CN102085445A - Modification solution for removing acid gas of low-temperature methanol cleaning process - Google Patents

Modification solution for removing acid gas of low-temperature methanol cleaning process Download PDF

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CN102085445A
CN102085445A CN2010105998410A CN201010599841A CN102085445A CN 102085445 A CN102085445 A CN 102085445A CN 2010105998410 A CN2010105998410 A CN 2010105998410A CN 201010599841 A CN201010599841 A CN 201010599841A CN 102085445 A CN102085445 A CN 102085445A
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low
modified solution
sour gas
solvent
washing process
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宫万福
吕建宁
雷志刚
叶鑫
袁娟
张栓存
李延生
辛呈钦
张玉滨
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Wison Engineering Ltd
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Abstract

The invention relates to a modification solution for removing acid gas of a low-temperature methanol cleaning process. A composite solvent is prepared by adding a small amount of the modification solvent into a methanol solvent, and used for absorbing the acid gas. Compared with the prior art, the composite solvent prepared by the invention has higher solubility and selectivity than methanol adsorbent. As the solubility of the acid gas in the modified composite solvent is increased, the problems that the refrigeration effect of lean methanol is reduced, the circulation solvent amount is increased and the like in the CO2 deabsorption process resulting from the content reduction of CO2 in a raw material gas can be solved as well; and by applying the composite solvent prepared by the invention to the existing low-temperature methanol cleaning process, the usage of the circulation solvent in a device is reduced, the thermal regeneration energy consumption is low, the registration load is small, and the energy consumption is remarkably reduced.

Description

A kind ofly be used for the modified solution that the low-temp methanol washing process sour gas removes
Technical field
The present invention relates to the modified solution that a kind of sour gas removes, especially relate to a kind of modified solution that the low-temp methanol washing process sour gas removes that is used for.
Background technology
In the common exploitation of the fifties in last century, purpose is in order to remove CO from synthesis gas to low-temp methanol washing process (Rectiso1Process) by German woods moral (Linde) company and Lu Qi (Lurgi) company 2And H 2S, organic sulfur compound, COS, HCN, aromatic hydrocarbons and other higher hydrocarbon have been widely used at present that domestic and international synthetic ammonia, synthesizing methanol and other carbonyls are synthetic, in the gas cleaning plants such as town gas, industrial hydrogen production and selexol process.The patent that relates to low-temperature rectisol purification technology has: CN1506150 (2004), CN1218866 (2005), CN1036319 (1997), CN1003352 (1989), CN1036245 (1997), CN1157327 (2004), CN1202897 (2005), CN100415346 (2008), US3453835 (1969), US4050909 (1977), US4381926 (1983), US4488890 (1984), US4430316 (1984), US4609384 (1986), US20040065199 (2004).
Low-temp methanol washing process is a lyosoption with the cold methanol, utilizes methyl alcohol at low temperatures to the great good characteristic of sour gas solubility, removes the sour gas in the unstripped gas, is a kind of Physical Absorption method.Methyl alcohol depends on the dividing potential drop of dissolved absorbing material and the operating temperature of absorbent to the solvability of sour gas.Under same pressure, temperature is low more, and methyl alcohol is big more to the solubility of sour gas, therefore for improving the absorbability of methyl alcohol to sour gas, reduces the internal circulating load of solvent, must keep washing device for methanol and operate under lower temperature.The required low temperature of washing device for methanol is provided by two aspects: the one, replenish cold by refrigeration system to washing device for methanol, and the 2nd, by having absorbed CO 2Methanol solution in the process of desorb, reclaim cold.The CO that dissolves in the methyl alcohol of unit volume 2Many more, the cold of emitting during desorb is just many more, and temperature is also low more, and this part cold and poor methanol heat exchange can make the absorption tower operate under lower temperature.
Increase the solubility of sour gas, under requiring, same purification just can reduce the consumption of circulating solvent, reduce the energy consumption of heat regeneration, reduce replenishing of cold, simultaneously can also overcome following deficiency: when changing lightweight material such as natural gas into by heavy charges such as coal or residual oil when raw material, CO in the unstripped gas of low-temperature rectisol 2Content reduce because CO 2The reduction of gaseous phase partial pressure cause the CO that dissolves in the unit volume methyl alcohol 2Amount reduces, and the cold that the methyl alcohol behind the absorption sour gas is emitted when desorb also reduces, thereby causes the temperature on absorption tower to raise, and device can not normally move.
CN1506150A discloses a kind of method: CO in unstripped gas 2When content descended, will reduce pressure stripping gas or gas stripping gas (were rich in CO 2) compressed machine compresses, cooling back recycled back methyl alcohol washes in the unstripped gas of mouth, to increase CO in the unstripped gas 2Content owing to increased CO in the unstripped gas 2Gaseous phase partial pressure, make the CO that dissolves in the methyl alcohol of unit volume 2Increase, improved CO 2The refrigeration by adsorption effect, the system that keeps operates under lower temperature.The method will increase the material gas quantity of washing device for methanol more, and will increase compressor and cooler, and investment and energy consumption all will increase.
CN1218866C discloses a kind of method: for solving CO in the unstripped gas 2Content reduces, and causes CO 2The problem that during desorb the refrigeration of methyl alcohol is descended and cause system temperature to raise, behind ammonia cooler, set up propylene deep freezer or vacuum level ammonia cooler, to increase benefit cold to system, its objective is in order to reduce the absorption operating temperature, increase the solubility of sour gas.But this method has increased equipment investment and energy consumption simultaneously.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists that a kind of raw material is easy to get, stable performance be used for the modified solution that the low-temp methanol washing process sour gas removes.
Purpose of the present invention can be achieved through the following technical solutions:
A kind ofly be used for the modified solution that the low-temp methanol washing process sour gas removes, it is characterized in that the solute of this modified solution is one or more in ketone, alcohols, ethers or the ionic liquid, solvent is a methyl alcohol.
The concentration of modified solution is 2～20wt%.
Described ketone comprises acetone or butanone.
Described alcohols comprises ethanol or propyl alcohol.
Described ethers comprises glycol dimethyl ether or oxolane.
Described ionic liquid comprises 1-methyl-3-ethyl-tetrafluoroborate or N-ethylpyridine tetrafluoroborate.
Modified solution is-5 ℃～-65 ℃ to the absorption temperature of sour gas, and absorption pressure is 3～9MPa.
Preferred-35 ℃ of described absorption temperature.
Compared with prior art, the present invention has improved sour gas such as CO greatly 2, H 2The solubility of S etc. and selectivity, under the prerequisite that does not change original low-temp methanol washing process route, because modification solvent of the present invention improves greatly to the solubility of sour gas, can reduce the consumption of circulating solvent, save the energy consumption of high-pressure delivery, reduce cooling load, reduce heat regeneration energy consumption, thereby reach purpose of energy saving.
Description of drawings
Fig. 1 is the low-temp methanol washing process flow chart.
The specific embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Embodiment 1
Raw gas flow 150000NM 3/ h contains CO 243.14%, H 254.35%, H 2S 0.26%, 40 ℃ of temperature, pressure 6.0MPa (A).Modification double solvents of the present invention contains methyl alcohol 80wt%, acetone 20wt%.Modification double solvents of the present invention is applied in the existing low-temp methanol washing process device, can directly replaces pure methyl alcohol, need not change original process route, as shown in Figure 1.
With existing low-temp methanol washing process is example, unstripped gas 1 converges with circulation flashed vapour 3, reinject methyl alcohol 2 in case the water freezing in the unstripped gas, after cooling off, isolating liquid phase, enter absorption tower 10, with the low-temp methanol washing of cat head, purify good unstripped gas 8 and after heat exchanger 4 reclaims cold, send the battery limit (BL).The rich solution methyl alcohol 11, the rich solution methyl alcohol 13 that have absorbed sour gas in tower 10 enter flash tank 14 and flash tank 15 after the pressure-reducing valve decompression, deliver to the unstripped gas inlet after compressed machine 59 compressions of the effective gas that flashes off, the rich solution under the flash tank 14 is delivered to CO respectively after decompression 2Product tower 21 and H 2The cat head of S concentration tower 32, the rich solution of flash tank 15 bottoms is delivered to H after decompression 2The middle part of S concentration tower 32.CO 2The CO on product tower 21 tops 2Product 25 is sent the battery limit (BL) after reclaiming cold, the rich solution of bottom is delivered to H 2S concentration tower middle part.Be rich in CO 2, H 2The rich solution of S is at H 2S concentration tower 32, H 2Vacuum flashing in the S concentration tower 40, and carry with nitrogen 35, nitrogen 36 gas, the tail gas 33 of cat head are reclaimed behind the colds in home emptying.H 2The gas of S concentration tower 40 cats head enters tower 32, is rich in H at the bottom of the tower 2S, a spot of CO 2The liquid phase that reaches other component gases enters hot regenerator 45, and all gas that dissolves in the absorbent after heat regeneration is separated out from cat head, and after cooling, reclaiming absorbent, is rich in H 2The sour gas 48 of S is sent the battery limit (BL), and the good absorbent of regenerating at the bottom of the tower of hot regenerator 45 recycles.The aqueous liquid phase of flash tank 5 bottoms is delivered to the middle part of methanol knockout tower 55 after pressure-reducing valve 53 decompressions, the cat head gas phase absorbent 56 of recovery is delivered to hot regenerator 45 middle parts, and the waste water 57 at the bottom of the tower is sent the battery limit (BL).
Contrast pure methanol absorbing agent, adopt modification double solvents of the present invention, identical at the unstripped gas composition, and reach identical purified gas and CO 2The gas index request guarantees can reduce the absorbent consumption under the prerequisite of discharging gas index up to specification simultaneously.The temperature of absorbent 9 is-63.5 ℃ in the operation, and the intersegmental absorbent in absorption tower is cooled to-41.5 ℃, and the temperature of logistics 13 is-6.2 ℃.Because the internal circulating load of absorbent reduces in the whole system, therefore saved the energy consumption of circulating solvent high-pressure delivery, reduced the steam consumption of hot regeneration, the cooling load of whole system and recirculated cooling water consumption are reduced, therefore energy-saving effect is remarkable, and concrete correction data is as shown in table 1:
Table 1
Embodiment 1 Prior art
Circulation absorbent flow, kg/h 140240 165750
0.5MPa low-pressure steam, kg/h 5752 6555
1.0MPa steam, kg/h 1085 1109
Cooling load, KW 1751 2015
The recirculated cooling water consumption, kg/h 239925 278960
Embodiment 2
Raw gas flow 185000NM 3/ h, 40 ℃ of temperature, pressure 5.5MPa (A), unstripped gas is formed: contain CO 225.22%, H 241.19%, CO 33.02%.Modification double solvents of the present invention contains methyl alcohol 80wt%, acetone 20wt%.Modification double solvents of the present invention is applied in the existing low-temp methanol washing process device, can directly replaces pure methyl alcohol, need not change original process route.Because CO in the unstripped gas 2Lower (the CO of concentration 2Gaseous phase partial pressure is low), compare CO 2The unstripped gas that concentration is high is dissolved in the CO in the methyl alcohol 2Reduce the CO that dissolves in the unit volume methyl alcohol 2Amount reduces, the cold that methyl alcohol behind the absorption sour gas is emitted when desorb also reduces, and the poor methanol temperature of absorption cat head raises thereby cause into, and the flow that therefore need add the systemic circulation absorbent guarantees the purification requirement of logistics, especially for the device that has built up, CO in unstripped gas 2When concentration reduced, because the increase of circulation absorbent flow, public work consumption also will increase, and device often can not normally move.Adopt modification double solvents of the present invention (to contain methyl alcohol 80wt%, the mixture 20wt% that contains acetone, glycol dimethyl ether etc.), when replacing pure methyl alcohol as absorbent, because modification double solvents of the present invention obviously increases the purer methanol absorbing agent of the solubility of sour gas, low during the also purer methyl alcohol of the temperature of logistics, the temperature of logistics is-51 ℃, and the intersegmental absorbent in absorption tower is cooled to-30.5 ℃, and the temperature of logistics is-11.95 ℃.The circular flow of absorbent reduces significantly, the also corresponding reduction of its public work consumption, and circulation absorbent flow and public work consumed as shown in table 2 when the data in the following table were employing modification double solvents of the present invention and prior art:
Table 2
Embodiment 2 Comparative Examples
Circulation absorbent flow, kg/h 195230 235100
0.5MPa low-pressure steam, kg/h 7240 8200
1.0MPa steam, kg/h 3210 3215
Cooling load, KW 3180 3563
The recirculated cooling water consumption, kg/h 356085 385834
By above data contrast as can be known, adopt modification double solvents of the present invention, energy-saving effect clearly.
Embodiment 3
A kind ofly be used for the modified solution that the low-temp methanol washing process sour gas removes, the solute of this modified solution is an acetone, and solvent is a methyl alcohol, and the concentration of solution is controlled to be 10wt%.
Embodiment 4
A kind ofly be used for the modified solution that the low-temp methanol washing process sour gas removes, the solute of this modified solution is an acetone, and solvent is a methyl alcohol, and the concentration of solution is controlled to be 20wt%.
The modified solution that utilizes embodiment 3 and embodiment 4 to prepare absorbs under different condition sour gas, and the result is shown in table 3～6.
Table 3
Figure BSA00000394260500051
Table 4
Figure BSA00000394260500061
Table 5
Figure BSA00000394260500062
Table 6
Figure BSA00000394260500063
Embodiment 5
A kind ofly be used for the modified solution that the low-temp methanol washing process sour gas removes, the solute of this modified solution is the mixture of acetone and glycol dimethyl ether, and solvent is a methyl alcohol, and the concentration of this modified solution is 20wt%.During use, modified solution is-10 ℃～-50 ℃ to the absorption temperature of sour gas, and absorption pressure is 3MPa.
Embodiment 6
A kind ofly be used for the modified solution that the low-temp methanol washing process sour gas removes, the solute of this modified solution is 1-methyl-3-ethyl-tetrafluoroborate, and solvent is a methyl alcohol, and the concentration of this modified solution is 2wt%.During use, modified solution is-10 ℃～-65 ℃ to the absorption temperature of sour gas, and absorption pressure is 9MPa.

Claims (8)

1. one kind is used for the modified solution that the low-temp methanol washing process sour gas removes, and it is characterized in that, the solute of this modified solution is one or more in ketone, alcohols, ethers or the ionic liquid, and solvent is a methyl alcohol.
2. a kind of modified solution that the low-temp methanol washing process sour gas removes that is used for according to claim 1 is characterized in that the concentration of modified solution is 2～20wt%.
3. a kind of modified solution that the low-temp methanol washing process sour gas removes that is used for according to claim 1 is characterized in that described ketone comprises acetone or butanone.
4. a kind of modified solution that the low-temp methanol washing process sour gas removes that is used for according to claim 1 is characterized in that described alcohols comprises ethanol or propyl alcohol.
5. a kind of modified solution that the low-temp methanol washing process sour gas removes that is used for according to claim 1 is characterized in that described ethers comprises glycol dimethyl ether or oxolane.
6. a kind of modified solution that the low-temp methanol washing process sour gas removes that is used for according to claim 1 is characterized in that described ionic liquid comprises 1-methyl-3-ethyl-tetrafluoroborate or N-ethylpyridine tetrafluoroborate.
7. a kind of modified solution that the low-temp methanol washing process sour gas removes that is used for according to claim 1 is characterized in that, modified solution is-5 ℃～-65 ℃ to the absorption temperature of sour gas, and absorption pressure is 3～9MPa.
8. a kind of modified solution that the low-temp methanol washing process sour gas removes that is used for according to claim 7 is characterized in that, preferred-35 ℃ of described absorption temperature.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096453A (en) * 2014-07-11 2014-10-15 中国科学院过程工程研究所 High-selectivity decarbonization absorbent adopting physical method
CN107011950A (en) * 2016-01-28 2017-08-04 惠生工程（中国）有限公司 A kind of method for gas purification for coal base synthesis of natural device of air
CN107311173A (en) * 2017-08-09 2017-11-03 惠生工程（中国）有限公司 A kind of preparation method of high pressure vapor carbon dioxide for coal gasification unit
CN107399737A (en) * 2017-08-09 2017-11-28 惠生工程（中国）有限公司 A kind of preparation method of high pressure vapor carbon dioxide for gasification of high-pressure pulverized coal
CN108261887A (en) * 2018-03-12 2018-07-10 崔静思 A kind of method that carbinol-modified low-temp methanol is washed
CN114907894A (en) * 2022-06-09 2022-08-16 上海中集天照清洁能源有限公司 Method for removing methanol from natural gas

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609384A (en) * 1983-12-05 1986-09-02 Linde Aktiengesellschaft Multiple temperature level regeneration of CO2 from physical solvent
US20040065199A1 (en) * 2002-10-07 2004-04-08 Alexandre Rojey Natural gas deacidizing method
CN1491882A (en) * 2002-04-03 2004-04-28 中国石油化工集团公司 Low temperature methanol cleaning process
CN1157327C (en) * 2002-04-12 2004-07-14 中国石化集团兰州设计院 Low-temperature methanol washing process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609384A (en) * 1983-12-05 1986-09-02 Linde Aktiengesellschaft Multiple temperature level regeneration of CO2 from physical solvent
CN1491882A (en) * 2002-04-03 2004-04-28 中国石油化工集团公司 Low temperature methanol cleaning process
CN1157327C (en) * 2002-04-12 2004-07-14 中国石化集团兰州设计院 Low-temperature methanol washing process
US20040065199A1 (en) * 2002-10-07 2004-04-08 Alexandre Rojey Natural gas deacidizing method

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096453A (en) * 2014-07-11 2014-10-15 中国科学院过程工程研究所 High-selectivity decarbonization absorbent adopting physical method
CN104096453B (en) * 2014-07-11 2016-06-22 中国科学院过程工程研究所 A kind of high selectivity Physical decarburization absorption agent
CN107011950A (en) * 2016-01-28 2017-08-04 惠生工程（中国）有限公司 A kind of method for gas purification for coal base synthesis of natural device of air
CN107011950B (en) * 2016-01-28 2019-12-27 惠生工程（中国）有限公司 Gas purification method for coal-based natural gas synthesis device
CN107311173A (en) * 2017-08-09 2017-11-03 惠生工程（中国）有限公司 A kind of preparation method of high pressure vapor carbon dioxide for coal gasification unit
CN107399737A (en) * 2017-08-09 2017-11-28 惠生工程（中国）有限公司 A kind of preparation method of high pressure vapor carbon dioxide for gasification of high-pressure pulverized coal
CN107311173B (en) * 2017-08-09 2020-01-14 惠生工程（中国）有限公司 Preparation method of high-pressure gas-phase carbon dioxide for pulverized coal gasification unit
CN108261887A (en) * 2018-03-12 2018-07-10 崔静思 A kind of method that carbinol-modified low-temp methanol is washed
CN114907894A (en) * 2022-06-09 2022-08-16 上海中集天照清洁能源有限公司 Method for removing methanol from natural gas

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