CN114225643A - Method for removing ammonium salt in ionic liquid in situ - Google Patents
Method for removing ammonium salt in ionic liquid in situ Download PDFInfo
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- CN114225643A CN114225643A CN202111310986.9A CN202111310986A CN114225643A CN 114225643 A CN114225643 A CN 114225643A CN 202111310986 A CN202111310986 A CN 202111310986A CN 114225643 A CN114225643 A CN 114225643A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 128
- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 ammonium salt cations Chemical class 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 18
- 150000001450 anions Chemical class 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002357 guanidines Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000005496 phosphonium group Chemical group 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 230000005588 protonation Effects 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 150000001412 amines Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 230000036314 physical performance Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000003795 desorption Methods 0.000 description 7
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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Classifications
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- 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
- B01D19/00—Degasification of liquids
- B01D19/0005—Degasification of liquids with one or more auxiliary substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Gas Separation By Absorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a method for removing ammonium salt in ionic liquid in situ, in particular to a method for replacing ammonium salt cations in ionic liquid with ammonia gas to escape by adding a solvent, and combining ammonium salt anions with a protonized solvent to form ionic liquid again so as to realize the removal of the ammonium salt in the ionic liquid in situ. The method mainly comprises the steps of mixing a solvent and ionic liquid containing ammonium salt at a certain ratio at room temperature and normal pressure, removing the ammonium salt in the ionic liquid in situ by heating and decompressing after uniform mixing, and collecting and recycling the evaporated ammonia gas and excessive solvent. The process for removing the ammonium salt in situ by the ionic liquid is simple and easy to control, the added solvent is a part of the ionic liquid to be purified, the ammonium salt can be converted into the required ionic liquid and ammonia gas, no impurity is introduced, no side reaction is caused, the removal rate of the ammonium salt is high, and the industrial application is easy. The method can not only efficiently convert the ammonium salt in the ionic liquid into the required substance, but also keep the structure, physical properties and performance of the ionic liquid stable. The technology has wide application prospect in the fields of ammonia-containing gas separation, organic amine synthesis catalysis, ammonia-containing wastewater treatment and the like.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a method for removing ammonium salt in ionic liquid in situ.
[ background of the invention ]
Ionic Liquids (ILs) are substances that are composed of organic cations, inorganic or organic anions, and that are liquid at or near room temperature, and these substances are usually organic salts with a melting point below 100 ℃, and are also called room-temperature ionic liquids or low-temperature molten salts. The ionic liquid is used as an environment-friendly green solvent, and has the characteristics of extremely low volatility, functional design, stable physicochemical property, structural designability and the like, so that the ionic liquid has wide application prospects in gas separation, organic synthesis, extraction separation, preparation of natural polymers and nano materials and catalytic reaction at present, and particularly shows attractive application prospects in the aspect of separating ammonia-containing substances.
The ionic liquid has good effects in the aspects of ammonia-containing gas purification, ammonia nitrogen wastewater treatment and organic amine catalytic synthesis reaction. For example, in the aspect of ammonia-containing gas treatment, the principle is that ammonia-containing gas and an ionic liquid absorbent are in reverse contact to form a rich solution containing ammonia gas, the ammonia gas is desorbed from the ionic liquid by heating and decompressing in a desorption tower, and the desorbed ionic liquid can be recycled. However, in the long-term use process of the ionic liquid, due to incomplete desorption, ammonia gas can be converted into ammonium radicals to be gradually accumulated along with the increase of the operation time, when the ammonium radicals in the ionic liquid are accumulated to a certain concentration, the enriched ammonium radicals can be combined with anions of the ionic liquid to generate ammonium salts and be separated out, and the lower the temperature is, the higher the ammonium radical concentration is, the more ammonium salts are crystallized and separated out. The ammonium salt separated out by crystallization can cause the viscosity of the ionic liquid to increase, further the fluidity of the ionic liquid is influenced, the pressure drop of equipment and pipelines is increased, and if the ionic liquid is not treated for a long time, the pipelines are blocked, so that the in-situ removal of the ammonium salt in the ionic liquid is particularly important.
The prior method for purifying and removing impurities from ionic liquid mainly comprises an adsorption method, a filtration method and an extraction method, wherein the adsorption method mainly comprises the steps of adsorbing by using ion exchange resin or metal oxide, and then separating the adsorbed adsorbent from the purified ionic liquid, for example, in the patent with the application number of CN202011324962.4, in order to remove metal ions in the ionic liquid, an ionic liquid aqueous solution containing metal ion impurities is introduced into a purification device containing a metal ion remover for adsorption reaction, then the metal ion remover adsorbing the metal ions is separated from the purified feed liquid removing the metal ions, the metal ion remover adsorbing the metal ions is recycled after being regenerated, the adsorbent in the method has a porous structure, generally can adsorb not only the metal ions but also a small amount of ionic liquid, so that the ionic liquid loss is caused, and the used adsorbent is required to be regenerated by using hydrochloric acid and can become solid waste if the adsorbent cannot be repeatedly used, so that secondary pollution is caused, and the operation is complicated. The extraction method is to use organic solvent such as methanol for extraction, for example, as the patent with application number of CN201811544407.5, in order to remove sulfate ions and chloride ions in organic amine absorbent, alkali liquor is added into ionic liquid for reaction, then, the solid phase mixture is obtained by atmospheric distillation, organic solvent is added into the solid phase mixture for extraction, the extract liquor is collected and distilled under normal pressure to obtain organic salt solid, HCl is added into the organic salt solid for reaction, then, the target product is obtained by atmospheric distillation, finally, the product is dried to obtain a cation intermediate, the target anion is added into the intermediate to replace halogen ions to obtain the target acidic ionic liquid. In the long-term use process of the ionic liquid, ammonia gas is converted into ammonium radicals to be gradually accumulated along with the increase of the operation time, when the ammonium radicals in the ionic liquid are accumulated to a certain concentration, ammonium salts are crystallized and separated out, the lower the temperature is, the higher the ammonium radical concentration is, the more the ammonium salts are crystallized and separated out, and aiming at the ionic liquid with higher viscosity, the efficiency of directly removing solid ammonium salts crystallized and separated out from the ionic liquid by adopting a filtration method is extremely low, a large amount of ionic liquid can be lost, and the ammonium salts dissolved in the ionic liquid can not be removed.
[ summary of the invention ]
Aiming at the technical requirement of in-situ removal of ammonium salt from the ionic liquid, the invention aims to provide a method which has simple and easily controllable process, high removal rate of ammonium salt from the ionic liquid and easy industrial application.
The added solvent is part of the ionic liquid to be desalted, no other impurities are introduced, no side reaction is caused, ammonium salt cations are replaced by ammonia gas to escape only by simple replacement, ammonium salt anions and the protonized solvent are combined to form the ionic liquid again, the ammonium salt in the ionic liquid is efficiently converted into the required substance, and the in-situ ammonium salt removal of the ionic liquid is realized.
Specifically, the invention is realized by the following technical scheme:
a method for removing ammonium salt in ionic liquid in situ is characterized in that: according to the method, a solvent is added, ammonium salt cations in the ionic liquid are replaced by ammonia gas to escape, ammonium salt anions and a protonation solvent are combined to form the ionic liquid again, so that the ammonium salt in the ionic liquid is removed in situ, wherein the solvent is combined with hydrogen ions to form a cation component of the ionic liquid, and an anion component of the ammonium salt is the same as an anion component of the ionic liquid. The method mainly comprises the following steps: mixing a solvent and an ionic liquid containing ammonium salt at room temperature and normal pressure according to a certain proportion, uniformly mixing, reacting in a heating and pressure reduction mode within a certain time until ammonium salt cations are completely converted into ammonia gas to escape, combining ammonium salt anions and a protonated solvent to form the ionic liquid again, realizing in-situ removal of the ammonium salt in the ionic liquid, and collecting and recycling the escaped ammonia gas and excessive solvent.
The ionic liquid comprises one or a mixture of more of imidazole ionic liquid, pyrroline ionic liquid, guanidine salt ionic liquid, alcohol amine ionic liquid, quaternary ammonium salt ionic liquid, thiazoline ionic liquid, pyridine ionic liquid, thiazole ionic liquid, polyamine ionic liquid and quaternary phosphonium ionic liquid.
The solvent of the invention is an alkaline parent species of ionic liquid cations, and the composition proportion of the solvent is consistent with that of the ionic liquid.
The solvent is used in an amount of 1: 1-5: 1, wherein the amount of the solvent is calculated by the molar amount of ammonium ions in the ionic liquid, and the molar ratio of the amount of the added solvent to the ammonium ions is 1: 1-5: 1.
In the ionic liquid containing ammonium salt, the concentration of ammonium ions is 0.1-100%.
The heating temperature is room temperature-200 ℃, and the operating pressure (absolute pressure) is 1.0 x 10-5Pa～0.1MPa。
The reaction time of the invention is 5 min-300 min.
The invention has the beneficial effects that:
(1) compared with the prior art and method, the method for removing the ammonium salt in the ionic liquid in situ has high removal rate, and the removal rate of the ammonium salt in the ionic liquid can reach more than 99 percent.
(2) Compared with the prior art and the method, the method for removing the ammonium salt in the ionic liquid in situ only utilizes simple replacement to efficiently convert the ammonium salt in the ionic liquid into the required substance, does not introduce other impurities, has no side reaction, and keeps stable structure, physical property and performance of the ionic liquid.
(3) Compared with the prior art and the method, the method for removing the ammonium salt in the ionic liquid in situ has the advantages of simple and easily controlled process, rapidness, high efficiency and easy industrial application.
Therefore, the method for removing the ammonium salt in the ionic liquid in situ can solve the industrial application problem that the ammonium salt in the ionic liquid is difficult to remove, not only can remove the ammonium salt in the ionic liquid, but also can efficiently convert the ammonium salt into the required ionic liquid.
[ description of the drawings ]
FIG. 1 is a schematic diagram of the process flow for in-situ removal of ammonium salt from ionic liquid according to the present invention
[ detailed description ] embodiments
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples, and various modifications and implementations are included in the technical scope of the present invention without departing from the spirit of the invention described before and after.
Example 1:
ionic liquid [ Bim][Cl]In the process of absorbing and desorbing ammonia gas for a long time, as the desorption is not thorough, the ammonia gas can be converted into ammonium radicals to be gradually accumulated along with the increase of the operation time, and NH can be crystallized and separated out when the concentration of the ammonium radical ions in the ionic liquid is accumulated to a certain concentration4And (4) Cl. To contain NH4Ionic liquid of Cl [ Bim][Cl](ammonium ion concentration is 40g/L) is placed in a round-bottom flask, then 1-butyl-imidazole with concentration of 40g/L is added, the mixture is placed in a water bath pot after mixing, a rotary evaporator is arranged to heat the mixture at 70 ℃, the pressure is-0.08 MPa, reaction is carried out for 30min, ammonia gas escapes, and NH simultaneously4Anion of Cl-And 1-butyl-imidazole to regenerate ionic liquid [ Bim][Cl]The removal rate of the ammonium salt is 99.5 percent through inspection and calculation.
Example 2:
ionic liquids [ Eim][Cl]In the process of absorbing and desorbing ammonia gas for a long time, as the desorption is not thorough, the ammonia gas can be converted into ammonium radicals to be gradually accumulated along with the increase of the operation time, and NH can be crystallized and separated out when the concentration of the ammonium radical ions in the ionic liquid is accumulated to a certain concentration4And (4) Cl. To contain NH4Ionic liquid of Cl[Eim][Cl](ammonium ion concentration is 42g/L) is placed in a round-bottom flask, then 1-ethyl-imidazole with concentration of 42g/L is added, the mixture is placed in a water bath pot after mixing, a rotary evaporator is arranged to heat the mixture at 80 ℃, the pressure is-0.09 MPa, reaction is carried out for 20min, ammonia gas escapes, and NH simultaneously4Anion of Cl-And 1-Ethyl-imidazole regeneration of Ionic liquids [ Eim][Cl]The removal rate of the ammonium salt is 99.6 percent through inspection and calculation.
Example 3:
ionic liquids [ Eim][SCN]In the process of absorbing and desorbing ammonia gas for a long time, as the desorption is not thorough, the ammonia gas can be converted into ammonium radicals to be gradually accumulated along with the increase of the operation time, and NH can be crystallized and separated out when the concentration of the ammonium radical ions in the ionic liquid is accumulated to a certain concentration4SCN. To contain NH4Ionic liquids of SCN [ Eim][SCN](ammonium ion concentration is 48g/L) is placed in a round-bottom flask, 1-ethyl-imidazole with concentration of 48g/L is added, the mixture is placed in a water bath pot after mixing, a rotary evaporator is arranged to heat the mixture at 75 ℃ and the pressure is-0.1 MPa, the reaction is carried out for 25min, ammonia gas escapes, and NH is simultaneously carried out4Anion of SCN-And 1-Ethyl-imidazole regeneration of Ionic liquids [ Eim][SCN]The removal rate of the ammonium salt is 99.8 percent through inspection and calculation.
Example 4:
the ionic liquid is [ Bim][SCN]And [ Bim][Cl]The mixture can be used for absorbing and desorbing ammonia gas for a long time, the ammonia gas can be converted into ammonium radicals to be gradually accumulated along with the increase of the operation time due to incomplete desorption, and NH can be crystallized and separated out when the concentration of the ammonium radical ions in the ionic liquid is accumulated to a certain concentration4SCN and NH4And (4) Cl. Taking ionic liquid [ Bim][SCN]And [ [ Bim ]][Cl]Mixture of (containing NH)4SCN and NH4Cl and ammonium ion concentration of 45g/L) is placed in a round-bottom flask, then 1-butyl-imidazole with the concentration of 45g/L is added, the mixture is placed in a water bath pot after mixing, a rotary evaporator is arranged to heat the mixture at 80 ℃, the pressure is-0.1 MPa, the reaction is carried out for 20min, ammonia gas escapes, and NH is simultaneously carried out4SCN and NH4SCN anion of Cl-And Cl-Respectively regenerating ionic liquid [ Bim ] with 1-butyl-imidazole][SCN]And [ Bim][Cl]By inspectionAnd the removal rate of ammonium salt is calculated to be 99.7%.
Example 5:
ionic liquid [ Bim][SCN]In the process of absorbing and desorbing ammonia gas for a long time, as the desorption is not thorough, the ammonia gas can be converted into ammonium radicals to be gradually accumulated along with the increase of the operation time, and NH can be crystallized and separated out when the concentration of the ammonium radical ions in the ionic liquid is accumulated to a certain concentration4SCN. To contain NH4Ionic liquid of SCN [ Bim][SCN](ammonium ion concentration is 50g/L) is placed in a round-bottom flask, then 1-butyl-imidazole with concentration of 50g/L is added, the mixture is placed in a water bath pot after mixing, a rotary evaporator is arranged to heat at 85 ℃, the pressure is-0.1 MPa, reaction is carried out for 30min, ammonia gas escapes, and NH simultaneously4Anion of SCN-And 1-butyl-imidazole to regenerate ionic liquid [ Bim][SCN]The removal rate of the ammonium salt is 99.8 percent through inspection and calculation.
Claims (7)
1. A method for removing ammonium salt in ionic liquid in situ is characterized in that: according to the method, a solvent is added, ammonium salt cations in the ionic liquid are replaced by ammonia gas to escape, ammonium salt anions and a protonation solvent are combined to form the ionic liquid again, so that the ammonium salt in the ionic liquid is removed in situ, wherein the solvent is combined with hydrogen ions to form a cation component of the ionic liquid, and an anion component of the ammonium salt is the same as an anion component of the ionic liquid. The method mainly comprises the following steps: mixing a solvent and an ionic liquid containing ammonium salt at room temperature and normal pressure according to a certain proportion, uniformly mixing, reacting in a heating and pressure reduction mode within a certain time until ammonium salt cations are completely converted into ammonia gas to escape, combining ammonium salt anions and a protonated solvent to form the ionic liquid again, realizing in-situ removal of the ammonium salt in the ionic liquid, and collecting and recycling the escaped ammonia gas and excessive solvent.
2. The ionic liquid according to claim 1, which is one or a mixture of more of imidazole ionic liquid, pyrroline ionic liquid, guanidine salt ionic liquid, alcohol amine ionic liquid, quaternary ammonium salt ionic liquid, thiazoline ionic liquid, pyridine ionic liquid, thiazole ionic liquid, polyamine ionic liquid and quaternary phosphonium ionic liquid.
3. The solvent according to claim 1 is a basic parent species of ionic liquid cation, and the solvent composition ratio is consistent with the ionic liquid composition ratio.
4. The method according to claim 1, wherein the amount of the solvent is 1:1 to 5:1, based on the molar amount of the ammonium ions in the ionic liquid.
5. The ammonium salt-containing ionic liquid according to claim 1, wherein the concentration of ammonium ions is 0.1% to 100%.
6. The method of claim 1, wherein the heating temperature is room temperature to 200 ℃ and the operating pressure (absolute pressure) is 1.0 x 10-5Pa～0.1MPa。
7. The process of claim 1, wherein the reaction time is 5 to 300 min.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004016571A2 (en) * | 2002-08-16 | 2004-02-26 | Sachem, Inc. | Lewis acid ionic liquids |
| US20070142211A1 (en) * | 2005-12-20 | 2007-06-21 | Chevron U.S.A. Inc. | Regeneration of ionic liquid catalyst |
| CN101058745A (en) * | 2007-05-16 | 2007-10-24 | 中国科学院过程工程研究所 | Removal and recovery of naphthenic acid in oil based on ion switch principle |
| WO2009079079A1 (en) * | 2007-12-19 | 2009-06-25 | Chevron U.S.A. Inc. | Removal of excess metal halides from regenerated ionic liquid catalysts |
| CN101925408A (en) * | 2007-12-28 | 2010-12-22 | 雪佛龙美国公司 | Process for ionic liquid catalyst regeneration |
| CN106310931A (en) * | 2015-07-06 | 2017-01-11 | 中国石油化工股份有限公司 | Method for simultaneously removing hydrogen sulfide and ammonia gas by using iron-based ionic liquid |
| CN106914102A (en) * | 2017-03-31 | 2017-07-04 | 中国科学院过程工程研究所 | A kind of metal ion liquid-absorbant of efficient reversible absorption ammonia |
-
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004016571A2 (en) * | 2002-08-16 | 2004-02-26 | Sachem, Inc. | Lewis acid ionic liquids |
| US20070142211A1 (en) * | 2005-12-20 | 2007-06-21 | Chevron U.S.A. Inc. | Regeneration of ionic liquid catalyst |
| CN101360563A (en) * | 2005-12-20 | 2009-02-04 | 雪佛龙美国公司 | Regeneration of ionic liquid catalyst |
| CN101058745A (en) * | 2007-05-16 | 2007-10-24 | 中国科学院过程工程研究所 | Removal and recovery of naphthenic acid in oil based on ion switch principle |
| WO2009079079A1 (en) * | 2007-12-19 | 2009-06-25 | Chevron U.S.A. Inc. | Removal of excess metal halides from regenerated ionic liquid catalysts |
| CN101925408A (en) * | 2007-12-28 | 2010-12-22 | 雪佛龙美国公司 | Process for ionic liquid catalyst regeneration |
| CN106310931A (en) * | 2015-07-06 | 2017-01-11 | 中国石油化工股份有限公司 | Method for simultaneously removing hydrogen sulfide and ammonia gas by using iron-based ionic liquid |
| CN106914102A (en) * | 2017-03-31 | 2017-07-04 | 中国科学院过程工程研究所 | A kind of metal ion liquid-absorbant of efficient reversible absorption ammonia |
Non-Patent Citations (3)
| Title |
|---|
| 华南工学院无机化学教研组编: "《高等学校教材 无机化学 第2版 下》", 高等教育出版社出版 * |
| 邹汉波, 董新法, 林维明: "离子液体及其在绿色有机合成中的应用", 化学世界, no. 02, pages 107 - 110 * |
| 钟永飞;郭斌;任爱玲;段二红;张淼淼;赵地顺;: "己内酰胺四丁基溴化铵离子液体吸收硫化氢的研究", 河北化工, no. 11, pages 3 - 5 * |
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