CN119016105A - Acidic ionic liquid catalyst, preparation method and application thereof in CO2 conversion - Google Patents
Acidic ionic liquid catalyst, preparation method and application thereof in CO2 conversion Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- 239000011831 acidic ionic liquid Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 9
- 239000007848 Bronsted acid Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 6
- -1 aliphatic diols Chemical class 0.000 abstract description 4
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 20
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 239000002608 ionic liquid Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229960004063 propylene glycol Drugs 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了酸性离子液体催化剂、制备方法及其在转化CO2中的应用，所述酸性离子液体催化剂结构式为[HO3S‑(CH2)3‑DBUH]X(X为HSO4 ‑或H2PO4 ‑）；计算量的1，8‑二氮杂双环十一碳‑7‑烯（DBU）、1，3‑丙磺酸内酯及无机酸通过接枝、酸化等反应得到酸性离子液体催化剂。其用于催化一系列生物基脂肪族二元醇和CO2反应合成生物基环状碳酸酯，具有高选择性、广适用性的特点；通过酸性离子液体催化剂催化生物基二醇和CO2合成生物基环状碳酸酯，与现有生物基环状碳酸酯的合成工艺相比，具有反应过程更安全、无污染，催化剂稳定性好、用量小、选择性高无副产以及对设备腐蚀性低等特点。
The invention discloses an acidic ionic liquid catalyst, a preparation method and an application thereof in the conversion of CO2 . The acidic ionic liquid catalyst has a structural formula of [ HO3S- ( CH2 ) 3 -DBUH]X (X is HSO4- or H2PO4- ); calculated amounts of 1,8-diazabicycloundecane- 7 -ene (DBU), 1,3-propanesultone and inorganic acid are subjected to grafting, acidification and other reactions to obtain the acidic ionic liquid catalyst. The acidic ionic liquid catalyst is used to catalyze a series of bio-based aliphatic diols and CO2 to react and synthesize bio-based cyclic carbonates, and has the characteristics of high selectivity and wide applicability. The acidic ionic liquid catalyst is used to catalyze the synthesis of bio-based cyclic carbonates from bio-based diols and CO2 , and compared with the existing synthesis process of bio-based cyclic carbonates, the reaction process is safer and pollution-free, the catalyst has good stability, small dosage, high selectivity, no by-products, and low corrosion to equipment.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an acidic ionic liquid catalyst, a preparation method and application thereof in CO 2 conversion.
Background
Cyclic carbonates are a class of compounds with wide application that can be synthesized by cycloaddition of carbon dioxide (CO 2) and an epoxy compound. The synthesis method not only can effectively fix CO 2 and reduce the emission of greenhouse gases, but also can produce chemicals with high added value. The cyclic carbonate is applied to the fields of industrial plastic synthesis, lithium ion battery electrolyte, fuel additive, green reagent, fine chemical production and the like. However, this process has problems in that epoxide has high activity, low boiling point, flammability and explosiveness, and requires special synthetic process technology and storage processing requirements. The synthesis of cyclic carbonates of bio-based diols with CO 2 is considered a green alternative, the reaction process produces only water, and diols can be produced from biomass with reproducibility. Thus, the process route for synthesizing carbonates using diols is very attractive.
The cyclic carbonate synthesized based on bio-based glycol and CO 2 has good biocompatibility and is an ideal green solvent. The development of a process route for synthesizing the cyclic carbonate based on the bio-based diol and the CO 2 is an important way for realizing the high-value utilization of resources, and has important research significance for green transformation, sustainable development and promotion of carbon peak and carbon neutralization in the power-assisted chemical industry. Compared with the traditional epoxy compound and CO 2 for synthesizing the cyclic carbonate, the method has the characteristics of safer and environment-friendly, and has become a new research direction for synthesizing the cyclic carbonate at present. However, the synthesis and use of bio-based diol cyclic carbonates also present challenges such as the difficulty of activation of CO 2 and bio-based diols, and the need for efficient catalysts to reduce the activation energy of the reaction. Furthermore, transesterification reactions may be involved in the synthesis of cyclic carbonates, which may affect the purity and stability of the product, the choice of catalyst and the construction of the catalytic system being critical. The traditional Bronsted catalyst can effectively activate bio-based diol to catalyze and synthesize cyclic carbonate, but the catalyst still has the problems of poor stability, strong corrosiveness, incapability of recycling and the like. Accordingly, there is a need for improvement and advancement in the art.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide an acidic ionic liquid catalyst, a preparation method and application thereof in CO 2 conversion, and aims to solve the problems of poor stability and strong corrosiveness of the traditional acidic catalyst in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
In a first aspect, an acidic ionic liquid catalyst is a1, 8-diazabicyclo undec-7-ene based acidic ionic liquid catalyst having the general formula: [ HO 3S-(CH2)3 -DBUH ] X, wherein X is HSO 4 - or H 2PO4 -, and the chemical formula is:
X=HSO4 -、H2PO4 -。
a second aspect, a method for preparing an acidic ionic liquid catalyst, comprising:
Step one: adding a molar ratio of 1.1 into a reaction kettle: 1, adding toluene as a solvent, condensing and refluxing at 80 ℃ for 24 hours under the protection of N 2, filtering the toluene solvent after the reaction is finished to obtain a white intermediate crude product, washing with ethyl acetate for three times, and drying at 80 ℃ in vacuum for 12 hours to obtain a white intermediate I;
Step two: adding a molar ratio of 1.1 into a reaction kettle: 1 and an intermediate I, and carrying out condensation reflux for 24 hours at 80 ℃ under the protection of N 2, washing 3 times by using ethyl acetate after the reaction is finished, and then carrying out vacuum drying for 12 hours at 80 ℃ to obtain the acidic ionic liquid.
Further, the inorganic acid is one of H 2SO4、H3PO4.
Further, in the first step, the molar ratio of toluene to DBU is preferably 2:1.
The third aspect, an application of an acidic ionic liquid catalyst in converting CO 2, is used for catalyzing bio-based glycol and CO 2 to synthesize cyclic carbonate; the bio-based glycol comprises one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and 1, 4-butanediol.
The technical scheme adopted by the invention has the following beneficial effects:
(1) Compared with the traditional catalyst, the catalyst of the system of the invention has the advantages of more stability, less corrosiveness and more cycle times, and can improve the conversion rate of reactants, the reaction selectivity and the catalytic activity.
(2) The catalyst system is based on ionic liquid physical properties, is viscous liquid at normal temperature, is not easy to burn, does not explode or oxidize, and has good thermal stability and chemical stability.
Drawings
FIG. 1 is an infrared spectrum of the catalysts prepared in example 1 and example 2;
FIG. 2 is a thermogram of the catalyst prepared in example 1 and example 2.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and more specific, the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood that when an element is referred to as being "mounted" or "disposed" on another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
It should also be noted that in the drawings of the embodiments of the present invention, the same or similar reference numerals correspond to the same or similar components; in the description of the present invention, it should be understood that, if there is an azimuth or positional relationship indicated by terms such as "upper", "lower", "left", "right", etc., based on the azimuth or positional relationship shown in the drawings, it is only for convenience of describing the present invention and simplifying the description, but it is not indicated or implied that the apparatus or element referred to must have a specific azimuth, be constructed and operated in a specific azimuth, and thus, terms describing the positional relationship in the drawings are merely for exemplary illustration and are not to be construed as limitations of the present patent, and specific meanings of the terms described above may be understood by those skilled in the art according to specific circumstances.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In a first aspect, an acidic ionic liquid catalyst is a1, 8-diazabicyclo undec-7-ene based acidic ionic liquid catalyst having the formula:
。
a second aspect, a method for preparing an acidic ionic liquid catalyst, comprising:
Step one: adding a molar ratio of 1.1 into a reaction kettle: 1, adding toluene as a solvent, condensing and refluxing at 80 ℃ for 24 hours under the protection of N 2, filtering the toluene solvent after the reaction is finished to obtain a white intermediate crude product, washing with ethyl acetate for three times, and drying at 80 ℃ in vacuum for 12 hours to obtain a white intermediate I;
Step two: adding a molar ratio of 1.1 into a reaction kettle: 1 and an intermediate I, and carrying out condensation reflux for 24 hours at 80 ℃ under the protection of N 2, washing 3 times by using ethyl acetate after the reaction is finished, and then carrying out vacuum drying for 12 hours at 80 ℃ to obtain the acidic ionic liquid.
Further, the inorganic acid is one of H 2SO4、H3PO4.
Further, in the first step, the molar ratio of toluene to DBU is preferably 2:1.
The third aspect, an application of an acidic ionic liquid catalyst in converting CO 2, is used for catalyzing bio-based glycol and CO 2 to synthesize cyclic carbonate; the bio-based glycol comprises one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol and 1, 4-butanediol.
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The catalyst disclosed by the invention is a DBU acidic ionic liquid catalyst system formed by coordination of DBU and 1,3 propane sultone to form cations and Bronsted acid to serve as anions, is stable in property, easy to store and free of pollution, and has higher selectivity and catalytic activity for the reaction.
In the invention, DBU has good catalytic activity for CO 2 reaction, and different Bronsted acid is introduced into anions to enhance the synergistic catalytic effect of anions and cations, the principle is that H on the DBU cations attacks hydroxyl on one side of glycol to form H 2 O and carbocation, and simultaneously, the H on the DBU cations can form N-C bond with C in a carbonyl carbon group of CO 2 to break carbon-oxygen double bond so that carbonyl carbon shows positive electricity, and meanwhile, free Bronsted acid anions abstract hydrogen on glycol hydroxyl to form oxo-anions, and activated glycol attacks positively charged carbonyl carbon and carbonyl oxygen to form ethylene carbonate. Compared with other types of catalysts, the selectivity and the conversion rate of the catalyst system can be effectively improved. Therefore, the invention aims to synthesize the acidic ionic liquid catalyst by acid-base neutralization with Brstoned acid after DBU and 1,3 propane sultone form an intermediate, thereby effectively improving the catalytic activity and the structural stability.
Firstly, DBU and 1,3 propane sultone are prepared into an intermediate, and the influence of different Bronsted acids on the catalytic performance of the catalyst is examined.
Example 1
(1) Preparation of intermediate I
Adding a molar ratio of 1.1 into a reaction kettle: 1 and 1, 3-propane sultone, adding toluene solvent, condensing and refluxing at 80 ℃ under the protection of N 2 for 24 hours, and filtering the toluene solvent after the reaction is finished to obtain a white intermediate crude product. After three washes with ethyl acetate, vacuum dried at 80 ℃ for 12h, to give white intermediate I.
(2) Preparation of the target catalyst
Adding a molar ratio of 1.1 into a reaction kettle: 1 and an intermediate I, and condensing and refluxing at 80 ℃ for 24 hours under the protection of N 2, washing with ethyl acetate three times after the reaction is finished, and then drying at 80 ℃ in vacuum for 12 hours to obtain the acidic ionic liquid.
Example 2
(1) Preparing an intermediate I;
Adding a molar ratio of 1.1 into a reaction kettle: 1 and 1, 3-propane sultone, adding toluene solvent, condensing and refluxing at 80 ℃ under the protection of N 2 for 24 hours, and filtering the toluene solvent after the reaction is finished to obtain a white intermediate crude product. After three washes with ethyl acetate, vacuum dried at 80 ℃ for 12h, to give white intermediate I.
(2) Preparation of the target catalyst
Adding a molar ratio of 1.1 into a reaction kettle: 1 and an intermediate I, and carrying out condensation reflux for 24 hours at 80 ℃ under the protection of N 2, after the reaction is finished, washing with ethyl acetate for three times, and then carrying out vacuum drying for 12 hours at 80 ℃ to obtain the acidic ionic liquid.
The prepared acidic ionic liquid catalyst is used for catalyzing the reaction of ethylene glycol and CO 2 to synthesize ethylene carbonate.
The catalytic experimental conditions were: the catalysts prepared in examples 1-3 were used to catalyze the synthesis of ethylene carbonate from CO 2 and ethylene glycol using a kettle reactor, respectively. The catalyst consumption accounts for 5% of the total mass of the raw materials, 50ml of ethylene glycol is reacted for 12 hours at the temperature of 120 ℃ and the pressure of 3.5 Mpa. And (3) after the reaction is finished, carrying out reduced pressure distillation, wherein residual heavy components are catalysts, measuring the purity of a product by adopting gas chromatography, and finally calculating the conversion rate, selectivity and yield.
The traditional catalysts CeO 2, triethylamine and zinc bromide, DBU and triethylamine are respectively used for catalyzing the reaction of ethylene glycol and CO 2 to synthesize ethylene carbonate, and the catalytic technological conditions and the catalytic process are the same as those described above. The effect of different catalyst types on the catalytic performance was examined and the catalytic results are shown in table 1.
TABLE 1 influence of catalyst species on catalytic Properties
From the data in Table 1, the effect of the acidic ionic liquid is better than CeO 2, triethylamine, zinc bromide and DBU, the catalytic effect of the sulfuric acid acidified ionic liquid is better than that of the hydrochloric acid and phosphoric acid acidified ionic liquid, the glycol conversion rate can reach 18.36%, and the selectivity of ethylene carbonate is as high as 98.36%.
Example 3
Taking the catalyst of example 1 as an example, performance evaluation of the synthesis of cyclic carbonates by catalyzing the synthesis of different bio-based diols (ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, 1,4 butylene glycol) and CO 2. The catalytic results are shown in Table II.
TABLE 2 evaluation of catalytic Properties of different fatty diols
From the data in Table 2, it is understood that the yields of five-membered ring carbonates synthesized from ethylene glycol, 1, 2-propanediol are higher, and the yields of six-membered ring carbonates and seven-membered ring carbonates synthesized from 1, 3-propanediol, 1, 4-butanediol are lower, because the structures of five-membered rings are most stable and easily formed, and the stability of six-membered rings and seven-membered rings is poor.
Example 4
Taking the DBU-based acidic ionic liquid catalyst of example 1 as an example, the performance study of the circulating catalytic ethylene glycol was carried out, and the catalytic reaction conditions were the same as above, so as to obtain the circulating catalytic evaluation results as shown in Table 2.
TABLE 3 evaluation of the circulating catalytic Performance of DBU-based acidic ionic liquids
As can be seen from the data in table 3, with increasing catalyst cycle times, both the selectivity and yield of the product decreased because the acidity of the catalyst decreased and the active site providing acidity decreased within a certain time period with increasing catalyst usage, resulting in a decrease in catalytic activity. After five times of recycling, the conversion rate of the ethylene glycol still reaches 16.91 percent, and the selectivity of the ethylene carbonate reaches 96.79 percent.
The catalysts prepared in examples 1-3 were chemically characterized using a Fourier infrared spectrometer (FI-IR) and the results are shown in FIG. 1.
The infrared spectrograms of the 2 DBU-based acidic ionic liquid catalysts are shown in the figure 1, wherein a is a phosphoric acid-acidified ionic liquid, b is a sulfuric acid-acidified ionic liquid, C-H telescopic vibration frequency on the DBU is near 2943cm < -1 >, C=N telescopic vibration absorption peak is near 1673cm < -1 >, C-N telescopic vibration absorption peak is near 1445cm < -1 >, C-C telescopic vibration absorption peak is near 723cm < -1 >, C-S telescopic vibration absorption peak on 1,3 propane sultone is near 881, P=O telescopic vibration absorption peak on phosphoric acid is near 1137cm < -1 >, P-O telescopic vibration absorption peak is near 977cm < -1 >, S-O telescopic vibration absorption peak on sulfuric acid is near 1111cm < -1 >, S=O telescopic vibration absorption peak is near 1027cm < -1 >, and O-H telescopic vibration absorption peak in phosphoric acid is near 2101cm < -1 >. In conclusion, the structure of the series of catalysts was confirmed to be correct.
The thermograms of the 2 DBU-based acidic ionic liquid catalysts prepared are shown in fig. 2. Wherein a is sulfuric acid acidified ionic liquid, b is phosphoric acid acidified ionic liquid catalyst a, sample slowly decomposes when the temperature is lower than 280 ℃, and when the temperature reaches about 320 ℃, the mass fraction of the sample is still higher than 80%, because the residual bronsted acid in the sample volatilizes, the sample rapidly decomposes at about 350 ℃, the maximum decomposition rate is reached, the decomposition tends to be stable at about 400 ℃, and the sample mass residual rate is close to 25%. The catalyst b slowly decomposes at 300 ℃, and when the temperature reaches about 320 ℃, the mass fraction of the sample is still higher than 90%, because phosphoric acid in the sample volatilizes, the sample rapidly decomposes at about 360 ℃, the maximum decomposition rate is reached, the decomposition tends to be stable at about 500 ℃, and the mass residual rate of the sample is close to 36%. The actual reaction temperature is lower than 160 ℃, which proves that the catalyst of the system has good thermal stability.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the disclosed embodiments. This invention is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
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