CN109174176A - Alkaline ionic liquid catalyst and preparation method thereof - Google Patents
Alkaline ionic liquid catalyst and preparation method thereof Download PDFInfo
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- CN109174176A CN109174176A CN201810863967.0A CN201810863967A CN109174176A CN 109174176 A CN109174176 A CN 109174176A CN 201810863967 A CN201810863967 A CN 201810863967A CN 109174176 A CN109174176 A CN 109174176A
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- methanol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 111
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- -1 methoxylated alkyl imidazole Chemical compound 0.000 claims abstract description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 230000011987 methylation Effects 0.000 claims description 3
- 238000007069 methylation reaction Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 14
- 238000005809 transesterification reaction Methods 0.000 abstract description 8
- 230000003068 static effect Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011830 basic ionic liquid Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006198 methoxylation reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000002779 inactivation Effects 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 229960004217 benzyl alcohol Drugs 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 231100000004 severe toxicity Toxicity 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000000640 hydroxylating effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 description 1
- BXOAIZOIDUQOFA-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;hydroxide Chemical compound [OH-].CCCC[N+]=1C=CN(C)C=1 BXOAIZOIDUQOFA-UHFFFAOYSA-M 0.000 description 1
- DVNFMHWKXQEEAH-UHFFFAOYSA-N 1-dodecyl-3-methyl-2h-imidazole Chemical compound CCCCCCCCCCCCN1CN(C)C=C1 DVNFMHWKXQEEAH-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- VDDUQRTVFVQZQJ-UHFFFAOYSA-N 1-methyl-3-octadecyl-2h-imidazole Chemical compound CCCCCCCCCCCCCCCCCCN1CN(C)C=C1 VDDUQRTVFVQZQJ-UHFFFAOYSA-N 0.000 description 1
- NOIWSPXMNWKZPJ-UHFFFAOYSA-N 2-bromo-1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1Br NOIWSPXMNWKZPJ-UHFFFAOYSA-N 0.000 description 1
- NNWNNQTUZYVQRK-UHFFFAOYSA-N 5-bromo-1h-pyrrolo[2,3-c]pyridine-2-carboxylic acid Chemical compound BrC1=NC=C2NC(C(=O)O)=CC2=C1 NNWNNQTUZYVQRK-UHFFFAOYSA-N 0.000 description 1
- 229920002574 CR-39 Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- YSTQDJNWDMBAOZ-UHFFFAOYSA-N [Br].C(C)N1CN(C=C1)C Chemical compound [Br].C(C)N1CN(C=C1)C YSTQDJNWDMBAOZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- SPFUWSBRIIKPOR-UHFFFAOYSA-N carbonyl dichloride;methanol Chemical compound OC.ClC(Cl)=O SPFUWSBRIIKPOR-UHFFFAOYSA-N 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YWOITFUKFOYODT-UHFFFAOYSA-N methanol;sodium Chemical compound [Na].OC YWOITFUKFOYODT-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- B01J31/0284—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 aromatic ring, e.g. pyridinium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种用于甲醇酯交换反应的碱性离子液体催化剂的制备方法，特别涉及一种甲氧基化烷基咪唑离子液体催化剂的制备方法。本发明在催化剂制备过程中，首先合成卤代烷基咪唑离子液体，再用活泼的甲氧基负离子通过置换反应取代卤素阴离子，合成甲氧基化烷基咪唑离子液体。该离子液体催化剂与甲醇原料具有同离子效应与协同作用，在甲醇酯交换反应中，发挥出极强的催化效果。生成的碳酸二甲酯可以与甲醇形成共沸物，在反应过程中蒸馏共沸物，并补加甲醇原料，可打破静态平衡，促进反应向正方向移动，形成新的动态反应平衡，进而实现连续化工业生产。
The invention relates to a preparation method of a basic ionic liquid catalyst for methanol transesterification, in particular to a preparation method of a methoxylated alkyl imidazole ionic liquid catalyst. In the catalyst preparation process of the present invention, the halogenated alkyl imidazole ionic liquid is first synthesized, and then the halogen anion is replaced by an active methoxy anion through a substitution reaction to synthesize the methoxylated alkyl imidazole ionic liquid. The ionic liquid catalyst has the same ion effect and synergistic effect with the methanol raw material, and exerts an extremely strong catalytic effect in the methanol transesterification reaction. The generated dimethyl carbonate can form an azeotrope with methanol. During the reaction process, the azeotrope is distilled and methanol is added to break the static equilibrium, promote the reaction to move in the positive direction, and form a new dynamic reaction equilibrium, thereby realizing Continuous industrial production.
Description
Technical field: the present invention relates to a kind of preparation sides of alkaline ionic liquid catalyst for methanol ester exchange reaction
Method, in particular to a kind of preparation method of methoxylation alkyl imidazo ion liquid catalyst.
Background technique: dimethyl carbonate is the green solvent and important organic synthesis intermediate of a kind of good properties, by
Nontoxic in its, the phosgene of alternative severe toxicity, methylchloroformate, the methylating reagents such as dimethyl suflfate or hydroxylating agent make
With thus being widely used in weaving, print and dye, leather, synthetic fibers, the fields such as papermaking and machinery industry are known as that " 21 century has
The new matrix in machine synthesis field ".With the progress of technological means, and high-grade electronic product universal, the demand of dimethyl carbonate
Amount is continuously increased, and in terms of industrial production, the phosgene of the alternative severe toxicity of dimethyl carbonate makees hydroxylating agent, polycarbonate synthesis
Equal engineering material；In terms of production technology, can synthesis of allyl diglycol carbonate rouge this thermosetting resin for haveing excellent performance, use
In the exploitation and application of photoelectric material.Therefore, dimethyl carbonate added value with higher and development potentiality.
China's one's early years industrialized production uses phosgene methanol method Synthesis of dimethyl carbonate, with CO and Cl2Effect generates phosgene,
Then it is reacted by phosgene with methanol or sodium methoxide and generates dimethyl carbonate, but due to phosgene severe toxicity, transport is inconvenient, thus has
There is certain limitation.
In recent years, China's industrial production exploration develops methanol ester exchange reaction, with cyclic carbonate and methanol transesterification
Generate dimethyl carbonate.Currently, most of workshop is using sodium methoxide as catalyst, good catalytic activity, but using static state
Reaction, conversion ratio is low, using dynamic response, improves conversion ratio, but catalyst usage amount is big, and side reaction easily occurs, and is catalysis
Agent inactivation, and sodium salt blocking reacting pipe is generated, methanol sodium inactivation and the correlated response for blocking pipeline are as follows.
CH3ONa+H2O→NaOH+CH3OH
2NaOH+CH3OCOOCH3→NaOCOONa+2CH3OH
CH3ONa+CO2→CH3OCONa
The research for occurring largely being used as new catalyst system about ionic liquid in recent years reports that development prospect is by generation
The extensive concern of various countries of boundary, compared with the catalyst such as traditional sodium methoxide, ionic-liquid catalyst shows preferable catalytic
Can, and be expected to solve the existing inactivation of traditional catalyst and blocking pipe problems.
Zhang Zhifang in 2006 et al. is put forward for the first time in the 13rd whole nation catalysis academic conference by load-type ion liquid
For catalytic synthesizing dimethyl carbonate.Research finds newly synthesized several quaternary ammonium bromide salt ionic liquids and some anion
Acid or reactant salt more can react Synthesis of dimethyl carbonate by significantly catalysis carbon dioxide and methanol.
The same year, Cai Zhenqin et al. (chemical industry progress, 2006 (05): 546-550.) have investigated several ionic liquids to synthesis carbon
The effect of dimethyl phthalate, it is most of without obvious catalytic effect, only use 1-ethyl-3-methyl-imidazole bromine salt [Emim] Br ion
Liquid catalyst reaction, the mass yield of DMC improve about 1%.
Fabris Massimo in 2009 etc. (Chemistry:A European Journal, 2009,15 (45)) passes through
Anion exchange synthesizing methyl ammonium and Phosphorus ionic liquid are reacted for catalytic synthesizing dimethyl carbonate.It, should by Experimental Characterization
Class ionic liquid catalytic performance with higher, and can be applied in green syt reaction.
Lv Junmin in 2012 etc. (Qingdao University of Science and Technology's journal, 2012,33 (06): 556-559+563.) for the first time will
[Bmim] OH ionic liquid is used for catalytic transesterification carbonate synthesis dipropyl.Catalyst performance, reaction condition, weight have been investigated simultaneously
The factors such as renaturation and stability obtain in reaction temperature being 130 DEG C, reaction time 3h, and dosage is n (catalyst): n (DMC)
Under=0.007:0.1, n (n-PrOH): n (DMC)=4:1 optimum reaction condition, MPC and higher, the carbonic acid two of DPC selectivity
Propyl ester yield about reaches 11.4%
The methylation alkyl imidazo ion liquid of this patent design, is to react N- methylimidazole with halogenated alkane, synthesis
Halogenated alkyl imidazole ion liquid intermediate, then reacted with sodium methoxide, the methoxylation imidazole ion liquid of preparation had been catalyzed
Methoxy root anion is released in journey, and ester exchange reaction is promoted to carry out.This kind of ionic liquid by common-ion effect with cooperate with work
With being more advantageous to the activation and open loop of ethylene carbonate, further increase catalytic activity and selectivity, both solve conventional catalyst
Agent blocks the problem of reacting pipe, and reduces catalyst amount, and can realize recycling, greatly reduces cost, has
Good prospects for commercial application.
Summary of the invention:
Goal of the invention: the object of the present invention is to provide one kind to prepare carbonic acid two by transesterification by cyclic carbonate and methanol
Methyl esters used catalyst.
Technical solution:
A kind of alkaline ionic liquid catalyst is used for methanol ester exchange reaction, it is characterised in that: the liquid catalyst is
Methoxylation alkyl imidazo ion liquid catalyst, general structure are as follows:
Wherein R is CH3, R ' is alkyl side chain CnH2n-1, n=1,2,3 ... 18.
The preparation method of the alkaline ionic liquid catalyst, it is characterised in that:
Steps are as follows:
Halogenated alkane is added to the container and is condensed back according to the molar ratio of 1:1.2 with N- methylimidazole, added by step 1
Enter magneton stirring, revolving speed is 150~200r/min, and is condensed back, and is taken out after reacting 48h at 80 DEG C；
Step 2 is washed with ethyl acetate after cooling and obtains thick pale yellow shape liquid three times, and at 70 DEG C, 0.08MPa is depressurized
Under the conditions of rotary evaporation, and place 70 DEG C of drying in a vacuum drying oven for 24 hours, obtained halogenated alkyl imidazole ion liquid intermediate
[CnMIM]X；
Step 3 takes suitable intermediate [CnMIM] X to be dissolved in 50mL methanol, is uniformly mixed, equimolar solid is added
10h is stirred at room temperature in sodium methoxide, reflux condensation mode, then step-up temperature keeps the temperature 6h, obtains NaX crystal and [CnMIM] CH3O is mixed
Close object；
Step 4 removes sodium halide NaX using Suction filtration device, then at 55 DEG C, 0.08MPa depressurizes rotary evaporation and removes first
Alcohol；
Product is dried under vacuum to constant weight at 65 DEG C, obtains brown color viscous liquid by step 5, as methylation 1- fourth
Base -3- methylimidazole ionic liquid [CnMIM] CH3O。
The preparation method of the alkaline ionic liquid catalyst, it is characterised in that: reaction carries out under nitrogen protection.
Advantage and effect:
(1) being bonded by methoxy anion and alkyl imidazole forms new function ionic liquid.Activity in its structure
Methoxy group and material benzenemethanol have common-ion effect and synergistic effect, significantly improve conversion ratio, reduce side reaction, improve selection
Property.
(2) catalyst amount is few, and group utilization rate is high, and transformation frequency is fast, after reaction the easily separated purification of product.
(3) catalyst circulation is high-efficient, while guaranteeing highly selective and conversion ratio, realizes catalyst and material benzenemethanol
Recycling, significantly reduce production cost.
(4) methoxyl group anion catalytic activity with higher, can catalyzed transesterification efficiently carry out, overcome existing life
The inactivation of sodium alkoxide and blocking pipe phenomenon in production. art.
(5) azeotropic distillation that methanol feedstock and dimethyl carbonate product are realized by adding methanol, promotes reaction to pros
To movement, catalytic process is made to switch to dynamic equilibrium by static balancing, realize serialization industrial production, reaction process environmental protection is high
Effect.
Detailed description of the invention:
Fig. 1 is methoxylation alkyl imidazo ion liquid catalyst preparation schematic diagram；
Fig. 2 is catalytic mechanism schematic diagram；
Fig. 3 is methanol ester exchange reaction device figure；
Specific embodiment:
Method for preparing catalyst proposed by the present invention is carried out according to the following steps:
1) halogenated alkane of certain mass and N- methylimidazole 250mL round bottom is added to according to the molar ratio of 1:1.2 to burn
It stirs and is condensed back in bottle, revolving speed is 150~200r/min, is taken out after reacting 48h at 80 DEG C.
2) it is washed with ethyl acetate and obtains thick pale yellow shape liquid three times, rotated and steam under 70 DEG C, 0.08MPa reduced pressure
Hair, and place 70 DEG C of dryings in a vacuum drying oven for 24 hours, [CnMIM] X ionic liquid intermediate is made.
3) it takes appropriate ionic liquid intermediate [CnMIM] X to be dissolved in 50mL methanol, is uniformly mixed.It is added equimolar solid
Body sodium methoxide stirs 10h at room temperature, then step-up temperature keeps the temperature 6h, obtains NaX and [CnMIM] CH3O mixture.
4) NaX is removed using Suction filtration device to precipitate, remove methanol in 55 DEG C, 0.08MPa decompression rotary evaporation.
5) 4) crude product obtained is dried under vacuum at 65 DEG C constant weight, obtains brown color viscous liquid, as methoxy
Base alkyl imidazo ion liquid [CnMIM] CH3O。
The present invention is in catalyst preparation process, synthesizing halogen alkyl imidazo ion liquid first, then with active methoxy
Base anion passes through displacement substituted in reaction halide anion, synthesizing methoxy alkyl imidazo ion liquid.The ionic liquid is urged
Agent and methanol feedstock have common-ion effect and synergistic effect, in methanol ester exchange reaction, play extremely strong catalysis effect
Fruit.The dimethyl carbonate of generation can form azeotropic mixture with methanol, distill azeotropic mixture during the reaction, and add methanol original
Material can break static balancing, promote reaction mobile to positive direction, form new dynamic response balance, and then realize continuous production.
By taking bromo 1- butyl -3- methylimidazole as an example, methoxylation alkyl imidazo ion liquid catalyst process such as Fig. 1 institute of preparation
Show.
Compared with other ionic-liquid catalysts, this novel ion liquid and raw material with methoxyl group anion group
Methanol methoxy root anion having the same is more advantageous to the activation of ethylene carbonate by common-ion effect and synergistic effect
It with open loop, reduces by-product and generates, the process for being catalyzed ethylene carbonate and methanol reaction is as shown in Figure 2.
The present invention has a characteristic that
(1) being bonded by methoxy anion and alkyl imidazole forms new function ionic liquid.Activity in its structure
Methoxy group and material benzenemethanol have common-ion effect and synergistic effect, significantly improve conversion ratio, reduce side reaction, improve selection
Property.
(2) catalyst amount is few, and group utilization rate is high, and transformation frequency is fast, after reaction the easily separated purification of product.
(3) catalyst circulation is high-efficient, while guaranteeing highly selective and conversion ratio, realizes catalyst and material benzenemethanol
Recycling, significantly reduce production cost.
(4) methoxyl group anion catalytic activity with higher, can catalyzed transesterification efficiently carry out, overcome existing life
The inactivation of sodium alkoxide and blocking pipe phenomenon in production. art.
(5) azeotropic distillation that methanol feedstock and dimethyl carbonate product are realized by adding methanol, promotes reaction to pros
To movement, catalytic process is made to switch to dynamic equilibrium by static balancing, realize serialization industrial production, reaction process environmental protection is high
Effect.
By specific embodiment, the present invention will be described
Embodiment 1
The bromination of n-butane of certain mass and N- methylimidazole are added to 250ml circle according to the molar ratio of 1:1.2 first
It in the flask of bottom and is condensed back, magneton stirring is added, revolving speed is 150~200r/min, and is condensed back, and is reacted at 80 DEG C
It is taken out after 48h, is then washed with ethyl acetate and obtain thick pale yellow shape liquid three times, at 70 DEG C, 0.08Mpa reduced pressure backspin
Turn evaporative removal ethyl acetate, then is placed in 70 DEG C of dryings in vacuum oven and for 24 hours, ionic liquid intermediate [Bmim] Br is made.
It takes appropriate [Bmim] Br to be dissolved in 50mL methanol, adds equimolar solid sodium methylate, stir 10h at room temperature,
50 DEG C of heat preservation 3h are being to slowly warm up to, then are being warming up to 80 DEG C of heat preservation 3h, are obtaining [Bmim] CH3O and NaBr mixture.Then it utilizes
Suction filtration device removes NaBr precipitating, and at 55 DEG C, 0.08MPa depressurizes rotary evaporation and removes methanol.It is finally that product is true at 65 DEG C
Sky is dry to constant weight, obtains brown color viscous liquid, as methoxylation 1- butyl -3- methylimidazole ionic liquid [Bmim]
CH3O。
Methanol and ethylene carbonate raw material that molar ratio is 8:1 are weighed, three mouthfuls of burnings with distilling apparatus are mixed to join
In bottle, as shown in figure 3, reacting under the conditions of 85-90 DEG C, because of product dimethyl carbonate and methanol azeotropic, and reaction is easy to reach quiet
State balance, therefore when there is drop outflow in distillation cascade, drop methanol is mended into reaction system using dropping funel, breaks system
Static balancing keeps reaction mobile to positive direction, realizes the dynamic equilibrium of tandem reaction sequence.To reaction system without distillate, say
Bright ethylene carbonate end of reaction, weighs distillate quality, and with its purity of gas Chromatographic Determination, calculates dimethyl carbonate
Yield is 69.2%.
Embodiment 2
With same equipment used in embodiment 1, under the same terms, bromination of n-butane is changed to bromododecane,
Obtain methoxylation 1- dodecyl -3- methylimidazole ionic liquid [C12MIM]CH3O.With the catalyst methanol and carbonic acid second
The ester exchange reaction of enester, the yield for obtaining dimethyl carbonate is 71.6%.
Embodiment 3
With same equipment used in embodiment 1, under the same terms, bromination of n-butane is changed to bromo-octadecane,
Obtain methoxylation 1- octadecyl -3- methylimidazole ionic liquid [C18MIM]CH3O.With the catalyst methanol and carbonic acid second
The ester exchange reaction of enester, the yield for obtaining dimethyl carbonate is 72.5%.
Embodiment 4
With in same equipment used in embodiment 3, under the same terms, only by methanol and ethylene carbonate molar ratio
It is changed to 10:1, using [C18MIM]CH3The yield that O catalysis methanol ester exchange reaction obtains dimethyl carbonate is 73.4%.
Embodiment 5
With same equipment used in embodiment 3, under the same terms, transesterification reaction temperature is only changed to 75
DEG C, using [C18MIM]CH3The yield that O catalysis methanol ester exchange reaction obtains dimethyl carbonate is 48.2%.
Embodiment 6
With in same equipment used in embodiment 4, under the same terms, only by the ionic-liquid catalyst of recycling into
The multiple reuse of row, the relationship for reusing number and dimethyl carbonate yield are as shown in the table.
Influence of the 1 catalyst circulation access times of table to DMC yield
Data illustrate that the type ionic-liquid catalyst can be recycled for multiple times in table 1.With the increase of number of use,
The yield of conversion ratio, selectivity and DMC is all gradually reduced, but after circular response 5 times, and each index decline tends to be steady.Due to
Reaction is in the continuous reaction process of dynamic equilibrium, therefore the variation tendency of These parameters will not influence it substantially and produce
Journey.This illustrates that the type catalyst activity component is highly stable, compared with traditional alcohol sodium catalyst, not only may be implemented to move
The continuous production of state balance, the problem of also solving the by-product blocking pipeline of sodium alkoxide class catalyst inactivation and its generation, and
The recycling of ionic liquid also reduces production cost, and energy-saving consumption is economic and environment-friendly, before having good industrial applications
Scape.
Claims (3)
1. a kind of alkaline ionic liquid catalyst is used for methanol ester exchange reaction, it is characterised in that: the liquid catalyst is first
Oxygroup alkyl imidazo ion liquid catalyst, general structure are as follows:
Wherein R is CH3, R ' is alkyl side chain CnH2n-1, n=1,2,3 ... 18.
2. the preparation method of alkaline ionic liquid catalyst as described in claim 1, it is characterised in that:
Steps are as follows:
Halogenated alkane is added to the container and is condensed back according to the molar ratio of 1:1.2 with N- methylimidazole by step 1, and magnetic is added
Son stirring, revolving speed is 150~200r/min, and is condensed back, and is taken out after reacting 48h at 80 DEG C；
Step 2 is washed with ethyl acetate after cooling and obtains thick pale yellow shape liquid three times, at 70 DEG C, 0.08MPa reduced pressure
Lower rotary evaporation, and place 70 DEG C of dryings in a vacuum drying oven for 24 hours, halogenated alkyl imidazole ion liquid intermediate is made
[CnMIM]X；
Step 3 takes suitable intermediate [CnMIM] X to be dissolved in 50mL methanol, is uniformly mixed, equimolar solid methanol is added
10h is stirred at room temperature in sodium, reflux condensation mode, then step-up temperature keeps the temperature 6h, obtains NaX crystal and [CnMIM] CH3O mixture；
Step 4 removes sodium halide NaX using Suction filtration device, then at 55 DEG C, 0.08MPa depressurizes rotary evaporation and removes methanol；
Product is dried under vacuum to constant weight at 65 DEG C, obtains brown color viscous liquid by step 5, as methylation 1- butyl-
3- methylimidazole ionic liquid [CnMIM] CH3O。
3. the preparation method of alkaline ionic liquid catalyst according to claim 2, it is characterised in that: reaction is in nitrogen protection
Lower progress.
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