CN114591771A - Decarbonizing solvent and method for decarbonizing high carbon-containing natural gas - Google Patents

Decarbonizing solvent and method for decarbonizing high carbon-containing natural gas Download PDF

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CN114591771A
CN114591771A CN202210310375.2A CN202210310375A CN114591771A CN 114591771 A CN114591771 A CN 114591771A CN 202210310375 A CN202210310375 A CN 202210310375A CN 114591771 A CN114591771 A CN 114591771A
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tower
solvent
absorption tower
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gas
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于海洋
黄启玉
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China University of Petroleum Beijing
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50—Combinations of absorbents
    • B01D2252/504—Mixtures of two or more absorbents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

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Abstract

The invention discloses a decarbonization solvent and a method for decarbonizing natural gas with high carbon content. The decarbonization solvent comprises 80 to 91 weight percent of main agent, 5 to 16 weight percent of activating agent and 0.75 to 4 weight percent of auxiliary agent; the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine; the activator is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine; the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite. The invention improves the decarbonization solvent, improves the higher absorption and regeneration performance of the decarbonization solvent, and improves the technical economy of the decarbonization process by reducing the power consumption and the heat consumption.

Description

Decarbonizing solvent and method for decarbonizing high carbon-containing natural gas
Technical Field
The invention relates to the field of natural gas, in particular to a decarbonization solvent and a method for decarbonizing natural gas with high carbon content.
Background
At present, natural gas is a high-quality, high-efficiency and clean low-carbon energy source, plays an important role in the global carbon dioxide emission reduction process, and is also significant in improving the energy structure and realizing the double-carbon target. Due to different geological conditions, part of the natural gas contains carbon dioxide (CO)2) Massage deviceThe content of the mole fraction exceeds 10 percent, even reaches more than 20 percent, and becomes high carbon-containing natural gas with higher exploitation cost.
Industrial CO removal from natural gas2There are a number of well established processes, of which chemical absorption is the most widely used, especially absorption using amine solvents. The decarbonization solvent is used for removing CO in natural gas by a chemical absorption method2The key point of (2) is that the absorption and regeneration performance of the catalyst determines the selection of more process parameters and the quality of technical economy in the decarburization process. Typical amine solvent type decarbonizing solvents include Monoethanolamine (MEA), Diethanolamine (DEA), and N-Methyldiethanolamine (MDEA) based formulation solvents. When natural gas contains CO2When the molar fraction content of (A) is high, especially for high carbon-containing natural gas, various formula solvents mainly containing MDEA are mostly used. The MDEA can increase CO2Absorption capacity and reduction of regeneration heat consumption, while the activator can increase CO2The absorption speed of the decarbonizing solvent is high, so that the use efficiency of the decarbonizing solvent is obviously improved, the technical economy of the decarbonizing process is improved through the good comprehensive performance of absorption and regeneration of the decarbonizing solvent, and therefore, the proper improvement of CO is used2The main agent of absorption capacity and the activating agent for promoting the absorption speed to be accelerated are the key points for obtaining better decarburization effect of the decarburization solvent.
It is known that the energy consumption required for the regeneration of the decarbonization type natural gas purification plant is obtained by burning natural gas to heat steam or heat conduction oil. Therefore, the higher absorption and regeneration performance of the decarbonization solvent is improved, and the technical economy of the decarbonization process can be improved by reducing the power consumption and the heat consumption.
Disclosure of Invention
The invention aims to provide a decarbonization solvent and a method for decarbonizing natural gas with high carbon content, so as to improve the higher absorption and regeneration performance of the decarbonization solvent and improve the technical economy of the decarbonization process by reducing the power consumption and the heat consumption.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a decarbonization solvent for decarbonizing from high carbon-containing natural gas, which comprises 80 to 91 weight percent of main agent, 5 to 16 weight percent of activating agent and 0.75 to 4 weight percent of auxiliary agent;
the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine;
the activator is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine;
the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite.
The main agent of the decarbonization solvent of the invention selects the combination of two tertiary amines to adjust the absorption rate, and the mixed amine liquid can complete CO more quickly than a single amine liquid2The absorption of (2) can realize the complementary advantages of single amine liquid. Compared with a single amine liquid with the same total amine concentration, the mixed amine liquid of methyldiethanolamine and triethanolamine or diisopropylethanolamine has higher CO under the same absorption load2Absorption rate and higher final absorption load.
When a small amount of primary or secondary amine activator R is added to the amine solution2R3NH, the reaction proceeds according to the following scheme:
Figure BDA0003567904690000021
Figure BDA0003567904690000022
Figure BDA0003567904690000023
in the formula, R1、R2、R3Is alkyl, alkanol or H. The above reaction involves two key parameters: CO22Second order reaction rate constant K with alcohol amine1And stability constant K of carbamate2. The size of the alkyl group adjacent to the amino nitrogen atom influences the K of the alcohol amine1And K2Choose primaryThe amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol, and the secondary amine is sterically hindered amine which is influenced by diethanolamine or methyl monoethanolamine, so that the purpose of the invention is realized.
In addition, the research of the invention finds that the assistant adopts the combination of hydroxyethyl hexahydro-s-triazine and sodium sulfite, so that the corrosion problem in the system can be greatly delayed, the amine oxidation problem caused by trace oxygen in the feed gas can be inhibited, and the loss of the decarbonization solvent can be reduced.
According to the decarbonizing solvent, the mass ratio of the methyl diethanol amine to the triethanolamine or the diisopropyl ethanolamine is preferably 3:1-5: 1.
According to the decarbonizing solvent of the present invention, preferably, the mass ratio of the primary amine to the secondary amine is 0.75:1 to 1.5: 1.
According to the decarbonizing solvent of the invention, preferably, the hydroxyethyl hexahydro-s-triazine accounts for 0.5 wt% to 2 wt% of the decarbonizing solvent, and the sodium sulfite accounts for 0.25 wt% to 2 wt% of the decarbonizing solvent.
According to the decarbonizing solvent of the present invention, it is preferable that the decarbonizing solvent is diluted to a45 wt% to 55 wt% solution using desalted water when used.
In another aspect, the invention provides a method for decarbonizing from high carbon-containing natural gas, which uses the decarbonizing solvent to absorb and remove CO in the high carbon-containing natural gas2. Specifically, the method comprises the following steps:
the high carbon content natural gas enters the bottom of the absorption tower and is in countercurrent contact with the barren solution of the decarburization solvent sprayed from the top of the absorption tower, and the barren solution absorbs CO in the high carbon content natural gas2The rich solution is output from the bottom of the absorption tower and enters a regeneration tower for regeneration, and the regenerated rich solution becomes barren solution and enters the top of the absorption tower for cyclic utilization;
CO in high carbon content natural gas in absorption tower2And after the catalyst is removed to a control index, the catalyst is output from the top of the absorption tower.
According to the method of the present invention, preferably, the operating pressure of the absorption column is 3MPa to 10 MPa; the temperature of the barren solution entering the absorption tower is 55-70 ℃, and more preferably 60-65 ℃; the gas-liquid ratio of the absorption tower is 100-300.
According to the method, preferably, the high-carbon-content natural gas enters the bottom of the absorption tower after passing through a high-carbon natural gas separator through a gas inlet pipeline.
According to the method, preferably, the rich liquid enters the top of the regeneration tower from the bottom of the absorption tower through a rich liquid turbine pump, a solution heat exchanger and a flash tank, and the rich liquid is regenerated into lean liquid in the regeneration tower and a tower bottom reboiler;
the regenerated barren solution is output from the bottom of the regeneration tower, the heat recovered by the solution heat exchanger heats the rich solution output from the bottom of the absorption tower, and then the rich solution enters the top of the absorption tower for cyclic utilization after passing through a barren solution pump and a first cooler;
according to the method of the invention, preferably, the pressure of the rich liquid after passing through the rich liquid turbine pump is 0.6-1.0 MPa.
According to the method of the present invention, preferably, the flash drum performs the flash at a pressure of 0.5 to 0.8 MPa.
According to the method of the invention, preferably, when the rich liquid enters the regeneration tower for regeneration, the tower top pressure of the regeneration tower is 110-200kPa, more preferably 130-170kPa, and the bottom lean liquid temperature of the regeneration tower is 70-90 ℃, more preferably 75-85 ℃.
According to the method of the invention, preferably, CO in the high carbon-containing natural gas is introduced into the absorption tower2And (4) after the gas is removed to the control index, the gas is output from the top of the absorption tower, and is cooled by a second cooler and then enters a purification gas separator for purification, so that purified gas is obtained.
According to the method of the present invention, preferably, the acid gas discharged from the top of the regeneration tower is cooled by a third cooler and then fed into CO2In the separator, the acid gas passes through CO2The condensate is recovered by the separator and discharged from the CO2The condensate separated in the separator is pumped back to the regeneration column by a reflux pump to maintain the system solution concentration.
The beneficial effects of the invention include:
when the decarbonization solvent and the method provided by the invention are used, the existing decarbonization device of the traditional amine process can be put into use only by adding a small amount of equipment, properly modifying and adjusting part of process parameters. The decarbonization solvent and the process parameters provided by the invention replace the traditional process parameters, the absorption and regeneration performance of the decarbonization solution is improved under the condition of meeting the purification index, the treatment load of a decarbonization device is improved under the same circulation quantity or the circulation quantity of the decarbonization solution is reduced under the same treatment load, the power consumption required by a barren liquor pump and the purified natural gas used as fuel gas in the regeneration process are saved, and the equipment investment and the operating cost are reduced.
Drawings
FIG. 1 is a schematic view of a decarburization apparatus and a process in a preferred embodiment of the present invention.
Description of reference numerals:
1. an absorption tower;
2. regeneration tower
3. Purification gas separator
4、CO2Separator
5. Air inlet pipeline
6. High-carbon natural gas separator
7. First pipeline
8. Rich liquid turbine pump
9. Solution heat exchanger
10. Flash tank
11. First branch
12. Barren liquor pump
13. First cooler
14. Second branch
15. The second pipeline
16. Second cooler
17. Third pipeline
18. Third cooler
19. Fourth pipeline
20. Reflux pump
21. A reboiler.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The solvent for decarbonizing from high carbon-containing natural gas provided by the invention comprises 80-91 wt% of main agent, 5-16 wt% of activating agent and 0.75-4 wt% of auxiliary agent. When the decarbonization solvent is used, the decarbonization solvent is diluted into a solution with the mass fraction of 45-55% by using desalted water.
The main agent consists of methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine; the mass ratio of the methyldiethanolamine to the triethanolamine or the diisopropylethanolamine is 3:1-5: 1.
The activating agent is a mixture of primary amine and secondary amine, and the mass ratio of the primary amine to the secondary amine is 0.75:1-1.5: 1. The primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine.
The auxiliary agent consists of hydroxyethyl hexahydro-s-triazine and sodium sulfite. Wherein, the hydroxyethyl hexahydro-s-triazine accounts for 0.5wt percent to 2wt percent of the decarbonization solvent, and the sodium sulfite accounts for 0.25wt percent to 2wt percent of the decarbonization solvent.
As shown in FIG. 1, the apparatus for decarbonizing natural gas containing high carbon content using the decarbonizing solvent of the present invention comprises an absorption tower 1, a regeneration tower 2, a clean gas separator 3 and CO2The separator 4, wherein the lower part of the absorption tower 1 is connected with an air inlet pipeline 5 of natural gas with high carbon content, a high-carbon natural gas separator 6 is arranged on the air inlet pipeline 5 of the natural gas with high carbon content, the bottom of the absorption tower 1 is connected with the upper part of the regeneration tower 2 through a first pipeline 7, a rich liquid turbine pump 8, a solution heat exchanger 9 and a flash tank 10 are sequentially arranged on the first pipeline 7 connecting the absorption tower 1 and the regeneration tower 2, the solution heat exchanger 9 is further connected with the top of the absorption tower 1 through a first branch 11, a lean liquid pump 12 and a first cooler 13 are sequentially arranged on the first branch 11, the bottom of the regeneration tower 2 is connected with the solution heat exchanger 9 through a second branch 14, the top of the absorption tower 1 is connected with the purification gas separator 3 through a second pipeline 15, a second cooler 16 is arranged on the second pipeline 15, and the top of the regeneration tower 2 is connected with the solution heat exchanger 9 through a third branch 14Line 17 with CO2The upper part of the separator 4 is connected and a third cooler 18, CO, is fitted to the third line 172The bottom of the separator 4 is connected to the upper part of the regeneration tower 2 via a fourth line 19, a reflux pump 20 is provided on the fourth line 19, and a reboiler 21 is further connected to the lower part of the regeneration tower 2 via a line.
As shown in fig. 1, the method for decarbonizing natural gas using the above decarbonization apparatus includes the steps of:
after the high carbon-containing natural gas enters the absorption tower 1 from the bottom of the absorption tower 1 through the air inlet pipeline 5 and the high carbon-containing natural gas separator 6, the high carbon-containing natural gas is in countercurrent contact with lean liquid sprayed from the top of the absorption tower 1, so that CO in the high carbon-containing natural gas2Entering into lean solution, and absorbing CO in high carbon content natural gas by the lean solution2And then the rich liquid is changed into rich liquid, the rich liquid enters the top of the regeneration tower 2 through a first pipeline 7 after passing through a rich liquid turbine pump 8, a solution heat exchanger 9 and a flash tank 10, the rich liquid is regenerated in the regeneration tower 2 and a reboiler 21, and the regenerated rich liquid becomes lean liquid which is circulated to the upper part of the absorption tower 1 for recycling through a second branch 14 through a lean liquid pump 12 and a first cooler 13.
The operation pressure of the absorption tower 1 is 3MPa-10MPa, the temperature of the barren solution entering the absorption tower 1 is 55-70 ℃, preferably 60-65 ℃, and the gas-liquid ratio of the absorption tower is 100-300. The rich liquid passing through the first pipeline 7 passes through a rich liquid turbo pump 8, the pressure is 0.6-1.0MPa, and then the rich liquid enters a flash evaporation tank 10 for flash evaporation, and the pressure is controlled to be 0.5-0.8MPa in the flash evaporation process. When the rich liquid enters the regeneration tower 2 for regeneration, the pressure at the top of the regeneration tower 2 is controlled at 110-200kPa, preferably 130-170kPa, and the temperature of the poor liquid at the bottom of the regeneration tower 2 is 70-90 ℃, preferably 75-85 ℃.
CO in high carbon content natural gas in absorption tower 12Removing to control index, cooling from the top of the absorption tower 1 by a second pipeline 15 through a second cooler 16, inputting into a purification gas separator 3, and inputting CO into the purification gas separator 32Purified and then led out for delivery.
The acid gas discharged from the top of the regeneration tower 2 is cooled by a third pipeline 17 through a third cooler 18 and then is input with CO2In the separator 4, the acid gas passes through CO2The condensate is recovered by the separator 4 and discharged from the CO2Cold separated in separator 4The condensate is returned to the regeneration column 2 via a fourth line 19 via a reflux pump 20 to maintain the system solution concentration.
The following comparative examples and examples were carried out using the decarburization apparatus and flow path of FIG. 1. Wherein the high carbon content natural gas adopts simulated gas with the pressure of 4.0MPa, room temperature and CO2The molar content of (A) is 15.0%, and the rest is N2。
Comparative example 1:
the decarburization solvent of this comparative example was a typical decarburization formulation for internationally activated MDEA, consisting of MDEA35 wt%, piperazine 5 wt%, and water in balance.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of the lean liquor at the bottom of the regeneration tower is 80 ℃, the top pressure of the regeneration tower is controlled at 110-200kPa, and CO in the obtained purified gas2The molar content of (a) is 2.61%.
Comparative example 2
The decarbonizing solvent of this comparative example used a typical decarbonizing formulation for internationally activating MDEA, consisting of MDEA45 wt%, piperazine 5 wt%, and water as the remainder.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of barren liquor at the bottom of a regeneration tower is 75 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 4.23%.
Example 1
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein MDEA70.00wt% and diisopropylethanolamine 19.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 wt% of 2-amino-2-methyl-1, 3-propanediol and 5.00 wt% of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 1.48%.
Example 2
The decarburization solvent of this example was composed of: the main agent is MDEA + triethanolamine, wherein the MDEA accounts for 72.00 wt% and the triethanolamine accounts for 17.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operating pressure of the regeneration tower is 0.15MPa, and CO in purified gas2Is 1.71%.
Example 3
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein MDEA70.00wt% and diisopropylethanolamine 19.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and methyl monoethanolamine, wherein 5.00 wt% of 2-amino-2-methyl-1, 3-propanediol and 5.00 wt% of methyl monoethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 1.66%.
Comparative example 1 compares with examples 1-3 to illustrate that: different formulations of the present application have better performance results than comparative example 1 under the same process conditions.
Example 4
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein MDEA70.00wt% and diisopropylethanolamine 19.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 240, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 2.21%.
Example 5
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein MDEA70.00wt% and diisopropylethanolamine 19.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 260, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (b) is 2.86%.
Examples 4-5 and comparative example 1: it is demonstrated that the decarburization formula of the present application can process more amount of gas under the same conditions (circulation amount, absorption temperature, absorption pressure, regeneration temperature, regeneration pressure) while satisfying the requirement of CO in the purified gas2<Index requirement of 3%.
Example 6
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein MDEA70.00wt% and diisopropylethanolamine 19.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 wt% of 2-amino-2-methyl-1, 3-propanediol and 5.00 wt% of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of barren liquor at the bottom of a regeneration tower is 75 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 2.38%.
Example 7
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein MDEA70.00wt% and diisopropylethanolamine 19.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 85 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 1.47%.
Example 8
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein MDEA70.00wt% and diisopropylethanolamine 19.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of lean liquid at the bottom of a regeneration tower is 90 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 1.43%.
Examples 6-8 compare with comparative example 2 to illustrate that the regeneration temperature of the present invention is 80 ℃ and the CO in the purified gas is increased2The reduction is not large, but the increase of the regeneration temperature means the increase of the regeneration heat consumption.
Example 9
The decarbonizing solvent composition of the present example was: the main agent is MDEA, wherein the MDEA accounts for 89.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of lean solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 2.11%.
Compared with the embodiment 1, the main agent is less than diisopropylethanolamine, and the decarburization effect is reduced under the same condition.
Example 10
The decarbonizing solvent composition of the present example was: the main agent is MDEA, wherein the MDEA accounts for 89.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 1.71%.
Compared with the example 2, the main agent is less than the diisopropylethanolamine, and the decarburization effect is reduced under the same condition.
Example 11
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein the MDEA80.00wt% and the diisopropylethanolamine 19.25 wt%; no activator; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 5.33%.
Compared with the example 1, the decarbonization effect under the same condition is greatly reduced without using the activating agent, and the content of CO2 in the purified gas exceeds the control index by 3 percent.
Example 12
The decarbonizing solvent composition of the present example was: the main agent is MDEA + triethanolamine, wherein the MDEA accounts for 82.00 wt% and the triethanolamine accounts for 17.25 wt%; no activator; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 5.87%.
Compared with the example 2, the decarburization effect under the same condition is greatly reduced without using the activating agentLow CO content in purified gas2The content exceeds the control index by 3 percent.
Example 13
The decarbonizing solvent composition of the present example was: the main agent is MDEA + diisopropylethanolamine, wherein the MDEA70.00wt% and the diisopropylethanolamine 20.00 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; no auxiliaries are used. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 1.45%.
Compared with the example 1, the decarburization effect under the same conditions is not obviously changed without using the auxiliary agent.
Example 14
The simulated gas pressure of the high carbon-containing natural gas is 4.0MPa, the room temperature and the CO content2The content is 15.0 percent, and the rest is N2。
The decarbonization solvent comprises the following components: the activator is 2-amino-2-methyl-1, 3-propanediol and diethanol amine, wherein the 2-amino-2-methyl-1, 3-propanediol accounts for 50.00 wt% and the diethanol amine accounts for 49.25.00 wt%; the auxiliary agent is 0.25 wt% of hydroxyethyl hexahydro-s-triazine and 0.50 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 2.11%.
In comparison with example 1, the decarburization effect under the same conditions was inferior without using the main agent.
Example 15
The simulated gas pressure of the high carbon-containing natural gas is 4.0MPa, the room temperature and the CO content2The content is 15.0 percent, and the rest is N2。
The decarbonization solvent comprises the following components: the main agent is MDEA + diisopropylethanolamine, wherein the MDEA accounts for 55.00 wt%, and the diisopropylethanolamine accounts for 34.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operating pressure of the regeneration tower is 0.15MPa, and CO in purified gas2The molar content of (b) is 2.65%.
Example 16
The simulated gas pressure of the high carbon-containing natural gas is 4.0MPa, the room temperature and the CO content2The content is 15.0 percent, and the rest is N2。
The decarbonization solvent comprises the following components: the main agent is MDEA + diisopropylethanolamine, wherein the MDEA accounts for 77.00 wt%, and the diisopropylethanolamine accounts for 12.25 wt%; the activator is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein 5.00 percent by weight of 2-amino-2-methyl-1, 3-propanediol and 5.00 percent by weight of diethanolamine; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operating pressure of the regeneration tower is 0.15MPa, and CO in purified gas2The molar content of (a) is 2.29%.
In comparison with example 1, the amount of the main component is not within the range of the ratio defined in the present invention, and the decarburization effect under the same conditions is deteriorated.
Example 17
The simulated gas pressure of the high carbon-containing natural gas is 4.0MPa, the room temperature and the CO content2The content is 15.0 percent, and the rest is N2。
The decarbonization solvent comprises the following components: the main agent is MDEA + diisopropylethanolamine, wherein the MDEA accounts for 65.00 wt%, and the diisopropylethanolamine accounts for 15.25 wt%; the activating agent is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein the 2-amino-2-methyl-1, 3-propanediol accounts for 10.00 wt% and the diethanolamine accounts for 9.00 wt%; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
At the gas-liquid ratio of 200 of the absorption towerThe pressure of a flash tank is 0.6MPa, the temperature of barren liquor at the bottom of a regeneration tower is 80 ℃, the operating pressure of the regeneration tower is 0.15MPa, and CO in purified gas2The molar content of (a) is 2.44%.
In comparison with example 1, the amount of the activator used was out of the range defined in the present invention, and the decarburization effect under the same conditions was deteriorated.
Example 18
The simulated gas pressure of the high carbon-containing natural gas is 4.0MPa, the room temperature and the CO content2The content is 15.0 percent, and the rest is N2。
The decarbonization solvent comprises the following components: the main agent is MDEA + diisopropylethanolamine, wherein the MDEA accounts for 65.00 wt%, and the diisopropylethanolamine accounts for 15.25 wt%; the activating agent is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein the 2-amino-2-methyl-1, 3-propanediol accounts for 10.00 wt% and the diethanolamine accounts for 9.00 wt%; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 2.14%.
In comparison with example 1, the amount of the activator used was out of the range defined in the present invention, and the decarburization effect under the same conditions was deteriorated.
Example 19
The simulated gas pressure of the high carbon-containing natural gas is 4.0MPa, the room temperature and the CO content2The content is 15.0 percent, and the rest is N2。
The decarbonization solvent comprises the following components: the main agent is MDEA + diisopropylethanolamine, wherein the MDEA accounts for 70.00 wt%, and the diisopropylethanolamine accounts for 15.25 wt%; the activating agent is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein the 2-amino-2-methyl-1, 3-propanediol accounts for 8.00 wt% and the diethanolamine accounts for 6.00 wt%; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 1.42%.
Compared with the embodiment 1, the main agent and the activating agent are adjusted within the range of the mixture ratio and the proportion defined by the invention, and the decarburization effect is stable under the same condition.
Example 20
The simulated gas pressure of the high carbon-containing natural gas is 4.0MPa, the room temperature and the CO content2The content is 15.0 percent, and the rest is N2。
The decarbonization solvent comprises the following components: the main agent is MDEA + diisopropylethanolamine, wherein the MDEA accounts for 70.00 wt%, and the diisopropylethanolamine accounts for 15.25 wt%; the activating agent is 2-amino-2-methyl-1, 3-propanediol and diethanolamine, wherein the 2-amino-2-methyl-1, 3-propanediol accounts for 6.00 wt% and the diethanolamine accounts for 8.00 wt%; the auxiliary agent is 0.50 wt% of hydroxyethyl hexahydro-s-triazine and 0.25 wt% of sodium sulfite. When the decarbonization solvent is used, the decarbonization solvent is diluted to 50 wt% by using desalted water.
Under the condition that the gas-liquid ratio of the absorption tower is 200, the pressure of a flash tank is 0.6MPa, the temperature of a barren solution at the bottom of a regeneration tower is 80 ℃, the operation pressure of the regeneration tower is 0.15MPa, and CO in the obtained purified gas2The molar content of (a) is 1.53%.
Compared with the embodiment 1, the main agent and the activating agent are adjusted within the range of the mixture ratio and the proportion defined by the invention, and the decarburization effect is stable under the same condition.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. The decarbonization solvent for decarbonizing from high carbon-containing natural gas is characterized by comprising 80-91 wt% of main agent, 5-16 wt% of activating agent and 0.75-4 wt% of auxiliary agent;
the main agent comprises methyldiethanolamine and triethanolamine or methyldiethanolamine and diisopropylethanolamine;
the activator is a mixture of primary amine and secondary amine, and the primary amine is hydroxyethyl ethylenediamine or 2-amino-2-methyl-1, 3-propanediol; the secondary amine is diethanolamine or methyl monoethanolamine;
the auxiliary agent comprises hydroxyethyl hexahydro-s-triazine and sodium sulfite.
2. The decarbonization solvent of claim 1, wherein the mass ratio of the methyldiethanolamine to the triethanolamine or the diisopropylethanolamine is 3:1 to 5: 1.
3. The decarbonization solvent of claim 1, wherein the mass ratio of the primary amine to the secondary amine is from 0.75:1 to 1.5: 1.
4. The decarbonization solvent of claim 1, wherein the hydroxyethylhexahydro-s-triazine comprises 0.5 wt% to 2 wt% of the decarbonization solvent, and the sodium sulfite comprises 0.25 wt% to 2 wt% of the decarbonization solvent.
5. The decarbonization solvent of claim 1, wherein the decarbonization solvent is diluted to a45 wt% to 55 wt% solution using desalted water when in use.
6. A method for decarbonizing from high carbon-containing natural gas, which is characterized in that the decarbonization solvent of any one of claims 1 to 5 is used for absorbing and removing CO in the high carbon-containing natural gas2。
7. Method according to claim 6, characterized in that it comprises the following steps:
the high carbon content natural gas enters the bottom of the absorption tower and is in countercurrent contact with the barren solution of the decarburization solvent sprayed from the top of the absorption tower, and the barren solution absorbs CO in the high carbon content natural gas2Then the rich liquor is changed into rich liquor, the rich liquor is output from the bottom of the absorption tower and enters a regeneration tower for regeneration, and the regenerated rich liquor becomes barren liquor and enters the regeneration towerThe top of the absorption tower is recycled;
CO in high carbon content natural gas in absorption tower2And after the catalyst is removed to a control index, the catalyst is output from the top of the absorption tower.
8. The process according to claim 7, wherein the operating pressure of the absorption column is from 3MPa to 10 MPa;
the temperature of the barren solution entering the absorption tower is 55-70 ℃, and preferably 60-65 ℃;
the gas-liquid ratio of the absorption tower is 100-300.
9. The method of claim 7, wherein the high carbon content natural gas enters the bottom of the absorption tower after passing through a high carbon natural gas separator through a gas inlet pipeline.
10. The method of claim 7, wherein the rich liquid enters the top of the regeneration tower from the bottom of the absorption tower through a rich liquid turbine pump, a solution heat exchanger and a flash tank, and the rich liquid is regenerated into lean liquid in the regeneration tower and a tower bottom reboiler;
the regenerated barren solution is output from the bottom of the regeneration tower, the heat recovered by the solution heat exchanger heats the rich solution output from the bottom of the absorption tower, and then the rich solution enters the top of the absorption tower for cyclic utilization after passing through a barren solution pump and a first cooler;
preferably, the pressure of the rich liquid after passing through the rich liquid turbine pump is 0.6-1.0 MPa;
preferably, the pressure of the flash evaporation tank is 0.5-0.8 MPa;
preferably, when the rich liquid enters the regeneration tower for regeneration, the tower top pressure of the regeneration tower is 110-200kPa, more preferably 130-170kPa, and the bottom lean liquid temperature of the regeneration tower is 70-90 ℃, more preferably 75-85 ℃;
preferably, CO in the high carbon-containing natural gas is absorbed in the absorption tower2The gas is discharged from the top of the absorption tower after being removed to the control index, and enters a purification gas separator for purification after being cooled by a second cooler to obtain purified gas;
preferably, the acid gas discharged from the top of the regeneration tower is cooled by a third cooler and then is input into CO2In the separator, the acid gas passes through CO2The condensate is recovered by the separator and discharged from the CO2The condensate separated in the separator is pumped back to the regeneration column by a reflux pump to maintain the system solution concentration.
CN202210310375.2A 2022-03-28 2022-03-28 Decarbonizing solvent and method for decarbonizing high carbon-containing natural gas Pending CN114591771A (en)

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