for removing CO from the process gas residue 2 、H 2 Removing O, sulfide and the like; and
a low-temperature impurity removal unit 17 disposed downstream of the re-purification system for removing CH contained in the process gas 4 、N 2 、Ar、O 2 And Ne, etc.
The precision oil filter 1 of the embodiment may adopt a plurality of stages of filters connected in series or in parallel, and the filters may be in the form of one or more of sintered type, activated carbon adsorption type, fiber type and coalescence type.
The membrane separation system a of the present embodiment is a multi-stage series membrane separator set, and may also be connected in parallel, and may be specifically configured as required. The membrane separation system A of the embodiment comprises a 1# membrane separator 2, a 2# membrane separator 6 and a 3# membrane separator 14 which are connected in series in sequence, wherein a 1# compressor 3 for boosting the process gas is arranged between the 1# membrane separator 2 and the 2# membrane separator 6, a 2# compressor 7 for boosting the process gas is arranged between the 2# membrane separator 6 and the 3# membrane separator 14, a 2# supercharger 11 is arranged between the 3# membrane separator 14 and a re-purification system 16, and a 3# compressor 15 for boosting the process gas is arranged between the re-purification system 16. The acid gas removal unit B is arranged between the No. 1 membrane separator 2 and the No. 2 membrane separator 6 and is positioned at the downstream of the No. 1 compressor 3; the fine desulfurization unit C is arranged between the No. 2 membrane separator 6 and the No. 3 membrane separator 14 and is positioned between the No. 2 compressor 7 and the No. 2 supercharger 11; the dehydrogenation unit D is provided between the # 2 membrane separator 6 and the # 3 membrane separator 14 and downstream of the # 2 supercharger 11.
The acid gas removal unit B comprises an amine washing tower 4 and an amine washing tower 5 which are sequentially connected in series along the gas flow direction, wherein the amine washing tower 4 is used for removing a large amount of CO in the process gas 2 、H 2 S, the amine scrubber 5 is used for removing amine liquid entrained in the process gas.
The fine desulfurization unit C comprises a COS medium-temperature hydrolysis tower 8, a water cooler 9 and a fine desulfurization tower 10 which are sequentially connected in series, wherein the COS medium-temperature hydrolysis tower 8 is used for converting COS into H 2 And S, the water cooler 9 is used for cooling the process gas, and the fine desulfurization tower 10 is used for removing all sulfides. This embodiment may also be implementedAn electrolytic water device 19 for providing oxygen is arranged, and the oxygen output end of the electrolytic water device 19 is connected with the inlet of the fine desulfurization tower 10 and is used for providing required high-purity oxygen for the fine desulfurization tower 10 and the dehydrogenation unit D.
The dehydrogenation unit D comprises a catalytic dehydrogenation reactor 12 located at the upstream and a dehydrogenation cooler 13 located at the downstream, the catalytic dehydrogenation reactor 12 is used for removing residual hydrogen in the process gas, and the dehydrogenation cooler 13 is used for removing residual H 2 The latter process gas is cooled in preparation for entering the downstream membrane separator.
In this embodiment, the top of the # 1 membrane separator 2 is connected to a first pipe 01 connecting its non-permeate side to the natural gas pipe network, the top of the # 2 membrane separator 6 is connected to a second pipe 02 connecting its non-permeate side to the first pipe 01, and the top of the # 3 membrane separator 14 is connected to a third pipe 03 connecting its non-permeate side to the line between the inlets of the # 1 compressor 3 and the # 2 membrane separator 6. The re-purification system 16 is a TSA purification system comprising an adsorption unit filled with a material for adsorbing CO and a regeneration unit 2 The regeneration unit comprises a fourth pipeline 04 and a fifth pipeline 05, the fourth pipeline 04 is connected between the position near the inlet of the first pipeline 01 and the top inlet of the TSA purification system and is used for inputting part of non-permeable gas in the first pipeline 01 into the TSA purification system to blow off impurities adsorbed in the adsorbent, and the fifth pipeline 05 is connected between the top outlet of the TSA purification system and the second pipeline 02.
In this embodiment, the low-temperature impurity removal unit 17 may be a low-temperature purification unit, and may also be PSA process equipment, and the tail gas of PSA may be recycled to the inlet of the 1# compressor 3 or the inlet of the 2# compressor 7, so as to obtain high-purity helium gas. The non-permeable gas of the 3# membrane separator 14 can be directly returned to the inlet of the 2# membrane separator 6, or can be returned to the 1# compressor 2, so that the same purpose can be achieved. The amine scrubber 4 and the amine scrubber 5 may be disposed at appropriate positions between the 2# compressor 7 and the 2# supercharger 11 as needed. According to the optimization and adjustment of the processing parameters, the 2# compressor 7 and the 2# supercharger 11 can be two sections of one compressor, so that the investment can be reduced, and the occupied land can be saved. This embodiment may further include a liquefier 18 downstream of the cryogenic impurity removal unit 17 to convert helium gas into liquid helium for storage and transportation.
The process for directly obtaining high-purity helium from natural gas comprises the following steps of:
the pressure of purified natural gas from a natural gas treatment plant is 4.0MPa, the purified natural gas firstly enters a precision oil filter 1 to remove suspended oil drops brought into the natural gas from an upstream oil injection lubrication piston type compressor and then enters a No. 1 membrane separator 2;
after the permeation treatment of a No. 1 membrane separator 2, obtaining non-permeable gas (200 ppm) without helium and permeable gas (7-9 times of concentration) containing helium, wherein the non-permeable gas is almost not decompressed and is directly sent to a natural gas pipe network; the concentration of helium in the permeation gas is increased and the flow is greatly reduced when the permeation gas is near normal pressure or vacuum, the pressure is increased to 4.0MPa through a 1# compressor 3, and the permeation gas is sent to an amine washing tower 4;
amine scrubber 4 removes a substantial amount of CO 2 、H 2 S, removing amine liquid carried in the process gas through an amine washing tower 5, and entering a No. 2 membrane separator 6;
after the permeation treatment by a 2# membrane separator 6, the helium concentration in the obtained permeation gas is further concentrated (4-6 times), the pressure is increased to 2.0MPa and 100 ℃ through a 2# compressor 7, and the gas enters a COS medium temperature hydrolysis tower 8;
in a COS medium temperature hydrolysis tower 8, the COS is converted into H by using compression heat and a hydrolysis catalyst 2 S, cooling to 40 ℃ by a water cooler, and then feeding into a fine desulfurization tower to be treated with O 2 Removing sulfides to below 0.1ppm under the action of a desulfurization machine, entering a 2# supercharger 11, boosting the pressure to be close to 4.0MPa, directly entering a catalytic dehydrogenation reactor 12 at 135 ℃ to remove all hydrogen, cooling to 40 ℃ through a dehydrogenation cooler 13, and then entering a 3# membrane separator 14;
after the permeation treatment by the 3# membrane separator 14, the helium concentration in the obtained permeation gas is concentrated to the concentration (> 40%) required by the low-temperature purification unit, is boosted to 2.0MPa by the 2# supercharger 11 and is sent to a TSA purification system;
removal of residual CO in a TSA purification system 2 、H 2 O and sulfide enter a low-temperature purification unit;
removing residual CH in a low temperature purification unit in a temperature region close to the operating temperature of-200 DEG C 4 、N 2 、Ar、O 2 Ne impurity to obtain helium with purity of 99.999%;
wherein, the helium content of the non-permeable gas of the No. 1 membrane separator 2 and the No. 2 membrane separator 6 is less than 200ppm, and the non-permeable gas of the No. 3 membrane separator 14 contains a large amount of helium which returns to the inlet of the No. 2 membrane separator 6 for recovery; a regeneration medium of the TSA purification system adopts non-permeable gas of a No. 1 membrane separator 2, and the regeneration tail gas is merged into a natural gas tail gas pipe network. The helium recovery rate of the whole process is more than 93%.
Example 2:
as shown in fig. 2 to 5, the equipment for obtaining high purity helium gas directly from natural gas in this embodiment may also adopt such a structural modification, and of course, the operation principle and the basic process steps thereof are consistent with those of embodiment 1.
Claims (9)
1. An apparatus for obtaining high purity helium gas directly from natural gas, comprising:
the precise oil filter is provided with an air inlet for inputting the helium-poor sulfur-containing natural gas and is used for removing suspended oil drops in the natural gas;
the membrane separation system is arranged at the downstream of the precision oil filter, comprises at least two groups of membrane separators which are connected in series and is used for carrying out permeation separation on materials to obtain non-permeation gas sent to a natural gas tail gas pipe network and permeation gas after helium concentration;
an acid gas removal unit connected to the membrane separation system for removing CO from the process gas 2 、H 2 S, removing amine liquid;
the fine desulfurization unit is connected to the membrane separation system, is positioned at the downstream of the acid gas removal unit and is used for removing sulfur-containing substances in the process gas;
the dehydrogenation unit is connected to the membrane separation system, is positioned at the downstream of the fine desulfurization unit and is used for removing residual hydrogen in the process gas;
the secondary purification system is arranged at the downstream of the membrane separation system and the dehydrogenation unit; and
and the low-temperature impurity removal unit is arranged at the downstream of the re-purification system.
2. The apparatus of claim 1 for recovering high purity helium gas directly from natural gas, wherein: the acid gas removal unit is connected between two adjacent membrane separators in series and comprises an amine washing tower and an amine washing tower which are connected in series along the gas flow direction in sequence, wherein the amine washing tower is used for removing a large amount of CO in the process gas 2 、H 2 And S, the amine washing tower is used for removing the amine liquid entrained in the process gas.
3. The apparatus for obtaining high purity helium gas directly from natural gas as claimed in claim 1, wherein: the fine desulfurization unit is connected between two adjacent membrane separators in series and comprises a COS medium-temperature hydrolysis tower, a water cooler and a fine desulfurization tower which are connected in series in sequence, wherein the COS medium-temperature hydrolysis tower is used for converting COS into H 2 And S, the water cooler is used for cooling the process gas, and the fine desulfurization tower is used for removing all sulfides.
4. The apparatus of claim 3 for recovering high purity helium gas directly from natural gas, wherein: the device also comprises an electrolytic water device for providing oxygen, wherein the oxygen output end of the electrolytic water device is connected with the inlet of the fine desulfurization tower and is used for providing required high-purity oxygen for the fine desulfurization tower and the dehydrogenation unit.
5. The apparatus for obtaining high purity helium gas directly from natural gas as claimed in any one of claims 1 to 4, wherein: the dehydrogenation unit is connected between two adjacent membrane separators in series and comprises a catalytic dehydrogenation reactor positioned at the upstream and a dehydrogenation cooler positioned at the downstream, and the catalytic dehydrogenation reactor is used for removing residual H in the process gas 2 Removing hydrogen, wherein the dehydrogenation cooler is used for removing residual H 2 The latter process gas is cooled in preparation for entering the downstream membrane separator.
6. The apparatus for obtaining high purity helium gas directly from natural gas as claimed in any one of claims 1 to 4, wherein: the membrane separation system comprises a 1# membrane separator, a 2# membrane separator and a 3# membrane separator which are sequentially connected in series, wherein a 1# compressor for boosting the process gas is arranged between the 1# membrane separator and the 2# membrane separator, a 2# compressor and a 2# supercharger for boosting the process gas are arranged between the 2# membrane separator and the 3# membrane separator, and a 3# compressor for boosting the process gas is arranged between the 3# membrane separator and the re-purification system.
7. The apparatus of claim 6 for obtaining high purity helium gas directly from natural gas, wherein: the acid gas removal unit is arranged between the 1# membrane separator and the 2# membrane separator and is positioned at the downstream of the 1# compressor; the fine desulfurization unit is arranged between the 2# membrane separator and the 3# membrane separator and is positioned between the 2# compressor and the 2# supercharger; the dehydrogenation unit is arranged between the No. 2 membrane separator and the No. 3 membrane separator and is positioned at the downstream of the No. 2 booster.
8. The apparatus of claim 6 for obtaining high purity helium gas directly from natural gas, wherein: the top of the No. 1 membrane separator is connected with a first pipeline connecting the non-permeating gas side of the No. 1 membrane separator with a natural gas pipe network, the top of the No. 2 membrane separator is connected with a second pipeline connecting the non-permeating gas side of the No. 2 membrane separator with the first pipeline, and the top of the No. 3 membrane separator is connected with a third pipeline connecting the non-permeating gas side of the No. 3 membrane separator with a pipeline between the No. 1 compressor and the inlet of the No. 2 membrane separator.
9. The apparatus of claim 8 for recovering high purity helium gas directly from natural gas, wherein: the re-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 material for adsorbing CO 2 Water, heavy hydrocarbon and partial sulfide adsorbent, the regeneration unit comprises a fourth pipeline and a fifth pipeline, the fourth pipeline is connected to the inlet of the first pipeline and is attached to the inlet of the first pipelineAnd between the near-top inlet of the TSA purification system, the fifth pipeline is connected between the top outlet of the TSA purification system and the second pipeline, and is used for inputting part of the non-permeable gas in the first pipeline into the TSA purification system to blow off impurities adsorbed in the adsorbent.
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