CN105237336B - A kind of method of load-type ion liquid catalyzed transesterification Synthesis of dimethyl carbonate coproduction ethylene glycol - Google Patents
A kind of method of load-type ion liquid catalyzed transesterification Synthesis of dimethyl carbonate coproduction ethylene glycol Download PDFInfo
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- CN105237336B CN105237336B CN201410327843.2A CN201410327843A CN105237336B CN 105237336 B CN105237336 B CN 105237336B CN 201410327843 A CN201410327843 A CN 201410327843A CN 105237336 B CN105237336 B CN 105237336B
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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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
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Abstract
The invention belongs to industrial catalysis technical field, there is provided a kind of method of load-type ion liquid catalyzed transesterification Synthesis of dimethyl carbonate coproduction ethylene glycol.The load-type ion liquid, it is using chlorine-containing resins particle as carrier, using hydroxyl anion construction unit and the ionic liquid of glyoxaline cation construction unit pairing as catalytic active center, loaded by chemical bond, functionalization load-type ion liquid catalyst is made, for being catalyzed the ester exchange reaction of ethylene carbonate and methanol, simultaneously synthesizing two kinds of chemical products of dimethyl carbonate and ethylene glycol.Catalyst preparation process is simple, easily operation, it is that the recovery of catalyst can be achieved through simple filtration, this separates that difficulty is highly beneficial for solving the problems, such as product with catalyst, and by with larger application potential and market prospects in fixed bed catalyst rectifying Synthesis of dimethyl carbonate coproduction ethylene glycol.
Description
Technical field
The invention belongs to industrial catalysis technical field, is related to a kind of load-type ion liquid catalytic synthesizing dimethyl carbonate connection
The method, in particular to one kind of production ethylene glycol are raw material by ethylene carbonate and methanol, are handed over through load-type ion liquid catalysis ester
The method for changing reaction Synthesis of dimethyl carbonate coproduction ethylene glycol.
Background technology
Dimethyl carbonate is that a kind of toxicity is smaller, active higher green chemical industry basic material.Utilize dimethyl carbonate
Multi-functional organic synthesis research platform [Zhang SJ, Chen YH, Li FW et al.Fixation and conversion
of CO2using ionic liquids.Catalysis Today,2006,115:61-69.], reacted by ester exchange
[Kim WB,Lee JS.Anew process for the synthesis of diphenyl carbonate from
dimethyl carbonate and phenol over heterogeneous catalyst.Catal.Lett.,1999,59
(1):83-88.], methylation reaction [Selva M, Perosa A, Tundo P, Memoli S.Selective mono-C-
methylations of arylacetonitrilies and arylacetates with dimethylcarbonate:A
methanistic investigation.J.Org.Chem.,2002,67:1071-1077.] and Infectious disease reaction
[Nagaraju N,Kuriakose G.Anew catalyst for synthesis of N,N-biphenylurea from
Aniline and dimethyl carbonate.Green Chem., 2002,269-271.] etc., can polycarbonate synthesis, different
A variety of important chemical materials, its market value and the application potentials such as cyanate, poly- carbonate diol ester and carbamate are huge.
In addition, ethylene glycol is both one of primary raw material of synthesizing polyester material, and prepares the important additives of anti-icing fluid, the product
Production and market directly affect the development and growth of polyester and automobile industry.By ester exchange reaction, using ethylene carbonate as
Reaction substrate, develop the new technology of dimethyl carbonate coproduction ethylene glycol, be advantageous to structure low cost, the industrial chain of high added value,
And the competitiveness of product in market can be strengthened.
At present, that has reported has two kinds on ester exchange reaction catalyst：First, alkali metal or alkali metal salt
[(1980) of Buysch HJ, Krimm H, Rudolph H.US Pat 4181676] and conventional ion liquid [Dharman MM,
Ju HY,Shim HL,Lee MK,Kim KH,Park DW.Significant influence of microwave
dielectric heating on ionic liquid catalyzed transesterification of ethylene
carbonate with methanol.J.Mol.Catal.A:Chem.,2009,303:96-101.] etc., the catalysis shown
Active universal not high, product separates difficulty with catalyst, and subsequent product purification process is complicated；Second, heterogeneous catalysis includes
Metal oxide such as CaO, MgO, ZnO, Fe2O3Or they mixture [Urano Y, Kirishikik M, Onda Y,
(1995) of Tsuneki H.US Pat 5430170] and season by unformed inorganic material, SBA-15, MCM-41 even load
Amine or the season supported ionic-liquid catalyst of phosphine [Cho HJ, Kwon HM, Tharun J, Park DW.Synthesis of
glycerol carbonate from ethylene carbonate and glycerol using immobilized
ionic liquid catalysts.J.Ind.Eng.Chem.,2010,16:679-683；Kim DW,Kim CW,Koh JC,
Park DW.Synthesis of dimethyl carbonate from ethylene carbonate and methanol
using immobilized ionic liquid on amporphous silica.J.Ind.Eng.Chem.,2010,16:
474-478], though this can solve the separation problem of catalyst, because substrate and catalyst lack compatibility well, show
Catalytic activity it is universal not high, and generally need inert gas CO2Pressurize under the conditions of (0.51~1.34MPa), could smoothly enter
OK.
High molecular polymer is a kind of carrier material with reaction substrate with excellent compatibility, and reaction substrate can be preferable
Ground is distributed to around activated centre, and this is advantageous to reduce resistance to mass tranfer, promotes reaction forward to carry out.Due to ester exchange reaction course
Key be RO—Nucleophilic attack carbonylic carbon atom, the acetal intermediates of formation enter catalytic mechanism process, with catalyst
The enhancing of proton ability is taken in activated centre by force, and catalytic reaction is more easily smoothed out.In consideration of it, the present invention is with high-molecular organic material
Imidazole type ion liquid for carrier, hydroxyl anion structure unit is catalytic active center, and catalyzed transesterification synthesizes
Dimethyl carbonate coproduction ethylene glycol, solves the problems, such as that product separates difficulty with catalyst, establishes high added value, environmentally friendly height
Imitate ester exchange reaction load-type ion liquid catalyst system and catalyzing.
The content of the invention
It is an object of the invention to propose that one kind using load-type ion liquid as catalyst, is catalyzed ethylene carbonate and methanol
Ester exchange reaction, the method for efficiently synthesizing dimethyl carbonate coproduction ethylene glycol.Involved load-type ion liquid catalyst,
Using high-molecular organic material as carrier, using imidazoles and its compound, by substitution reaction, to containing halide resin particle
Modification is learned, recycles alkali metal hydroxide to carry out anion structure unit ion exchange, realizes the change of functionalized ion liquid
Load is learned, obtained catalyst is used for using ethylene carbonate and methanol as the ester exchange reaction of reaction substrate, high activity, high selection
Property two kinds of chemical products of catalytic synthesizing dimethyl carbonate coproduction ethylene glycol, catalyst recovery and again can be achieved through simple filtration
Utilize.
Technical scheme is as follows：
1. the synthesis of load-type ion liquid catalyst
Using containing halide resin particle as carrier, by substitution reaction, using chemical bond, by imidazolium compounds and its derivative
Load；Then, using alkali metal hydroxide, by ion-exchange reactions, the negative of hydroxyl anion construction unit modification is obtained
Load type ionic-liquid catalyst, see formula (1).
Wherein X=Cl, Br, I；R=-CnH2n+1, n=0,1,2,3,4 ... waits natural number；High molecular polymer is polyphenyl second
Alkene and its derivative, resin microparticle etc., signified resin particle particle size range are 0.1~2000 μm；Solvent 1 be toluene, acetonitrile,
Benzene, dichloromethane, DMSO, dioxanes, N, any one in N-dimethylformamide and chloroform；Reaction time is 0~48h；
Solvent 2 is any one in deionized water, tetrahydrofuran and ether；Alkali is in sodium hydroxide, potassium hydroxide and lithium hydroxide
Any one, the mass concentration of alkali metal hydroxide is 0.01~1.2g/mL, and anion pairing temperature is 25~90 DEG C,
Its reaction time is 0.5~48h.
2. ester exchange reaction
It will be stirred equipped with magneton, the 100mL round-bottomed flasks of condenser pipe are inserted and are heated in advance in the oil bath pan of reaction temperature；
Then, ethylene carbonate, catalyst and methanol are sequentially added, after question response terminates, room temperature (see formula (2)) is cooled to, passes through letter
Single-filtering or the mode of centrifugation, realize recovery and the recycling of catalyst, and filtrate is quantitatively divided using gas chromatograph
Analysis, and the conversion ratio of reaction substrate and the selectivity of product are calculated, specific computational methods are shown in annex I.
Wherein the mass ratio of methanol and ethylene carbonate is 2:1~20:1, catalyst amount accounts for ethylene carbonate dosage
0.5~20wt%, reaction temperature are 30~85 DEG C, and the reaction time is 0.5~32h.
Load-type ion liquid catalyst provided by the invention is used for ester exchange reaction Synthesis of dimethyl carbonate coproduction second two
Two kinds of chemical products of alcohol, have the effect that and benefit：
1. using halogenated polymer high polymer material as carrier, by substitution reaction, by imidazole and its derivants chemical load,
Handled through alkali metal hydroxide, after anion structure unit ion-exchange reactions occurs, can obtain the support type of functionalization from
Sub- liquid catalyst, the catalyst preparation process is simple, easily operation, added value are high, beneficial to industrial amplification production.
2. substrate has compatibility well with catalyst, preferably can be distributed to around catalytic active center, so
The diffusion mass transfer resistance of substrate is advantageously reduced, improves rate of catalysis reaction, promotes reaction to be smoothed out.
3. anion structure unit pairing is carried out to imidazole type ion liquid through ion exchange by alkali metal hydroxide,
The load-type ion liquid catalyst of the hydroxyl anion construction unit chemical modification of preparation, help to strengthen RO—Nucleophilic enter
Carbonylic carbon atom is attacked, and then accelerates catalytic reaction process, promotes reaction balance positive mobile, this is to improving dimethyl carbonate coproduction
The yield of ethylene glycol product is highly beneficial.
After 4. reaction terminates, catalyst is through simple filtration or centrifuges i.e. achievable recycling and reuse, separation process
Simply, easily operation, for raising catalyst use efficiency, the green catalysis system of constructing environment friendly, have important
Theoretical significance and scientific value.
Embodiment
Load-type ion liquid catalyst used in the present invention is used for following examples, in order to understand in the present invention
Hold, but under conditions of objective of the present invention is not departed from, do not represent or limit the scope of the present invention, and not with
Any mode limits present invention.
The synthesis of the catalyst of embodiment 1
Chloride 18~the 19wt% of 8.36g polystyrene resin is sequentially added into the 100mL three-necked flasks equipped with magneton
Particle, the methylimidazole of two equivalents and 50mL toluene, after heating reflux reaction 24h, stop reaction, be cooled to room temperature, mixed liquor
After simple filtration, vacuum drying, the resin particle of glyoxaline cation functionalization is obtained.Then, weight/mass percentage composition is recycled
For the 20% KOH aqueous solution, after ion-exchange reactions 24h, obtain catalyst crude product, and successively with deionized water (3 ×
100mL), ethanol (3 × 50mL) washs, vacuum dried, be made the support type of hydroxyl anion construction unit chemical modification from
Sub- liquid catalyst, quantitative analysis is carried out to element by elemental analyser and obtained：C, H, N, O content be respectively 131.25wt%,
12.29wt%, 25.61wt% and 5.99wt%, the load capacity for thus speculating hydroxyl anion is 6.36wt%.
The ester exchange reaction of embodiment 2
Into the 250mL three neck round bottom flask equipped with ball-type reflux condensing tube, 10g ethylene carbonates, 80g first are sequentially added
Alcohol and the catalyst of embodiment 1 for accounting for ethylene carbonate weight/mass percentage composition 8.0wt%, after being well mixed, insert 80 DEG C of oil bath pans
In, magnetic agitation reaction 8h, room temperature is cooled to, after catalyst filtration is separated, filtrate carries out quantitative analysis with gas chromatograph, presses
Annex I is calculated：For the conversion ratio of ethylene carbonate up to 99.4%, the selectivity for generating dimethyl carbonate and ethylene glycol is 99.9%.
Embodiment 3
Into 250mL three neck round bottom flask, sequentially add 10g ethylene carbonates, 80g methanol and account for ethylene carbonate quality
Percentage composition is the 5.0wt% catalyst of embodiment 1, and other steps are with embodiment 2, the conversion ratio of ethylene carbonate
68.4%, the selectivity for generating dimethyl carbonate is 73.1%, and the selectivity of ethylene glycol is 99.9%.
Embodiment 4
Into 250mL three neck round bottom flask, sequentially add 10g ethylene carbonates, 100g methanol and account for ethylene carbonate matter
The catalyst of embodiment 1 that percentage composition is 8.0wt% is measured, with embodiment 2, the conversion ratio of ethylene carbonate is 89.4% for other,
The selectivity for generating dimethyl carbonate is 97.4%, and the selectivity of ethylene glycol is 97.1%.
Embodiment 5
Into 250mL three neck round bottom flask, sequentially add 10g ethylene carbonates, 80g methanol and account for ethylene carbonate quality
Percentage composition is the 8.0wt% catalyst of embodiment 1, after being well mixed, is inserted in 70 DEG C of oil bath pans, reacts 8h, and other are the same as real
Example 2 is applied, the conversion ratio for obtaining ethylene carbonate is 64.1%, and the selectivity for generating dimethyl carbonate is 67.4%, ethylene glycol
Selectivity is 82.3%.
Embodiment 6
Into 250mL three neck round bottom flask, the raw material proportioning that sequentially adds with embodiment 5, operating condition with embodiment 2,
After well mixed, 5h is reacted, the conversion ratio for obtaining ethylene carbonate is 77.1%, and the selectivity for generating dimethyl carbonate is
98.7%, the selectivity of ethylene glycol is 99.9%.The catalyst of embodiment 7 recycles situation
After ester exchange reaction terminates, mixed liquor rinses filter cake after simple filtration, with absolute ethyl alcohol (3 × 100mL), then passes through
Vacuum drying, realizes the recovery of catalyst.Then, the catalyst of recovery is added in three neck round bottom flask, is re-used for urging
Change ester exchange reaction, with embodiment 2, the conversion ratio for obtaining ethylene carbonate is 86.3%, generates dimethyl carbonate and second for other
The selectivity of glycol is 99.9%.Then, catalyst is recovered recycling again, and catalytic activity can at least keep five bases
This is constant, and concrete outcome is shown in Table 1.
The recycling situation of the catalyst of table 1a
| Cycle-index | 1 | 2 | 3 | 4 | 5 | 6 |
| EC conversion ratios (%) | 89.4 | 86.3 | 83.4 | 84.0 | 84.6 | 84.0 |
| Generate DMC selectivity (%) | 99.9 | 99.9 | 99.9 | 99.9 | 97.8 | 80.5 |
| Generate EG selectivity (%) | 99.9 | 99.9 | 99.9 | 99.9 | 96.5 | 86.0 |
aComputational methods are shown in annex I.
Although the present invention is described in detail with a general description of the specific embodiments for the above,
On the basis of the present invention, the ordinary person of art can to work some modifications or improve, this is to people in the art
Member is obvious.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to this hair
Bright claimed scope.
Annex I
Claims (1)
1. a kind of method of load-type ion liquid catalyzed transesterification Synthesis of dimethyl carbonate coproduction ethylene glycol, its feature exist
In：Sequentially added into the 100mL three-necked flasks equipped with magneton the chloride 18~19wt% of 8.36g polystyrene resin beads,
The methylimidazole and 50mL toluene of two equivalents, after heating reflux reaction 24h, stop reaction, be cooled to room temperature, mixed liquor is through simple
After filtering, vacuum drying, the resin particle of glyoxaline cation functionalization is obtained；Then, it is 20% to recycle weight/mass percentage composition
The KOH aqueous solution, after ion-exchange reactions 24h, obtain catalyst crude product, and washed successively with deionized water, ethanol, through true
Sky is dried, and the load-type ion liquid catalyst of hydroxyl anion construction unit chemical modification is made；To equipped with ball-type returned cold
In the 250mL three neck round bottom flask of solidifying pipe, sequentially add 10g ethylene carbonates, 80g methanol and account for ethylene carbonate quality hundred
Divide the load-type ion liquid catalyst of the content 8.0wt% hydroxyl anion construction unit chemical modification, be well mixed
Afterwards, insert in 80 DEG C of oil bath pans, magnetic agitation reaction 8h, be cooled to room temperature, after catalyst filtration is separated, filtrate is with gas phase color
Spectrometer carries out quantitative analysis.
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| CN105688993B (en) * | 2016-03-04 | 2018-02-06 | 河北科技大学 | A kind of load type polymerization acidic ionic liquid catalysts and its preparation method and application |
| CN107362826A (en) * | 2017-07-24 | 2017-11-21 | 陕西煤业化工技术研究院有限责任公司 | For oxirane, carbon dioxide and Dimethyl Carbonate Synthesis from Methanol and the solid heterogeneous catalyst and preparation method of ethylene glycol |
| CN107812538A (en) * | 2017-11-22 | 2018-03-20 | 林州市科能材料科技有限公司 | A kind of preparation method of support type glyoxaline ion liquid catalyst |
| CN110857273B (en) * | 2018-08-21 | 2022-08-12 | 中国石油化工股份有限公司 | Method for preparing carbonic ester from oxalate |
| CN109704968B (en) * | 2019-02-21 | 2021-10-15 | 南开大学 | Method for synthesizing dimethyl carbonate by ionic liquid catalysis |
| CN112844473B (en) * | 2021-01-19 | 2023-08-11 | 中科南京绿色制造产业创新研究院 | Alumina-supported polyion liquid catalyst and preparation method and application thereof |
| CN114890895A (en) * | 2022-04-20 | 2022-08-12 | 中国石油大学(华东) | Method for producing dimethyl carbonate by catalytic reaction and rectification of immobilized basic ionic liquid |
| CN114805074B (en) * | 2022-06-06 | 2024-03-26 | 中国石油大学(华东) | Method for directly preparing methyl ethyl carbonate from ethylene carbonate or propylene carbonate |
| CN115322098B (en) * | 2022-09-21 | 2023-09-26 | 胜华新材料集团股份有限公司 | Method for synthesizing dimethyl carbonate by ionic liquid catalysis |
| CN116393169A (en) * | 2023-05-22 | 2023-07-07 | 沈阳化工大学 | Preparation method of carbon-nitrogen bonding method immobilized ionic liquid heterogeneous catalyst |
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| CN102513158B (en) * | 2011-12-05 | 2013-10-16 | 上海师范大学 | Method for preparing ethylene carbonate through continuous heterogeneous catalysis and catalyst |
| US8735608B2 (en) * | 2012-02-28 | 2014-05-27 | Saudi Basic Industries Corporation | Process for preparing carbonate and diol products |
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| CN101225176A (en) * | 2007-12-18 | 2008-07-23 | 南京大学 | Imidazolyl modified complex functional high-crosslinked adsorption resin and preparation method thereof |
| CN102060657A (en) * | 2009-11-13 | 2011-05-18 | 中国科学院兰州化学物理研究所 | Method for preparing dibasic alcohol |
| CN103495437A (en) * | 2013-09-18 | 2014-01-08 | 华东师范大学 | Supported ionic liquid catalyst, as well as preparation and application thereof |
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