CN108129314A - By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate - Google Patents
By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate Download PDFInfo
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- CN108129314A CN108129314A CN201711380524.8A CN201711380524A CN108129314A CN 108129314 A CN108129314 A CN 108129314A CN 201711380524 A CN201711380524 A CN 201711380524A CN 108129314 A CN108129314 A CN 108129314A
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- 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
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7019—EMT-type, e.g. EMC-2, ECR-30, CSZ-1, ZSM-3 or ZSM-20
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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Abstract
By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, it is related to the method for Catalysts of Preparing Methyl Ethyl Carbonate, the present invention has the efficient alkaline catalyst of composite pore structural, for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate.Containing dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and ethylene glycol in crude product obtained by the reaction, wherein, methyl ethyl carbonate selectively can reach 77%.By-product dimethyl carbonate and diethyl carbonate can be directly separated as product, also can be recycled, and the reaction was continued generates methyl ethyl carbonate, and by-product ethylene glycol is separated as largeization raw material by simple distillation.Entire reaction process cleaning, efficient, pollution-free, no any waste generation.Work as ethylene carbonate：Methanol：Ethyl alcohol molar ratio 1:3:2,5 MPa of reaction pressure, 100 DEG C of reaction temperature, 5 h of air speed‑1, catalyst uses 5000h non-inactivations, and stability is preferable.
Description
Technical field
The present invention relates to a kind of method of Catalysts of Preparing Methyl Ethyl Carbonate, more particularly to one kind by ethylene carbonate, methanol and
The method of ethyl alcohol one-step synthesis methyl ethyl carbonate.
Background technology
Methyl ethyl carbonate（Methyl Ethyl Carbonate, abbreviation MEC）, molecular formula：C4H8O3, colourless transparent liquid,
1.01 g/mL of density, -55 DEG C of fusing point, 107 DEG C of boiling point is flammable, can be mixed with arbitrary proportion with organic solvent such as alcohol, ketone, ester,
It is a kind of excellent solvent, methyl ethyl carbonate due to having methyl and ethyl simultaneously in its molecular structure, so it has carbonic acid concurrently
The characteristic of dimethyl ester, diethyl carbonate, can be as certain special organic synthesis reagents, while it is also the molten of extraordinary fragrance
Agent.
Since the viscosity of methyl ethyl carbonate is small, dielectric constant is big, strong to the dissolubility of lithium salts, therefore it is a kind of excellent
Lithium ion battery electrolyte solvent can improve the energy density and discharge capacity of battery, can more improve the safety of battery
Energy and service life.
Consulting literatures are it is found that methyl ethyl carbonate is mainly the following synthetic method at present：
（One）Phosgenation
Phosgenation is the process using phosgene and methanol/ethanol as Material synthesis methyl ethyl carbonate, and reaction equation is as follows：
COCl2 + CH3OH→CH3OCOCl...................................................
.......................(1)
CH3OCOCl + C2H5OH→CH3OCOOC2H5.............................................
............(2)
COCl2 +C2H5OH→C2H5OCOCl...................................................
......................(3)
C2H5OCOCl + CH3OH→CH3OCOOC2H5.............................................
............(4)
The method Catalysts of Preparing Methyl Ethyl Carbonate byproduct of reaction is more（Main By product is dimethyl carbonate, diethyl carbonate, chloro-carbonic acid
Methyl esters, ethyl chloroformate）, operating difficulties generates the hydrogen chloride of strong corrosive during simultaneous reactions, it is desirable that equipment has corrosion resistant
Corrosion increases equipment investment.Phosgene has hypertoxicity, and great risk, and the method are caused to the health of operating personnel
Methyl ethyl carbonate yield is relatively low, therefore is gradually eliminated.
（Two）Oxidative carbonylation
Oxidative carbonylation is using carbon monoxide, oxygen, methanol and ethyl alcohol as raw material, in certain temperature and pressure and in catalyst
Under existence condition, Catalysts of Preparing Methyl Ethyl Carbonate, reaction equation is as follows：
CH3OH + C2H5OH + CO + O2→CH3OCOOC2H5 + H2O..................................(5)
The method major defect is that byproduct of reaction is more（Main By product has dimethyl carbonate, diethyl carbonate, water）, follow-up point
From purification difficult, production cost is increased.
（Three）Ester-interchange method
1st, methylchloroformate and ethyl alcohol ester-interchange method
Edmund PWoo and Ichiro Minami etc. is reported using methylchloroformate and ethyl alcohol as raw material, passes through ester-interchange method
Catalysts of Preparing Methyl Ethyl Carbonate, reaction equation are as follows：
C2H5OH + CH3OCOCl→CH3OCOOC2H5 +
HCl.......................................................(6)
The catalysts are alkali（Such as pyridine, organic amine）, purer methyl ethyl carbonate can be obtained, but shortcoming is to have used poison
Property higher methylchloroformate, simultaneous reactions generate corrosive hydrogen chloride gas, higher to equipment requirement.
2nd, dimethyl carbonate and diethyl carbonate ester-interchange method
Load metal oxide such as SnO of the Shen Zhen lands et al. using load on alumina2/Al2O3、MoO3/Al2O3、TiO2/
Al2O3Deng as catalyst, using dimethyl carbonate and diethyl carbonate as raw material, by Synthesis of Ethyl Methyl Carbonate by Transesterification,
The mass percent of the catalyst metal oxide of preparation is 2%-30%, remaining is aluminium oxide, and the amount of metal oxide accounts for raw material
The 0.1%-10% of total amount, 50-100 DEG C of reaction temperature carry out 2-48 h under normal pressure, and methyl ethyl carbonate yield is 43.6%.The route
The advantages of be that reaction process is simple, non-environmental-pollution, but shortcoming is that the reaction time is long, the catalyst activity reported at this stage compared with
It is low.
3rd, dimethyl carbonate and ethyl alcohol ester-interchange method
Using dimethyl carbonate and ethyl alcohol as raw material, by Synthesis of Ethyl Methyl Carbonate by Transesterification, raw material used in the route is all
It is non-toxic, reaction condition is mild, environmentally safe, therefore has very by the report of this route Catalysts of Preparing Methyl Ethyl Carbonate
More, the reaction equation involved by the route is as follows：
CH3OCOOCH3 + CH3CH2OH→CH3OCOOCH2CH3 + CH3OH...............................(7)
CN1900047 A are using aluminium oxide, activated carbon, molecular sieve as carrier, carrying alkali metal oxide, alkaline-earth metal oxide
One kind of object and rare-earth oxide, although separation problem is not present in catalyst, activity is not so good as homogeneous catalyst.
CN101289395 A are with NaOH, KOH, CH3ONa、CH3The strong alkaloids such as OK are as catalyst, and the catalyst is in reaction solution
Solubility is bad, and easily precipitation, easy fouling.CN103483200 A are using modified molecular sieve as catalyst, wherein modified member
Element is one or more of alkali metal, alkaline-earth metal, Fe, Zn, Ni, Cu, although catalyst preparation process is simple, reacts institute
The temperature needed is high.CN102850223 A, CN102863339 A and CN102850224 A are using the ionic liquid of imidazoles as catalysis
Agent, recoverable, long lifespan, but catalyst recycling is needed by specially treated.US5962720 is with SmL2、Li、CH3OLi
And CaH2Deng for catalyst, but reaction reaches balance needs three days.
At present, mainly using ester-interchange method as mainstream synthetic route in all of above methyl ethyl carbonate synthetic method, but ester is handed over
Changing the oxide spinel dimethyl ester of method need to be synthesized by ethylene carbonate or propene carbonate by methanol transesterification, above-mentioned reaction
Route need to be segmented progress, and each elementary reaction object conversion ratio and selectivity of product are relatively low, and industrial processes energy consumption is larger, runs into
This increase.
Due to ethylene carbonate/propylene carbonate and methanol ester exchange reaction and subsequent dimethyl carbonate and ethyl alcohol ester
The available basic catalyst of exchange reaction is catalyzed, therefore it is proposed that a kind of reaction road of one-step synthesis method methyl ethyl carbonate
Diameter.The reaction of the one-step synthesis methyl ethyl carbonate is short with synthesis path, and technological process is simple, selectivity of product and high income,
The characteristics of catalyst stabilization non-inactivation.
Invention content
The purpose of the present invention is to provide a kind of sides by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate
Method,.
The purpose of the present invention is what is be achieved through the following technical solutions：
By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, the method includes following preparation process：
One-step synthesis method methyl ethyl carbonate reaction route equation is as follows：
Raw material is respectively ethylene carbonate, methanol and ethyl alcohol, glycol product and carbonic ester molar ratio 1：1 generation, ethylene glycol are
A kind of China largely relies on the bulk chemical of import, can effectively a large amount of coproduction ethylene glycol using the path；
The catalyst of catalysis single step reaction of the present invention is with mesoporous and microcellular structure compound basic catalyst；Catalyst Formula
For X/S, wherein X is includes Li, Na, K, Rb, Cs；Be、Mg、Ca、Sr、Ba；La、Ce、Y、Zr；Cr、W、Mn；Fe、Ru；Co、Rh、
Ir；Pd、Pt；Cu、Ag；The oxide of one or more kinds of elements in Zn, B, Al, Ga；S is the carrier of different topology structure, is wrapped
Topological structure is included as EMT, MOR, MWW, FAU, MFI, FER, BEA molecular sieve and routine SiO2、Al2O3、ZrO2, MgO and ZnO
Wait one or more of carriers oxide；
With mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, the preparation of Jie's micro porous molecular sieve carrier
Method：
1）Dealuminzation：Certain mass M-S carriers are added separately to the molten stirring of acidity of certain temperature, volume, concentration, using pumping
Filter is washed, dry, obtains the M-S-DAl carriers after dealuminzation；
2）Desiliconization：M-S-DAl carriers made from certain mass process 1 are added to certain temperature, concentration, the alkalinity of certain volume
It stirs in solution, using suction filtration, washs, it is dry, obtain multi-stage porous M-S-DAl-DSi carriers；
3）M-S-DAl-DSi carriers made from process 2 are finally put into Muffle furnace roasting, obtaining carrier indicium is：M-meso-S；
Methyl ethyl carbonate is prepared through continuous fixed bed reaction or continuous.
By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, the S molecular sieve carriers, hydrogen
Type molecular sieve first passes around ion exchange, and Bronsted acid is poisoned by metal ion, it is made not have Bronsted acid；Poison
The ion-exchanger of chemoattractant molecule sieve is hydrochloride, sulfate or the nitrate of Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu；Other points
Son sieve and support preparation method are similar, are designated generally as M-S, and wherein M includes Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu.
By the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, micro porous molecular sieve carrier is given an account of
Preparation, the molecular sieve of the different topology structure of carrier includes one kind or more of EMT, MOR, MWW, FAU, MFI, FER, BEA
Kind；The acid solution includes H4EDTA、HCl、HNO3One or more, preferably H4EDTA；The addition of acid solution is minimum
All molecular sieves are flooded, can be 10-20 times, preferably 15 times of molecular sieve volume；The alkaline solution include NaOH,
Na2CO3Deng one or more, preferably NaOH；A concentration of 0.05mol/L-2.0mol/L of alkaline solution；Alkaline solution
Addition will at least flood all molecular sieves, can be 5-15 times, preferably 10 times of molecular sieve volume.
The method by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate gives an account of micropore point
The preparation of son sieve carrier, the M-meso-S carrier mesoporous pore sizes obtained are distributed as 4-34nm, and specific aperture and alkalinity used are molten
Liquid concentration is related.
The method by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, it is described have it is mesoporous and
The loading type alkali metal oxide catalyst of microcellular structure carrier, using coprecipitation method or infusion process：
1）Coprecipitated alkaline solution includes but not limited to the hydroxide of alkali metal and ammonium, such as lithium hydroxide, sodium hydroxide, hydrogen-oxygen
Change potassium and ammonium hydroxide；Carbonate, bicarbonate, formates and the acetate of alkali metal, such as lithium carbonate, sodium carbonate, potassium carbonate
Solution or above-mentioned alkaline solution two or more mixed liquors；Liquid medium used in alkaline substance solution is preferably
Water, but it is also not necessarily limited to water；
2）The addition of alkaline solution will at least flood all carriers, be 10-20 times or more of carrier bulk, and preferably 15
Times, it is 10-14 that solution PH value is controlled when coprecipitated, and preferably PH is 11.Coprecipitation method bath temperature can be -99 DEG C of room temperature, preferably 70
℃；Aging temperature be -80 DEG C of room temperature, ageing time be -20 days 1 hour, preferably 60 DEG C, ageing time 5 days；Catalyst detergent
Medium is preferably water, but is also not necessarily limited to water, liquid medium can be 2-10 times of catalyst volume and more than, preferably 2-5 times, wash
Number is depending on efflux pH is washed；Catalyst drying temperature can be -150 DEG C of room temperature, and the time can be -10 days 1 hour, preferably
It is 120 DEG C, 3-5 days dry；Calcination temperature be 150-800 DEG C, the time be 1-50 hours, preferably 500-700 DEG C, 30 hours time；
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural；
3）The active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al (NO3)3、KNO3、CsNO3、Mg
(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3、AlCl3、KCl、CsCl、MgCl2、
CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3、Al2(SO4)3、K2SO4、Cs2SO4、MgSO4、CaSO4、La2(SO4)3、
Fe2(SO4)3、Mn2(SO4)3One or more of mixing；
4）Dipping method co-impregnation or the method with step impregnation；Drying temperature can be room temperature~150 DEG C, and the time can be 1
Hour~20 days；Calcination temperature can be 550~650 DEG C, and the time can be 1~50 hour；The loaded catalyst of composite pore structural
The content of metal X is the 0.1-50% of vehicle weight in general formula；
5）In preferred embodiments, the active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al
(NO3)3、KNO3、CsNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3With
AlCl3、KCl、CsCl、MgCl2、CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3Middle one or more of mixing.
The method by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, the one-step synthesis carbon
Sour methyl ethyl ester path, continuous fixed bed reaction or continuous concrete scheme are：Under normal pressure to 10MPa reaction pressures, liquid original is beaten with pump
Expect that the mixture of ethylene carbonate, methanol and ethyl alcohol is fed, three's molar ratio 5:1:5-1:5:1 in above-mentioned catalyst existence condition
Reaction Catalysts of Preparing Methyl Ethyl Carbonate in next step, air speed are 0.1-30 h-1, under conditions of 50-250 DEG C of reaction temperature, catalyst is
The various multi-functional compound base catalysts protected in the present invention, 0.1-3wt% of the catalyst amount for material quality, product carbonic acid
For methyl ethyl ester selectively not less than 50%, yield is not less than 20%.
The method by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, the fixed bed are continuous
Reaction, during preparing methyl ethyl carbonate, optimum condition is ethylene carbonate：Methanol：Ethyl alcohol molar ratio 1:3:2, air speed
0.5-5 h-1, 78-130 DEG C of reaction temperature.
The method by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, the one-step synthesis carbon
Sour methyl ethyl ester path, still reaction concrete scheme are：Reaction pressure 0.1-10MPa, ethylene carbonate, methanol and ethyl alcohol three
Molar ratio 5:1:5-1:5:1, under catalyst existence condition reaction prepare methyl ethyl carbonate, in reaction kettle closed 25-150 DEG C it is anti-
0.5-10 h are answered, catalyst is basic catalyst of the present invention, and catalyst amount is the 0.1-10 wt % of material quality.
Advantages of the present invention is with effect：
1. path of the present invention is using multi-functional compound basic matterial as catalyst, former for reaction by ethylene carbonate, methanol and ethyl alcohol
Expect a step high selectivity methyl ethyl carbonate, basic catalyst is completely insoluble in reaction raw materials and product, and reaction process is not deposited
In any pollutant, glycol product is a kind of bulk chemical, has a vast market application prospect；It is subsidiary in reaction process
The dimethyl carbonate and diethyl carbonate of generation can be directly separated as product, also can be recycled, and the reaction was continued generates carbonic acid
Methyl ethyl ester.Therefore it may be said that being generated almost without any by-product, entire response path green, energy-saving and environmental protection, height in reaction process
Effect.
2. the catalyst that the present invention is protected is multi-functional compound basic catalyst, it is advantageous that mesoporous significantly improve biography
Matter effect, and micropore significantly improves carrier specific surface area, improves the dispersion degree in activated centre.In continuous fixed bed reaction or continuous, urge
Agent reacts non-inactivation for a long time, even if feed space velocity is 100h-1When, product methyl ethyl carbonate remains to keep higher yield,
Catalyst preparation is simple, and environmentally safe, energy conservation and environmental protection.In still reaction, post catalyst reaction is by simple place
Reason can reuse again, and catalyst be reused many times after remain to keep higher activity.
Description of the drawings
Fig. 1 is that reactant is turned by catalyst differential responses temperature of 15%BaO-5%MgO-3%La2O3/Cs-meso-EMT
The influence of rate and selectivity of product.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The present invention by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate response path and the response path
Used catalyst, the response path are as follows：
The present invention protects the multi-functional compound basic catalyst of one-step synthesis methyl ethyl carbonate simultaneously.
Such catalyst is specially the loading type alkali metal oxide catalyst with mesoporous and microcellular structure carrier.It is described
Be X/S with the mesoporous and loading type alkali metal oxide catalyst of microcellular structure carrier its general formula, wherein X be comprising Li, Na,
K、Rb、Cs；Be、Mg、Ca、Sr、Ba；La、Ce、Y、Zr；Cr、W、Mn；Fe、Ru；Co、Rh、Ir；Pd、Pt；Cu、Ag；Zn、B、Al、
The oxide of one or more kinds of elements in Ga；S be different topology structure carrier, including topological structure for EMT, MOR, MWW,
FAU, MFI, FER, BEA molecular sieve and routine SiO2、Al2O3、ZrO2, one or more of carriers such as MgO and ZnO oxygen
Compound.Wherein molecular sieve first passes around ion exchange, and Bronsted acid is poisoned by metal ion, it is made not have Bronsted
It is acid.The EMT molecular sieve carriers poisoned with alkali metal ion（M-EMT, M can be Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu）For
Example, preparation method are as follows：The H-EMT molecular sieves that 20g is prepared by hydrothermal synthesis method, be placed in 90 DEG C of 90 mL go from
In sub- water, meanwhile, add in the hydrochloride, sulfate or nitric acid of Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu of 2 M thereto respectively
Salt carries out EMT at 90 DEG C the ion exchange of 2 hours.After exchange, obtained molecular sieve precursor is carried out with deionized water
Washing, until no longer containing ion in eluate.It will wash to filter obtained filter cake and be placed in 120 DEG C of baking ovens and be dried, done
Presoma after dry is put into Muffle furnace and carries out 600 DEG C of 6 h of roasting, and Li-EMT, Na-EMT, K-EMT, Rb- are can obtain after roasting
EMT, Ca-EMT, Fe-EMT, Mg-EMT, Cu-EMT and Cs-EMT.Other molecular sieves and support preparation method are similar, unified to mark
For M-S, wherein M is including Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu etc..
1. the preparation method of Jie's micro porous molecular sieve carrier：
The present invention is handled by carrying out orderly soda acid to different carriers, and final high temperature roasting is made compound with mesoporous and micropore
The molecular sieve carrier of pore structure.Sour processing intent is the Al removed in framework of molecular sieve, so as to fulfill pore-creating, alkali process it is main
The Si that effect is to remove in framework of molecular sieve makes molecular sieve form meso-hole structure, and preparation process includes the following steps：
1）Dealuminzation：Certain mass M-S carriers are added separately in the acid solution of certain volume, a concentration of 0.11 mol/L,
Then in oil bath 100 DEG C be stirred at reflux 6 h, using suction filtration, washing, 120 DEG C of dry 8h obtain the M-S-DAl after dealuminzation and carry
Body.
2）Desiliconization：M-S-DAl carriers made from certain mass process 1 are added to the alkalinity of a certain concentration, certain volume
In solution, then 65 DEG C of 30 min of water bath processing, using suction filtration, are washed, 120 DEG C of dry 8h obtain multi-stage porous M-S-DAl-
DSi carriers.
3）Finally M-S-DAl-DSi carriers made from process 2 are put into Muffle furnace, 550 DEG C of guarantors are warming up to 1 DEG C/min
6h is held, obtaining carrier indicium is：M-meso-S.
The molecular sieve of heretofore described different topology structure includes one kind of EMT, MOR, MWW, FAU, MFI, FER, BEA
It is or a variety of；The acid solution includes H4EDTA、HCl、HNO3Deng one or more, preferably H4EDTA；The addition of acid solution
Amount will at least flood all molecular sieves, can be 10-20 times, preferably 15 times of molecular sieve volume；The alkaline solution includes
NaOH、Na2CO3Deng one or more, preferably NaOH；A concentration of 0.05mol/L-2.0mol/L of alkaline solution；Alkalinity is molten
The addition of liquid will at least flood all molecular sieves, can be 5-15 times, preferably 10 times of molecular sieve volume.
The M-meso-S carrier mesoporous pore sizes obtained in the present invention are distributed as 4-34nm, specific aperture and alkaline solution used
Concentration is related.
2. the preparation method of composite catalyst：
The preparation of the loaded catalyst X/M-meso-S with composite pore structural uses coprecipitation method or infusion process in the present invention,
Include the following steps：
2.1 wherein coprecipitation methods include：
1）The carrier with composite pore structural being prepared is put into Muffle furnace 500 DEG C of roastings 4 hours to remove M-meso-
The water adsorbed in S；
2）X metal nitrates, chlorate and the sulfate of M-meso-S mass 0.1-50% is taken, is dissolved in the deionization of certain volume
In water, the mixed solution of certain density X metal nitrates, chlorate and sulfate is made into, it is molten to prepare certain density alkalinity
The M-meso-S carriers for the certain mass being prepared with the deionized water of 10-20 times of volume are mixed, stirred evenly by liquid, and
Afterwards under certain bath temperature and intense agitation, X metal nitrates, chlorate, sulfuric acid is added dropwise simultaneously into mixed liquor
The mixed solution and alkaline solution of salt, control solution pH value during being added dropwise.
3）After the mixed solution of X metal nitrates, chlorate and sulfate is added dropwise, will be coprecipitated after suspension continue
Stir certain time, then aging at room temperature.
4）The solution that aging is finished filters, and the precipitation then washed with the deionized water of certain volume is until washing
Liquid PH is 7.
5）Washing dry certain time at 110-120 DEG C to the catalyst precursor after neutrality.
6）Dried catalyst precursor in Muffle furnace at 550-650 DEG C is roasted to 3-5 h, obtains having compound
The loaded catalyst X/M-meso-S of pore structure.
Coprecipitated alkaline solution of the present invention includes but not limited to the hydroxide of alkali metal and ammonium, such as hydroxide
Lithium, sodium hydroxide, potassium hydroxide and ammonium hydroxide etc.；Carbonate, bicarbonate, formates and the acetate of alkali metal, such as carbon
Two or more mixed liquors of the solution of sour lithium, sodium carbonate, potassium carbonate etc. or above-mentioned alkaline solution.Alkaline substance solution
Liquid medium used is preferably water, but is also not necessarily limited to water.The addition of alkaline solution will at least flood all carriers, can be
10-20 times or more of carrier bulk, preferably 15 times, it is 10-14 that solution PH value is controlled when coprecipitated, and preferably PH is 11.
Above-mentioned coprecipitation method bath temperature can be -99 DEG C of room temperature, preferably 70 DEG C；Aging temperature can be -80 DEG C of room temperature, aging
Time can be -20 days 1 hour, preferably 60 DEG C, ageing time 5 days；Catalyst detergent medium is preferably water, but is also not necessarily limited to water,
Liquid medium can be 2-10 times of catalyst volume and more than, preferably 2-5 times, washing times are depending on efflux pH is washed.
Catalyst drying temperature can be -150 DEG C of room temperature, and the time can be -10 days 1 hour, preferably 120 DEG C, 3-5 days dry；
Calcination temperature can be 150-800 DEG C, the time can be 1-50 hours, preferably 500-700 DEG C, 30 hours time.
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural in the present invention.
The active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al (NO in the present invention3)3、KNO3、
CsNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3、AlCl3、KCl、
CsCl、MgCl2、CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3、Al2(SO4)3、K2SO4、Cs2SO4、MgSO4、CaSO4、
La2(SO4)3、Fe2(SO4)3、Mn2(SO4)3One or more of mixing.
2.2 infusion processes include：
1）The M-meso-S carriers with composite pore structural being prepared are put into Muffle furnace first and are roasted 4 hours for 500 DEG C,
Remove the water adsorbed in M-meso-S.
2）Metal X mass is taken as the X metal nitrates of M-meso-S mass 0.1-50% and the mixed solution of chlorate,
It is impregnated into several times in ultrasound environments in the M-meso-S carriers duct after roasting；
3）Catalyst precursor after dipping 110 DEG C of dryings 10 hours in an oven.
4）Dried catalyst precursor is roasted into 3h for 550 DEG C in Muffle furnace, obtains that there is urging for composite pore structural
Agent X/M-meso-S.
Dipping method described in the present invention can use co-impregnation, the method that can also use step impregnation；Drying temperature can
For room temperature~150 DEG C, the time can be 1 hour~20 days；Calcination temperature can be 550~650 DEG C, and the time can be 1~50 hour.
The content of metal X is the 0.1-50% of vehicle weight in the loaded catalyst general formula of composite pore structural.
In preferred embodiments, the active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al
(NO3)3、KNO3、CsNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3With
AlCl3、KCl、CsCl、MgCl2、CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3Middle one or more of mixing.
The present invention is using ethylene carbonate, methanol and ethyl alcohol as raw material, in the catalyst existence condition next step of above-mentioned preparation
Catalysts of Preparing Methyl Ethyl Carbonate, reactive mode are two kinds of continuous fixed bed reaction or continuous and slurry bed system still reaction.
Continuous fixed bed reaction or continuous specific embodiment of the present invention is：Under normal pressure to 10MPa reaction pressures, liquid is beaten with pump
The mixture charging of oxide spinel vinyl acetate, methanol and ethyl alcohol, three's molar ratio 5:1:5-1:5:1 in above-mentioned catalyst, there are items
Reaction Catalysts of Preparing Methyl Ethyl Carbonate, air speed are 0.1-100 h to part in next step-1, under conditions of 50-250 DEG C of reaction temperature, catalyst
For the various multi-functional compound base catalysts protected in the present invention, 0.1-3wt% of the catalyst amount for material quality, product carbon
For sour methyl ethyl ester selectively not less than 65%, yield is not less than 60%.
During methyl ethyl carbonate is prepared with fixed bed reaction, optimum condition is ethylene carbonate：Methanol：Ethyl alcohol rubs
That ratio 1:3:2, air speed 0.5-5 h-1, 78-130 DEG C of reaction temperature.
Still reaction specific embodiment of the present invention is：Reaction pressure 0.1-10MPa, ethylene carbonate, methanol and ethyl alcohol
Three's molar ratio 5:1:5-1:5:1, under catalyst existence condition reaction prepare methyl ethyl carbonate, closed 25-150 in reaction kettle
DEG C reaction 0.5-10 h, catalyst is the various basic catalysts protected in the present invention, and catalyst amount is material quality
0.1-10 wt %。
During methyl ethyl carbonate is prepared with still reaction, preferred ethylene carbonate：Methanol：Ethyl alcohol molar ratio 1:3:
2,90-140 DEG C of reaction temperature.
Embodiment
Embodiment 1
In 50L paste state bed reactor kettles, reaction pressure 2MPa, reaction raw materials ethylene carbonate：Methanol：Ethyl alcohol=1:3:2, point
Each 1.2kg of basic catalyst that above-mentioned preparation method obtains is not put into, and reaction solution total volume is 40 L.Mechanic whirl-nett reaction, instead
100 DEG C of temperature is answered, reacts sampling progress chromatography calculating after 10h, feed stock conversion, selectivity of product are as shown in table 1.
Influence of the 1 variety classes catalyst of table to feed stock conversion, selectivity of product
Under all reaction conditions, there is ethylene carbonate in table（EC）, dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）And carbon
Diethyl phthalate（DEC）, a large amount of ethylene glycol are also generated, since ethylene glycol is free of ester bond, when selectivity is calculated on the basis of ester bond
It is not counted in.Other specific examples use same data expression method.As can be seen from Table 1, if only using molecular sieve carrier as
Catalyst, reaction result is very poor, and reaction hardly occurs.When alkali metal oxide is carried on molecular sieve carrier, catalysis
Agent effect has very big promotion, and when containing Cs elements particularly in catalyst, the catalytic effect of reaction is best.With 15%BaO-5%
MgO-3%La2O3/ Cs-meso-EMT is catalyst, and ethylene carbonate ester conversion rate is up to 92%, and EMC molar selectivities are reachable in product
68%。
Embodiment 2
In fixed bed reactors, influence of the differential responses pressure to feed stock conversion and selectivity of product is probed into.In fixed bed
Middle loading 15%BaO-5%MgO-3%La2O350 g of/Cs-meso-EMT catalyst, using constant flow pump by ethylene carbonate, methanol with
Ethyl alcohol is according to molar ratio 1:3:2 ratio is pumped into reactor, and air speed is 5 h-1, it is as shown in the table for reaction pressure, reaction temperature
100 DEG C, and stablize 500 h, sampling progress chromatography calculating after stablizing, feed stock conversion, selectivity of product are as shown in table 2.
Influence of the 2 differential responses pressure of table to feed stock conversion, selectivity of product
As can be seen from Table 2, with 15%BaO-5%CaO-3%La2O3When/Cs-meso-EMT is catalyst, with reaction pressure
Raising reaction-ure conversion-age and selectivity of product all increase.When reaction pressure reach 5MPa and more than when, reactant conversion
Rate and EMC selectivity of product nearly all reach maximum value, it is seen that 5MPa is the optimal reaction pressure of the reaction.
Embodiment 3
In fixed bed reactors, influence of the differential responses temperature to feed stock conversion and selectivity of product is probed into.In fixed bed
Middle loading 15%BaO-5%MgO-3%La2O350 g of/Cs-meso-EMT catalyst, using constant flow pump by ethylene carbonate, methanol with
Ethyl alcohol is according to molar ratio 1:3:2 ratio is pumped into reactor, and air speed is 5 h-1, reaction pressure 5Mpa, reaction temperature such as table
It is shown, and stablize 500 h, sampling progress chromatography calculating after stablizing, feed stock conversion, selectivity of product are as shown in table 3.
Influence of the 3 differential responses temperature of table to feed stock conversion, selectivity of product
From table 3 it can be seen that the raising reaction-ure conversion-age and EMC with reaction temperature selectively increase, but work as temperature
After 100 DEG C, continue to increase temperature, reaction-ure conversion-age and selectivity of product are almost unchanged, therefore the temperature of the reaction
Suitable for control near 100 DEG C.
Embodiment 4
In fixed bed reactors, influence of the differential responses object molar ratio to feed stock conversion and selectivity of product is probed into.Solid
15%BaO-5%MgO-3%La is packed into fixed bed2O350 g of/Cs-meso-EMT catalyst, using constant flow pump by ethylene carbonate, first
Alcohol is pumped into ethyl alcohol in reactor, and air speed is 5 h-1, methanol with ethyl alcohol specifically reacts molar ratio, and it is as shown in the table, reaction pressure
5MPa, 100 DEG C of reaction temperature, and stablize 500 h, and sampling progress chromatography calculating after stablizing, feed stock conversion, product selection
Property is as shown in table 4.
The different methanol of table 4 and influence of the ethyl alcohol molar ratio to feed stock conversion, selectivity of product
From table 4, it can be seen that methanol and ethyl alcohol molar ratio are very big on reaction result influence, when methanol and ethyl alcohol low mole prop0rtion,
Methyl ethyl carbonate and diethyl carbonate selectivity are higher, the reason is that the dimethyl carbonate of more ethyl alcohol substitution generations.Work as on the contrary
When methanol is with ethyl alcohol high molar ratio, dimethyl carbonate selectivity is higher, the reason is that ethylene carbonate replaces generation by a large amount of methanol
Dimethyl carbonate, and the amount of ethyl alcohol is less, dimethyl carbonate cannot further be replaced by ethyl alcohol, therefore a large amount of dimethyl carbonates
It is remaining.It can be seen that from upper table, when methanol and ethyl alcohol molar ratio are 3:When 2, methanol is opposite with the conversion ratio of ethyl alcohol higher, former
Expect that utilization rate is high.Therefore, the optimum response molar ratio of methanol and ethyl alcohol is 3:2.
Embodiment 5
In fixed bed reactors, influence of the differential responses air speed to feed stock conversion and selectivity of product is probed into.In fixed bed
Middle loading 15%BaO-5%MgO-3%La2O350 g of/Cs-meso-EMT catalyst, using constant flow pump by ethylene carbonate, methanol with
Ethyl alcohol is according to molar ratio 1:3:2 ratio is pumped into reactor, and it is as shown in the table for differential responses air speed, reaction pressure 5MPa, instead
100 DEG C of temperature is answered, and stablizes 500 h, sampling progress chromatography calculating, feed stock conversion, selectivity of product such as table 5 after stablizing
It is shown.
Influence of the 5 differential responses air speed of table to feed stock conversion, selectivity of product
As can be seen from Table 5, as the increase reaction-ure conversion-age and methyl ethyl carbonate of air speed selectivity are constant at the beginning, work as sky
Speed is more than 5h-1When, the two declines apparent.The reason is that since air speed is excessive, reaction raw materials have little time to react.Therefore air speed 5h-1For
Optimum response air speed.
Embodiment 6
In fixed bed reactors, influence of the differential responses duration to feed stock conversion and selectivity of product is probed into, investigates catalysis
The stability of agent.15%BaO-5%MgO-3%La is packed into fixed bed2O350 g of/Cs-meso-EMT catalyst, utilizes constant flow pump
By ethylene carbonate, methanol and ethyl alcohol according to molar ratio 1:3:2 ratio is pumped into reactor, and air speed is 5 h-1, reaction pressure
Power 5MPa, 100 DEG C of reaction temperature, and stablize in table the reaction time respectively, sampling progress chromatography calculating, raw material turn after stablizing
Rate, selectivity of product are as shown in table 6.
Influence of the reaction experience duration of table 6 to feed stock conversion, selectivity of product
As can be seen from Table 6,5000 h feed stock conversions of reaction experience, product methyl ethyl carbonate are selectively basically unchanged, and are catalyzed
Agent does not inactivate substantially, and catalyst has fabulous stability.
The above is only several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical solution.
Claims (8)
1. by the method for ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, which is characterized in that the method includes
Following preparation process：
One-step synthesis method methyl ethyl carbonate reaction route equation is as follows：
Raw material is respectively ethylene carbonate, methanol and ethyl alcohol, glycol product and carbonic ester molar ratio 1：1 generation, ethylene glycol are
A kind of China largely relies on the bulk chemical of import, can effectively a large amount of coproduction ethylene glycol using the path；
The catalyst of catalysis single step reaction of the present invention is with mesoporous and microcellular structure compound basic catalyst；Catalyst Formula
For X/S, wherein X is includes Li, Na, K, Rb, Cs；Be、Mg、Ca、Sr、Ba；La、Ce、Y、Zr；Cr、W、Mn；Fe、Ru；Co、Rh、
Ir；Pd、Pt；Cu、Ag；The oxide of one or more kinds of elements in Zn, B, Al, Ga；S is the carrier of different topology structure, is wrapped
Topological structure is included as EMT, MOR, MWW, FAU, MFI, FER, BEA molecular sieve and routine SiO2、Al2O3、ZrO2, MgO and ZnO
Wait one or more of carriers oxide；
With mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, the preparation of Jie's micro porous molecular sieve carrier
Method：
1）Dealuminzation：Certain mass M-S carriers are added separately to the molten stirring of acidity of certain temperature, volume, concentration, using pumping
Filter is washed, dry, obtains the M-S-DAl carriers after dealuminzation；
2）Desiliconization：M-S-DAl carriers made from certain mass process 1 are added to certain temperature, concentration, the alkalinity of certain volume
It stirs in solution, using suction filtration, washs, it is dry, obtain multi-stage porous M-S-DAl-DSi carriers；
3）M-S-DAl-DSi carriers made from process 2 are finally put into Muffle furnace roasting, obtaining carrier indicium is：M-meso-S；
Methyl ethyl carbonate is prepared through continuous fixed bed reaction or continuous.
2. the method according to claim 1 by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, special
Sign is that the S molecular sieve carriers, hydrogen type molecular sieve first passes around ion exchange, Bronsted acid by metal ion poison
Change, it is made not have Bronsted acid；The ion-exchanger for poisoning molecular sieve is Li, Na, K, Rb, Cs, Ca, Fe, Mg, Cu
Hydrochloride, sulfate or nitrate；Other molecular sieves and support preparation method are similar, are designated generally as M-S, wherein M include Li,
Na、K、Rb、Cs、Ca、Fe、Mg、Cu。
3. the method according to claim 1 by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, special
Sign is, gives an account of the preparation of micro porous molecular sieve carrier, the molecular sieve of the different topology structure of carrier include EMT, MOR,
MWW, FAU, MFI, FER, BEA's is one or more；The acid solution includes H4EDTA、HCl、HNO3It is one or more, it is excellent
Select H4EDTA；The addition of acid solution will at least flood all molecular sieves, can be 10-20 times of molecular sieve volume, best
It is 15 times；The alkaline solution includes NaOH, Na2CO3Deng one or more, preferably NaOH；The alkaline solution is a concentration of
0.05mol/L-2.0mol/L；The addition of alkaline solution will at least flood all molecular sieves, can be the 5- of molecular sieve volume
15 times, preferably 10 times.
4. the method according to claim 1 by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, special
Sign is, gives an account of the preparation of micro porous molecular sieve carrier, and the M-meso-S carrier mesoporous pore sizes obtained are distributed as 4-34nm, has
Body aperture is related with alkaline solution concentration used.
5. the method according to claim 1 by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, special
Sign is, described with mesoporous and microcellular structure carrier loading type alkali metal oxide catalyst, using coprecipitation method or leaching
Stain method：
1）Coprecipitated alkaline solution includes but not limited to the hydroxide of alkali metal and ammonium, such as lithium hydroxide, sodium hydroxide, hydrogen-oxygen
Change potassium and ammonium hydroxide；Carbonate, bicarbonate, formates and the acetate of alkali metal, such as lithium carbonate, sodium carbonate, potassium carbonate
Solution or above-mentioned alkaline solution two or more mixed liquors；Liquid medium used in alkaline substance solution is preferably
Water, but it is also not necessarily limited to water；
2）The addition of alkaline solution will at least flood all carriers, be 10-20 times or more of carrier bulk, and preferably 15
Times, it is 10-14 that solution PH value is controlled when coprecipitated, and preferably PH is 11；
Coprecipitation method bath temperature can be -99 DEG C of room temperature, preferably 70 DEG C；Aging temperature is -80 DEG C of room temperature, and ageing time is small for 1
When -20 days, preferably 60 DEG C, ageing time 5 days；Catalyst detergent medium is preferably water, but is also not necessarily limited to water, and liquid medium can be
2-10 times of catalyst volume and more than, preferably 2-5 times, washing times are depending on efflux pH is washed；Catalyst drying temperature
Can be -150 DEG C of room temperature, the time can be -10 days 1 hour, preferably 120 DEG C, 3-5 days dry；Calcination temperature is 150-800 DEG C, when
Between for 1-50 hours, preferably 500-700 DEG C, 30 hours time；Metal X's contains in the loaded catalyst general formula of composite pore structural
Measure the 0.1-50% for vehicle weight；
3）The active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al (NO3)3、KNO3、CsNO3、Mg
(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3、AlCl3、KCl、CsCl、MgCl2、
CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3、Al2(SO4)3、K2SO4、Cs2SO4、MgSO4、CaSO4、La2(SO4)3、
Fe2(SO4)3、Mn2(SO4)3One or more of mixing；
4）Dipping method co-impregnation or the method with step impregnation；Drying temperature can be room temperature~150 DEG C, and the time can be 1
Hour~20 days；Calcination temperature can be 550~650 DEG C, and the time can be 1~50 hour；The loaded catalyst of composite pore structural
The content of metal X is the 0.1-50% of vehicle weight in general formula；
5）In preferred embodiments, the active constituent presoma of the loaded catalyst of compound pore passage structure is preferably Al
(NO3)3、KNO3、CsNO3、Mg(NO3)2、Ca(NO3)2、Ba(NO3)2、Sr(NO3)2、La(NO3)3、Fe(NO3)3、Mn(NO3)3With
AlCl3、KCl、CsCl、MgCl2、CaCl2、BaCl2、SrCl2、LaCl3、FeCl3、MnCl3Middle one or more of mixing.
6. the method according to claim 1 by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, special
Sign is, the one-step synthesis methyl ethyl carbonate path, and continuous fixed bed reaction or continuous concrete scheme is：It is anti-to 10MPa in normal pressure
It answers under pressure, the mixture that liquid charging stock ethylene carbonate, methanol and ethyl alcohol are played with pump is fed, three's molar ratio 5:1:5-1:5:
1 reacts Catalysts of Preparing Methyl Ethyl Carbonate in next step in above-mentioned catalyst existence condition, and air speed is 0.1-30 h-1, reaction temperature 50-
Under conditions of 250 DEG C, catalyst is the various multi-functional compound base catalysts protected in the present invention, and catalyst amount is raw material matter
The 0.1-3wt% of amount, for product methyl ethyl carbonate selectively not less than 50%, yield is not less than 20%.
7. the method according to claim 6 by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, special
Sign is that the continuous fixed bed reaction or continuous, during preparing methyl ethyl carbonate, optimum condition is ethylene carbonate：Methanol：
Ethyl alcohol molar ratio 1:3:2, air speed 0.5-5 h-1, 78-130 DEG C of reaction temperature.
8. the method according to claim 7 by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, special
Sign is, the one-step synthesis methyl ethyl carbonate path, and still reaction concrete scheme is：Reaction pressure 0.1-10MPa, carbonic acid
Vinyl acetate, methanol and ethyl alcohol three molar ratio 5:1:5-1:5:1, under catalyst existence condition reaction prepare methyl ethyl carbonate,
Closed 25-150 DEG C of reaction 0.5-10 h in reaction kettle, catalyst are the various basic catalysts protected in the present invention, catalyst
Dosage is the 0.1-10 wt % of material quality.
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| CN115634682A (en) * | 2022-10-31 | 2023-01-24 | 南京工业大学 | Double-component monoatomic solid base catalyst, preparation and application thereof |
| CN115634683A (en) * | 2022-10-31 | 2023-01-24 | 南京工业大学 | Supported three-component monatomic solid base catalyst, and preparation and application thereof |
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Application publication date: 20180608 |