CN110280040B - Device and method for stripping carbon dioxide gas - Google Patents
Device and method for stripping carbon dioxide gas Download PDFInfo
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- CN110280040B CN110280040B CN201910576048.XA CN201910576048A CN110280040B CN 110280040 B CN110280040 B CN 110280040B CN 201910576048 A CN201910576048 A CN 201910576048A CN 110280040 B CN110280040 B CN 110280040B
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- B01D3/06—Flash distillation
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Abstract
A device and a method for stripping carbon dioxide gas are provided, wherein a methanol-rich pipeline is connected with a methanol-rich pressure reduction control valve; the methanol-rich pressure reduction control valve is connected with the methanol-rich flash separation tank; the methanol-rich flash separation tank is connected with a liquid level control valve; the liquid level control valve is connected with the stripping tower, and the carbon dioxide gas pipeline is connected with the stripping tower; the stripping tower is connected with a stripping tower pressure control valve, and the stripping tower pressure control valve is connected to a circulating gas pipeline. The process is rich methanol which absorbs gas in the low-temperature methanol washing process, and part of effective gas stripping (H) is correspondingly dissolved in the methanol2CO), reducing the effective gas (H) in the methanol-rich gas through pressure reduction flash evaporation and gas stripping of carbon dioxide gas2CO) content, reducing the effective gas (H) in the process2CO), the energy-saving benefit of the process is increased, and the environmental pollution of carbon monoxide emission atmosphere is reduced.
Description
Technical Field
The invention belongs to the field of gas purification, and particularly relates to a low-temperature methanol washing processEffective gas (H)2CO) recovery.
Background
Methanol used for purification in the low-temperature methanol washing process absorbs acid gas which is not beneficial to the requirement of downstream processes and also absorbs and dissolves a part of effective gas (H)2CO), reducing the effective gas (H) in the low-temperature methanol washing process2CO), and increases the environmental pollution of carbon monoxide discharged atmosphere. Although the pressure reduction flash evaporation is also applied in the current low-temperature methanol washing process, namely the pressure reduction flash evaporation of the rich methanol which absorbs the dissolved gas is carried out, so that the effective gas (H) in the rich methanol is reduced2CO) but rich in effective gas (H) in methanol2CO), especially in the purification of carbon monoxide-rich process gases, the methanol-rich dissolution of residual carbon monoxide leads to carbon monoxide contents in the gas discharged to the atmosphere during the low-temperature methanol washing process of more than 5000 ppm. Current hydrogen stripping methods for reducing carbon monoxide in methanol-rich processes reduce the carbon monoxide content of the methanol-rich process, but result in increased hydrogen content in the methanol-rich process and increased process hydrogen losses.
Disclosure of Invention
The invention aims to provide a device and a method for stripping carbon dioxide gas, which are used for reducing effective gas (H) in rich methanol in the process of low-temperature methanol washing2CO) content, reducing effective gas (H) in the process of low-temperature methanol washing2CO) to achieve the purpose of saving energy and reducing consumption in the process of low-temperature methanol washing.
The technical conception of the invention is as follows:
low-temperature methanol washing process in the process of purifying process gas, a part of effective gas (H)2CO) is taken out of the system along with the absorbed rich methanol and is discharged to the atmosphere, so that the effective gas (H) in the low-temperature methanol washing process is reduced2CO), the current processes of methanol-rich pressure reduction flash evaporation and hydrogen stripping are not ideal.
The technical idea of the invention is to utilize the rich methanol after flash evaporation in the low-temperature methanol washing process of carbon dioxide gas stripping and utilize the carbon dioxide gas strippingReduction of effective gas (H) in gas phase2CO) partial pressure, thereby reducing the effective gas (H)2CO) in methanol, reducing the effective gas (H) in methanol-rich2CO) content, increasing the effective gas (H)2CO) recovery and utilization rate. In the low-temperature methanol washing process, the carbon dioxide gas is rich, and meanwhile, the carbon dioxide gas cannot cause gas pollution in the low-temperature methanol washing process and the subsequent process.
The technical solution of the invention is (see the attached figure 1):
the rich methanol absorbed by the process gas in the low-temperature methanol washing process engineering not only dissolves the acid gas which is not beneficial to the production of the downstream process, but also dissolves a part of effective gas (H)2CO). The recovery rate of the effective gas directly influences the energy conservation of the whole low-temperature methanol washing process, and carbon monoxide is also discharged to pollute the atmosphere.
The current effective gas recovery means comprises a process method for recovering hydrogen and carbon monoxide by methanol-rich pressure reduction flash evaporation and hydrogen gas stripping methanol-rich carbon monoxide recovery. Depressurization flash does not allow more complete recovery of the useful gas (H)2CO), and the loss of hydrogen is increased while carbon monoxide is recovered by hydrogen stripping.
The method for stripping the methanol from the carbon dioxide gas can recover more effective gas (H) dissolved in the methanol2CO), more hydrogen in the rich methanol is recovered while the carbon monoxide is recovered, the carbon dioxide cannot pollute the downstream process, the recovery rate of effective gas in the low-temperature methanol washing process is increased, and the environmental pollution caused by the emission of the carbon monoxide to the atmosphere is reduced.
The method comprises the following specific steps:
a device for stripping carbon dioxide gas is characterized in that a first methanol-rich pipeline is connected with a methanol-rich pressure reduction control valve; the methanol-rich pressure reduction control valve is connected with the methanol-rich flash separation tank; the methanol-rich flash separation tank is connected with a liquid level control valve; the liquid level control valve is connected with the stripping tower, and the carbon dioxide pipeline is connected with the stripping tower; the stripping tower is connected with a stripping tower pressure control valve, and the stripping tower pressure control valve is connected to a circulating gas pipeline.
The methanol-rich flash evaporation separation tank is connected with a flash evaporation gas pressure control valve, and the flash evaporation gas pressure control valve is connected to a circulating gas pipeline. The stripping tower is also connected with a methanol-rich pipeline II.
According to the technical scheme, the methanol-rich gas absorbing the process gas in the depressurized low-temperature methanol washing process enters a stripping tower, and gas stripping is performed by using gaseous carbon dioxide.
The rich methanol is decompressed and flashed by a flash separation tank, the flashed rich methanol enters a stripping tower, the rich methanol is stripped in the stripping tower by gas carbon dioxide, and the flash steam flashed by the flash separation tank is converged with the stripping gas at the outlet of the stripping tower to form cycle gas for recycling; the rich methanol at the outlet of the stripping tower is sent to a downstream regeneration process for regeneration.
Rich methanol absorbing the process gas in the low-temperature methanol washing process enters a flash separation tank under the control of a pressure reduction control valve, and part of gas is flashed; the flashed rich methanol enters a stripping tower under the control of a liquid level control valve, and is stripped by gas carbon dioxide, part of gas in the flashed rich methanol is determined by the amount of the stripped carbon dioxide; the stripped rich methanol is sent to a downstream regeneration process for regeneration; and the flash steam of the flash separation tank and the stripping gas of the stripping tower are converged to form circulating gas so as to be recycled.
And a tower tray or a filler is arranged in the stripping tower so as to complete the stripping process of mass and heat transfer of the gaseous carbon dioxide and the rich methanol.
Wherein the top parts of the flash separation tank and the stripping tower are provided with defoaming devices for reducing liquid drops carried by gas.
The methanol absorbing gas in the low-temperature methanol washing process comprises desulfurized rich methanol and decarbonized rich methanol;
wherein the desulfurized rich methanol is at-28 deg.C and 5.3Mpa, and contains 0.2-0.7% of H2CO with the mole fraction of 0.4-1.0%;
the decarbonized methanol-rich product is 10833Kmol/H, at-36 deg.C and 5.6Mpa, and contains 0.2-0.8% of H2And CO with the mole fraction of 0.4-1.0%.
In the flash separation process, the pressure in the flash separation process is 1.1-1.5MPa, and the temperature is-25 ℃ to-35 ℃.
The flow ratio of the rich methanol and the carbon dioxide after the flash separation to the stripping tower is 6-30: 1.
the desulfurized methanol-rich gas after stripping comprises 5-10% of H2, 15-28% of CO and 65-78% of CO in molar fraction2。
The decarbonized rich methanol after stripping comprises 25 to 35 percent of CO in molar fraction and 50 to 65 percent of CO in molar fraction25-12% mole fraction of H2。
According to the technical scheme, in the low-temperature methanol washing process, rich methanol which absorbs process gas is subjected to pressure reduction and flash evaporation to obtain partial gas;
the rich methanol which flashes out part of the gas enters a stripping tower to be stripped by stripping carbon dioxide so as to drive more effective gas dissolved in the rich methanol;
the flash steam of the methanol-rich pressure reduction flash evaporation and the stripping gas of the stripping tower are merged for reutilization.
Drawings
FIG. 1 shows a carbon dioxide stripping apparatus, an L1 pressure-reducing control valve for methanol-rich, a V methanol-rich flash separation tank, an L2 liquid level control valve, a T stripper, a P1 flash gas pressure control valve, a P2 stripper pressure control valve, a recycle gas pipeline 1, a methanol-rich pipeline I, a carbon dioxide pipeline 3, and a methanol-rich pipeline II 4.
Detailed Description
The invention will be further described with reference to fig. 1 and the following examples.
Example 1
A carbon dioxide gas stripping device is characterized in that a methanol-rich pipeline I2 is connected with a methanol-rich pressure reduction control valve L1; a methanol-rich pressure reduction control valve L1 is connected with the methanol-rich flash separation tank V; the methanol-rich flash separation tank V is connected with a liquid level control valve L2; the liquid level control valve L2 is connected with the stripping tower T, and the carbon dioxide pipeline 3 is connected with the stripping tower T; the stripper column T is connected to a stripper column pressure control valve P2, which is connected to the recycle gas line P2. The methanol-rich flash separation tank V is connected with a flash gas pressure control valve P1, and the flash gas pressure control valve P1 is connected to the circulating gas pipeline 1. And the stripping tower T is also connected with a methanol-rich pipeline II 4. And a demister for reducing gas carrying liquid is arranged at the top of the methanol-rich flash separation tank V and the top of the stripping tower T, and a tower tray or a filler is arranged in the gas tower T and used for convection mass transfer and heat transfer of the gas and the liquid in the tower.
Example 2
Take a process for preparing methanol by gasifying coal water slurry capable of producing 90 ten thousand tons of methanol in a year as an example
A gas stripping process of carbon dioxide gas comprises the steps of separating rich methanol which absorbs gas in the low-temperature methanol washing process of pressure reduction flash evaporation through a rich methanol flash separation tank and then feeding the separated rich methanol into a gas stripping tower; carbon dioxide enters a stripping tower; recovering effective gas H after stripping carbon dioxide2CO; the flash steam flashed by the flash separation tank is converged with the stripping gas at the outlet of the stripping tower to form circulating gas for recycling; the rich methanol at the outlet of the stripping tower is sent to a downstream regeneration process for regeneration.
The methanol absorbed in the low-temperature methanol washing process is divided into desulfurized rich methanol and decarbonized rich methanol.
Desulfurized sulfur-rich methanol: 10030Kmol/H, -28 deg.C, 5.3Mpa, containing 42.938Kmol/H of H267.953Kmol/H CO, reducing pressure to 1.3Mpa, flashing, concentrating sulfur-rich methanol at-30 deg.C under 1.3Mpa, and containing 3.799346 Kmol/H H215.50317 Kmol/h CO.
And (3) carrying out gas stripping on the sulfur-rich methanol subjected to flash evaporation by carbon dioxide gas at 1.3Mpa, 40 ℃ and 350Kmol/h through a gas stripping tower, wherein the gas stripped gas is as follows: at 30 ℃ under 1.2MPa 49.06921Kmol/H, wherein 3.794907Kmol/H of H210.44067Kmol/h CO, 34.49991Kmol/h CO2；
Sulfur-rich methanol after flash evaporation: -22 ℃ at 1.21MPa, residual 0.00443837H25.062504 Kmol/h CO;
the sulfur-rich methanol is stripped by carbon dioxide gas, and the effective gas (H) in the sulfur-rich methanol2CO) recovery 14.2356Kmol/H of effective gas (H) in sulfur-rich methanol2CO) 73.75%.
Carbon dioxide enriched after decarburizationCarbon conversion of methanol: 10833Kmol/H, -36 ℃, 5.6Mpa, containing 46.116Kmol/H of H274.834364Kmol/H CO, reducing pressure to 1.3Mpa, flashing, concentrating carbon dioxide methanol at-37 deg.C under 1.3Mpa, and containing 5.517838Kmol/H H222.50381Kmol/h CO.
And (3) after flash evaporation, stripping the carbon dioxide-rich methanol by a stripping tower with carbon dioxide gas of 1.3Mpa, 40 ℃ and 600Kmol/h, wherein the stripped gas is as follows: -36 ℃ at 1.2MPa 58.50896Kmol/H, wherein 5.51664Kmol/H H218.04061Kmol/h CO, 34.71969Kmol/h CO2；
Carbon dioxide-rich methanol after flash evaporation: -23 ℃, 1.21MPa, residual 0.00119773H24.463196 Kmol/h CO;
the carbon dioxide-rich methanol is stripped by carbon dioxide gas, and the effective gas (H) in the carbon dioxide-rich methanol2CO) recovery 23.55725Kmol/H of effective gas (H) in sulfur-rich methanol2CO) 84.07%;
the carbon monoxide content in the gas discharged to the atmosphere during the regeneration of the sulfur-rich methanol and the carbon dioxide-rich methanol is reduced to below 2000ppm, which is far lower than 6000ppm before the regeneration of the carbon dioxide gas.
34.793 Kmol/h or 847NM is recovered in the process3H effective gas (H)2、CO)。
The economic benefit of the low-temperature methanol washing process is improved, and the pollution of carbon monoxide in the discharged gas to the atmosphere is reduced.
Example 3
Take the process of producing 20 ten thousand tons of methanol in a year by gasification of pulverized coal as an example
A gas stripping process of carbon dioxide gas comprises the steps of separating rich methanol which absorbs gas in the low-temperature methanol washing process of pressure reduction flash evaporation through a rich methanol flash separation tank and then feeding the separated rich methanol into a gas stripping tower; carbon dioxide enters a stripping tower; recovering effective gas H after stripping carbon dioxide2CO; the flash steam flashed by the flash separation tank is converged with the stripping gas at the outlet of the stripping tower to form circulating gas for recycling; the rich methanol at the outlet of the stripping tower is sent to a downstream regeneration process for regeneration.
The methanol absorbed in the low-temperature methanol washing process is divided into desulfurized rich methanol and decarbonized rich methanol.
Desulfurized sulfur-rich methanol: 1802.056Kmol/H, at-22 deg.C and 3.2Mpa, contains 5.073Kmol/H of H26.998Kmol/H of CO, and the balance of methanol, reducing the pressure to 1.3Mpa for flash evaporation, and obtaining sulfur-rich methanol at-24 ℃ and 1.3Mpa after flash evaporation, wherein the sulfur-rich methanol contains 0.6878672Kmol/H of H22.18267Kmol/h CO.
And (3) carrying out gas stripping on the sulfur-rich methanol subjected to flash evaporation by using a gas stripping tower by using carbon dioxide gas at 1.3Mpa, 40 ℃ and 80Kmol/h, wherein the gas stripped gas is as follows: at 24 ℃ under 1.29MPa 8.366343Kmol/H, wherein 0.6877123Kmol/H of H21.84359Kmol/h CO, 5.750681Kmol/h CO2；
Sulfur-rich methanol after flash evaporation: 14 ℃ at 1.3MPa, residual 0.000154843H20.3390792 Kmol/h CO;
the sulfur-rich methanol is stripped by carbon dioxide gas, and the effective gas (H) in the sulfur-rich methanol2CO) recovery 2.5313Kmol/H of effective gas (H) in sulfur-rich methanol2CO) 88.18%.
The decarbonized carbon dioxide-rich methanol: 4060.661Kmol/H, at-20 deg.C and 3.16Mpa, contains 11.10394Kmol/H of H214.93867Kmol/H CO, reducing pressure to 1.3Mpa, flashing, concentrating carbon dioxide methanol at-21 deg.C and 1.3Mpa, and containing 1.586159Kmol/H H24.763985Kmol/h CO.
And (3) after flash evaporation, stripping the carbon dioxide-rich methanol by a stripping tower with carbon dioxide gas of 1.3Mpa, 40 ℃ and 180Kmol/h, wherein the stripped gas is as follows: at 21 ℃ under 1.29MPa, 17.46211Kmol/H, where 1.585554Kmol/H of H23.866485Kmol/h CO, 11.92431Kmol/h CO2；
Carbon dioxide-rich methanol after flash evaporation: 11 ℃ at 1.3MPa, residual 0.000604379H20.8974995 Kmol/h CO;
the carbon dioxide-rich methanol is stripped by carbon dioxide gas, and the effective gas (H) in the carbon dioxide-rich methanol2CO) recovery 5.452039Kmol/H of effective gas (H) in sulfur-rich methanol2CO) 85.86%;
the carbon monoxide content in the gas discharged to the atmosphere during the regeneration of the sulfur-rich methanol and the carbon dioxide-rich methanol is reduced to less than 2000ppm, which is far lower than 12000ppm before the carbon dioxide gas is not carried out.
7.9833 Kmol/h or 178.937NM are recovered in the process3H effective gas (H)2、CO)。
The economic benefit of the low-temperature methanol washing process is improved, and the pollution of carbon monoxide in the discharged gas to the atmosphere is reduced.
Example 4
Take a process of preparing methanol by gasifying certain coal water slurry as an example
A gas stripping process of carbon dioxide gas comprises the steps of separating rich methanol which absorbs gas in the low-temperature methanol washing process of pressure reduction flash evaporation through a rich methanol flash separation tank and then feeding the separated rich methanol into a gas stripping tower; carbon dioxide enters a stripping tower; recovering effective gas H after stripping carbon dioxide2CO; the flash steam flashed by the flash separation tank is converged with the stripping gas at the outlet of the stripping tower to form circulating gas for recycling; the rich methanol at the outlet of the stripping tower is sent to a downstream regeneration process for regeneration.
And (3) carrying out reduced pressure flash evaporation on the desulfurized rich methanol, and carrying out flash evaporation on the methanol: 1.3MPa, -30 ℃, 312.05733Kmol/H, wherein 39.9654Kmol/H of H20.4224Kmol/h N252.275Kmol/h CO, 0.2616Kmol/h AR, 0.3321Kmol/h CH4217.2587Kmol/h CO21.3822Kmol/H of H2S, 0.004031Kmol/H COS, 0.1517Kmol/H CH3OH, 0.000157Kmol/H H2O；
Rich methanol after flash evaporation: 1.3MPa, -30 ℃, 9719.1625Kmol/H, wherein 2.974Kmol/H of H20.0825Kmol/h N215.685Kmol/h CO, 0.09Kmol/h AR, 0.249Kmol/h CH42461.663Kmol/h CO241.711Kmol/H of H2S, COS at 0.954Kmol/H, CH3OH at 7158.649Kmol/H, H at 37.105Kmol/H2O。
The methanol-rich after flash evaporation carries with it the lost effective gas (H)2CO)18.659Kmol/h or 418.22NM3The carbon monoxide content in the exhaust gas is 6372 ppm.
After flash evaporation, the rich methanol is subjected to gas stripping by carbon dioxide of 1.2Mpa, 40 ℃ and 250Kmol/h through a gas stripping tower, and the stripping gas after gas stripping is as follows: 1.1MPa, -24.8 ℃, 145.1843Kmol/H, wherein 2.5645Kmol/H of H20.07395Kmol/h of N210.6444Kmol/h CO, 0.0533Kmol/h AR, 0.113628Kmol/h CH4131.0155Kmol/h CO20.6092Kmol/H of H2S, 0.01301Kmol/H COS, 0.0967Kmol/H CH3OH, 0.000147Kmol/H H2O；
After stripping, the methanol is enriched by 1.1Mpa, 24.8 ℃ and 9823.97843Kmol/H, wherein 0.4095Kmol/H of H20.00855Kmol/h of N25.041Kmol/h CO, 0.0367Kmol/h AR, 0.1354Kmol/h CH42580.648Kmol/h CO241.102Kmol/H of H2S, COS at 0.941Kmol/H, CH3OH at 7158.552Kmol/H, H at 37.1057Kmol/H2O；
Recovery of the useful gas (H)2CO)13.20887Kmol/h or 296.0609 NM3H, effective gas (H) carried by the rich methanol after flash evaporation2CO) and the carbon monoxide content in the exhaust gas after the regeneration of rich methanol is reduced to 1953 ppm.
The economic benefit of the low-temperature methanol washing process is improved, and the pollution of carbon monoxide in the discharged gas to the atmosphere is reduced.
Claims (6)
1. The gas stripping process of the carbon dioxide gas is characterized in that rich methanol which absorbs the gas in the low-temperature methanol washing process is separated by a rich methanol flash separation tank and then enters a gas stripping tower; the carbon dioxide enters a stripping tower, the pressure in the flash evaporation process is 1.1-1.5MPa, the temperature is-25 ℃ to-35 ℃, and the flow ratio of the methanol rich after flash evaporation separation to the carbon dioxide introduced into the stripping tower is 6-30: 1; recovering effective gas H after stripping carbon dioxide2And CO; the flash steam flashed by the flash separation tank is converged with the stripping gas at the outlet of the stripping tower to form circulating gas for recycling; after stripping, the rich methanol is sent to a downstream regeneration process for regeneration;
the methanol absorbing gas in the low-temperature methanol washing process comprises desulfurized rich methanol and decarbonized rich methanol; wherein, take offSulfur-enriched methanol at-28 deg.C and 5.3Mpa, and containing 0.2-0.7% mole fraction of H2CO with the mole fraction of 0.4-1.0%; the decarbonized methanol-rich product is 10833Kmol/H, at-36 deg.C and 5.6Mpa, and contains 0.2-0.8% of H2And CO with the mole fraction of 0.4-1.0%.
2. The stripping process of claim 1, wherein the desulfurized methanol-rich stripped gas comprises 5-10 mole percent H215-28% of CO in molar fraction and 65-78% of CO in molar fraction2。
3. The stripping process of claim 1, wherein the decarbonized, methanol-rich stripped stripping gas comprises 25-35 mole percent CO and 50-65 mole percent CO25-12% mole fraction of H2。
4. The stripping process according to claim 1, characterized in that the carbon dioxide gas stripping device is characterized in that a methanol-rich pipeline I (2) is connected with a methanol-rich pressure reduction control valve L1; a methanol-rich pressure reduction control valve (L1) is connected with the methanol-rich flash separation tank (V); the methanol-rich flash separation tank (V) is connected with a liquid level control valve (L2); the liquid level control valve (L2) is connected with the stripping tower (T), and the carbon dioxide pipeline (3) is connected with the stripping tower (T); the stripper column (T) is connected to a stripper column pressure control valve (P2), which stripper column pressure control valve (P2) is connected to the recycle gas line (1).
5. Stripping process according to claim 4, characterized in that the methanol-rich flash separation tank (V) is connected to a flash gas pressure control valve (P1), the flash gas pressure control valve (P1) being connected to the recycle gas line (1).
6. The stripping process according to claim 4, characterized in that the stripping column (T) is also connected to the methanol-rich line two (4).
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