CN106318475A - Improvement technology of low temperature methanol washing - Google Patents
Improvement technology of low temperature methanol washing Download PDFInfo
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- CN106318475A CN106318475A CN201510330874.8A CN201510330874A CN106318475A CN 106318475 A CN106318475 A CN 106318475A CN 201510330874 A CN201510330874 A CN 201510330874A CN 106318475 A CN106318475 A CN 106318475A
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Abstract
The invention discloses an improvement technology of low temperature methanol washing. The technology is an improvement to a traditional low temperature methanol washing technology, and is characterized in that a sulfur-free methanol solution at the bottom of the decarburization segment of an absorbing tower undergoes reduced pressure flash evaporation in a flash evaporation tank to recover CO and H2, the obtained solution undergoes reduced pressure flash evaporation through a pressure reducing valve to separate an organic matter-rich CO2 gas, the organic matter-rich CO2 gas is extracted from a low temperature methanol washing system, can be directly output as a fuel gas, and a liquid phase obtained after the separation enters a CO2 desorbing tower and an H2S enriching tower. The improvement technology is suitable for cleaning carbonyl synthetic gas, city gas and other gases produced from coal, heavy oil, asphalt and other heavy hydrocarbons, and is especially suitable for cleaning crude synthetic gas containing a large amount of light hydrocarbons (methane, ethane and other organic matters).
Description
Technical field
The present invention relates to the improvement technique of a kind of novel hydrocarbon-containifirst sour gas low-temp methanol washing process, specifically exist
On the basis of Conventional cryogenic methanol cleaning process, to absorption tower decarbonization section not sulfur-bearing CO2CO is reclaimed in methanol solution flash distillation
And H2After liquid solution again carry out vacuum flashing, and drawing rich in organic gas phase stream stock of obtaining of flash distillation
Go out outside rectisol system, can export directly as fuel gas, the liquid phase after flash distillation then with Conventional cryogenic first
Alcohol washes technique unanimously, enters CO2Desorber and H2S rectifying column processes.
Background technology
Low-temp methanol washing process is to be developed jointly by Linde Co of Germany and LURGI the 1950's
A kind of gas purifying technique with low-temp methanol as absorbent, this method is widely used in coal or residual oil as raw material
Produce in the devices such as synthesis ammonia, town gas, industrial hydrogen, synthesizing methanol.Two kinds of low-temp methanol wash journeys are big
Cause identical, simply improve at heat-exchange network and be slightly different (Wang Xianyan, Zheng Ming in concrete technology flow process details
Peak, Zhang Junchi, Linde and Lurgi low-temp methanol washing process process analysis, Coal Chemical Industry, 2010,1 (16):
34-37), as in figure 2 it is shown, whole flow process can be divided mainly into following components: crude synthesis gas cools down, acid
Property gas washing removing, middle pressure flash distillation reclaim effective gas (CO and H2), hydrogen sulfide stripping enrichment, methanol again
Life, refining methanol and washing tail gas emptying etc..The raw material of rectisol system is crude synthesis gas, is finally
System output includes: purifies gas and (purifies CO and H2, absorbing tower top gas), CO2Product gas (CO2Solve
Inhale column overhead gas), CO2Tail gas (H2S rectifying column tower overhead gas), rich in H2S tail gas (Mathanol regenerating tower tower
Top gas, delivers to downstream sulphur recovery unit).The Organic substances such as methane in crude synthesis gas, ethane are main
With H2S rectifying column tower top CO2Tail gas is discharged.Along with now along with environmental requirement increasingly stringent, to industry tail
The improvement of gas technique becomes the important topic of industry, and the vent gas treatment that therefore low-temp methanol is washed is by certain pass
Note.
Conventional cryogenic methanol cleaning process mainly stresses reclaiming clean gas, sulfur and by-product CO2Product gas, right
In H2S rectifying column tower top CO2There is certain defect in the process of tail gas.Especially big when crude synthesis gas contains
During C1～the C3 lighter hydrocarbons measured, Organic substance is finally primarily present in the CO of hydrogen sulfide column overhead2In tail gas, directly
The difficulty, scale and the investment that process are the hugest.
Summary of the invention
The defect existed for Lin De and Lu Qi low-temp methanol washing process, according to embodiments of the invention, proposes
The improvement technique of a kind of low-temp methanol washing process, makes H2S rectifying column tower top CO2Content of organics fall in tail gas
Low, thus reduce scale and the investment of exhaust treatment system；Reclaim simultaneously one rich in organic gas,
Can be used as fuel gas and produce steam, there is good economic benefit.Present invention process achieves vent gas treatment system
System equipment investment is low, the advantages such as energy consumption is low, reclaims the fuel gas obtained simultaneously and enters boiler generation steam, reaches
To certain economic benefit and environmental benefit.
According to embodiment, the improvement technique that a kind of low-temp methanol that the present invention proposes is washed, its innovative point is:
In Lin De and Lu Qi low-temp methanol washing process, by the methanol solution warp of not sulfur-bearing bottom methanol absorber tower decarbonization section
CO and H is reclaimed in flash tank vacuum flashing2After, again through air relief valve vacuum flashing, isolate one rich in organic
The CO of thing2Gas is drawn outside rectisol system, can export directly as fuel gas, and liquid phase enters CO2Solve
Inhale tower and H2S rectifying column.
In technical solution of the present invention, by crude synthesis gas from sending into methanol absorber tower at the bottom of tower, low with what tower top flowed down
Temperature methanol counter current contacting, sour gas (CO therein2、H2S and COS etc.) by methanol absorption, absorption tower
Tower top obtains pure CO and H2Synthesis gas (purification gas).Absorption tower is divided into decarbonization section (epimere) and desulfurization
Section (hypomere), bottom decarbonization section not sulfur-bearing methanol solution through vacuum flashing cutting out partial CO and H2After gas,
It is further added by one-level vacuum flashing, isolates one and draw low-temp methanol wash rich in the organic gas phase such as methane and be
Outside system, liquid solution is directly entered follow-up CO2Desorber and H2S rectifying column.Sulfur-bearing methanol bottom desulfurization section
Solution is then only through vacuum flashing cutting out partial CO and H2After gas, enter directly into H2S rectifying column.?
CO2Desorber tower top obtains CO2Product gas, and tower reactor solution enters H2S rectifying column.H2S rectifying column tower top produces
Raw tail gas is directly entered exhaust treatment system and processes, tower reactor obtain rich in sulfur methanol solution needs
Enter follow-up low-temp methanol to wash unit and process.
The technology washed relative to Lin De and Lu Qi low-temp methanol, the composite can be widely applied to coal or residual oil be
In the devices such as raw material production synthesis ammonia, town gas, industrial hydrogen, synthesizing methanol.Wash with Conventional cryogenic methanol
Technique is compared, and in the unstripped gas that the present invention is suitable for, hydro carbons composition and concentration range are more extensive, make H simultaneously2S is rich
In collection column overhead tail gas, the content of Organic substance (methane, ethane etc.) reduces, thus reduces exhaust treatment system
Scale and investment, reach certain economic benefit and environmental benefit.It addition, reclaim rich in organic
Gas, can make fuel gas and enter boiler generation steam, have good economic benefit and social benefit.
Embodiment subsequently will demonstrate that, the present invention, compared with traditional low-temp methanol washing process, can not only reduce
H2The S rectifying column organic content of tower top tail gas, reduces the difficulty directly processed, one richness the most recyclable
Containing organic gas, and then a certain amount of steam of by-product, there is good environmental benefit and economic benefit.
The present invention is on the basis of Conventional cryogenic methanol cleaning process, to absorption tower decarbonization section not sulfur-bearing CO2Methanol is molten
CO and H is reclaimed in liquid flash distillation2After liquid solution again carry out vacuum flashing, and flash distillation obtain rich in organic
The gas phase stream stock of thing is drawn outside rectisol system, can export directly as fuel gas, the liquid phase after flash distillation
Then consistent with Conventional cryogenic methanol cleaning process, enter CO2Desorber and H2S rectifying column processes.
Accompanying drawing explanation
Fig. 1 be the low-temp methanol according to the embodiment of the present invention wash improve technique flow chart (compared with traditional process,
The technique improved is further added by primary flash on the basis of primary flash, and exports one fuel gas).
Process chart (the only primary flash, and the gas flashed off that the low-temp methanol that Fig. 2 is traditional is washed
Body again follows through overcompression cooling and badly enters into absorption tower).
Wherein: T1 is methanol absorber tower；V1 is air relief valve；F1, F2 are flash tank；F3 is flash column；
T2 is CO2Desorber；T3 is H2S rectifying column.
Detailed description of the invention
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is expanded on further.These embodiments are only interpreted as
For the present invention being described rather than limiting the scope of the invention.Reading the content that the present invention records
Afterwards, the present invention can be made various changes or modifications by those skilled in the art, these equivalence change and modifications
Fall into the scope of the claims in the present invention equally.
Embodiment 1
As it is shown in figure 1, raw material working condition is as shown in table 1 in the present embodiment.The present invention is in this embodiment
Technological process is: by this tail gas from sending into methanol absorber tower T1, and-53.5 DEG C of low temperature flowed down with tower top at the bottom of tower
Methanol carries out counter current contacting, sour gas (CO therein2、H2S and COS etc.) by methanol absorption, methanol
Absorption tower T1 tower top obtains pure purification gas, and the pressure of this purification gas is 5.48MPa, and temperature is-39.0 DEG C,
And directly transfer out rectisol system.Methanol absorber tower T1 is divided into decarbonization section and desulfurization section, at the bottom of decarbonization section
Portion obtains not sulfur-bearing methanol solution, and temperature is-35.0 DEG C, through flash tank F1 vacuum flashing cutting out partial CO and
H2After gas, being further added by one-level pressure relief valve V1 and being down to pressure is 1.0MPa, subsequently into flash column F3 flash distillation,
Isolating one to draw outside rectisol system rich in organic gas phases such as methane, liquid solution is directly entered
Enter follow-up CO2Desorber T2 and H2S rectifying column T3.Bottom desulfurization section, sulfur-bearing methanol solution temperature is-47.0 DEG C,
Only through flash tank F2 vacuum flashing cutting out partial CO and H2After gas, liquid phase enters directly into H2S is enriched with
Tower T3.At CO2Desorber T2 tower top obtains 0.3MPa, the CO of-51.0 DEG C2Product gas, and tower reactor sulfur-bearing methanol
Solution temperature is-47.0 DEG C, enters H2S rectifying column.H2The CO that S rectifying column T3 tower top produces2Exhaust temperature is
-61.0 DEG C, pressure is 0.19MPa, is directly entered exhaust treatment system and processes, tower reactor obtain rich in
Sulfur methanol solution needs to enter follow-up low-temp methanol and washes unit and process.
After measured, H in this embodiment2CO and hydro carbons total content fall in the tail gas of S rectifying column T3 tower top
Low by 64.4%, greatly reduce the load of exhaust treatment system；The gas phase of flash column F3 tower top is as fuel
Gas exports, and can produce quantity of steam 4.0t/h；Record CO simultaneously2The composition of product gas brings up to 99.1%.
Table 1. crude synthesis gas tables of data
| Molar flow | 1786.0kg-mol/hr |
| Temperature | -12.0℃ |
| Pressure | 5.6MPa |
| Component | Mol% (molar content) |
| CO2 | 31.25 |
| CO | 21.34 |
| H2 | 45.55 |
| CH4 | 1.07 |
| N2 | 0.23 |
| H2S | 0.24 |
| H2O | 0.23 |
| AR | 0.099 |
Embodiment 2
Second preferred embodiment of the present invention, in the present embodiment, methanol absorber tower T1 tower top pressure is
5.50MPa, air relief valve outlet pressure is 0.8MPa, and CO2Desorber T2 tower top pressure is 0.27MPa,
Remaining is with embodiment 1.
After measured, H in this embodiment2CO and hydro carbons total content fall in the tail gas of S rectifying column T3 tower top
Low by 65.1%；The gas phase of flash column F3 tower top exports as fuel gas, can produce quantity of steam 4.2t/h；
Record CO simultaneously2The composition of product gas brings up to 99.2%.
Embodiment 3
3rd preferred embodiment of the present invention, in the present embodiment, the composition of crude synthesis gas is shown in Table 2, and remaining is with implementing
Example 1.
After measured, H in this embodiment2CO and hydro carbons total content fall in the tail gas of S rectifying column T3 tower top
Low by 64.7%；The gas phase of flash column F3 tower top exports as fuel gas, can produce quantity of steam 4.6t/h；
Record CO simultaneously2The composition of product gas brings up to 99.0%.
Table 2. crude synthesis gas tables of data
| Molar flow | 1786.0kg-mol/hr |
| Temperature | -12.0℃ |
| Pressure | 5.6MPa |
| Component | Mol% (molar content) |
| CO2 | 31.05 |
| CO | 21.21 |
| H2 | 45.27 |
| CH4 | 1.06 |
| C2H6 | 0.41 |
| C3H8 | 0.21 |
| N2 | 0.23 |
| H2S | 0.24 |
| H2O | 0.23 |
| AR | 0.098 |
Embodiment 4
4th preferred embodiment of the present invention, in the present embodiment, methanol absorber tower T1 tower top pressure is
5.50MPa, air relief valve V1 outlet pressure is 0.8MPa, and CO2Desorber T2 tower top pressure is
0.27MPa, remaining is with embodiment 3.
After measured, H in this embodiment2CO and hydro carbons total content fall in the tail gas of S rectifying column T3 tower top
Low by 65.3%；The gas phase of flash column F3 tower top exports as fuel gas, can produce quantity of steam 4.8t/h；
Record CO simultaneously2The composition of product gas brings up to 99.2%.
Embodiment 5
5th preferred embodiment of the present invention, in the present embodiment, methanol absorber tower T1 tower top pressure is
5.50MPa, air relief valve V1 outlet pressure is 0.7MPa, and CO2Desorber T2 tower top pressure is
0.27MPa, remaining is with embodiment 3.
After measured, H in this embodiment2CO and hydro carbons total content fall in the tail gas of S rectifying column T3 tower top
Low by 65.7%；The gas phase of flash column F3 tower top exports as fuel gas, can produce quantity of steam 5.0t/h；
Record CO simultaneously2The composition of product gas brings up to 99.2%.
Claims (9)
1. the improvement technique that a low-temp methanol is washed, it is characterised in that Lin De and Lu Qi low-temp methanol washing process
In, by bottom methanol absorber tower decarbonization section not sulfur-bearing methanol solution through flash tank vacuum flashing reclaim CO and
H2After, again through air relief valve vacuum flashing, isolate one rich in organic CO2Gas draws low temperature first
Alcohol is washed outside system, can export directly as fuel gas, and liquid phase enters CO2Desorber and H2S rectifying column.
The improvement technique that low-temp methanol the most according to claim 1 is washed, it is characterised in that rich in organic
The CO of thing2In gas, Organic substance is methane, ethane and propane.
The improvement technique that low-temp methanol the most according to claim 1 and 2 is washed, it is characterised in that
Methanol absorption column overhead temperatures is-25.0～-60.0 DEG C, and pressure is 3.0～6.0MPa；Bottom temperature is
-10.0～-60.0 DEG C, pressure is 3.0～6.5MPa；
Enter the rich CO of air relief valve2Methanol solution temperature is-10.0～-60.0 DEG C, and pressure is 3.0～6.5MPa；Subtract
The outlet temperature of pressure valve is-15.0～-60.0 DEG C, and pressure is 0.5～1.5MPa；
CO2Desorber tower top temperature is-25.0～-60.0 DEG C, and pressure is 0.1～0.5MPa；Bottom temperature is
-20.0～-60.0 DEG C, pressure is 0.1～0.5MPa；
H2S rectifying column tower top temperature is-25.0～-70.0 DEG C, and pressure is 0.05～0.3MPa；Bottom temperature is
-10.0～-50.0 DEG C, pressure is 0.1～0.5MPa.
The improvement technique that low-temp methanol the most according to claim 3 is washed, it is characterised in that enter methanol
The temperature of the absorbent low-temp methanol on absorption tower is-30.0～-60.0 DEG C, and pressure is 4.0～7.0MPa.
The improvement technique that low-temp methanol the most according to claim 4 is washed, it is characterised in that enter methanol
The temperature of the absorbent low-temp methanol on absorption tower is-53.5 DEG C, and pressure is 5.48MPa.
The improvement technique that low-temp methanol the most according to claim 3 is washed, it is characterised in that methanol absorption
Column overhead temperatures is-39.0 DEG C, and pressure is 5.48MPa；Bottom temperature is-47.0 DEG C, and pressure is 5.56MPa.
The improvement technique that low-temp methanol the most according to claim 3 is washed, it is characterised in that enter air relief valve
Rich CO2Methanol solution temperature is-35.0 DEG C, and pressure is 5.54MPa；The outlet temperature of air relief valve is-40.3 DEG C,
Outlet pressure is 1.0MPa.
The improvement technique that low-temp methanol the most according to claim 3 is washed, it is characterised in that CO2Desorbing
The tower top temperature of tower is-51.0 DEG C, and pressure is 0.3MPa；Bottom temperature is-47.0 DEG C, and pressure is 0.34MPa.
The improvement technique that low-temp methanol the most according to claim 3 is washed, it is characterised in that H2S is enriched with
Column overhead temperatures is-61.0 DEG C, and pressure is 0.19MPa；Bottom temperature is-35.0 DEG C, and pressure is 0.25MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107033974A (en) * | 2017-04-21 | 2017-08-11 | 北京三泰天洁气体净化技术有限公司 | The method that low-temp methanol elution removes lighter hydrocarbons in crude synthesis gas, conversion gas |
| CN110548369A (en) * | 2019-08-01 | 2019-12-10 | 中石化宁波工程有限公司 | Control method for CO content in tail gas generated by removing acid gas |
| CN111420515A (en) * | 2020-03-07 | 2020-07-17 | 湖北宜化化工股份有限公司 | Improved low temperature methanol scrubbing of CO2Product gas stripping and pressing process |
| CN114015481A (en) * | 2021-11-16 | 2022-02-08 | 兰州理工大学 | Short-flow low-temperature methanol washing system and process thereof |
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| CN110548369B (en) * | 2019-08-01 | 2022-02-15 | 中石化宁波工程有限公司 | Control method for CO content in tail gas generated by removing acid gas |
| CN111420515A (en) * | 2020-03-07 | 2020-07-17 | 湖北宜化化工股份有限公司 | Improved low temperature methanol scrubbing of CO2Product gas stripping and pressing process |
| CN114015481A (en) * | 2021-11-16 | 2022-02-08 | 兰州理工大学 | Short-flow low-temperature methanol washing system and process thereof |
| CN114015481B (en) * | 2021-11-16 | 2023-09-05 | 兰州理工大学 | Short-flow low-temperature methanol washing system and process thereof |
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Application publication date: 20170111 |