CN118146104A - Novel carbonyl functionalized proton type ionic liquid and preparation method and application thereof - Google Patents

Novel carbonyl functionalized proton type ionic liquid and preparation method and application thereof Download PDF

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CN118146104A
CN118146104A CN202410089121.1A CN202410089121A CN118146104A CN 118146104 A CN118146104 A CN 118146104A CN 202410089121 A CN202410089121 A CN 202410089121A CN 118146104 A CN118146104 A CN 118146104A
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ionic liquid
gas
carbonyl
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carboxylate
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吴有庭
史名珍
张效敏
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Nanjing University
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    • C07—ORGANIC CHEMISTRY
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    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
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    • 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
    • B01D53/1468—Removing hydrogen sulfide
    • 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
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C07C211/12—1,6-Diaminohexanes
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    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
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    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/18—Saturated compounds containing keto groups
    • C07C62/24—Saturated compounds containing keto groups the keto group being part of a ring
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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Abstract

The invention discloses a novel carbonyl functionalized proton type ionic liquid for selective removal of H2S, belonging to the technical field of gas separation and purification in green chemical industry. The ionic liquid system is proton ionic liquid formed by directly carrying out acid-base neutralization reaction on tertiary amine and keto acid compounds, wherein cations of the ionic liquid are ammonium ions containing or not containing free tertiary amine groups, anions of the ionic liquid are cyclic or chain carboxylate ions, and the ionic liquid contains free ketocarbonyl besides carboxylate. Unlike the usual acid-base mechanism, the invention innovatively proposes a novel mechanism for realizing efficient trapping of H 2 S by nucleophilic addition of carbonyl sites and H 2 S. Based on the specific recognition effect on H 2 S, the ionic liquid prepared by the invention has excellent H 2 S absorption capacity and H 2S/CO2 selectivity. In addition, the preparation process of the series of ionic liquids is simple and convenient, and the H 2 S trapping process is highly reversible, so that the series of ionic liquids are expected to be applied to the actual industrial desulfurization process.

Description

Novel carbonyl functionalized proton type ionic liquid and preparation method and application thereof
Technical Field
The invention relates to a novel carbonyl functionalized proton type ionic liquid for selectively removing H 2 S in energy gas, belongs to the technical field of gas separation and purification in green chemical industry, and particularly relates to a novel carbonyl functionalized ionic liquid, a preparation method and application thereof.
Background
Hydrogen sulfide (H 2 S) is a very irritating, highly toxic and corrosive chemical that is commonly present with CO 2 in natural gas, synthesis gas, and biogas. The existence of the acid gas not only causes corrosion to pipelines and equipment and affects the service life of the pipelines and equipment, but also forms a serious threat to the safe and efficient utilization of the energy gas. In particular H 2 S, which not only poses a significant threat to environmental and personal safety, but also can cause equipment and pipe corrosion, catalyst poisoning, reduced fuel heating value, etc. Therefore, the removal of H 2 S from the energy gas is an indispensable process. Similar to the carbon capture, conversion and sequestration (CCUS) process, captured H 2 S can also be used as a feedstock for the development of high value sulfur-containing chemicals and hydrogen (H 2). Therefore, the realization of the selective removal of H 2 S has important significance for energy gas purification and the efficient utilization of sulfur and hydrogen resources.
Currently, absorption-based processes predominate in most acid gas treatment processes. Ionic liquids (Ionic liquids, ILs) are room temperature molten salts composed of adjustable anions and cations, and are emerging green solvents in recent years and are widely applied to the field of gas trapping. Ionic liquids have a range of excellent properties such as high thermal stability, almost negligible vapor pressure, good affinity for acid gases, etc., and thus play a vital role in energy-related separation processes. The functionalized ionic liquid reported in the prior literature utilizes the weak acidic nature of H 2 S to trap H2S through an acid-base strategy. Specifically, researchers have introduced some basic groups (including tertiary amines, carboxylate groups, oxazolyl and phenolic groups, etc.) into the ionic liquid structure to achieve trapping of H 2 S. For example Xu Yun et al reported a class of carboxylate ionic liquids containing sulfhydryl groups on anions for H 2 S capture (CN 111943858A), any row et al reported a series of processes for the solution absorption of H 2 S by basic ionic liquids (amino acid salts, carboxylates and imidazole salts) (CN 107115761A). These basic groups achieve efficient enrichment of H 2 S in liquid phase media by forming strong hydrogen bonds (e.g., -N.cndot.H and-O.cndot.H) with the polar protons of H 2 S. It is worth mentioning that ionic liquids containing basic sites also have considerable absorption of CO 2, which is also an acid gas molecule, often resulting in poor separation selectivity of H 2S/CO2, which means that high purity H 2 S or CO 2 gas streams cannot be obtained.
Aiming at the separation dilemma, the invention designs the structure of the ionic liquid based on the chemical property of H 2 S except weak acidity, so that the ionic liquid has specific recognition function on H 2 S. It is well known that H 2 S is nucleophilic, so the invention innovatively introduces a carbonyl structure with electrophilic activity into an ionic liquid structure, and achieves reactive absorption of H 2 S through nucleophilic addition reaction of carbonyl and H 2 S. In particular, nucleophilic addition products have metastability with carbon diols, which corresponds to a highly reversible absorption process. In addition, the carbonyl site has no specific affinity for non-nucleophilic CO 2. In combination with the advantages described above, the series of carbonyl-functionalized ionic liquids present a series of advantages: excellent H 2 S absorption capacity, excellent H 2S/CO2 selectivity, and excellent recycling performance. The ionic liquid is expected to be oriented to high-selectivity removal of H 2 S in energy gas, and has good industrial application prospect.
Disclosure of Invention
Aiming at the defects of the existing H 2 S trapping strategy, the first aim of the invention is to disclose a novel carbonyl functionalized proton type ionic liquid;
the second purpose of the invention is to disclose a preparation method of a novel carbonyl functionalized proton type ionic liquid;
the third purpose of the invention is to disclose the application of a novel carbonyl functionalized proton type ionic liquid.
The specific technical scheme of the invention is as follows:
A novel carbonyl functionalized proton type ionic liquid is characterized in that: (1) The cation is ammonium ion containing or not containing free tertiary amine group; (2) The anions are cyclic or chain carboxylate ions and contain free ketocarbonyl groups besides carboxylate groups; (3) Is a proton type ionic liquid formed by directly carrying out acid-base neutralization reaction on tertiary amine and keto acid compound.
In the ionic liquid, the structural formula of cations is shown as general formulas (A) and (B).
Wherein R 1,R2 and R 3 can be C 1～C4 straight chain alkyl, cyclohexyl, hydroxyalkyl with or without ether linkages; the central atom of the group X may be C, N and O, such as [ -CH 2-],[-N(CH3) - ] and [ -O- ], etc.; the subscript m, n represents the number of carbon atoms (1.ltoreq.m+n.ltoreq.6). Examples of the general formula (A) include, but are not limited to, 2- [2- (dimethylamino) ethoxy ] ethanol, N-methyldiethanolamine, N-diethylethanolamine, triethylamine, N-dimethylcyclohexylamine, N-methyldipropylamine, N-methyldibutylamine and the like-derived ammonium ions, and the structures thereof are as follows:
Taking general formula (B) as an example, ammonium ions derived from N, N, N ', N' -tetramethyl ethylenediamine, N, N, N ', N' -tetramethyl-1, 3-propanediamine, N, N, N ', N' -tetramethyl-1, 6-hexanediamine, pentamethyl diethylenetriamine, pentamethyl dipropylenetriamine, and bis-dimethylaminoethyl ether, etc., the structure is as follows:
quaternary ammonium cations of dimorpholinoethyl ether and 1,3, 5-tris (dimethylaminopropyl) -1,3, 5-hexahydrotriazine can also be derived:
In the ionic liquid, anions include, but are not limited to, 4-cyclohexanone carboxylate, 3-oxo-cyclohexane carboxylate, 3-oxo-1-cyclopentane carboxylate, 3-oxo-cyclobutane carboxylate, levulinate, 5-oxo-hexanoate and the like, and the structures thereof are as follows:
further, the ionic liquid of the present invention may contain only one kind of cation and one kind of anion, or may be a complex solution containing a plurality of cations and/or a plurality of anions.
The invention also provides a method for preparing the ionic liquid, which comprises the following steps: firstly, a certain amount of tertiary amine compound is weighed and dissolved in ethanol, an ethanol solution in which a keto acid compound with a stoichiometric ratio is dissolved is dropwise added under the conditions of ice bath and stirring, after reaction is carried out for 1h, the temperature is raised to the vicinity of the boiling point of the ethanol, and the reaction is continued for 2 h under the condition of reflux. After the reaction, most of the solvent was removed by rotary evaporation, and then dried in vacuo at 60 ℃ for use.
The performance test method of the ionic liquid comprises the following steps:
(1) H 2 S absorption and desorption properties: testing the solubility of H 2 S in the prepared ionic liquid at a certain temperature and in a H 2 S pressure range; and then desorbing the absorbed H 2 S under certain temperature and pressure conditions to realize the regeneration of the ionic liquid.
(2) H 2S/CO2 and H 2S/CH4 selectivities (for natural gas as an example): the solubility of CO 2(CH4) in the ionic liquid prepared was tested over a range of temperatures and CO 2(CH4) pressures.
In the method, the temperature range of the ionic liquid for absorbing H 2S、CO2 and CH 4 is 30-70 ℃.
In the method, the pressure range of the ionic liquid for absorbing H 2 S is 0-1.0 bar, and the pressure range of the ionic liquid for absorbing CO 2(CH4) is 0-3.0 bar.
In the above method, the regeneration temperature of the ionic liquid is 60 to 120 ℃, preferably 90 to 110 ℃.
In the above method, the ionic liquid regeneration pressure is 0-101.3 kPa, preferably 101.3 kPa.
The invention also provides a process for selectively removing H 2 S from the energy gas by using the ionic liquid. The process flow is mainly divided into two parts: the ionic liquid selectively absorbs the H 2 S portion and the ionic liquid desorbs portion. As shown in fig. 1, the process specifically comprises the following steps:
Step one: the feed mixed gas 1 containing H 2 S enters from the bottom of an absorption tower A, reversely contacts with the ionic liquid from top to bottom, the ionic liquid rich liquid 2 after absorbing H 2 S is pumped into an evaporator C through a rich liquid pump B1, and the desulfurization gas is discharged from the top of the tower;
step two: and (3) desorbing the ionic liquid rich liquid under the action of steam after the ionic liquid rich liquid enters an evaporator C, and obtaining an air flow rich in H 2 S and an ionic liquid lean liquid after the desorption. The ionic liquid lean solution is conveyed to the heat exchanger D through the evaporator bottom pump B2, and enters the absorption tower again for recycling after heat exchange.
In the process, the absorption tower A in the first step is a plate tower or a packed tower, the theoretical plate number is more than or equal to 25, and the packing adopts regular packing. The operating temperature of the absorption tower A is 20-40 ℃, the operating pressure is normal pressure, and the operating liquid-gas ratio is 1.1-1.5 times of the minimum liquid-gas ratio.
In the above process, the pressure of the feed mixture 1 containing H 2 S in the first step is normal pressure.
In the process, the evaporation process in the second step is single-effect or multi-effect evaporation, the evaporation temperature is 90-110 ℃, and the pressure is normal pressure.
Compared with the prior art, the invention has the beneficial effects that:
(1) The carbonyl functionalized ionic liquid can specifically identify H 2 S through a nucleophilic addition mechanism, so that high-efficiency removal of H 2 S from a gas source containing or not containing CO 2 can be realized.
(2) The process of trapping H 2 S by the functionalized ionic liquid is highly reversible, so that the ionic liquid can be recycled for multiple times with almost no performance loss.
Drawings
FIG. 1 is a schematic diagram of the mechanism of action between carbonyl-functionalized ionic liquid and H 2 S in the present invention. Specifically, polar c=o double bonds in ionic liquids can undergo nucleophilic addition reactions with H 2 S to form new C-S (H) bonds, thereby generating "heterogeminal diol" species. This species has been confirmed by spectral characterization and theoretical calculations. In one aspect, the process corresponds to reactive absorption of H 2 S; on the other hand, the c=o double bond has no special affinity with CO 2. This means that the carbonyl site can selectively recognize H 2 S from both acid gases. In particular, since homocarbon diols have thermodynamic instability, the addition process of ketocarbonyl groups to H 2 S is highly reversible, and the equilibrium is easily shifted to the direction of decomposition of the hybrid geminal diol into ketocarbonyl species by changing the external conditions. This corresponds to a good reversibility of the H 2 S trapping process in the series of ionic liquids.
Fig. 2 is a schematic diagram of a process flow for selectively removing H 2 S from energy gas by using the carbonyl functionalized ionic liquid provided by the invention. Wherein: 1 is gas to be treated (energy gas containing H 2 S), 2 is ion liquid rich liquid after absorbing H 2 S,3 is ion liquid lean liquid after desorption, and 4 is fresh ion liquid supplementing position. A is an absorption tower, B1 is a rich liquid pump, B2 is an evaporator bottom pump, C1 and C2 are heat exchangers, and D is an evaporator.
Detailed Description
The technical scheme of the present invention is further described below by way of specific examples, but the present invention is not limited to the following examples.
Example 1
8.01G (0.05 mol) of dimethylaminoethyl ether is weighed and dissolved in 20mL of ethanol, an ethanol solution in which the 4-cyclohexanone carboxylic acid with a stoichiometric ratio is dissolved is dropwise added under the conditions of ice bath and stirring, after the reaction is carried out for 1h, the temperature is raised to the vicinity of the boiling point of the ethanol, and the reaction is continued for 2h under the condition of reflux. After the reaction is finished, the majority of solvent is removed by rotary evaporation, and then the solvent is dried in vacuum at 60 ℃ to obtain the 4-cyclohexanone carboxylate of the bis-dimethylaminoethyl ether, which is named as [ BDH ]6ca. The chemical structural formula is shown as the formula (C).
Examples 2 to 8
Other steps are the same as in example 1, and the types of tertiary amine compounds or keto acid compounds are changed, so that different types of carbonyl functionalized ionic liquids can be prepared, and the chemical structural formulas of the carbonyl functionalized ionic liquids are respectively shown in the formulas (D) to (J).
Example 9
8.01G (0.05 mol) of dimethylaminoethyl ether was weighed and dissolved in 20mL of ethanol, an ethanol solution containing 0.025mol of 4-cyclohexanone carboxylic acid and 0.025mol of 5-oxohexanoic acid was added dropwise with stirring in an ice bath, the temperature was raised to the vicinity of the boiling point of ethanol after 1 hour of reaction, and the reaction was continued for 2 hours under reflux. After the reaction is finished, removing most of the solvent by rotary evaporation, and then drying in vacuum at 60 ℃ to obtain the mixed ketonate of the dimethylaminoethyl ether, which is named as [ BDH ]6ca- [ BDH ] Glu, wherein the chemical structural formula of the mixed ketonate is shown as the formula (K).
Examples 10 to 18
The H 2 S absorption capacities of the respective 9 ionic liquids of examples 1 to 9 were measured at 30℃under different H2S partial pressures, and the results are shown in Table 1.
TABLE 1 absorption capacity of H 2 S in 9 ionic liquids at 30 DEG C
Examples 19 to 22
Four ionic liquids from examples 1-4 were used for the absorption of H 2S、CO2 and CH 4, respectively. The performance data for the uptake of the three gases and the selectivity of H 2S/CO2 and H 2S/CH4 at 30℃and 1.0 bar are shown in Table 2.
Table 2.30 ℃ and 1.0 bar H 2S、CO2 and CH 4 uptake in four ionic liquids, and H 2S/CO2 and H 2S/CH4 selectivities
Example 23
After the H2S absorption of [ BDH ]6ca prepared according to example 1 was saturated at 30℃and 1.0 bar, desorption was performed at 90℃and 101.3: 101.3 kPa. The desorption time was 1 h. The sample was then repeatedly assayed for H2S uptake at 30℃and 1.0 bar. The regeneration and circulation properties of the ionic liquids tested are shown in table 3.
Table 3 regeneration and cycle Performance of [ BDH ]6ca
Example 24
According to the process shown in fig. 1, a feed mixture gas (H 2S/CO2/CH4 =3/5/92) containing H 2 S was fed from the bottom of the absorption column a at a gas flow rate of 100Nm 3/H. The ionic liquid [ BDH ]6ca prepared according to the embodiment 1 is sprayed from the top of the tower from top to bottom, the operation liquid-gas ratio is 1.5, and the ionic liquid flow is 234L/h. The operating temperature of the absorber A was 30℃and the operating pressure was normal. The absorbed ionic liquid rich liquid is conveyed to a heat exchanger C1 through a rich liquid pump B1, and is sent to an evaporator D after heat exchange, and the desulfurization gas is discharged from the top of the tower. And (3) desorbing the ionic liquid rich liquid in the evaporator D under the action of steam, wherein the desorption temperature is 100 ℃, and obtaining the gas flow rich in H 2 S and the ionic liquid lean liquid after desorption. Under the conveying action of the bottom pump B2 of the evaporator, the ionic liquid lean solution sequentially passes through the heat exchangers C1 and C2, and is sent into the absorption tower again for recycling after heat exchange.
Analysis of results: the H2S content in the desulfurization gas discharged from the top of the tower is reduced to 41 ppm, the volume fractions of CO 2 and CH 4 are respectively 4.8 percent and 95.2 percent, and the desulfurization rate reaches 99.86 percent. The volume fraction of H 2 S in the H2S-enriched gas stream discharged from the top of the evaporator is more than or equal to 98%, the volume fraction of CO 2 is less than or equal to 1%, and the volume fraction of CH 4 is less than or equal to 1%.
Example 25
According to the process shown in fig. 1, a feed mixture gas (H 2S/CO2/CH4 =3/5/92) containing H 2 S was fed from the bottom of the absorption column a at a gas flow rate of 100Nm 3/H. The ionic liquid [ TMH ]6ca prepared according to the embodiment 2 is sprayed from the top of the tower from top to bottom, the operation liquid-gas ratio is 1.4, and the ionic liquid flow is 227L/h. The operating temperature of the absorber A was 30℃and the operating pressure was normal. The absorbed ionic liquid rich liquid is conveyed to a heat exchanger C1 through a rich liquid pump B1, and is sent to an evaporator D after heat exchange, and the desulfurization gas is discharged from the top of the tower. And (3) desorbing the ionic liquid rich liquid in the evaporator D under the action of steam, wherein the desorption temperature is 100 ℃, and obtaining the gas flow rich in H 2 S and the ionic liquid lean liquid after desorption. Under the conveying action of the bottom pump B2 of the evaporator, the ionic liquid lean solution sequentially passes through the heat exchangers C1 and C2, and is sent into the absorption tower again for recycling after heat exchange.
Analysis of results: the H2S content in the desulfurization gas discharged from the top of the tower is reduced to 48 ppm, the volume fractions of CO 2 and CH 4 are respectively 4.8 percent and 95.2 percent, and the desulfurization rate reaches 99.84 percent. The volume fraction of H 2 S in the H2S-enriched gas stream discharged from the top of the evaporator is more than or equal to 98%, the volume fraction of CO 2 is less than or equal to 1%, and the volume fraction of CH 4 is less than or equal to 1%.
Example 26
According to the process shown in fig. 1, a feed mixture gas (H 2S/CO2/CH4 =3/5/92) containing H 2 S was fed from the bottom of the absorption column a at a gas flow rate of 100Nm 3/H. The ionic liquid [ DMAEEH ]6ca prepared according to the embodiment 3 is sprayed from top to bottom, the operation liquid-gas ratio is 1.3, and the ionic liquid flow is 192L/h. The operating temperature of the absorber A was 30℃and the operating pressure was normal. The absorbed ionic liquid rich liquid is conveyed to a heat exchanger C1 through a rich liquid pump B1, and is sent to an evaporator D after heat exchange, and the desulfurization gas is discharged from the top of the tower. And (3) desorbing the ionic liquid rich liquid in the evaporator D under the action of steam, wherein the desorption temperature is 100 ℃, and obtaining the gas flow rich in H 2 S and the ionic liquid lean liquid after desorption. Under the conveying action of the bottom pump B2 of the evaporator, the ionic liquid lean solution sequentially passes through the heat exchangers C1 and C2, and is sent into the absorption tower again for recycling after heat exchange.
Analysis of results: the H2S content in the desulfurization gas discharged from the top of the tower is reduced to 59 ppm, the volume fractions of CO 2 and CH 4 are respectively 4.9 percent and 95.1 percent, and the desulfurization rate reaches 99.80 percent. The volume fraction of H 2 S in the H 2 S-enriched gas stream discharged from the top of the evaporator is more than or equal to 98%, the volume fraction of CO 2 is less than or equal to 1%, and the volume fraction of CH 4 is less than or equal to 1%.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiment, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the invention without departing from the principles thereof are intended to be within the scope of the invention as set forth in the following claims.

Claims (7)

1. A novel carbonyl functionalized proton ionic liquid has the following three characteristics: (1) The cation is ammonium ion containing or not containing free tertiary amine group; (2) The anions are cyclic or chain carboxylate ions and contain free ketocarbonyl groups besides carboxylate groups; (3) Is a proton type ionic liquid formed by directly carrying out acid-base neutralization reaction on tertiary amine and keto acid compound.
2. The carbonyl-functionalized proton type ionic liquid according to claim 1, wherein the cation is 2- [2- (dimethylamino) ethoxy ] ethanol, N-methyldiethanolamine, N, N-diethylethanolamine, triethylamine, N, N-dimethylcyclohexylamine, N-methyldipropylamine, N-methyldibutylamine, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', one of the ammonium ions derived from N' -tetramethyl-1, 3-propanediamine, N, N, N ', N' -tetramethyl-1, 6-hexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, dimyrimidinylethyl ether, dimorpholinoethyl ether, 1,3, 5-tris (dimethylaminopropyl) -1,3, 5-hexahydrotriazine, and the like, and two or more of them may be mixed cations.
3. The carbonyl-functionalized proton type ionic liquid according to claim 1, wherein the anion can be one of 4-cyclohexanone carboxylate, 3-oxo-cyclohexane carboxylate, 3-oxo-1-cyclopentane carboxylate, 3-oxo-cyclobutane carboxylate, levulinate and 5-oxo-hexanoate, and can be two or more mixed anions thereof.
4. The method for preparing the carbonyl-functionalized proton-type ionic liquid according to claim 1, which comprises the following steps:
(1) Firstly, a certain amount of tertiary amine compound is weighed and dissolved in ethanol, an ethanol solution in which a keto acid compound with a stoichiometric ratio is dissolved is dropwise added under the conditions of ice bath and stirring, after the reaction is carried out for 1h, the temperature is raised to the vicinity of the boiling point of the ethanol, and the reaction is continued for 2h under the condition of reflux;
(2) After the reaction, most of the solvent was removed by rotary evaporation, and then dried in vacuo at 60 ℃ for use.
5. Use of a carbonyl-functional protic ionic liquid according to claim 1 for energy stripping of H 2 S, in particular for achieving efficient selective stripping of H 2 S from a CO 2 -containing gas source.
6. The use of a carbonyl-functionalized proton-type ionic liquid for energy gas stripping of H 2 S according to claim 5, which process mainly comprises two parts of absorption of H 2 S in an absorption tower and desorption in an evaporator, characterized in that:
(1) The absorption tower is a plate tower or a packed tower, the theoretical plate number is more than or equal to 25, and the packing adopts regular packing. The operating temperature of the absorption tower is 20-40 ℃, the operating pressure is normal pressure, and the operating liquid-gas ratio is 1.1-1.5 times of the minimum liquid-gas ratio;
(2) The evaporation process is single effect or multiple effect evaporation, the evaporation temperature is 90-110 ℃, and the pressure is normal pressure.
7. Use of the carbonyl-functional protic ionic liquid of claim 5 for energy stripping H 2 S, the specific sources of which include, but are not limited to, natural gas, synthesis gas, biogas, hydrodesulfurization gas, coal gasification gas, and the like.
CN202410089121.1A 2024-01-22 2024-01-22 Novel carbonyl functionalized proton type ionic liquid and preparation method and application thereof Pending CN118146104A (en)

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