CN115125042A - Process for the fine removal of thiol-type organic sulfur - Google Patents
Process for the fine removal of thiol-type organic sulfur Download PDFInfo
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- CN115125042A CN115125042A CN202110321838.0A CN202110321838A CN115125042A CN 115125042 A CN115125042 A CN 115125042A CN 202110321838 A CN202110321838 A CN 202110321838A CN 115125042 A CN115125042 A CN 115125042A
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 125000001741 organic sulfur group Chemical group 0.000 title description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 223
- 239000003345 natural gas Substances 0.000 claims abstract description 112
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 36
- 230000023556 desulfurization Effects 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 34
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 21
- 230000007062 hydrolysis Effects 0.000 claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 230000018044 dehydration Effects 0.000 claims abstract description 12
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 21
- 238000011069 regeneration method Methods 0.000 claims description 15
- 230000008929 regeneration Effects 0.000 claims description 14
- -1 alcohol amine Chemical class 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000007517 polishing process Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims 3
- 239000000243 solution Substances 0.000 description 68
- 238000006243 chemical reaction Methods 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 150000003573 thiols Chemical class 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Gas Separation By Absorption (AREA)
- Industrial Gases (AREA)
Abstract
The invention discloses a method for removing thiol organic sulfur, which comprises the following steps: filling nano mercaptan hydrolysis catalysts in tube passes of a plurality of reactors; introducing natural gas to be purified containing mercaptan organic sulfur into a tube pass to generate hydrogen sulfide; wherein, a plurality of open pores are arranged on the tube pass, and the gas in the tube pass flows into the shell pass of the reactor through the plurality of open pores; introducing a desulfurization solution into the shell side of each reactor for absorbing hydrogen sulfide to form purified natural gas; introducing the purified natural gas flowing out of the natural gas outlet of the reactor into a dehydration device; and introducing the natural gas dehydrated by the dehydration device into a natural gas pipe network. Because the natural gas to be purified containing the mercaptan organic sulfur fully reacts with the nano mercaptan hydrolysis catalyst in the reactor, the high-efficiency fine removal of the mercaptan organic sulfur in the natural gas is realized, and the natural gas with higher quality is formed.
Description
Technical Field
The invention relates to the technical field of natural gas purification, in particular to a method for removing thiol organic sulfur.
Background
In 2018, GB17820-2018 natural gas is officially issued by the nation, and the total sulfur content of the natural gas entering a long-distance pipeline is from 200mg/m in the national standard of the natural gas 3 Reduced to 20mg/m 3 The content of hydrogen sulfide is 20mg/m 3 Reduced to 6mg/m 3 . According to the standard, the total sulfur content and the hydrogen sulfide content in commercial natural gas produced by most sulfur-containing natural gas purification plants at present cannot meet the requirement of the standard, so that the development of gas quality upgrading and reconstruction are imperative for the sulfur-containing natural gas purification plants, and the core point is in deep removal of the hydrogen sulfide and organic sulfur so as to realize the stable standard of the total sulfur and the hydrogen sulfide content.
At present, the following methods are commonly used for removing organic sulfur in natural gas: the first type is a solvent method, which adopts MDEA (methyldiethanolamine) or a formula-type selective desulfurization solvent based on MDEA, or adopts a physical formula solution or a strong alkaline chemical solution with high capability of removing organic sulfur, so as to purify natural gas. The second type is a solid adsorption method, which adopts a molecular sieve or active carbon and other solid adsorbents to purify natural gas. The third type is a catalytic method, which adopts a high-efficiency catalyst aiming at the hydrolysis of COS (carbonyl sulfide) to realize the purification of natural gas.
In the process of implementing the present invention, the inventor finds that the related art has at least the following problems:
the solvent method has a limited removal rate of organic sulfur, especially lower removal rate of thiol organic sulfur. The solid adsorption method needs to adopt an operation mode of adsorption and regeneration in the using process, the regeneration process not only has higher energy consumption, but also can lead to the regeneration of COS to carry out advanced treatment on the COS, and the solid adsorbent has limited adsorption capacity and higher cost of the method and operation cost. In the catalytic method, the temperature required by the reaction is higher, namely the reaction temperature is usually controlled at 150-400 ℃, so that purified natural gas can enter a reactor after being heated to a high temperature, and meanwhile, purified gas containing hydrogen sulfide after hydrolysis needs to be cooled and then is absorbed by alkaline solution. The above methods can not realize deep removal of thiol organic sulfur in natural gas.
Disclosure of Invention
In view of this, the present application provides a method for fine removal of thiol organic sulfur, which can achieve deep removal of thiol organic sulfur in natural gas.
Specifically, the method comprises the following technical scheme:
the embodiment of the application provides a thiol organic sulfur fine removal method, which comprises the following steps:
filling nano mercaptan hydrolysis catalysts in tube passes of a plurality of reactors;
introducing natural gas to be purified containing mercaptan organic sulfur into the tube pass to generate hydrogen sulfide; the tube pass is provided with a plurality of open pores, and gas in the tube pass flows into the shell pass of each reactor through the plurality of open pores;
introducing a desulfurization solution into the shell side of each of the reactors for absorbing the hydrogen sulfide to form a purified natural gas;
introducing the purified natural gas flowing out of the natural gas outlet of the reactor into a dehydration device;
and introducing the natural gas dehydrated by the dehydration device into a natural gas pipeline network.
Optionally, the method further comprises: introducing the reacted hot rich liquid flowing out of a hot rich liquid outlet of the reactor into a lean rich liquid heat exchange unit;
and introducing cold rich liquid formed after heat exchange of the lean rich liquid heat exchange unit into a regeneration unit.
Optionally, the concentration of the desulfurization solution is 30% to 80%.
Optionally, the plurality of reactors comprises a first reactor and a second reactor;
the first reactor and the second reactor are connected in series through a pipeline.
Optionally, when the concentration of mercaptan in the natural gas to be purified is 20-40mg/m 3 Closing the first reactor and opening the second reactor;
when the concentration of mercaptan in the natural gas to be purified is 40-60mg/m 3 And then opening the first reactor and the second reactor.
Optionally, the nano mercaptan hydrolysis catalyst contains one or more components of alumina, titania, nano cobalt, nano nickel, nano molybdenum or nano palladium.
Optionally, the temperature within each of the reactors is from 80 to 130 ℃.
Optionally, the desulfurization solution includes an alcohol amine solvent or a physicochemical solvent.
Optionally, a plurality of baffles are arranged on the inner wall of each reactor.
Optionally, the tube side comprises a first tube bank and a second tube bank;
the first tube bank and the second tube bank are connected by a first conduit;
the pipe wall of the second pipe bundle is provided with a plurality of open air holes in the direction towards the plurality of baffle plates;
and after the natural gas to be purified flows through the first tube bundle, the first pipeline and the second tube bundle in sequence, the natural gas flows out of the plurality of open pores and reacts with the desulfurization solution.
The technical scheme provided by the embodiment of the application has the beneficial effects that at least:
the natural gas to be purified containing the thiol organic sulfur fully reacts with the nano mercaptan hydrolysis catalyst in the reactor, and the generated hydrogen sulfide is fully absorbed by the desulfurization solution, so that the purification of the natural gas is realized. Because the catalyst is a nano-scale catalyst, the high-efficiency fine removal of the mercaptan organic sulfur in the natural gas can be realized, and the natural gas with higher quality is formed.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic diagram of a mercaptan organosulfur polishing process provided in an embodiment of the present application;
fig. 2 is a schematic view of a reactor in a mercaptan organosulfur polishing process according to an embodiment of the present application.
The reference numerals in the figures denote:
a-a reactor;
b-tube pass;
1-a first reactor;
2-a second reactor;
101-natural gas inlet;
102-a natural gas outlet;
103-hot rich liquid outlet;
104-hot lean liquor inlet;
105-a first tube bundle;
106-a second tube bundle;
107-a first conduit;
108-shell side;
109-opening air holes;
3-a dewatering device;
4-a lean-rich liquid heat exchange unit;
5-a regeneration unit;
6-hot lean first valve;
7-hot lean liquor second valve;
8-third valve of hot lean liquor;
9-cold lean liquor valve;
10-hot pregnant solution first valve;
11-a second valve for hot pregnant solution;
12-third valve of hot pregnant solution;
13-a first inlet channel valve;
14-a second inlet channel valve;
15-a first outlet channel valve;
16-a second outlet channel valve;
17-regeneration unit valve;
18-baffle plate.
With the above figures, there are shown specific embodiments of the present application, which will be described in more detail below. These drawings and written description are not intended to limit the scope of the inventive concepts in any manner, but rather to illustrate the inventive concepts to those skilled in the art by reference to specific embodiments.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Before the embodiments of the present application are described in further detail, the positional terms referred to in the examples of the present application are only used to clearly describe the thiol organosulfur purification method according to the examples of the present application with reference to the positions shown in the drawings, and do not have a meaning of limiting the scope of the present application.
Embodiments of the present application will be described in further detail below with reference to the accompanying drawings.
Referring to fig. 1 and 2, an embodiment of the present invention provides a method for removing thiol organosulfur compounds, the method comprising the steps of:
the nano mercaptan hydrolysis catalyst is filled in a tube pass B in a plurality of reactors A.
Introducing natural gas to be purified containing thiol organic sulfur into a tube pass B in a reactor A to generate hydrogen sulfide; wherein, a plurality of open pores 109 are arranged on the tube pass B, and the gas in the tube pass B flows into the shell pass 108 of the reactor A through the plurality of open pores 109.
The desulfurization solution is introduced into the shell side 108 of each reactor a for absorption of hydrogen sulfide to form a purified natural gas.
The purified natural gas flowing out of the natural gas outlet 102 of the reactor a is introduced into the dehydration apparatus 3.
And introducing the natural gas dehydrated by the dehydration device 3 into a natural gas pipeline network.
By utilizing the method for finely removing the thiol organic sulfur, the natural gas to be purified containing the thiol organic sulfur fully reacts with the nano thiol hydrolysis catalyst in the reactor A, and the generated hydrogen sulfide is fully absorbed by the desulfurization solution, so that the natural gas can be purified. Meanwhile, the catalyst is a nano-scale catalyst, so that the high-efficiency fine removal of the mercaptan organic sulfur in the natural gas can be realized, and the natural gas with higher quality is formed.
The thiol organosulfur refining process provided in the examples of the present application is described in more detail below.
In some embodiments herein, the nano thiol hydrolysis catalyst may be a nano noble metal low temperature thiol hydrolysis catalyst.
In some embodiments of the present application, the temperature of the natural gas to be purified at the inlet of the reactor a is preferably in the range of 30 to 100 ℃.
It is understood that in this temperature range, the effect of absorbing hydrogen sulfide is better, and thus the effect of removing thiol organic sulfur is also better.
In some embodiments of the present application, the gas space velocity in the reactor A is preferably 1000- -1 。
It should be noted that the gas space velocity refers to the ratio of the volume of the process gas to the volume of the catalyst per unit time. Under the gas airspeed, the natural gas to be purified can fully react with the catalyst in the reactor A, so that the high-efficiency removal of the mercaptan organic sulfur in the natural gas can be realized.
As shown in fig. 1, in some embodiments of the present application, the method further comprises: introducing the reacted hot rich liquid flowing out of a hot rich liquid outlet 103 of the reactor A into a lean rich liquid heat exchange unit 4; and introducing cold rich liquid formed after heat exchange of the lean rich liquid heat exchange unit 4 into a regeneration unit 5.
Note that the lean-rich liquid heat exchange unit 4 is a device that transfers part of the heat of the hot fluid to the cold fluid. The regeneration unit 5 is a device for separating out the sulfuration hydrogen contained in the reacted desulfurization solution, so that the desulfurization solution can be regenerated and recycled.
The pregnant solution is a solution containing hydrogen sulfide formed after the desulfurization solution absorbs the hydrogen sulfide; the lean solution is a solution containing no hydrogen sulfide or only a small amount of hydrogen sulfide after hydrogen sulfide in the reacted solution is separated out. Depending on the temperature of the rich or lean liquor itself, it may be further referred to as hot or cold rich liquor, hot or cold lean liquor. The solution entering the lean-rich liquor heat exchange unit 4 comprises hot rich liquor and cold lean liquor.
It will be appreciated that the solution formed is now a hot rich solution, since some heat is generated during the reaction to absorb hydrogen sulphide. The temperature of the hot rich liquid is reduced after the heat exchange of the lean rich liquid heat exchange unit 4, and the solution formed at this time is the cold rich liquid. After the hydrogen sulfide is removed from the cold rich liquid through the regeneration unit 5, the regenerated solution is a cold lean liquid. The cold lean solution circularly enters the lean-rich solution heat exchange unit 4 through a pipeline, and the solution formed at the moment is the hot lean solution because the heat of the hot rich solution in the lean-rich solution heat exchange unit 4 is transferred to the cold lean solution. The hot lean solution is then introduced directly into the shell side 108 of each reactor a through a pipeline to react and absorb the hydrogen sulfide. Because the lean and rich liquor heat exchange unit 4 is arranged, the cold lean liquor does not need to be heated independently by other heat sources and then is introduced into the reactor A for reaction, and the cold lean liquor can be regenerated, so that the desulfurization solution can be recycled, the energy is saved, the consumption is reduced, the cost is saved, and the operation process of the method is simpler.
In some embodiments of the present application, the lean-rich liquid heat exchange unit 4 may be a coil heat exchanger.
In some embodiments of the present application, the concentration of the desulfurization solution is 30% to 80%.
The concentration of the desulfurization solution refers to the content of amine in the desulfurization solution. The concentration of the desulfurization solution is selected according to the content of mercaptan in the natural gas to be purified, and the higher the content of mercaptan is, the higher the concentration of the selected desulfurization solution is; the lower the mercaptan content, the lower the concentration of the desulfurization solution selected.
As shown in fig. 1, in some embodiments of the present application, the plurality of reactors a includes a first reactor 1 and a second reactor 2. Meanwhile, the first reactor 1 and the second reactor 2 are connected in series through a pipe.
It should be noted that the number of the reactors a may be two or more, the selection of the specific number is determined according to the content of the mercaptan concentration in the natural gas to be purified, and the structure in each reactor is the same. When more than two reactors are arranged, the reactors are connected in series through pipelines in sequence.
In some embodiments of the present application, the mercaptan concentration in the natural gas to be purified is 20-40mg/m 3 At this time, the first reactor 1 is closed and the second reactor 2 is opened.
When the concentration of mercaptan in the natural gas to be purified is 40-60mg/m 3 At this time, the first reactor 1 and the second reactor 2 are opened.
It should be noted that, because the method is to selectively open or close the reactor a according to the concentration of mercaptan, unnecessary resource investment can be reduced while ensuring high-efficiency desulfurization, and the purposes of saving resources and reducing cost are achieved.
In some embodiments of the present disclosure, the nano mercaptan hydrolysis catalyst comprises one or more of alumina, titania, nano cobalt, nano nickel, nano molybdenum, or nano palladium.
In some embodiments of the present application, the temperature in each reactor A is in the range of 80 to 130 ℃.
It should be noted that the nano mercaptan hydrolysis catalyst can be reused, and the catalyst is nano-sized, so that the catalyst has good performance, and can sufficiently catalyze the natural gas to be purified without high reaction temperature, thereby saving energy while purifying the natural gas. In addition, when the nano mercaptan hydrolysis catalyst is in the reaction temperature range, the catalyst has high activity and best reaction performance, so that the high-efficiency removal of the mercaptan organic sulfur in the natural gas can be realized.
In some embodiments of the present application, the desulfurization solution includes an alcohol amine solvent or a physicochemical solvent.
It should be noted that when the alcohol amine solvent is used to absorb hydrogen sulfide, only chemical reaction occurs; when the physical chemical solvent is used for absorbing the hydrogen sulfide, the physical absorption is firstly carried out, and then the chemical reaction is carried out. The physical-chemical solvent includes not only a chemical solvent, i.e., an alcohol amine solvent, but also other physical solvents such as sulfolane, and is a mixture of the physical solvent and the chemical solvent. It is understood that, during the use process of the alcohol amine solvent or the physical chemical solvent, a certain amount of water is added to dilute the alcohol amine solvent or the physical chemical solvent according to the requirement, so as to form a desulfurization solution with the amine content of 30-80%.
As shown in FIG. 2, in some embodiments of the present application, a plurality of baffles 18 are provided on the inner wall of each reactor A.
In some embodiments of the present application, each baffle 18 is angled, as shown in FIG. 2, and may be at an angle of 45 degrees.
It should be noted that each baffle 18 is fixed at one end to the inner wall of each reactor a and extends at the other end into the inner cavity of the reactor a. The size of the baffle 18 is set according to the size of the inside of the reactor A.
Because the arrangement of the plurality of baffle plates 18 can increase the disturbance of gas, namely, the hydrogen sulfide gas flowing out of the open pores on the tube pass B of each reactor A is disturbed better, the hydrogen sulfide gas can fully react with the desulfurization solution, and the hydrogen sulfide gas is fully absorbed, thereby realizing the deep desulfurization of the natural gas to be purified.
As shown in fig. 2, in some embodiments of the present application, the natural gas outlet 102 of each reactor a is disposed on a side adjacent to the natural gas inlet 101, and the natural gas outlet 102 is located on an opposite side of the plurality of baffles 18.
It will be appreciated that the natural gas to be purified enters from the natural gas inlet 101, passes through the pipeline into the tube pass B to react with the catalyst, and finally the purified natural gas flows out from the natural gas outlet 102. Since the natural gas outlet 102 is arranged at a position which enables the natural gas to be purified to travel the farthest distance in each reactor a, hydrogen sulfide generated by the natural gas to be purified can be fully absorbed, and the desulfurization effect is better.
In some embodiments of the present application, each reactor a may include a plurality of tube bundles, preferably 2 tube bundles, in the tube pass B, and the plurality of tube bundles are sequentially connected by a pipeline.
It is preferable that 2 bundles of tubes ensure efficient desulfurization and that the cost for the removal of the thiol organosulfur compounds is low.
As shown in fig. 2, in some embodiments of the present application, tube pass B includes a first tube bank 105 and a second tube bank 106; first tube bank 105 and second tube bank 106 are connected by first conduit 107; the tube wall of the second tube bundle 106 is provided with a plurality of open air holes 109 in the direction towards the plurality of baffles 18; after flowing through the first tube bundle 105, the first pipeline 107 and the second tube bundle 106 in sequence, the natural gas to be purified flows out from the plurality of open pores 109 and reacts with the desulfurization solution.
It can be understood that, since the natural gas to be purified is transported to the first tube bundle 105 through the pipeline, starts to perform catalytic reaction with the nano-mercaptan hydrolysis catalyst, and then enters the second tube bundle 106 through the first pipeline 107 to perform catalytic reaction, the natural gas to be purified can fully react with the nano-mercaptan hydrolysis catalyst in the tube pass B of the reactor a, thereby realizing efficient removal of the mercaptan organic sulfur.
In some embodiments of the present application, the total sulfur concentration in the purified natural gas exiting the outlet of the second reactor 2 is monitored to be less than 20mg/m 3 The product gas is considered to meet the requirements of new standards regulated by the state.
When more than two reactors are used, each reactor is connected in sequence, the natural gas outlet of the previous reactor is connected with the natural gas inlet of the next reactor through a pipeline, and gas is introduced into the tube pass of the next reactor, so that a series structure is formed; and a valve is arranged on each pipeline connecting the front reactor and the rear reactor. The outlet of the endmost reactor is connected to the dehydration unit 3 by a pipeline, and the monitored gas is purified natural gas flowing out of the outlet of the endmost reactor.
In some embodiments of the present application, a monitoring method comprises: the total sulfur concentration in the purified natural gas flowing out of the outlet of the reactor at the tail end is sampled every hour by an operator, so that manual monitoring is realized; or real-time monitoring the total sulfur concentration in the purified natural gas flowing out of the outlet of the reactor by using real-time on-line monitoring equipment connected with the endmost reactor.
By utilizing the method for finely removing the thiol organic sulfur, the natural gas to be purified containing the thiol organic sulfur fully reacts with the nano thiol hydrolysis catalyst in the reactor A, and the generated hydrogen sulfide is fully absorbed by the desulfurization solution, so that the natural gas can be purified. Meanwhile, the catalyst is a nano-scale catalyst, so that the high-efficiency fine removal of the mercaptan organic sulfur in the natural gas can be realized, and the natural gas with higher quality is formed. In addition, the purified natural gas is monitored, so that the purified natural gas can be ensured to meet the national natural gas standard.
The flow of the method for removing mercaptan-type organic sulfur from the organic sulfur compounds provided in the embodiments of the present invention will be described in more detail with reference to practical application procedures.
As shown in fig. 1, in some embodiments of the present application, a first hot lean valve 6 and a second hot lean valve 7 are provided in the apparatus.
It is understood that the hot lean first valve 6 is the overall valve before the hot lean liquid is introduced into the reactor a. The hot lean liquid second valve 7 is a branch valve for introducing the hot lean liquid into the second reactor 2. A branch valve (not shown) may be provided in the pipe for introducing the hot lean solution into the first reactor 1.
With reference to fig. 1 and 2, the overall steps of the method are as follows:
the first step is as follows: filling a nano mercaptan hydrolysis catalyst into the tube pass B of each reactor A for carrying out catalytic reaction; and opening the first valve 6, the hot lean liquid second valve 7 and a hot lean liquid branch valve in front of the inlet of the first reactor 1, and introducing hot lean liquid with a certain temperature into the shell side 108 from the hot lean liquid inlet 104 of each reactor A through a pipeline respectively for absorbing hydrogen sulfide gas in the catalyzed natural gas flowing out of the open pores on the tube side B of each reactor A. And opening a first inlet channel valve 13 and a second inlet channel valve 14 which are respectively arranged in front of the inlet of the first reactor 1 and the inlet of the second reactor 2, and respectively introducing the natural gas to be purified into the tube side of the first reactor 1 and the tube side of the second reactor 2 through two parallel pipelines to start reaction.
It should be noted that when the concentration of mercaptan in the natural gas to be purified is 20-40mg/m 3 When the reaction is carried out, the first inlet channel valve 13 is closed, the second inlet channel valve 14 is opened, and the gas only enters the second reactor 2 for reaction; when the concentration of mercaptan in the natural gas to be purified is 40-60mg/m 3 When the first inlet channel valve 13 and the second inlet channel valve 14 are opened, the natural gas to be purified respectively enters the first reactor 1 and the second reactor 2 for reaction.
The first outlet passage valve 15 on the pipeline connecting the first reactor 1 and the second reactor 2 is opened, the purified natural gas in the first reactor 1 flows out through the outlet of the first reactor 1 and is introduced into the tube pass of the second reactor 2 through the inlet of the second reactor 2, so that the secondary purification of the natural gas introduced into the first reactor 1 can be realized.
The second step: and opening a second outlet channel valve 16 on a pipeline connecting the outlet of the second reactor 2 and the dehydration device 3, enabling the purified natural gas in the second reactor 2 to flow out of the outlet of the second reactor 2 and enter the dehydration device 3 for dehydration, and introducing the dehydrated natural gas into a natural gas pipe network.
A certain amount of heat is generated during the reaction, and the desulfurization solution with an increased temperature, i.e., the hot rich solution, flows out from the hot rich solution outlet 103 of each reactor a after the reaction. The hot rich liquid outflow pipelines of the first reactor 1 and the second reactor 2 are arranged in parallel, and the collected hot rich liquid enters the lean rich liquid heat exchange unit 4. Meanwhile, the low-temperature desulfurization solution before the reaction, i.e., the cold lean solution, enters the lean-rich solution heat exchange unit 4 through a pipeline.
It will be appreciated that the hot rich liquor in the lean-rich liquor heat exchange unit 4 transfers its heat to the cold lean liquor, thereby forming hot lean liquor and cold rich liquor. The hot lean solution directly flows through each hot lean solution valve through an outlet of the lean rich solution heat exchange unit 4 and is respectively introduced into the first reactor 1 and the second reactor 2 for absorbing hydrogen sulfide gas in the reactor A without independently heating other heat sources. And the cold rich solution enters the regeneration unit 5 through the other outlet of the lean-rich solution heat exchange unit 4 to regenerate the cold lean solution, the cold lean solution flows out of the outlet of the regeneration unit 5, and then circularly enters the lean-rich solution heat exchange unit 4 through a pipeline to form a hot lean solution, and the hot lean solution is introduced into the first reactor 1 and the second reactor 2 to react.
The hot rich liquid outflow lines of the first reactor 1 and the second reactor 2 are provided with a hot rich liquid first valve 10 and a hot rich liquid second valve 11, respectively. A third valve 12 for the hot rich liquid is arranged before the hot rich liquid enters the lean rich liquid heat exchange unit 4. A cold barren liquor valve 9 is arranged on the pipeline for introducing the cold barren liquor. And a third valve 8 for hot lean solution is arranged behind the outlet of the lean-rich solution heat exchange unit 4. A regeneration unit valve 17 is arranged on a pipeline for the cold rich liquid to enter the regeneration unit 5.
The third step: sampling and monitoring the total sulfur concentration in the purified natural gas flowing out from the outlet of the second reactor 2, when the total sulfur concentration is lower than 20mg/m 3 The product gas is considered to meet the requirements of new standards regulated by the state.
In summary, with the method for fine removal of thiol organic sulfur, firstly, the natural gas to be purified containing thiol organic sulfur fully reacts with the nano thiol hydrolysis catalyst in the plurality of reactors A, when the sulfur concentration is high, the natural gas can be purified for the second time, and the generated hydrogen sulfide can be fully absorbed by the desulfurization solution; secondly, the catalyst is a nano-scale catalyst, so that the high-efficiency fine removal of the mercaptan organic sulfur in the natural gas to be purified can be realized, and the natural gas with higher quality is formed. The nano-scale catalyst can be recycled, so that energy can be saved and cost can be reduced. Further, by arranging the lean rich liquid heat exchange unit 4 and the regeneration unit 5, the reactants are not required to be additionally heated by other heat sources, and the desulfurization solution for absorbing hydrogen sulfide can be regenerated, so that the energy is saved, and the cost is reduced. In addition, the method also monitors the purified natural gas, and ensures that the purified natural gas meets the national natural gas standard.
In this application, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. The term "plurality" means two or more unless expressly limited otherwise.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the present application disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only.
It will be understood that the present application is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.
Claims (10)
1. A method for the removal of organosulfur mercaptans, the method comprising the steps of:
filling nano mercaptan hydrolysis catalysts in tube passes (B) in a plurality of reactors (A);
introducing natural gas to be purified containing mercaptan organic sulfur into the tube pass (B) to generate hydrogen sulfide; wherein a plurality of open pores (109) are arranged on the tube side (B), and the gas in the tube side (B) flows into the shell side (108) of the reactor (A) through the plurality of open pores (109);
introducing a desulfurization solution into said shell side (108) of each of said reactors (a) for absorbing said hydrogen sulfide to form a purified natural gas;
introducing the purified natural gas flowing out of the natural gas outlet (102) of the reactor (A) into a dehydration device (3);
and introducing the natural gas dehydrated by the dehydration device (3) into a natural gas pipeline network.
2. The method of organosulfur polishing of claim 1, further comprising: introducing the reacted hot rich liquid flowing out of a hot rich liquid outlet (103) of the reactor (A) into a lean rich liquid heat exchange unit (4);
and introducing cold rich liquid formed after heat exchange of the lean rich liquid heat exchange unit (4) into a regeneration unit (5).
3. The method of organosulfur polishing of claim 1, wherein the concentration of the desulfurization solution is 30% to 80%.
4. The organosulfur upgrading process according to claim 1, wherein the plurality of reactors (a) includes a first reactor (1) and a second reactor (2);
the first reactor (1) and the second reactor (2) are connected in series through a pipeline.
5. The method of organosulfur polishing as recited in claim 4,
when the concentration of mercaptan in the natural gas to be purified is 20-40mg/m 3 Closing the first reactor (1) and opening the second reactor (2);
when the concentration of mercaptan in the natural gas to be purified is 40-60mg/m 3 While opening the first reactor (1) and the second reactor (2).
6. The method of claim 1, wherein the nano mercaptan hydrolysis catalyst comprises one or more components selected from the group consisting of alumina, titania, nano cobalt, nano nickel, nano molybdenum, and nano palladium.
7. The organosulfur polishing process according to claim 1, wherein the temperature in each of the reactors (a) is 80 to 130 ℃.
8. The method of claim 1, wherein the desulfurization solution comprises an alcohol amine solvent or a physicochemical solvent.
9. The method for organosulfur upgrading of claim 1, wherein a plurality of baffles (18) are provided on the inner wall of each of the reactors (a).
10. The organosulfur upgrading process of claim 9, wherein the tube side (B) comprises a first tube bundle (105) and a second tube bundle (106);
-the first tube bank (105) and the second tube bank (106) are connected by a first duct (107);
the tube wall of the second tube bank (106) is provided with the plurality of open pores (109) in a direction towards the plurality of baffles (18);
the natural gas to be purified flows through the first tube bank (105), the first pipeline (107) and the second tube bank (106) in sequence, then flows out of the plurality of open pores (109) and reacts with the desulfurization solution.
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