CN111925847A - Process for removing organic sulfur in natural gas by hydrogenation - Google Patents
Process for removing organic sulfur in natural gas by hydrogenation Download PDFInfo
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Abstract
The invention relates to a process for removing organic sulfur in natural gas by hydrogenation, wherein the system of the process comprises a sulfur-containing natural gas solvent coarse removal unit, a wet purified gas heat exchanger, a hydrogenation reactor preheater, a static mixer, a hydrogenation reactor and a hydrogen source device, wherein the sulfur-containing natural gas solvent coarse removal unit is connected with the wet purified gas heat exchanger; the bottom outlet of the hydrogenation reactor is connected with a wet purified gas cooler, the wet purified gas heat exchanger is connected with the wet purified gas cooler, and the wet purified gas cooler is connected with a wet purified gas fine desulfurization unit and the like. The method is to completely convert organic sulfur which is difficult to remove in natural gas into H which is easy to remove by hydrogenation2S, the sulfur content in the product natural gas can not only meet the national standard, but also can even meet the foreign product natural gas standard.
Description
Technical Field
The invention belongs to the field of purification and desulfurization in the natural gas industry, relates to a process technology for removing natural gas with high content of various organic sulfur, and particularly relates to a process for removing organic sulfur in natural gas through hydrogenation.
Background
At present, the removal of organic sulfur in natural gas is a technical problem, and the conventional amine desulphurization process is difficult to deeply remove the organic sulfur in the natural gas, such as mercaptan (methyl mercaptan, ethyl mercaptan, etc.), COS, CS2And various forms of organic sulfur such as thioether and thiophene, especially the national standard 'natural gas' GB17820-2018 has more and more strict requirements on the sulfur content in the natural gas, and at present, no process method capable of deeply removing various organic sulfur in the natural gas exists at home and abroad.
All the year roundThe environmental protection concept of countries in the world is stronger and stronger, and the reduction of the sulfur content in natural gas is the development trend of countries in the world. The raw material natural gas or associated gas of most gas fields in the world contains H2S, the conventional desulfurization process mainly comprises a solvent desulfurization process, a solid desulfurization process and a membrane separation desulfurization process.
The solvent desulfurization process is the most widely used process in the field of natural gas purification at home and abroad, has approximately the same flow method, mainly lies in the difference of solvents, and is divided into a chemical solvent, a physical solvent and a chemical-physical solvent. Mature and simple solvent desulfurization process and capability of treating H in natural gas2The S removal effect is good, but the following defects exist: CO 22The co-absorption rate is high, the adsorptivity to heavy hydrocarbon is strong, the selectivity is not good enough, especially physical solvent and physical chemical solvent; can absorb less kinds of organic sulfur, has good absorption effect on only one or two kinds of organic sulfur, and if the raw material gas contains COS and CS at the same time2And various organic sulfur such as mercaptan, thioether, thiophene, etc., the absorption effect is poor; the desorption heat is large during solvent regeneration, and the energy consumption is high; the absorption efficiency for organic sulfur is low, usually less than 80%. In the process of removing organic sulfur by a solvent method, a physical and chemical solvent method such as Sufinol-D, Sulfinol-M and the like is mostly applied at present, but the organic sulfur removal rate of the method is not high, particularly the removal rate of mercaptan is low, and the engineering requirements of high organic sulfur content and high purification degree requirement cannot be met.
The solid desulfurization process is suitable for the working condition of low sulfur content, and the common adsorbents comprise iron oxide, molecular sieves and activated carbon-carried oxidants. At present, the process for removing the organic sulfur by using the molecular sieve in the natural gas purification is mainly mercaptan removal, the molecular sieve for purifying the natural gas mercaptan is mainly 13X and 5A molecular sieves, and the process for removing the mercaptan by using the molecular sieve is usually applied to the fine removal of the mercaptan in the purified gas after the solvent desulfurization, and the application performance of removing a large amount of mercaptan by using the molecular sieve is not realized. The activated carbon can be used for mercaptan and CS2But the performance of the activated carbon in the industrial application of natural gas purification and mercaptan absorption is not collected at present.
The membrane separation desulfurization process is often used for a crude desulfurization process, and has fewer industrial application cases.
Current mature natural gas desulfurization process for H2The S removal has good effect, and the sulfur content in the natural gas can reach the technical requirement (H) of the national standard 'natural gas' (GB17820-2012)2S≤20mg/Nm3The total sulfur content is less than or equal to 200mg/Nm3) However, the requirement (H) of the total sulfur content of the product natural gas in the natural gas (GB17820-2018) is to be met2S≤6mg/Nm3The total sulfur content is less than or equal to 20mg/Nm3) However, it is very difficult, especially under the conditions of high content and many kinds of organic sulfur, the above process is not ideal for removing organic sulfur, and how to reasonably, economically and effectively remove organic sulfur in natural gas becomes a problem to be seriously treated. According to research, most of the organic sulfur in the engineering raw material natural gas is a large amount of mercaptan, but it is gradually found that the individual engineering raw material natural gas contains higher COS or CS2Even some of the raw natural gas of oil and gas fields contain a lot of thioethers and thiophenes. In the face of more and more working conditions of high organic sulfur content and complex composition of raw material natural gas in engineering projects, particularly COS, thiophene, thioether and CS2The process of using high-content raw gas to meet the increasingly strict standard is a very difficult choice.
Disclosure of Invention
The present invention aims at solving the above problems and provides a process for removing organic sulfur from natural gas by hydrogenation, which employs two-stage organic sulfur removal technology (rough removal and fine removal) to completely convert organic sulfur difficult to remove from natural gas by hydrogenation into easily removed H2S, organic sulfur (methyl mercaptan is less than or equal to 260, ethyl mercaptan is less than or equal to 200, propyl mercaptan is less than or equal to 60, COS is less than or equal to 300, thiophene is less than or equal to 60, and CS is added into natural gas2Less than or equal to 60, less than or equal to 60 of thioether and unit mg/Nm3) Almost completely removing the hydrogen so that the natural gas product treated by the system can reach H2S≤3mg/m3The total sulfur content is less than or equal to 8mg/m3) The sulfur content in the product natural gas can not only meet the national standard, but also can even meet the more rigorous requirements of the product natural gas standard abroad.
The invention also provides a system for removing organic sulfur in natural gas by hydrogenation, which achieves the aim.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a system for removing organic sulfur in natural gas by hydrogenation is used for H in wet purified gas after hydrogenation2The system comprises a sulfur-containing natural gas solvent crude removal unit, a wet purified gas heat exchanger, a hydrogenation reactor preheater, a static mixer, a hydrogenation reactor and a hydrogen source device, wherein the raw material gas source device is connected with the sulfur-containing natural gas solvent crude removal unit, the sulfur-containing natural gas solvent crude removal unit is connected with the wet purified gas heat exchanger, the wet purified gas heat exchanger is connected with the hydrogenation reactor preheater, the hydrogenation reactor preheater and the hydrogen source device are both connected with the static mixer, so that hydrogen and gas from the hydrogenation reactor preheater are uniformly mixed in the static mixer, and the static mixer is connected with an inlet at the upper part of the hydrogenation reactor.
The system also comprises a wet purified gas cooler and a wet purified gas fine desulfurization unit, wherein the bottom outlet of a hydrogenation reactor is connected with the shell pass inlet of the wet purified gas cooler, the shell pass outlet of the wet purified gas heat exchanger is connected with the wet purified gas cooler, the wet purified gas cooler is connected with the wet purified gas fine desulfurization unit, and the wet purified gas fine desulfurization unit is connected with a downstream dehydration device.
The process for removing organic sulfur in natural gas by hydrogenation by using the system comprises the following steps:
firstly, the process selects and adopts a solvent method to roughly remove organic sulfur in the raw material natural gas, and almost all H in the raw material natural gas can be removed after absorption and regeneration in a solvent rough removal unit2S, H in wet purified gas at the outlet of the solvent rough-removing unit2S content less than 6mg/Nm3The solvent coarse-removing unit can simultaneously remove most organic sulfur (COS and CS)2Methyl mercaptan, ethanethiol, thioether, etc.), the removal efficiency is about 80%, and the purpose of the raw gas crude desulfurization organic sulfur is to reduce the load of an organic sulfur fine removal unit.
Step two, sending the wet purified gas after the solvent coarse removal unit to organic sulfurA hydrogenation unit for removing COS and CS which cannot be removed by the solvent rough unit2The organic sulfur such as mercaptan, thioether, thiophene and the like is converted into H which is easily absorbed or adsorbed2And S. The natural gas from the solvent crude removal unit firstly passes through a wet purified gas heat exchanger, enters a hydrogenation reactor preheater, is preheated to 300-350 ℃, then is uniformly mixed with hydrogen in a static mixer, enters a hydrogenation reactor together, and organic sulfur (COS and CS) in the wet purified gas is removed under the action of a catalyst2Methyl mercaptan, ethyl mercaptan, thioether, etc.) are almost completely converted to H2S, unconverted organic sulphur less than 8mg/Nm3(calculated according to total sulfur), the excess hydrogen at the outlet of the hydrogenation reactor is 2-5%.
And step three, exchanging heat of the wet purified gas after hydrogenation is finished through a wet purified gas heat exchanger, recovering most of heat, cooling the wet purified gas through a wet purified gas cooler, and then entering a wet purified gas fine-removing unit.
Step four, H in wet purified gas from hydrogenation unit2S is absorbed by a desulfurization solvent of an absorption tower of a wet purified gas fine-removing unit, and H in the absorbed wet purified gas2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3And the desulfurized wet purified gas enters a downstream unit.
The invention provides another system for removing organic sulfur in natural gas by hydrogenation, which is used for removing H in wet purified gas after hydrogenation2The treatment when the S content is lower, the treatment of the system is divided into two modes, because different types of adsorbents can be selected in the rectifying tower, because the requirements of the adsorbents on the adsorption temperature are different, and the arrangement positions of the wet purified gas heat exchanger and the cooler are different. If the zinc oxide adsorbent is adopted, the adsorption temperature needs high temperature, the first mode can be adopted, and the high-temperature wet purified gas after the hydrogenation reaction directly enters a fine desulfurization tower to remove H2S is removed by adsorption, and then heat exchange, cooling and filtration are carried out to enter a downstream device. If molecular sieve adsorbent is used, the adsorption temperature needs low temperature, and the second mode can be adopted, the high-temperature wet purified gas after hydrogenation reaction is firstly subjected to heat exchange and cooling with the wet purified gas from the coarse desulfurization unit, and then enters fine desulfurizationTower pair H removal2S is adsorbed and removed, and enters a downstream device after being filtered. The first and second methods differ in flow path only in the positions of the wet-purge gas heat exchanger and the wet-purge gas cooler.
The high-temperature wet purified gas after hydrogenation reaction directly enters a fine desulfurization tower to remove H2S is removed by adsorption, and then heat exchange, cooling and filtration are carried out to enter a downstream device. If molecular sieve adsorbent is adopted, the adsorption temperature needs low temperature, the process of the second mode can be adopted, the high-temperature wet purified gas after hydrogenation reaction exchanges heat with the wet purified gas from the coarse desulfurization unit, is cooled, and then enters the fine desulfurization tower to remove H2S is adsorbed and removed, and enters a downstream device after being filtered.
The first mode is as follows:
the system comprises a sulfur-containing natural gas solvent coarse removal unit, a wet purified gas heat exchanger, a hydrogenation reactor preheater, a static mixer, a hydrogenation reactor, a hydrogen source device, a fine desulfurization tower and a wet purified gas dust filter, wherein the raw material gas source device is connected with the sulfur-containing natural gas solvent coarse removal unit, the sulfur-containing natural gas solvent coarse removal unit is connected with the wet purified gas heat exchanger, the wet purified gas heat exchanger is connected with the hydrogenation reactor preheater, the hydrogenation reactor preheater and the hydrogen source device are both connected with the static mixer, and the static mixer is connected with an inlet at the upper part of the hydrogenation reactor. The bottom export of hydrogenation ware passes through the upper portion entry linkage of pipeline with the smart desulfurizing tower, and the export of smart desulfurizing tower is connected with wet purification gas heat exchanger shell side access, and wet purification gas heat exchanger shell side export is connected with wet purification gas cooler, and wet purification gas cooler is connected with wet purification gas dust filter inlet, and wet purification gas dust filter is connected with low reaches device.
Preferably, the fine desulfurization tower is two towers, namely a first fine desulfurization tower and a second fine desulfurization tower, which are connected in parallel, namely, the bottom outlet of the hydrogenation reactor is respectively connected with the upper inlets of the first fine desulfurization tower and the second fine desulfurization tower through pipelines. And an outlet at the lower part of the first fine desulfurization tower is communicated with a pipeline entering the upper part of the second fine desulfurization tower.
The device that the second kind of mode adopted is unanimous with first kind of mode, only is connected the upper end entry linkage with the smart desulfurizing tower again after with the bottom of hydrogenation ware in proper order with wet purified gas heat exchanger and heat exchanger, smart desulfurizing tower export and wet purified gas heat exchanger shell side inlet connection, wet purification gas cooler is connected with wet purified gas dust filter inlet, wet purified gas dust filter is connected with low reaches device.
The fine desulfurization tower also adopts two towers, namely a first fine desulfurization tower and a second fine desulfurization tower which are connected in parallel, namely, the bottom outlet of the hydrogenation reactor is respectively connected with the upper inlets of the first fine desulfurization tower and the second fine desulfurization tower through pipelines. And an outlet at the lower part of the first fine desulfurization tower is communicated with a pipeline entering the upper part of the second fine desulfurization tower.
The process for removing organic sulfur in natural gas by hydrogenation by using the system of the first mode or the second mode comprises the following steps:
firstly, the method selects and adopts a solvent method to roughly remove organic sulfur in the raw material natural gas, and almost all H in the raw material natural gas can be removed after absorption and regeneration in a solvent rough removal unit2S, H in wet purified gas at the outlet of the solvent rough-removing unit2S content less than 6mg/Nm3The solvent coarse-removing unit can simultaneously remove most organic sulfur (COS and CS)2Methyl mercaptan, ethanethiol, thioether and the like) with the removal efficiency of about 80 percent, and the purpose of the raw material gas crude desulfurization organic sulfur is to reduce the load of an organic sulfur fine removal unit;
step two, the wet purified gas after the solvent coarse removal unit is sent to an organic sulfur hydrogenation unit, and COS and CS which can not be removed by the solvent coarse removal unit can be removed in the unit2The organic sulfur such as mercaptan, thioether, thiophene and the like is converted into H which is easily absorbed or adsorbed2And S. The natural gas from the solvent crude removal unit firstly passes through a wet purified gas heat exchanger, enters a hydrogenation reactor preheater, is preheated to 300-350 ℃, then is uniformly mixed with hydrogen in a static mixer, enters a hydrogenation reactor together, and organic sulfur (COS and CS) in the wet purified gas is removed under the action of a catalyst2Methyl mercaptan, ethyl mercaptan, thioether, etc.) are almost completely converted to H2S, unconverted organic sulphur less than 8mg/Nm3(in terms of total sulfur)) The excess hydrogen at the outlet of the hydrogenation reactor is 2 to 5 percent;
step three, H-containing from hydrogenation unit2S wet purified gas enters a fine desulfurization tower from top to bottom, and H in the wet purified gas2S is adsorbed by a solid adsorbent in a fine desulfurization tower, and H in the adsorbed wet purified gas2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3And even lower.
And step four, exchanging heat of the wet purified gas from the fine desulfurization tower to 60 ℃ through a wet purified gas heat exchanger, recovering most of heat, cooling to 40 ℃ through a wet purified gas cooler, and enabling the wet purified gas to enter a wet purified gas dust filter and enter a downstream unit.
The first method is different from the second method only in that the wet-purified gas heat exchanger and the wet-purified gas cooler are located differently according to the performance of the catalyst, and the first method is to perform heat exchange and cooling after the fine desulfurization tower on the wet-purified gas. The second is that the wet purified gas is heat exchanged and cooled after the fine desulfurizing tower.
Compared with the prior art, the invention has the following positive effects:
the invention can deeply process H with various concentrations in natural gas2S and organic sulfur, so that the total sulfur content in the treated natural gas of the final product is less than 8mg/Nm3Even lower, and meets the strict requirements of natural gas and commodity gas at home and abroad. In the field of natural gas purification, the process of carrying out fine removal on organic sulfur in raw material natural gas after hydrogenation is the first time.
(II) the invention can simultaneously process H in natural gas2S and organic sulfur in various forms, e.g. COS, CS2Thiols, thioethers, thiophenes, etc., H2The removal rate of S and organic sulfur in various forms reaches more than 99 percent, so that the treated natural gas meets the use requirements of natural gas of various commodities.
Thirdly, the invention is provided with a wet purification gas heat exchanger for adsorbing H2The wet purified gas after S exchanges heat with the wet purified gas from the coarse desorption unit, so that the energy is greatly recovered, and the energy consumption of the device can be greatly reduced.
(IV)) The present invention has strong selectivity for removing organic sulfur, and can convert various forms of organic sulfur into H2After S, the fine removal device can not remove CO in the natural gas2And hydrocarbons, the investment of the fine threshing device is reduced, and the operation load of the fine threshing device is reduced.
Drawings
FIG. 1 is a schematic flow chart of a system for removing organic sulfur from natural gas by hydrogenation as described in example 1.
The system comprises a sulfur-containing natural gas raw gas crude desulfurization unit 1, a wet purified gas heat exchanger 2, a hydrogenation reactor preheater 3, a static mixer 4, a hydrogenation reactor 5, a wet purified gas cooler 6 and a wet purified gas fine desulfurization unit 7.
Fig. 2 is a schematic flow chart of a system for removing organic sulfur from natural gas by hydrogenation as described in example 2.
FIG. 3 is a schematic flow chart of a system for removing organic sulfur from natural gas by hydrogenation as described in example 3.
In fig. 2 and 3, 1 is a sulfur-containing natural gas raw gas crude desulfurization unit, 2 is a wet purified gas heat exchanger, 3 is a hydrogenation reactor preheater, 4 is a static mixer, 5 is a hydrogenation reactor, 6 is a fine desulfurization tower, 7 is a fine desulfurization tower, 8 is a wet purified gas cooler, and 9 is a wet purified gas dust filter.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples.
The units or devices used in the following embodiments are all in the prior art, and the structure thereof is not described in detail.
Example 1:
system for removing organic sulfur from natural gas by hydrogenation, especially wet purified gas H after hydrogenation2When the S content is high, the system shown in fig. 1 is used for operation, and the system comprises: sulfur-containing natural gas feedGas coarse desulfurization unit, wet purification gas heat exchanger, hydrogenation reactor preheater, static mixer, hydrogenation ware, wet purification gas cooler, wet purification gas fine desulfurization unit etc. wherein: the sulfur-containing natural gas raw material gas coarse desulfurization unit is connected with a tube pass inlet of the wet purification gas heat exchanger through a pipeline; the export of wet purification gas heat exchanger's tube side passes through the entry linkage of pipeline and hydrogenation reactor preheater, arrange the export of hydrogenation reactor preheater and pass through pipeline and static mixer access connection, static mixer and hydrogenation reactor upper portion access connection, the bottom export of hydrogenation reactor passes through pipeline and wet purification gas heat exchanger shell side access connection, wet purification gas heat exchanger shell side export passes through pipeline and wet purification gas cooler's access connection, wet purification gas cooler's export passes through pipeline and wet purification gas fine desulfurization unit access connection, the export of wet purification gas fine desulfurization unit passes through pipeline and gets into low reaches device.
The process for removing organic sulfur in natural gas by hydrogenation by using the system comprises the following specific operation steps:
step one, enabling sulfur-containing natural gas to enter a raw material gas coarse desulfurization unit through a pipeline, wherein the raw material gas coarse desulfurization unit is removed by adopting a solvent, and almost all H in the sulfur-containing natural gas can be removed after absorption and regeneration2S, H in wet purified gas at outlet of raw gas crude desulfurization unit2S content less than 6mg/Nm3Simultaneously remove most organic sulfur (COS, CS)2Methyl mercaptan, ethyl mercaptan, thioether, etc.), the removal efficiency is about 80%. And the wet purified gas at the outlet of the raw gas coarse desulfurization unit enters the tube pass of the wet purified gas heat exchanger.
And step two, the wet purified gas after the amine liquid crude removal unit enters a wet purified gas heat exchanger tube side to exchange heat with wet natural gas from a hydrogenation reactor outlet at the temperature of about 300-350 ℃ after hydrogenation, the wet purified gas after heat exchange is at the temperature of about 260-280 ℃, and then the wet purified gas enters a hydrogenation reactor preheater.
Step three, heating the wet purified gas to 300-350 ℃ by adopting a fuel gas or an electric heater through a hydrogenation reactor preheater, and then feeding the wet purified gas into a static mixer;
step four, uniformly mixing wet purified gas from a hydrogenation reactor preheater in a static mixer with hydrogen from a device boundary area in the static mixer, and then feeding the mixture into a hydrogenation reactor;
step five, in the hydrogenation reactor, hydrogen gas is used for purifying organic sulfur (COS and CS) in the wet purified gas under the action of a catalyst2Methyl mercaptan, ethyl mercaptan, thioether, etc.) are almost completely converted to H2S, unconverted organic sulphur less than 8mg/Nm3(in terms of total sulfur), the hydrogen excess is 2-5%, and the H content after hydrogenation is finished2S, the wet purified gas enters a wet purified gas heat exchanger for heat exchange;
step six, H-containing from the hydrogenation reactor2S, the wet purified gas exchanges heat to 60 ℃ in a wet purified gas heat exchanger, and enters a wet purified gas cooler after most of heat is recovered;
seventhly, in the wet purified gas cooler, cooling the wet purified gas to about 40 ℃ by circulating cooling water, and then entering a wet purified gas fine desulfurization unit to remove H in the wet purified gas2S is absorbed by a desulfurizer in the fine desulfurization tower, and H in the absorbed wet purified gas2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3。
Example 2:
system for removing organic sulfur in natural gas through hydrogenation, in particular to H in wet purified gas after hydrogenation2As shown in fig. 2, the processing system with a low S content includes: the device comprises a sulfur-containing natural gas solvent rough-removing unit, a wet purified gas heat exchanger, a hydrogenation reactor preheater, a static mixer, a hydrogenation reactor, a first fine desulfurization tower, a second fine desulfurization tower, a wet purified gas cooler and a wet purified gas dust filter, wherein zinc oxide adsorbents are adopted in the first fine desulfurization tower and the second fine desulfurization tower, and the adsorption temperature is high.
The sulfur-containing natural gas solvent rough removal unit is connected with a tube pass inlet of the wet purified gas heat exchanger through a pipeline; the tube pass outlet of the wet purified gas heat exchanger is connected with the inlet of the hydrogenation reactor preheater through a pipeline, the outlet of the hydrogenation reactor preheater is connected with the inlet of a static mixer through a pipeline, the static mixer is connected with the inlet at the upper part of the hydrogenation reactor, the bottom outlet of the hydrogenation reactor is connected with the upper inlet of a first fine desulfurization tower or a second rectification tower (the first fine desulfurization tower and the second rectification tower are 1 for 1 and are connected in parallel) through a pipeline, the outlet of the first fine desulfurization tower or the second rectifying tower is connected with the shell pass inlet of the wet purification gas heat exchanger through a pipeline, the shell side outlet of the wet purified gas heat exchanger is connected with the inlet of the wet purified gas cooler through a pipeline, the outlet of the wet purified gas cooler is connected with the inlet of the wet purified gas dust filter through a pipeline, and the outlet of the wet purified gas dust filter enters a downstream device through a pipeline.
The process for removing organic sulfur in natural gas by hydrogenation by using the system comprises the following steps:
step one, enabling upstream sulfur-containing natural gas to enter a solvent rough removal unit through a pipeline, and removing almost all H in the sulfur-containing natural gas after absorption and regeneration2S, H in wet purified gas at outlet of solvent coarse-removing unit2S content less than 6mg/Nm3Simultaneously remove part of organic sulfur (COS, CS)2Methyl mercaptan, ethyl mercaptan, thioether, etc.), the removal efficiency is about 80%. And (4) enabling the wet purified gas at the outlet of the solvent rough-removing unit to enter a tube pass of a wet purified gas heat exchanger.
Step two, the wet purified gas after the amine liquid crude removal unit enters a wet purified gas heat exchanger tube pass to exchange heat with wet natural gas which is from a first fine desulfurization tower and a second rectification tower and subjected to fine desulfurization at the temperature of about 300-350 ℃, the wet purified gas after heat exchange is about 260-280 ℃, and then the wet purified gas enters a hydrogenation reactor preheater 3;
step three, entering a hydrogenation reactor preheater through a wet purified gas heat exchanger, preheating to 300-350 ℃ by adopting fuel gas or electricity, and then entering a static mixer;
step four, the wet purified gas from the hydrogenation reactor preheater is uniformly mixed with the hydrogen from the system or the pressure swing adsorption system in the static mixer and then enters the hydrogenation reactor;
step five, in the hydrogenation reactor, hydrogen gas is used for purifying organic sulfur (COS and CS) in the wet purified gas under the action of a catalyst2Methyl mercaptan, ethyl mercaptan, thioether, etc.) are almost completely converted to H2S, unconverted organic sulphur less than 8mg/Nm3(calculated according to total sulfur), the excess hydrogen is 2% -5%, and the wet purified gas after hydrogenation enters a fine desulfurization tower;
step six, H-containing from the hydrogenation reactor2S wet purified gas enters a first fine desulfurization tower or a second rectifying tower from top to bottom (the first fine desulfurization tower and the second rectifying tower are 1-used and 1-used, are connected in parallel and are switched for use), and H in the wet purified gas2S is adsorbed by a solid adsorbent in a fine desulfurization tower, and H in the wet purified gas after adsorption2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3。
Step seven, exchanging heat of the wet purified gas from the first fine desulfurization tower and the second rectifying tower to 60 ℃ through a wet purified gas heat exchanger 2, recovering most of heat, and then feeding the recovered heat into a wet purified gas cooler 8;
step eight, in the wet purified gas cooler, cooling the wet purified gas to about 40 ℃ by circulating cooling water, and then feeding the wet purified gas into a wet purified gas dust filter;
and step nine, removing dust possibly existing in the wet purifier in a wet purification gas dust filter, and then entering a downstream unit.
Example 3:
system for removing organic sulfur in natural gas through hydrogenation, in particular to H in wet purified gas after hydrogenation2As shown in fig. 3, the processing system with a low S content includes: the device comprises a sulfur-containing natural gas solvent rough-removing unit, a wet purified gas heat exchanger, a hydrogenation reactor preheater 3, a static mixer, a hydrogenation reactor, a first fine desulfurization tower, a second fine desulfurization tower, a wet purified gas cooler and a wet purified gas dust filter, wherein molecular sieve adsorbents are adopted in the first fine desulfurization tower and the second fine desulfurization tower, and the adsorption temperature is low.
The specific operation steps are the same as example 2, the high-temperature wet purified gas after hydrogenation reaction exchanges heat with the wet purified gas from the rough desulphurization unit, is cooled, and then enters the fine desulphurization tower to remove H2S is adsorbed and removed, and enters a downstream device after being filtered.
By combining the embodiment 1, the embodiment 2 and the embodiment 3, the working principle of the application is as follows: because of organic sulfur (COS, CS) in natural gas2Methyl mercaptan, ethanethiol, thioether, etc.) are difficult to remove if the content is high, so the solvent absorption method is adopted firstly to remove H in natural gas2S and organic sulfur are roughly removed, and most of H is removed2S and most of the organic sulfur.
Organic sulfur which cannot be removed by a solvent absorption method is subjected to hydrogenation reaction under the conditions of a catalyst (such as a cobalt-molybdenum catalyst) and a proper temperature (300-350 ℃) to remove the organic sulfur (COS and CS)2Methyl mercaptan, ethyl mercaptan, thioether, etc.) and the like into H which is easily absorbed or adsorbed2S, unconverted organic sulphur less than 8mg/Nm3(in terms of total sulfur), the excess hydrogen is 2% to 5%.
Organic sulfur is converted to H in a hydrogenation reactor2S, the obtained product enters a fine desulfurization tower or a fine wet purified gas removal unit filled with a solid adsorbent to perform fine solvent removal, and H in the wet purified gas is removed2S is absorbed again by solid adsorbent in the fine desulfurizing tower or solvent in the fine desulfurizing unit of wet purified gas, and H in the treated wet purified gas2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3This makes it possible to easily remove natural gas containing a large amount of organic sulfur (COS ≥ 300ppm) to the specified value in the national standard. H in commercial natural gas2S and total sulfur content are low, and SO is generated after combustion2The content is less, the environmental pollution is greatly reduced, and the environment-friendly benefit is good.
After the treatment of the device, H in natural gas can be effectively reduced2The concentration of S and total sulfur can be adjusted by adjusting parameters such as hydrogenation temperature, air speed ratio, catalyst type and the like to ensure that the natural gas H treated by the device2S concentration less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3。
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The utility model provides a system for organic sulfur in desorption natural gas through hydrogenation, includes that the crude unit that takes off of sulphur-containing natural gas solvent, wet purification gas heat exchanger, hydrogenation reactor preheater, static mixer, hydrogenation ware and hydrogen source device, its characterized in that: the raw material gas source device is connected with the sulfur-containing natural gas solvent rough removal unit, the sulfur-containing natural gas solvent rough removal unit is connected with the wet purified gas heat exchanger, the wet purified gas heat exchanger is connected with the hydrogenation reactor preheater, the hydrogenation reactor preheater and the hydrogen source device are both connected with the static mixer, and the static mixer is connected with an inlet at the upper part of the hydrogenation reactor.
2. The system for removing organic sulfur from natural gas by hydrogenation according to claim 1, wherein: the system also comprises a wet purified gas cooler and a wet purified gas fine desulfurization unit, and is characterized in that: the bottom export of hydrogenation ware and wet purification gas cooler shell side access connection, wet purification gas heat exchanger shell side export is connected with wet purification gas cooler, and wet purification gas cooler is connected with wet purification gas fine desulfurization unit, and wet purification gas fine desulfurization unit is connected with low reaches dewatering device.
3. The system for removing organic sulfur from natural gas by hydrogenation according to claim 1, wherein: the system also comprises a fine desulfurization tower and a wet purified gas dust filter, and is characterized in that: the bottom export of hydrogenation ware passes through the upper portion entry linkage of pipeline with the smart desulfurizing tower, and the export of smart desulfurizing tower is connected with wet purification gas heat exchanger shell side access, and wet purification gas heat exchanger shell side export is connected with wet purification gas cooler, and wet purification gas cooler is connected with wet purification gas dust filter inlet, and wet purification gas dust filter is connected with low reaches device.
4. The system for removing organic sulfur from natural gas by hydrogenation according to claim 3, wherein: the fine desulfurization tower comprises two towers, namely a first fine desulfurization tower and a second fine desulfurization tower which are connected in parallel, namely, the bottom outlet of the hydrogenation reactor is respectively connected with the upper inlets of the first fine desulfurization tower and the second fine desulfurization tower through pipelines; and an outlet at the lower part of the first fine desulfurization tower is communicated with a pipeline entering the upper part of the second fine desulfurization tower.
5. The system for removing organic sulfur from natural gas by hydrogenation according to claim 1, wherein: the bottom of hydrogenation ware is connected with wet purification gas heat exchanger and heat exchanger in proper order and is connected the back again with the upper end entry linkage of smart desulfurizing tower, and smart desulfurizing tower export is connected with wet purification gas heat exchanger shell side access, and wet purification gas cooler is connected with wet purification gas dust filter inlet, and wet purification gas dust filter is connected with low reaches device.
6. The system for removing organic sulfur from natural gas by hydrogenation according to claim 5, wherein: the fine desulfurization tower comprises two towers, namely a first fine desulfurization tower and a second fine desulfurization tower which are connected in parallel, namely, the bottom outlet of the hydrogenation reactor is respectively connected with the upper inlets of the first fine desulfurization tower and the second fine desulfurization tower through pipelines; and an outlet at the lower part of the first fine desulfurization tower is communicated with a pipeline entering the upper part of the second fine desulfurization tower.
7. The method for removing organic sulfur in natural gas by hydrogenation by using the system of claim 2, which comprises the following steps:
firstly, adopting a solvent method to roughly remove organic sulfur in raw material natural gas, and absorbing and regenerating most of H in the raw material natural gas in a solvent rough removal unit2S is removed, and H in wet purified gas at the outlet of the solvent rough-removing unit2S content less than 6mg/Nm3Most of organic sulfur can be removed simultaneously in the solvent coarse removal unit, and the removal efficiency is 80 percent;
step two, the wet purified gas after the solvent coarse removal unit is sent to an organic sulfur hydrogenation unit, and COS and CS which cannot be removed in the solvent coarse removal unit are removed in the unit2Sulfur alcohol, sulfur ether and thiophene organic sulfur into H easy to be absorbed or adsorbed2S; the natural gas from the solvent crude removal unit firstly passes through a wet purified gas heat exchanger, enters a hydrogenation reactor preheater, is preheated to 300-350 ℃, then is uniformly mixed with hydrogen in a static mixer, enters a hydrogenation reactor together, and almost all organic sulfur in the wet purified gas is converted into H under the action of a catalyst2S, unconverted organic sulphur < 8mg/Nm, based on total sulphur3The excess hydrogen at the outlet of the hydrogenation reactor is 2 to 5 percent;
step three, the wet purified gas after hydrogenation is subjected to heat exchange through a wet purified gas heat exchanger, most of heat is recovered, and the wet purified gas is cooled through a wet purified gas cooler and then enters a wet purified gas fine-removing unit;
step four, H in wet purified gas from hydrogenation unit2S is absorbed by a desulfurization solvent of an absorption tower of a wet purified gas fine-removing unit, and H in the absorbed wet purified gas2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3And the desulfurized wet purified gas enters a downstream unit.
8. The method for removing organic sulfur in natural gas by hydrogenation by using the system as claimed in any one of claims 3 to 6, characterized by comprising the following steps:
firstly, adopting a solvent method to roughly remove organic sulfur in raw material natural gas, and absorbing and regenerating most of H in the raw material natural gas in a solvent rough removal unit2S is removed, and H in wet purified gas at the outlet of the solvent rough-removing unit2S content less than 6mg/Nm3Most of organic sulfur can be removed simultaneously in the solvent coarse removal unit, and the removal efficiency is 80 percent;
step two, the wet purified gas after the solvent coarse removal unit is sent to an organic sulfur hydrogenation unit, and COS and CS which cannot be removed in the solvent coarse removal unit are removed in the unit2Sulfur alcohol, sulfur ether and thiophene into easily absorbed orAdsorbed H2S; the natural gas from the solvent crude removal unit firstly passes through a wet purified gas heat exchanger, enters a hydrogenation reactor preheater, is preheated to 300-350 ℃, then is uniformly mixed with hydrogen in a static mixer, enters a hydrogenation reactor together, and almost all organic sulfur in the wet purified gas is converted into H under the action of a catalyst2S, unconverted organic sulphur < 8mg/Nm, based on total sulphur3The excess hydrogen at the outlet of the hydrogenation reactor is 2 to 5 percent;
step three, H-containing from hydrogenation unit2S wet purified gas enters a fine desulfurization tower from top to bottom, and H in the wet purified gas2S is adsorbed by a solid adsorbent in a fine desulfurization tower, and H in the adsorbed wet purified gas2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3Even lower;
and step four, exchanging heat of the wet purified gas from the fine desulfurization tower to 60 ℃ through a wet purified gas heat exchanger, recovering most of heat, cooling to 40 ℃ through a wet purified gas cooler, and enabling the wet purified gas to enter a wet purified gas dust filter and enter a downstream unit.
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| CN113881464B (en) * | 2021-11-25 | 2023-08-15 | 安徽工业大学 | Fine desulfurization device and method for coke oven gas |
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