CN210888897U - Gas field well head CO2Device for improving natural gas recovery ratio by reinjection - Google Patents
Gas field well head CO2Device for improving natural gas recovery ratio by reinjection Download PDFInfo
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Abstract
The utility model discloses the operating mode has been described2And reinjecting to improve the natural gas recovery ratio. The device comprises a natural gas hydrogen production device arranged at a gas field wellhead, and H produced by the natural gas hydrogen production device2External transportationCO produced2And reinjecting the mixture to a gas field through a compressor. The utility model discloses the device can be at the gas field well head carbon desorption in the natural gas for high-purity CO2And is converted into high-purity H2，H2As market product export, export CO2And reinjecting the mixture to a gas field at a well mouth to improve the recovery ratio. The utility model discloses the device has following advantage: the natural gas decarbonization hydrogen production can be directly realized at the pithead of the natural gas field, and the method is particularly suitable for working conditions of high pressure and high airspeed, so that the natural gas pressure of the gas field does not need to be greatly reduced, and the energy loss is reduced; injecting the carbon dioxide removed from the pithead back to the natural gas field for improving the recovery ratio; obtaining a high-purity hydrogen product; the purity of the separated carbon dioxide is high, the cost of the carbon dioxide can be greatly reduced, and the whole carbon emission is reduced.
Description
Technical Field
The utility model relates to a gas field well head CO2A device for improving the recovery ratio of natural gas by reinjection belongs to the field of natural gas recovery.
Background
CO2Enhanced oil and gas reservoir recovery is one of the rapidly developing enhanced oil recovery techniques in recent years. Years of research and practice prove that CO is utilized2And CH4Difference in adsorptivity, CO2The shale gas, the coal bed gas and the conventional natural gas reservoir can be injected to effectively improve the natural gas recovery ratio (EGR), thereby not only improving the natural gas recovery ratioHigh natural gas extraction efficiency, increased economic benefit and capability of realizing CO2An important way of integrating gas capture, sealing and storage and application (CCUS) is a win-win way of increasing energy and protecting the environment. In fact, from CO2Stability of sequestration, scale of utilization, value of creation of utilization, etc., CO2Enhanced recovery is one of the best options to achieve CCUS.
Injecting CO, e.g. coal bed gas2The total cleat pressure of the coal bed can be increased, and the partial pressure of methane in cleat is locally reduced, so that the desorption speed and the diffusion speed are improved; the structural characteristics of the carbon dioxide molecules determine that the adsorption effect of the carbon dioxide molecules on the coal matrix is greater than that of the methane molecules, the carbon dioxide molecules and the methane molecules have a competitive effect on the adsorption of the coal matrix, and more methane is desorbed from the coal matrix through the competitive adsorption displacement effect.
However, it is often not possible to have large amounts of CO near the oil and gas field2Resource and scale application of CO must be solved2Source and price of. CO capture from cities, power plants, chemical plants, etc2And transportation to oil and gas fields generally requires laying of long-distance CO2The transportation cost of the pipeline or the compression tank truck is high, and the influence on CO is caused2The economic performance of recovery ratio and the feasibility of engineering technology are improved. It is therefore desirable to provide a gas field wellhead CO2And reinjecting to improve the natural gas recovery ratio.
SUMMERY OF THE UTILITY MODEL
The utility model aims at providing a gas field well head CO2The device for improving the recovery ratio of the natural gas by reinjection can remove carbon in the natural gas into high-purity CO at the wellhead of a gas field2And is converted into high-purity H2，H2As market product export, export CO2And reinjecting the mixture to a gas field at a well mouth to improve the recovery ratio.
The utility model discloses not only can reduce CO2Cost of, large scale CO elimination2The transportation of (2) can also supply high-purity hydrogen directly to the market, and provide hydrogen resources for the hydrogenation station.
The utility model provides a gas field well head CO2Reinjection of enhanced natureThe gas recovery device comprises a natural gas hydrogen production device arranged at a gas field wellhead;
h generated by the natural gas hydrogen production device2Export of produced CO2And reinjecting the mixture to a gas field through a compressor.
In the device, the natural gas hydrogen production device comprises a methane reforming decarbonization reactor, a CO conversion reactor and a low-temperature methanol washing and pressure swing adsorption unit which are connected in sequence;
obtaining the purified CO by the low-temperature methanol washing2；
Purified H is obtained by the pressure swing adsorption unit2。
The reforming reaction of the methane reforming and decarbonizing reactor can be carried out under the conventional conditions, wherein CH in natural gas4、C2H6、C3H8、C4H10And C5+A reforming reaction with steam occurs.
In the device, a heat exchanger is arranged between the methane reforming decarbonization reactor and the CO shift reactor;
the heat exchanger is connected with a steam drum and can be used for producing steam, the steam can be generated by the steam drum, one part of the steam is used as reaction raw materials, and the other part of the steam is output as a byproduct.
In the device, the CO shift reaction in the CO shift reactor can be carried out under the conventional condition and can be divided into a high-temperature CO shift reaction and a low-temperature CO shift reaction which are carried out in sequence, and CO and steam react under a catalyst to generate CO through the reaction2And H2And release a large amount of heat.
In the plant, the low-temperature methanol wash can be carried out under conventional conditions for removing sulphur, nitrogen and carbon dioxide, passing CO inside the section2Desorption tower, flash tank, etc., from CO2CO with purity more than 80% is obtained at the top of the product tower2。
In the device, the pressure swing adsorption unit is used for generating high-purity H2Can be carried out under conventional conditions; and is produced by the pressure swing adsorption unitPurge gas (containing CH at a certain concentration)4) After pressurization, the natural gas is mixed with the natural gas.
In the device, the natural gas hydrogen production device can also have the following structure:
comprises a methane reforming decarbonization reactor, a CO shift reactor and low-temperature methanol washing which are connected in sequence.
In the device, heat exchangers are arranged at the inlet of the methane reforming and decarbonizing reactor, between the methane reforming and decarbonizing reactor and the CO shift reactor and between the CO shift reactor and the low-temperature methanol scrubber.
In the device, the natural gas hydrogen production device can also have the following structure:
comprises a methane reforming decarbonization reactor, a CO shift reactor, a pressure swing adsorption unit and/or a membrane separator which are connected in sequence.
In the device, the inlet of the methane reforming decarbonization reactor is connected with a deep desulfurization reactor.
In the device, a pipeline for conveying oxygen or air is connected with the methane reforming decarbonization reactor and used for adding oxygen or air into natural gas so as to improve the temperature of methane decarbonization reaction, and the adding amount of the pipeline is 0-30% of the natural gas.
The utility model has the advantages of as follows:
(1) the natural gas decarburization hydrogen production is directly realized at the pithead of the natural gas field, and the method is particularly suitable for working conditions of high pressure and high airspeed, so that the natural gas pressure of the gas field does not need to be greatly reduced, and the energy loss is reduced;
(2) injecting the carbon dioxide removed from the pithead back to the natural gas field for improving the recovery ratio;
(3) the pressure adaptation range of the pressure regulator for the natural gas field is wide and ranges from 0.5MPa to 20 MPa;
(4) the reaction heat absorption and release characteristics are fully utilized, and the heat balance design is realized;
(5) adding high purity oxygen to increase natural gas reforming temperature and methane conversion efficiency;
(6) obtaining a high-purity hydrogen product;
(7) the purity of the separated carbon dioxide is high, the cost of the carbon dioxide can be greatly reduced, and the whole carbon emission is reduced.
Drawings
FIG. 1 shows the decarbonization and CO separation of natural gas at the wellhead of the gas field2And the first schematic diagram of the device for reinjecting the enhanced oil recovery factor.
FIG. 2 shows the decarbonization and CO separation of natural gas at the wellhead of the gas field2And a second schematic diagram of a device for reinjecting the enhanced oil recovery factor.
FIG. 3 shows the decarbonization and CO separation of natural gas at the wellhead of the gas field2And a third schematic diagram of a device for reinjecting the enhanced oil recovery factor.
FIG. 4 shows the decarbonization and CO separation of natural gas at the wellhead of the gas field2And a fourth schematic diagram of a device for reinjecting the enhanced oil recovery factor.
FIG. 5 shows the decarburization of natural gas and CO at the wellhead of the gas field2And a fifth schematic diagram of a device for reinjecting the enhanced oil recovery factor.
The respective labels in FIG. 1 are as follows:
1 deep desulfurization reactor, 2, gas-gas mixer, 3, reforming reactor, 4 high-temperature CO shift reactor, 5 low-temperature CO shift reactor, 6 low-temperature methanol washing, 7 pressure swing adsorption unit (PSA), 8 purge gas circulating compressor, 9 CO2 compressor, 10, steam drum, 11 membrane separation, G1 natural gas feed gas, G2 hydrogen, G3 CO2G4 air or oxygen, W1 boiler water.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to the following embodiments.
Examples 1,
A schematic of the apparatus is shown in figure 1.
The natural gas collected and transported and simply treated in a typical Sichuan gas field is used as raw material gas, and the chemical composition and parameters are shown in the table.
TABLE 1 feed gas composition and parameters (mol%)
| CH4 | C2H6 | C3H8 | C4H10 | C5+ | H2 | Temperature of | Pressure of |
| 97 | 2.7 | 0.2 | -- | -- | 0.1 | 25℃ | 2MPa |
The natural gas heated to 180 ℃ is mixed with a certain amount of saturated vapor (230 ℃) of 3.5MPa and then enters a deep desulfurization reactor 1 to carry out desulfurization reaction, and a small amount of H possibly contained in the natural gas is removed2And (4) removing the S. Then the purge gas of the pressure swing adsorption unit (PSA)7 after being mixed and compressed and pressurized is uniformly mixed in a gas-gas mixer 2, and enters a reforming reactor 3 after being heated to 750 ℃, wherein the space velocity is about 8000h-1CH in Natural gas4、C2H6、C3H8、C4H10And C5+The reforming reaction with the steam is carried out, and the reaction process is as follows:
the steam reforming reaction of methane mainly comprises the following reactions:
CH4+H2O(g)＝CO+3H2ΔH＝206.2KJ/mol
CH4+2H2O(g)＝CO2+4H2ΔH＝164.9KJ/mol
2CH4+O2＝2CO+4H2ΔH＝-71.4KJ/mol
CH4+2O2＝CO2+2H2O ΔH＝-802.7KJ/mol
the reaction process occurring for C2+ hydrocarbons is similar.
The composition of the process gas at the outlet of the reforming reactor 3 is about:
TABLE 2 effective gas composition (mol%) of reforming reactor outlet process gas
| CO2 | CO | H2 | CH4 | H2O | Others |
| 4.5 | 0.7 | 19.0 | 40.7 | 34.9 | 0.2 |
The gas temperature at the outlet of the reforming reactor 3 is about 570 ℃, heat is recovered through E1 heat exchange, the temperature is regulated to 360 ℃ through E5, the gas enters a high-temperature CO shift reactor 4 and a low-temperature CO shift reactor 5, CO and steam react under a catalyst to generate CO2And H2And release a large amount of heat. The heat released in the process is recovered by E2 and E3.
The reactions that occur are as follows:
CO+H2o (steam) ═ H2+CO2ΔH＝-41.16kJ/mol
The effective components of the off-gas after the low temperature CO shift reactor 5 are about:
TABLE 3 Low temperature CO shift export effective gas composition (mol%)
| CO2 | CO | H2 | CH4 | H2O |
| 37.8 | 1.12 | 47.4 | 8.28 | 5.4 |
The temperature was increased to about 330 ℃. Is cooled to 43 ℃ by heat exchangeAfter the temperature is lower than the temperature, the mixture enters a low-temperature methanol washing 6 working section to remove sulfur, nitrogen and carbon dioxide, and CO passes through the interior of the working section2Desorption tower, flash tank, etc., from CO2CO with purity more than 80% is obtained at the top of the product tower2。CO2After being pressurized by the compressor 9, is returned to the gas field for enhanced recovery (EGR).
After the process gas washed by 6 low-temperature methanol is subjected to gas-liquid separation, the effective gas composition is about:
TABLE 4 effective gas composition (mol%) of Process gas at Low temperature methanol purge outlet
| CO2 | CO | H2 | CH4 | H2O |
| 1.6 | 1.8 | 77.45 | 13.53 | 5.62 |
The temperature was about 40 ℃.
The outlet process gas after the low-temperature methanol washing 6 passes through a pressure swing adsorption unit 7 for producing G2H2(> 90%). The purge gas of the pressure swing adsorption unit 7 still contains CH with a certain concentration4The raw material gas is not completely reacted and is converged to the gas mixer 2 after being pressurized by the compressor 8.
The heat exchangers E1, E2 and E3 use the generated heat for the production of steam, which is generated by the drum 10 and partly as reaction raw material and partly exported as by-product.
Examples 2,
A schematic of the apparatus is shown in figure 2.
Natural gas collected and transported and simply treated in a typical Sichuan gas field is used as raw material gas, and the chemical composition and parameters are shown in the table 1.
Mixing natural gas heated to 180 ℃ with a certain amount of saturated vapor (230 ℃) of 3.5MPa, then entering a deep desulfurization reactor (1) for desulfurization reaction, and carrying out desulfurization reaction on a small amount of H possibly contained in the natural gas2And (4) removing the S. Then mixing the purge gas of the pressure swing adsorption unit 7 after compression and pressurization with the purified high-purity oxygen (more than 99 percent), adding the purified high-purity oxygen in a proportion of 5 percent of the process gas amount, uniformly mixing the purge gas and the purified high-purity oxygen in a gas-gas mixer 2, heating the mixture to 600 ℃, and then feeding the mixture into a reforming reactor 3, wherein the space velocity is about 10000h-1CH in Natural gas4、C2H6、C3H8、C4H10And C5+The reforming reaction with steam takes place in the same manner as in example 1.
The composition of the process gas at the outlet of the reforming reactor 3 is about:
TABLE 5 effective gas composition (mol%) of Process gas at the outlet of reforming reactor
| CO2 | CO | H2 | CH4 | H2O | Others |
| 7.2 | 11.5 | 43.8 | 13.4 | 24.0 | 0.1 |
The gas temperature at the outlet of the reforming reactor 3 is about 780 ℃, heat is recovered through E1 heat exchange, the temperature is adjusted to 360 ℃ through E5, the gas enters a high-temperature CO shift reactor 4 and a low-temperature CO shift reactor 5, CO and steam react under a catalyst to generate CO2And H2And release a large amount of heat. The heat released in the process is recovered by E2 and E3. The reaction occurred as in example 1.
The effective components of the off-gas after the low temperature CO shift reactor 5 are about:
TABLE 6 Low temperature CO shift export effective gas composition (mol%)
| CO2 | CO | H2 | CH4 | H2O |
| 31 | 0.7 | 15.3 | 8 | 45 |
The temperature was increased to about 330 ℃. Cooling to 43 deg.C by heat exchange, washing with methanol at low temperature to remove sulfur, nitrogen and carbon dioxide, and introducing CO gas into the section2Desorption tower, flash tank, etc., from CO2CO with purity more than 80% is obtained at the top of the product tower2。CO2After being pressurized by 9 compressors, the gas is sent back to the gas field for improving the recovery ratio (EGR).
After the process gas washed by 6 low-temperature methanol is subjected to gas-liquid separation, the effective gas composition is about:
TABLE 7 effective gas composition (mol%) of low temperature methanol wash outlet process gas
| CO2 | CO | H2 | CH4 | H2O |
| 0.8 | 1.2 | 78.8 | 13 | 6.2 |
The temperature was about 40 ℃.
The outlet process gas after the low-temperature methanol washing 6 passes through a pressure swing adsorption unit 7 for producing G2H2(> 90%). The purge gas of the pressure swing adsorption unit 7 still contains CH with a certain concentration4The raw material gas is not completely reacted and is converged to the gas mixer 2 after being pressurized by the compressor 8.
Examples 3,
A schematic of the apparatus is shown in figure 3.
The natural gas collected and transported and simply treated in a typical Sichuan gas field is used as raw material gas, and the chemical composition and parameters are shown in the table.
Mixing a certain amount of saturated vapor (230 ℃) with 3.5MPa with the raw material gas, exchanging heat to about 180 ℃ through a heat exchanger E8, then entering a deep desulfurization reactor 1 for desulfurization reaction, and carrying out desulfurization reaction on a small amount of H possibly contained in the natural gas2And (4) removing the S. Then heating to about 530 ℃ by a heat exchanger E7, mixing with a certain amount of saturated steam, entering a gas-gas mixer 2 for uniform mixing, heating to 750 ℃, entering a reforming reactor 3, and ensuring the space velocity to be about 6000h-1CH in Natural gas4、C2H6、C3H8、C4H10And C5+The reforming reaction with steam takes place in the same manner as in example 1.
The composition of the process gas at the outlet of the reforming reactor 3 is as shown in Table 2.
The temperature of the gas at the outlet of the reforming reactor 3 is about 570 ℃, the gas is subjected to heat exchange by E7, the temperature is adjusted to 360 ℃ by E6, the gas enters the medium-temperature CO shift reactor 5, CO and steam react under a catalyst to generate CO2And H2And release a large amount of heat. The heat released in the process is exchanged by E8. The reaction occurred as in example 1.
The effective components of the off-gas after the medium temperature CO shift reactor 5 are as in table 3.
The temperature was increased to about 330 ℃. Cooling to 43 deg.C by heat exchange, washing with methanol at low temperature to remove sulfur, nitrogen and carbon dioxide, and introducing CO gas into the section2Desorption tower, flash tank, etc., from CO2CO with purity more than 80% is obtained at the top of the product tower2(G2)。CO2After being pressurized by 9 compressors, the gas is sent back to the gas field for improving the recovery ratio (EGR).
After 6 low-temperature methanol washes of the process gas, the effective gas composition is the same as table 4 after gas-liquid separation. The temperature was about 40 ℃.
Process gas discharged after low-temperature methanol washing of 6 ℃ is used for producing G2H2(＞70％)。
Examples 4,
A schematic of the apparatus is shown in figure 4.
Natural gas collected and transported and simply treated in a typical Sichuan gas field is used as raw material gas, and the chemical composition and parameters are shown in the table 1.
Mixing a certain amount of saturated vapor (230 ℃) with 3.5MPa with the raw material gas, exchanging heat to about 180 ℃ through a heat exchanger E8, then entering a deep desulfurization reactor 1 for desulfurization reaction, and carrying out desulfurization reaction on a small amount of H possibly contained in the natural gas2And (4) removing the S. Then mixing with a certain amount of purified high-purity oxygen, heating to about 530 ℃ by a heat exchanger E7, mixing with a certain amount of saturated steam, entering a gas-gas mixer 2 for uniform mixing, heating to 600 ℃, entering a reforming reactor 3, wherein the space velocity is about 8000h-1CH in Natural gas4、C2H6、C3H8、C4H10And C5+The reforming reaction with steam takes place in the same manner as in example 1.
The outlet process gas composition of the reforming reactor 3 is given in table 8:
TABLE 8 effective gas composition (mol%) of Process gas at the outlet of reforming reactor
| CO2 | CO | H2 | CH4 | H2O | Others |
| 7.2 | 11.5 | 43.8 | 13.4 | 24.0 | 0.1 |
The temperature of the gas at the outlet of the reforming reactor 3 is about 780 ℃, the gas is subjected to heat exchange by E7, is subjected to temperature regulation to 360 ℃ by E6, enters the medium-temperature CO shift reactor 5, and CO and steam react under a catalyst to generate CO2And H2And release a large amount of heat. The heat released in the process is exchanged by E8.
The reaction occurred as in example 1.
The effective components of the off-gas after the medium temperature CO shift reactor 5 are shown in table 9:
TABLE 9 composition (mol%) of effective gas at the outlet of medium temperature CO shift
| CO2 | CO | H2 | CH4 | H2O |
| 1.6 | 1.8 | 77.45 | 13.53 | 5.62 |
The temperature was increased to about 330 ℃. Cooling to 43 deg.C by heat exchange, washing with methanol at low temperature to remove sulfur, nitrogen and carbon dioxide, and introducing CO gas into the section2Desorption tower, flash tank, etc., from CO2CO with purity more than 80% is obtained at the top of the product tower2(G2)。CO2After being pressurized by 9 compressors, the gas is sent back to the gas field for improving the recovery ratio (EGR).
After 6 low-temperature methanol washes of the process gas, the effective gas composition after gas-liquid separation is as shown in table 10.
TABLE 10 effective gas composition (mol%) of Low temperature methanol purge process gas
| CO2 | CO | H2 | CH4 | H2O |
| 0.8 | 1.2 | 78.8 | 13 | 6.2 |
The temperature was about 40 ℃.
Process gas discharged after low-temperature methanol washing of 6 ℃ is used for producing G2H2(＞70％)。
Examples 5,
A schematic of the apparatus is shown in figure 5.
Natural gas collected and transported and simply treated in a typical Sichuan gas field is used as raw material gas, and the chemical composition and parameters are shown in table 1.
Mixing a certain amount of saturated vapor (230 ℃) with 3.5MPa with the raw material gas, exchanging heat to about 180 ℃ through a heat exchanger E8, then entering a deep desulfurization reactor 1 for desulfurization reaction, and carrying out desulfurization reaction on a small amount of H possibly contained in the natural gas2And (4) removing the S. Then mixing with a certain amount of purified high-purity oxygen, heating to about 530 ℃ by a heat exchanger E7, mixing with a certain amount of saturated steam, entering a gas-gas mixer 2 for uniform mixing, heating to 600 ℃, entering a reforming reactor 3, wherein the space velocity is about 8000h-1CH in Natural gas4、C2H6、C3H8、C4H10And C5+The reforming reaction with steam takes place in the same manner as in example 1.
The composition of the process gas at the outlet of the reforming reactor 3 is as shown in Table 5.
The temperature of the gas at the outlet of the reforming reactor 3 is about 780 ℃, the gas is subjected to heat exchange by E7, is subjected to temperature regulation to 360 ℃ by E6, enters the medium-temperature CO shift reactor 5, and CO and steam react under a catalyst to generate CO2And H2And release a large amount of heat. The heat released in the process is exchanged by E8. The reaction occurred as in example 1.
The effective components of the off-gas after the medium temperature CO-shift reactor 5 are shown in table 4.
The temperature was increased to about 330 ℃. After the temperature is reduced to 43 ℃ through heat exchange, the mixture enters a pressure swing adsorption unit 7 or a membrane separation unit 11 or a series device of the pressure swing adsorption unit 7 and the membrane separation unit 11 and is used for separating CO2And H2. Separated CO2The purity is more than 50 percent, and the mixture is sent back to a gas field for improving the recovery ratio (EGR) after being pressurized by a 9-compressor.
Process gas at outlet of section 7/membrane separation 11 of pressure swing adsorption unit for producing G2H2(＞70％)。
Claims (8)
1. Gas field well head CO2The device for improving the recovery ratio of the natural gas by reinjection comprises a natural gas hydrogen production device arranged at a gas field wellhead; the method is characterized in that:
h generated by the natural gas hydrogen production device2Export of produced CO2And reinjecting the mixture to a gas field through a compressor.
2. The apparatus of claim 1, wherein: the natural gas hydrogen production device comprises a methane reforming decarbonization reactor, a CO conversion reactor, a low-temperature methanol washing unit and a pressure swing adsorption unit which are connected in sequence.
3. The apparatus of claim 2, wherein: a heat exchanger is arranged between the methane reforming decarbonization reactor and the CO shift reactor;
the heat exchanger is connected with a steam drum.
4. The apparatus of claim 1, wherein: the natural gas hydrogen production device comprises a methane reforming decarbonization reactor, a CO shift reactor and a low-temperature methanol scrubber which are sequentially connected.
5. The apparatus of claim 4, wherein: and heat exchangers are arranged at the inlet of the methane reforming and decarbonizing reactor, between the methane reforming and decarbonizing reactor and the CO shift reactor and between the CO shift reactor and the low-temperature methanol washing.
6. The apparatus of claim 1, wherein: the natural gas hydrogen production device comprises a methane reforming decarbonization reactor, a CO conversion reactor, a pressure swing adsorption unit and/or a membrane separator which are connected in sequence.
7. The apparatus according to any one of claims 2-6, wherein: and the inlet of the methane reforming decarbonization reactor is connected with the deep desulfurization reactor.
8. The apparatus of claim 7, wherein: and a pipeline for conveying oxygen or air is connected with the methane reforming and decarbonizing reactor.
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