CN212770603U - System for carbonyl sulfide and carbon disulfide in advanced treatment natural gas - Google Patents
System for carbonyl sulfide and carbon disulfide in advanced treatment natural gas Download PDFInfo
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- CN212770603U CN212770603U CN202021410181.2U CN202021410181U CN212770603U CN 212770603 U CN212770603 U CN 212770603U CN 202021410181 U CN202021410181 U CN 202021410181U CN 212770603 U CN212770603 U CN 212770603U
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Abstract
The utility model particularly relates to COS and CS in the deep processing of natural gas2The system of (1). The system comprises a hydrolysis device and a fine desulfurization device, wherein the hydrolysis device comprises a natural gas heat exchanger, a natural gas heater, a natural gas organic sulfur hydrolysis tower and a natural gas cooler; the fine desulfurization device is a downstream desulfurization device or a molecular sieve desulfurization dehydration device; the shell pass outlet of the natural gas heat exchanger is connected with a natural gas heater through a pipeline, and the natural gas heaterThe shell layer outlet is connected with the inlet of the natural gas organic sulfur hydrolysis tower through a pipeline, and the like. The system can be used for high-content COS and CS2The natural gas containing organic sulfur is effectively removed, and the organic sulfur hydrolysis tower is used for removing COS and CS in the natural gas containing sulfur2Hydrolyzing into H at one time2And S, entering a molecular sieve desulfurization and dehydration device or a downstream desulfurization device, and finishing desulfurization treatment at one time.
Description
Technical Field
The utility model relates to a to highly containing COS and CS2Natural gas of iso-organic sulfurA device for removing COS and CS in the natural gas2The system of (1).
Background
Most raw natural gas contains sulfur in a large amount, and the sulfur in the natural gas is in a large form, and most raw natural gas contains H2S is present in the form of H in some raw natural gas2S also contains more organic sulfur. According to some current engineering exploitation and development conditions, the organic sulfur in the raw material natural gas exists in the forms of mercaptan (methyl mercaptan, ethyl mercaptan and the like), COS and CS2Few natural gases contain organic sulfur, thioether and thiophene; most engineered organosulfurs are now abundant in mercaptans, but it has also been discovered that individual engineered organosulfurs are primarily higher COS, or CS2。
In order to meet the use of natural gas, sulfur in various forms must be removed from the natural gas. With the continuous development of society, human beings have stronger and stronger protection consciousness on the natural environment on which the human beings live, and at present, the release of the national standard natural gas (GB17820-2018) further improves the sulfur content index, H, in the natural gas product2S content is less than or equal to 20mg/m from old version3The increase is less than or equal to 6mg/m3Total sulfur content (in terms of sulfur) is from 200mg/m3The increase is less than or equal to 20mg/m3. The index has reached the requirement of most developed countries for the sulfur content in commodity natural gas.
At present, natural gas purification and desulfurization processes mainly include a solvent absorption method and an adsorption method, wherein the solvent absorption method includes a physical solvent method, a chemical solvent method and a mixed solvent method.
Adsorption method
The adsorption separation method is to adsorb organic sulfur to an adsorbent by utilizing the principle of physical adsorption to achieve the effect of adsorption separation, wherein the adsorbent can be regenerated in a certain mode. The adsorption method mainly includes a molecular sieve method and an activated carbon method.
The molecular sieve method is a method for selectively adsorbing polar organic sulfur molecules with the diameter smaller than the aperture of the molecular sieve into the molecular sieve through the molecular sieve so as to remove the organic sulfur. At present, molecular sieves used in natural gas purification for removing organic sulfur are mainly used for removing mercaptan, and molecular sieves used in natural gas mercaptan purification are mainly 13X and 5A molecular sieves. However, the process of removing mercaptan by using molecular sieve is usually applied to the fine removal of mercaptan in purified gas after solvent desulfurization, and the application performance of removing a large amount of mercaptan by using molecular sieve is not realized.
The literature mentions that activated carbon is a common hydrophobic adsorbent, and the activated carbon has a large number of micropores on the surface, a large specific surface area and a strong adsorption effect on many organic matters. The adsorption of mercaptan by the activated carbon is influenced by the surface properties such as the form and distribution of the pore diameter. The activated carbon can be used for mercaptan and CS2And (4) removing. But the performance of the industrial application of the activated carbon in the purification and absorption of mercaptan from natural gas is not collected at present.
Solvent process
At present, natural gas desulfurization solvents are mainly classified into physical solvents and chemical solvents.
The alcoholamine process is the most widely used chemical solvent for H2The removal rate of S is high, but the removal effect on organic sulfur is poor, such as MEA, DEA and MDEA.
Sulfolane (tetrahydrothiophene dioxide) is the most widely used physical solvent for desulfurizing natural gas at present, and can not only be used for acidic components in natural gas, especially H2S has high absorption capacity and relatively high removal efficiency for organic sulfur (COS, RSH and RSR), but because sulfolane has a relatively large absorption for hydrocarbons as a physical solvent, sulfolane is generally not used alone, but rather is used in combination with certain amines, such as Diisopropanolamine (DIPA) to form a sulfoamine-process (Sufinol-D) solution, Methyldiethanolamine (MDEA) to form a new sulfoamine-process (sulfofinol-M) solvent, and the like. The method has the advantages of both physical absorption method and chemical absorption method, and the operation condition is similar to the desulfurization effect of the alcohol amine method. In the solvent of the sulfone amine method, because of the existence of the physical solvent sulfolane, the mixed solvent has good effect of removing organic sulfides, and the acid gas load of the mixed solvent is greatly improved, so the method is still a main industrial method for treating natural gas containing organic sulfur and having high acid gas partial pressure. However, the removal rate of organic sulfur, especially of mercaptans, is not highThe removal rate is low, and the engineering requirements of high organic sulfur content and high purification degree requirement cannot be met.
1. And absorbing and removing organic sulfur in the natural gas by using a solvent. With the development requirements of industrial application, various patent solvents are developed at home and abroad, and the removal effect of the solvents on mercaptan is good. Proprietary solvents like EXXON MOBIL: sulfolane plus FLEXSORB, but this process is only applicable to sour natural gas containing primarily mercaptans. At present, only Longgang xi purification plants adopt the formula solvent of Dow company in America to remove COS once, but the formula solvent is not put into production operation. For CS2The removal is carried out, only Dow company carries out solvent removal technical exploration at home and abroad, and no use case exists. Meanwhile, the process for removing organic sulfur in natural gas by adopting the formula solution has the greatest defect of absorbing more hydrocarbons in the natural gas. And due to COS and CS2Physical properties of (1) and CO2Have similar physical properties, so that the selectivity of solvent absorption is poor, and COS and CS are removed2Will inevitably remove a large amount of CO2The solution circulation is large, the investment is high and the operation cost is high.
2. The solid adsorbs organic sulfur in natural gas. At present, only foreign UOP and GRACE molecular sieves can process sulfur-containing natural gas containing mercaptan and are used in Kazakhstan.
For removing COS in natural gas, except that solvent absorption process of Dow company is adopted in non-production Longgang xi purification plants, British BV company patent process package is adopted in plain purification plants at present, and after MDEA primary coarse desulfurization, COS hydrolysis process is adopted to hydrolyze COS to H2After S, MDEA secondary desulfurization is carried out, and a hydrolysis catalyst is catalyzed by Zhuangxinwan Feng; the indexes of the purified gas product can only reach the total sulfur content of less than 200mg/m3The total sulfur content of the natural gas product index is less than 20mg/m3. However, no domestic related desulfurization process technology can realize the removal of COS in the natural gas. For CS in natural gas2The removal of the catalyst is not carried out by industrial process technology at home and abroad. Therefore, the synchronous and advanced treatment of COS and CS in natural gas is not available at home and abroad2The process system of (1).
Disclosure of Invention
The invention aims to solve the problems and provide the COS and the CS in the deep treatment of the natural gas2The system of (1). The system device can be used for high-content COS and CS2The natural gas containing organic sulfur is effectively removed, and the organic sulfur hydrolysis tower is used for removing COS and CS in the natural gas containing sulfur2Hydrolyzing into H at one time2And S, entering a molecular sieve desulfurization and dehydration device or a downstream desulfurization device, and finishing desulfurization treatment at one time.
In order to realize the purpose of the invention, the technical scheme of the utility model is as follows:
COS and CS in advanced treatment of natural gas2The system comprises a hydrolysis device and a fine desulfurization device, wherein the hydrolysis device comprises a natural gas heat exchanger, a natural gas heater, a natural gas organic sulfur hydrolysis tower and a natural gas cooler; the fine desulfurization device is a downstream desulfurization device or a molecular sieve desulfurization dehydration device; the shell side outlet of the natural gas heat exchanger is connected with a natural gas heater through a pipeline, and the shell layer outlet of the natural gas heater is connected with the inlet of the natural gas organic sulfur hydrolysis tower through a pipeline; the outlet of the natural gas organic sulfur hydrolysis tower is connected with the tube pass inlet of the natural gas heat exchanger through a pipeline; the tube pass outlet of the natural gas heat exchanger is connected with the shell layer inlet of the natural gas cooler through a pipeline; the natural gas cooler is connected with a downstream desulphurization device or a molecular sieve desulphurization dehydration device.
Preferably, a condensed water injection pump and a gas-liquid separator are sequentially arranged on a pipeline between the natural gas heat exchanger and the natural gas heater; when the temperature of the raw material gas is higher, a condensed water filling pump and a gas-liquid separator can be omitted.
When the system adopts a downstream desulphurization device to carry out advanced treatment on COS and CS in the natural gas2The process comprises the following steps:
step one, removing H2The natural gas containing organic sulfur of S is heated by a natural gas heater or condensed water is added by a condensed water filling pump after the natural gas containing organic sulfur exchanges heat with the natural gas after hydrolysis reaction by a natural gas heat exchanger, the natural gas separated by a natural gas-liquid separator is heated by the natural gas heater and then enters the natural gas and the organic sulfurA hydrolysis tower;
step two, residual CS in natural gas2Hydrolysis to H2S, sequentially passing through a natural gas heat exchanger and a natural gas cooler to change the temperature to normal temperature;
and step three, the natural gas which is changed to the normal temperature is sent to a downstream desulphurization device.
When the system adopts a molecular sieve desulfurization dehydration device, the fine desulfurization device comprises a natural gas filtering separator, a molecular sieve dehydration desulfurization tower, a dust filter, a regenerated gas cooler, a regenerated gas heater and a regenerated gas separator; the outlet of the natural gas cooler is connected with the inlet of the natural gas filtering separator through a pipeline; the outlet of the natural gas filtering separator is connected with the inlet of the molecular sieve desulfurization dehydration tower through a pipeline; the outlet of the molecular sieve desulfurization dehydration tower is connected with the inlet of the dust filter through a pipeline; the outlet of the dust filter is connected with a downstream processing facility or an external conveying pipeline through a pipeline; a cold blowing regeneration outlet of the molecular sieve dehydration desulfurization tower is connected with a shell inlet of a regenerated gas heater through a pipeline; the shell layer outlet of the regenerated gas heater is connected with the hot blowing inlet of the molecular sieve dehydration desulfurization tower through a pipeline; the hot blowing outlet of the molecular sieve dehydration desulfurization tower is connected with the shell inlet of the regenerated gas cooler through a pipeline; the shell layer outlet of the regenerated gas cooler is connected with the inlet of the regenerated gas separator through a pipeline; the outlet of the regeneration gas separator is connected with a downstream treatment facility of the regeneration gas through a pipeline.
The natural gas organic sulfur hydrolysis tower is divided into a natural gas primary organic sulfur hydrolysis tower and a natural gas secondary organic sulfur hydrolysis tower, and the natural gas primary organic sulfur hydrolysis tower is connected with the natural gas secondary organic sulfur hydrolysis tower in series; a second-stage condensed water injection pump, a natural gas second-stage gas-liquid separator and a natural gas second-stage heater are sequentially arranged between the natural gas first-stage organic sulfur hydrolysis tower and the natural gas second-stage organic sulfur hydrolysis tower.
The molecular sieve dehydration desulfurization tower is a plurality of towers, such as 2 towers, 3 towers or 4 towers, and the molecular sieve dehydration desulfurization towers are connected in parallel.
According to the content of two kinds of organic sulfur in raw material gas and the proportion of the two kinds of organic sulfur, the hydrolysis process can be divided into 2 kinds: firstly, whenCS in Natural gas2The ratio of the content of the sulfur to the content of COS is larger (namely the content of one organic sulfur is small), or when only one organic sulfur is contained, primary heating and primary catalytic hydrolysis can be adopted; ② CS in natural gas2The ratio of the content of the catalyst to the content of COS is small, and when the content is high, two-stage heating and two-stage catalytic hydrolysis are adopted. The conversion rate of both hydrolysis processes is more than 99%.
In natural gas CS2The method can adopt a first-stage heating and first-stage catalytic hydrolysis process when the content of the COS is larger (namely the content of one organic sulfur is small) or only one organic sulfur is contained, and comprises the following steps:
step one, removing H2S-containing natural gas containing organic sulfur (mainly containing COS and CS)2) After the heat exchange between the natural gas heat exchanger and the natural gas after the hydrolysis reaction, sequentially adding condensed water through a primary condensed water filling pump, separating the natural gas by a primary gas-liquid separator (when the temperature of the raw gas is higher, the primary condensed water filling pump and the primary gas-liquid separator can be omitted), heating by a primary natural gas heater, and finally feeding the natural gas into a primary organic sulfur hydrolysis tower;
step two, in the natural gas first-stage organic sulfur hydrolysis tower, the residual CS in the natural gas2Hydrolysis to H2And S, sequentially passing through a natural gas heat exchanger and a natural gas cooler to change the temperature to the normal temperature.
And step three, the natural gas changed to the normal temperature enters a downstream solution desulfurization/solid desulfurization device or a molecular sieve desulfurization dehydration device.
Step four, the natural gas entering the molecular sieve desulfurization and dehydration device firstly passes through a filter separator and then enters a natural gas desulfurization and dehydration tower to convert the H converted from the organic sulfur2S and saturated water are adsorbed and removed. And then the gas is filtered by a dust filter and is transported out as product gas.
And step five, the regeneration and cold blowing of the molecular sieve are realized by the regenerated gas of the molecular sieve through a regenerated gas heater, a regenerated gas cooler, a regenerated gas liquid separation tank and a regenerated gas compressor, and the regenerated gas returns to the raw material gas for treatment or other treatable devices.
In natural gas CS2Has a small proportion to the content of COS, anWhen the content is higher, two-stage heating and two-stage catalytic hydrolysis are adopted. The method comprises the following specific steps:
step one, removing H2S-containing natural gas containing organic sulfur (mainly containing COS and CS)2) After the heat exchange between the natural gas heat exchanger and the natural gas after the hydrolysis reaction, sequentially adding condensed water through a primary condensed water filling pump, separating the natural gas by a primary gas-liquid separator (when the temperature of the raw gas is higher, the primary condensed water filling pump and the primary gas-liquid separator can be omitted), heating by a primary natural gas heater, and finally feeding the natural gas into a primary organic sulfur hydrolysis tower;
step two, in the natural gas first-stage organic sulfur hydrolysis tower, COS and a small amount of CS in the natural gas2Hydrolysis to H2S, sequentially adding condensed water through a secondary condensed water filling pump, separating a natural gas secondary gas-liquid separator and heating a natural gas secondary heater, and finally feeding the mixture into a natural gas secondary organic sulfur hydrolysis tower;
step three, in the natural gas second-stage organic sulfur hydrolysis tower, the residual CS in the natural gas2Hydrolysis to H2And S, sequentially passing through a natural gas heat exchanger and a natural gas cooler to change the temperature to the normal temperature.
And step four, the natural gas changed to the normal temperature enters a downstream solution desulfurization/ferric oxide desulfurization device or a molecular sieve desulfurization dehydration device.
Step five, the natural gas entering the molecular sieve desulfurization and dehydration device firstly passes through a filter separator and then enters a natural gas desulfurization and dehydration tower to convert the H converted from the organic sulfur2S and saturated water are adsorbed and removed. And then the gas is filtered by a dust filter and is transported out as product gas.
And step six, the regeneration and cold blowing of the molecular sieve are realized by the regenerated gas of the molecular sieve through a regenerated gas heater, a regenerated gas cooler, a regenerated gas liquid separation tank and a regenerated gas compressor, and the regenerated gas returns to the raw material gas for treatment or other treatable devices.
The process is to remove H from the solution2S, rich in COS and CS2After the natural gas hydrolysis treatment, almost all COS and CS in the natural gas2Conversion to H2S, after treatment, natural gas is refined by solution or molecular sieve to remove H2After S, finally making the total sulfur content in the natural gas product less than or equal to 8mg/m3Meets the current commodity natural gas standard and can be transported and sold by pipes.
Compared with the prior art, the utility model has the positive effects that:
the system is used for treating high-content COS and CS2The natural gas containing organic sulfur is subjected to hydrolysis reaction in a natural gas organic sulfur hydrolysis tower to remove COS and CS in the natural gas containing sulfur2Hydrolyzing into H at one time2And S, entering a molecular sieve desulfurization and dehydration device or a downstream desulfurization device, and finishing desulfurization treatment at one time.
(II) COS and CS can be ensured by the device2The hydrolysis conversion rate of the catalyst reaches more than 99 percent. The total sulfur content in the product natural gas treated by the system is less than 8mg/Nm3Can meet the latest natural gas standard in China and the strictest natural gas standard requirement in the world.
(III) the system is simple to operate, and the COS and the CS are combined2Conversion to H2After S, the downstream desulfurization device does not remove CO in the natural gas2And hydrocarbons, the investment of the desulphurization device is reduced, and the operation load of the desulphurization device is reduced.
And fourthly, when the engineering needs deep dehydration of the molecular sieve, the system combines further desulfurization and dehydration into a unit, and the desulfurization and dehydration treatment is completed once, so that a desulfurization device for further desulfurization treatment is omitted, and the energy consumption is saved.
Drawings
FIG. 1 is a graph of COS and CS in the advanced treatment of Natural gas as described in example 12Schematic diagram of the process system.
FIG. 2 is a graph of COS and CS in the advanced treatment of Natural gas as described in example 22Schematic diagram of the process system.
The device comprises a natural gas heat exchanger 1, a condensed water injection pump 2, a natural gas-liquid separator 3, a natural gas heater 4, a natural gas organic sulfur hydrolysis tower 5, a natural gas cooler 6, a natural gas filtering separator 7, a molecular sieve dehydration desulfurization tower 8, a dust filter 9, a regenerated gas cooler 10, a regenerated gas heater 11 and a regenerated gas separator 12.
FIG. 3 is a graph of COS and CS in the advanced treatment of Natural gas as described in example 32Schematic diagram of the process system.
The natural gas heat exchanger comprises a natural gas heat exchanger 1, a primary condensed water injection pump 2, a primary natural gas-liquid separator 3, a primary natural gas heater 4, a primary natural gas organosulfur hydrolysis tower 5, a secondary condensed water injection pump 6, a secondary natural gas-liquid separator 7, a secondary natural gas heater 8, a secondary natural gas organosulfur hydrolysis tower 9, a natural gas cooler 10, a natural gas filtering separator 11, a molecular sieve dehydration desulfurization tower 12, a dust filter 13, a regenerated gas cooler 14, a regenerated gas heater 15 and a regenerated gas separator 16.
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 the following embodiments, but it should not be construed that the scope of the above-described subject matter of the present invention is limited only by the following examples.
Example 1:
COS and CS in advanced treatment of natural gas2As shown in fig. 1, the process system of (a) includes: natural gas heat exchanger 1, condensate water injection pump 2, natural gas vapour and liquid separator 3, natural gas heater 4, natural gas organosulfur hydrolysis tower 5, natural gas cooler 6 and downstream desulphurization unit, wherein:
the shell side outlet of the natural gas heat exchanger 1 is connected with the inlet of the natural gas primary gas-liquid separator 3 through a pipeline; the outlet of the condensed water injection pump 2 is connected with the outlet of the shell layer of the natural gas heat exchanger 1 through a pipeline; the outlet of the natural gas-liquid separator 3 is connected with the shell inlet of the natural gas heater 4 through a pipeline; the shell layer outlet of the natural gas heater 4 is connected with the inlet of the natural gas organic sulfur hydrolysis tower 5 through a pipeline; the outlet of the natural gas organic sulfur hydrolysis tower 5 is connected with the tube pass inlet of the natural gas heat exchanger 1 through a pipeline; the tube pass outlet of the natural gas heat exchanger 1 is connected with the shell layer inlet of the natural gas cooler 6 through a pipeline; and the outlet of the shell layer 6 of the natural gas cooler is connected with a downstream solution desulfurization device through a pipeline.
By adopting the above systemAdvanced treatment of COS and CS in natural gas2The specific process comprises the following steps:
h in natural gas after desulfurization from upstream solution2S content less than 6mg/Nm3. This time is divided into two cases: 1) when the raw material gas only contains COS or mainly contains COS (CS)2The content is less than 20mg/m3) In the process, natural gas is heated to 70-90 ℃ and enters a reactor, and almost all COS and CS are contained in the reactor2Hydrolysis to H2And S. When the temperature of the natural gas is more than or equal to 50 ℃ after the upstream solution is desulfurized, a condensate water injection pump and a gas-liquid separator can be omitted; 2) when the feed gas contains only CS2In the process, natural gas is heated to 110-130 ℃ and enters a reactor, and almost all CS is contained in the reactor2Hydrolysis to H2And S. The unconverted organic sulfur is less than 8mg/Nm by catalytic hydrolysis of the hydrolysis reactor3(based on total sulfur). Then the H in the purified gas is treated by a downstream desulphurization device2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3。
Example 2:
COS and CS in advanced treatment of natural gas2As shown in fig. 1, the process system of (a) includes: natural gas heat exchanger 1, condensate water injection pump 2, natural gas vapour and liquid separator 3, natural gas heater 4, natural gas organosulfur hydrolysis tower 5, natural gas cooler 6, natural gas filtering separator 7, molecular sieve dehydration desulfurizing tower 8, dust filter 9, regeneration gas cooler 10, regeneration gas heater 11, regeneration gas separator 12, wherein:
the shell side outlet of the natural gas heat exchanger 1 is connected with the inlet of the natural gas primary gas-liquid separator 3 through a pipeline; the outlet of the condensed water injection pump 2 is connected with the outlet of the shell layer of the natural gas heat exchanger 1 through a pipeline; the outlet of the natural gas-liquid separator 3 is connected with the shell inlet of the natural gas heater 4 through a pipeline; the shell layer outlet of the natural gas heater 4 is connected with the inlet of the natural gas organic sulfur hydrolysis tower 5 through a pipeline; the outlet of the natural gas organic sulfur hydrolysis tower 5 is connected with the tube pass inlet of the natural gas heat exchanger 1 through a pipeline; the tube pass outlet of the natural gas heat exchanger 1 is connected with the shell layer inlet of the natural gas cooler 6 through a pipeline; the outlet of the shell layer 6 of the natural gas cooler is connected with the inlet of a natural gas filtering separator 7 through a pipeline; (if the next step needs solution desulfurization, the outlet of the shell layer 6 of the natural gas cooler is connected with a downstream solution desulfurization device through a pipeline); the outlet of the natural gas filtering separator 7 is connected with the inlet of the molecular sieve desulfurization dehydration tower 7 through a pipeline; the outlet of the molecular sieve desulfurization dehydration tower 8 is connected with the inlet of a dust filter 9 through a pipeline; the outlet of the dust filter 9 is connected via a pipeline to a downstream processing facility or to an export pipeline. The regenerated gas of the molecular sieve is blown by the molecular sieve dehydration desulfurization tower 8, and the regeneration outlet is connected with the shell inlet of a regenerated gas heater 11 through a pipeline; the shell layer outlet of the regeneration gas heater 11 is connected with the hot blowing inlet of the molecular sieve dehydration desulfurization tower 8 through a pipeline; the hot blowing outlet of the molecular sieve dehydration desulfurization tower 8 is connected with the shell inlet of the regenerated gas cooler 10 through a pipeline; the shell outlet of the regeneration gas cooler 10 is connected with the inlet of a regeneration gas separator 12 through a pipeline; the outlet of the regeneration gas separator 12 is connected by a line to a regeneration gas downstream processing facility.
The system is adopted for deeply treating COS and CS in natural gas2The process comprises the following specific steps:
h in natural gas after desulfurization from upstream solution2S content less than 6mg/Nm3. At this time, the treatment is divided into two cases: 1) when the raw material gas only contains COS or mainly contains COS (CS)2The content is less than 20mg/m3) In the process, natural gas is heated to 70-90 ℃ and enters a reactor, and almost all COS and CS are contained in the reactor2Hydrolysis to H2And S. When the temperature of the natural gas is more than or equal to 50 ℃ after the upstream solution is desulfurized, a condensate water injection pump and a gas-liquid separator can be omitted; 2) when the feed gas contains only CS2In the process, natural gas is heated to 110-130 ℃ and enters a reactor, and almost all CS is contained in the reactor2Hydrolysis to H2And S. The unconverted organic sulfur is less than 8mg/Nm by catalytic hydrolysis of the hydrolysis reactor3(based on total sulfur). Then enters a molecular sieve dehydration and desulfurization device to adsorb H by the molecular sieve2After S treatment, the H in the gas is purified2S content less than 3mg/Nm3The total sulfur content is less than 8mg/Nm3. And regenerating the molecular sieve and then carrying out adsorption desulfurization treatment again.
Example 3:
COS and CS in advanced treatment of natural gas2As shown in fig. 2, comprises: the natural gas heat exchanger 1, one-level condensate water injection pump 2, natural gas one-level vapour and liquid separator 3, natural gas one-level heater 4, natural gas one-level organosulfur hydrolysis tower 5, second grade condensate water injection pump 6, natural gas second grade vapour and liquid separator 7, natural gas second grade heater 8, natural gas second grade organosulfur hydrolysis tower 9, natural gas cooler 10, natural gas filtering separator 11, molecular sieve dehydration desulfurizing tower 12, dust filter 13, regeneration gas cooler 14, regeneration gas heater 15, regeneration gas separator 16, etc., wherein:
the shell side outlet of the natural gas heat exchanger 1 is connected with the inlet of the natural gas primary gas-liquid separator 3 through a pipeline; the outlet of the primary condensed water injection pump 2 is connected with the outlet of the shell layer of the natural gas heat exchanger 1 through a pipeline; the outlet of the natural gas primary gas-liquid separator 3 is connected with the shell inlet of the natural gas primary heater 4 through a pipeline; the shell outlet of the natural gas primary heater 4 is connected with the inlet of the natural gas primary organosulfur hydrolysis tower 5 through a pipeline; the outlet of the natural gas first-stage organic sulfur hydrolysis tower 5 is connected with the inlet of a natural gas second-stage gas-liquid separator 7 through a pipeline; the outlet of the secondary condensed water injection pump 6 is connected with the outlet of the natural gas primary organic sulfur hydrolysis tower 5 through a pipeline; an outlet of the natural gas secondary gas-liquid separator 7 is connected with a shell layer inlet of the natural gas secondary heater 7 through a pipeline; an outlet of the shell layer of the natural gas secondary heater 8 is connected with an inlet of the natural gas secondary hydrolysis tower 9 through a pipeline; the outlet of the natural gas secondary hydrolysis tower 9 is connected with the tube pass inlet of the natural gas heat exchanger 1 through a pipeline; the tube pass outlet of the natural gas heat exchanger 1 is connected with the shell layer inlet of the natural gas cooler 10 through a pipeline; the outlet of the shell layer 10 of the natural gas cooler is connected with the inlet of a natural gas filtering separator 11 through a pipeline; (if solution desulfurization is required next, the outlet of the shell 10 of the natural gas cooler is connected with a downstream solution desulfurization device through a pipeline); the outlet of the natural gas filtering separator 11 is connected with the inlet of the molecular sieve desulfurization dehydration tower 12 through a pipeline; the outlet of the molecular sieve desulfurization and dehydration tower 12 is connected with the inlet of a dust filter 13 through a pipeline; the outlet of the dust filter 13 is connected by a pipeline to a downstream processing facility or to an export pipeline. The regenerated gas of the molecular sieve is cold-blown by the molecular sieve dehydration desulfurization tower 12, and the regeneration outlet is connected with the shell inlet of a regenerated gas heater 15 through a pipeline; the shell layer outlet of the regenerated gas heater 15 is connected with the hot blowing inlet of the molecular sieve dehydration desulfurization tower 8 through a pipeline; the hot blowing outlet of the molecular sieve dehydration desulfurization tower 12 is connected with the shell inlet of the regenerated gas cooler 14 through a pipeline; the shell outlet of the regeneration gas cooler 14 is connected with the inlet of a regeneration gas separator 16 through a pipeline; the outlet of the regeneration gas separator 16 is connected by a line to a regeneration gas downstream processing facility.
The system is adopted for deeply treating COS and CS in natural gas2The specific process comprises the following steps:
h in natural gas after desulfurization from upstream solution2S content less than 6mg/Nm3(ii) a When the feed gas contains a large amount of COS and CS2In the first-stage COS hydrolysis process, natural gas is heated to 70-90 ℃ and enters a reactor, and almost all COS and part of CS in the reactor2Hydrolysis to H2And S. When the temperature of the natural gas is more than or equal to 50 ℃ after the upstream solution is desulfurized, a condensate water injection pump and a gas-liquid separator can be omitted; in a second stage of hydrolysis of CS2Meanwhile, natural gas is heated to 110-130 ℃ and enters the reactor. The unconverted organic sulfur is less than 8mg/Nm by catalytic hydrolysis of the hydrolysis reactor3(based on total sulfur). Then treated by a downstream desulfurization device or a molecular sieve desulfurization dehydration device to purify H in the gas2S content 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; although the present invention has been described in detail with reference to the foregoing embodiments, it should 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; such modifications and substitutions do not depart from the spirit and scope of the present invention.
Claims (6)
1. COS and CS in advanced treatment of natural gas2The system comprises a hydrolysis device and a fine desulfurization device, and is characterized in that: the hydrolysis device comprises a natural gas heat exchanger, a natural gas heater, a natural gas organic sulfur hydrolysis tower and a natural gas cooler; the shell side outlet of the natural gas heat exchanger is connected with a natural gas heater through a pipeline, and the shell layer outlet of the natural gas heater is connected with the inlet of the natural gas organic sulfur hydrolysis tower through a pipeline; the outlet of the natural gas organic sulfur hydrolysis tower is connected with the tube pass inlet of the natural gas heat exchanger through a pipeline; the tube pass outlet of the natural gas heat exchanger is connected with the shell layer inlet of the natural gas cooler through a pipeline; the natural gas cooler is connected with the fine desulfurization device.
2. The method for deeply processing COS and CS in natural gas as claimed in claim 12The system of (a), characterized by: the fine desulfurization device is a downstream desulfurization device or a molecular sieve desulfurization dehydration device.
3. The method for deeply processing COS and CS in natural gas as claimed in claim 22The system of (a), characterized by: the molecular sieve desulfurization and dehydration device comprises a natural gas filtering separator, a molecular sieve dehydration and desulfurization tower, a dust filter, a regenerated gas cooler, a regenerated gas heater and a regenerated gas separator; the outlet of the natural gas cooler is connected with the inlet of the natural gas filtering separator through a pipeline; the outlet of the natural gas filtering separator is connected with the inlet of the molecular sieve desulfurization dehydration tower through a pipeline; the outlet of the molecular sieve desulfurization dehydration tower is connected with the inlet of the dust filter through a pipeline; the outlet of the dust filter is connected with a downstream processing facility or an external conveying pipeline through a pipeline; a cold blowing regeneration outlet of the molecular sieve dehydration desulfurization tower is connected with a shell inlet of a regenerated gas heater through a pipeline; the shell layer outlet of the regenerated gas heater is connected with the hot blowing inlet of the molecular sieve dehydration desulfurization tower through a pipeline; molecular sieve dehydration and dehydrationThe hot blowing outlet of the sulfur tower is connected with the shell inlet of the regenerated gas cooler through a pipeline; the shell layer outlet of the regenerated gas cooler is connected with the inlet of the regenerated gas separator through a pipeline; the outlet of the regeneration gas separator is connected with a downstream treatment facility of the regeneration gas through a pipeline.
4. The deep processing of COS and CS in natural gas as claimed in any one of claims 1 to 32The system of (a), characterized by: a condensed water injection pump and a gas-liquid separator are sequentially arranged on a pipeline between the natural gas heat exchanger and the natural gas heater.
5. The method for deeply processing COS and CS in natural gas as claimed in claim 32The system of (a), characterized by: the molecular sieve dehydration desulfurization tower is 2 towers, 3 towers or 4 towers, and the molecular sieve dehydration desulfurization tower are connected in parallel.
6. The method for deeply processing COS and CS in natural gas as claimed in claim 32The system of (a), characterized by: the natural gas organic sulfur hydrolysis tower is divided into a natural gas primary organic sulfur hydrolysis tower and a natural gas secondary organic sulfur hydrolysis tower, and the natural gas primary organic sulfur hydrolysis tower is connected with the natural gas secondary organic sulfur hydrolysis tower in series; a second-stage condensed water injection pump, a natural gas second-stage gas-liquid separator and a natural gas second-stage heater are sequentially arranged between the natural gas first-stage organic sulfur hydrolysis tower and the natural gas second-stage organic sulfur hydrolysis tower.
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