CN105777504B - A method of preparing bi-end-blocking glycol ether - Google Patents
A method of preparing bi-end-blocking glycol ether Download PDFInfo
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- CN105777504B CN105777504B CN201410812315.6A CN201410812315A CN105777504B CN 105777504 B CN105777504 B CN 105777504B CN 201410812315 A CN201410812315 A CN 201410812315A CN 105777504 B CN105777504 B CN 105777504B
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- ether
- ethylene glycol
- glycol mono
- monohydric alcohol
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Abstract
This application discloses a kind of methods preparing bi-end-blocking glycol ether, include the following steps:A) raw material containing ethylene glycol mono-ether and monohydric alcohol, reaction temperature is 50~300 DEG C, reaction pressure is 0.1~15Mpa, the mass space velocity of ethylene glycol mono-ether is 0.01~15.0h‑1, monohydric alcohol and ethylene glycol mono-ether molar ratio be monohydric alcohol:Ethylene glycol mono-ether=1~100:It under conditions of 1, is passed through reactor and contacts and react with acid molecular sieve catalyst, product is isolated to bi-end-blocking glycol ether product, unreacted ethylene glycol mono-ether and monohydric alcohol, side components, remaining component;B) by the unreacted ethylene glycol mono-ether and monohydric alcohol, side components Returning reactor in step a).The present processes have the low separating energy consumption of long catalyst single pass life, the yield of target product and high selectivity, product, by-product economic value height, production scale size, using flexible advantage.
Description
Technical field
The application belongs to chemical field, in particular to a kind of preparation method of bi-end-blocking glycol ether
Background technology
Bi-end-blocking glycol ether refers to the glycol ether that the hydrogen on two terminal hydroxy groups of ethylene glycol is replaced gained by alkyl.Bi-end-blocking
Glycol ether does not have active hydrogen, and chemical stability is strong, pour point is low, glutinous temperature variation is small, heat-resist, ph stability enhances,
Emulsifying capacity is good, the low lipophile of foam is strong, anti-coking is preferable, has lower viscosity and density etc..Therefore, the poly- second of bi-end-blocking two
Alcohol ether has a wide range of applications in fields such as high-speed spin finishes, low-foaming detergent, food processing and biofermentations.
The preparation of bi-end-blocking glycol ether mainly has halogenated hydrocarbons and sodium alkoxide (Williamson is synthesized) method and direct etherification method,
Wherein Williamson synthetic methods refer to that halogenated hydrocarbons reacts generation ether, seriously polluted, operation danger with sodium alkoxide in anhydrous conditions
Danger, economy are relatively low;Direct etherification method refers to that spent glycol or ethylene glycol mono-ether are directly etherified with monohydric alcohol or unitary alcohol ether
Method.As glycol monoethyl ether and dimethyl ether can prepare glycol dimethyl ether using anion exchange resin as catalyst
(US4321413);Ethylene glycol is with methanol using perfluorinated sulfonic resin as catalyst preparation glycol dimethyl ether (US 2004/
0044253).Yield, selectivity and the service life for the catalyst that these methods use be not high, and resin catalyst is difficult to regenerate,
It is easily formed the by-products such as a large amount of 1,4- dioxane and high boiling more ethylene glycol bi-end-blocking ethers simultaneously.
Invention content
According to the one side of the application, a kind of method preparing bi-end-blocking glycol ether is provided, which is characterized in that extremely
Include the following steps less:
A) reactor is passed through with the raw material of monohydric alcohol containing ethylene glycol mono-ether to contact with the catalyst containing acidic molecular sieve
And react, product is isolated to bi-end-blocking glycol ether product, unreacted ethylene glycol mono-ether, unreacted monohydric alcohol, pair
Product component, remaining component;
B) unreacted ethylene glycol mono-ether isolated step a), unreacted monohydric alcohol and side components are returned
The reactor;
Reaction temperature in reactor described in step a) is 50~300 DEG C, and reaction pressure is 0.1~15MPa;
The mass space velocity of ethylene glycol mono-ether is 0.01~15.0h in the raw material-1;
The molar ratio of monohydric alcohol and ethylene glycol mono-ether is monohydric alcohol in the raw material:Ethylene glycol mono-ether=1~100:1.
In the application, bi-end-blocking glycol ether refers to the second two that hydrogen on two hydroxyls of ethylene glycol is all replaced gained by alkyl
Alcohol ether.
The ethylene glycol mono-ether is selected from least one of the compound with structural formula shown in formula I:
R-O-CH2-CH2- OH Formulas I;
The monohydric alcohol is selected from least one of the compound with the structural formula as shown in Formula II:
R-OH Formula II;
The bi-end-blocking glycol ether is selected from least one of the compound with the structural formula as shown in formula III:
R-O-CH2-CH2- O-R formula IIIs;
Preferably, wherein the one kind of substituent R in the alkyl that carbon atom number is 1~20.
In the application, the alkyl that carbon atom number is 1~20 refers to arbitrary linear paraffin, branched alkane that carbon atom number is 1~20
On hydrocarbon or naphthene hydrocarbon molecule, the group of any one hydrogen atom formation is lost.
Theoretically, in raw material the substituent R of ethylene glycol mono-ether and monohydric alcohol be arbitrary carbon atom number the equal energy of various alkyl
It is enough to realize the reaction for preparing bi-end-blocking glycol ether in this reaction system.Those skilled in the art are according to product bi-end-blocking second two
The type demand of alcohol ether, can choose the raw material type with corresponding substituent R.Preferably, R is not more than selected from carbon atom number
10 alkyl.It is further preferred that R is selected from the alkyl that carbon atom number is not more than 5.It is further preferred that R is selected from methyl, second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl.It is further preferred that R is methyl or ethyl.
In the application, the reaction equation of bi-end-blocking glycol ether is prepared as shown in formula IV:
ROCH2CH2OH+ROH=ROCH2CH2OR+H2O formula IVs
Side reaction equation is as follows:
2ROH=ROR+H2O Formula V
ROCH2CH2OH+H2O=ROH+HOCH2CH2OH Formula IV
2ROCH2CH2OH=ROCH2CH2OR+HOCH2CH2OH Formula VII
2ROCH2CH2OR=2ROR+ (CH2CH2O)2Formula VIII
ROCH2CH2OH+HOCH2CH2OH=R (OCH2CH2)2OH+H2O Formula IX
R(OCH2CH2)2OH+ROH=R (OCH2CH2)2R+H2O Formula X
Wherein (CH2CH2O)2For Isosorbide-5-Nitrae-dioxane, HOCH2CH2OH is ethylene glycol, R (OCH2CH2)2OH is diethylene glycol
Monoether, R (OCH2CH2)2R is diethylene glycol diether.
It is further preferred that the acidic molecular is screened from point that structure type is MWW, FER, MFI, MOR, FAU, BEA
It is one or more in son sieve.
It is further preferred that the acidic molecular is screened from Hydrogen MCM-22 molecular sieves, Hydrogen ferrierite, Hydrogen
It is one or more in ZSM-5 molecular sieve, h-mordenite, Hydrogen Y zeolites, Hydrogen Beta molecular sieves.
Preferably, the atomic ratio of the middle silicon of the acid molecular sieve catalyst and aluminium is Si/Al=4~140.
Preferably, the range of reaction temperature upper limit is selected from 200,230,300 DEG C, and lower limit is selected from 50,100,130 DEG C.Into
Preferably, the reaction temperature is 100~200 DEG C to one step.
Preferably, the reaction pressure range limit be selected from 8MPa, 15MPa, lower limit be selected from 0.1MPa, 2MPa, 3MPa,
3.5MPa.It is further preferred that the reaction pressure is 3.5~8MPa.
Preferably, the range limit of the mass space velocity of ethylene glycol mono-ether is selected from 5.0h in the fresh feed-1、9h-1、15h-1, lower limit selects 0.01h-1、0.5h-1、2h-1.It is further preferred that the mass space velocity of ethylene glycol mono-ether is in the fresh feed
0.5~5.0h-1。
Preferably, in the fresh feed monohydric alcohol and ethylene glycol mono-ether molar ratio, monohydric alcohol:The model of ethylene glycol mono-ether
It places limit and is selected from 5:1、15:1、25:1、50:1、100:1, lower limit is selected from 1:1、2:1、3:1.It is further preferred that described fresh
The molar ratio of monohydric alcohol and ethylene glycol mono-ether is monohydric alcohol in raw material:Ethylene glycol mono-ether=1~5:1.
Preferably, the side components contain ethylene glycol and/or unitary alcohol ether, and ethylene glycol and/or unitary alcohol ether are in pair
Weight content in product component is not less than 95%.It is further preferred that the side components are ethylene glycol and/or unitary
Alcohol ether.
As one preferred embodiment of the application, the reaction temperature is 100~200 DEG C, and the reaction pressure is
3.5~8MPa;
The side components contain ethylene glycol and/or unitary alcohol ether;
The mass space velocity of ethylene glycol mono-ether is 0.5~5.0h in the fresh feed-1;
The molar ratio of monohydric alcohol and ethylene glycol mono-ether is monohydric alcohol in the fresh feed:Ethylene glycol mono-ether=1~5:1.
Reaction system can not introduce carrier gas in the application, can also introduce carrier gas.Carrier gas is introduced into reaction system, it can
The reaction bed temperature fluctuation brought with the fuel factor of buffering reaction system, keeps more uniform temperature gradient, is conducive to improve
Reaction stability and catalyst life.
Preferably, carrier gas can be contained in the raw material, the carrier gas volume space velocity is 0~10000h-1;The carrier gas choosing
From one or more in nitrogen, helium, argon gas.
It is further preferred that the carrier gas volume space velocity is 100~2000h-1。
If introducing carrier gas in reaction system, the carrier gas can recycle.
Preferably, the reactor is one or more fixed bed reactors, using the form of successive reaction.Fixed bed is anti-
It can be one to answer device, or multiple.Can connect, simultaneously when using multiple fixed bed reactors, between reactor
Connection or the form being combined with parallel connection of connecting.
The advantageous effect that the application can generate includes at least:
A) method provided herein, using monohydric alcohol as raw material, source more extensively and more economic advantages.
B) the catalyst single pass life of method provided herein, use is long, and especially molecular sieve catalyst can be with
It is reused by repeated regeneration.
C) method provided herein, unreacted raw material and by-product cycle are reacted again, improve raw material availability, tool
There is higher economic sexual clorminance.
D) compared with prior art, the yield of target product, selectivity are obviously improved method provided herein.
E) method provided herein, the by-products such as low Isosorbide-5-Nitrae-dioxane of economic value are seldom.
F) method provided herein, scale of investment range is big, can on a small scale be given birth to suitable for medium-sized and small enterprises scalp
Production, using flexible.
Description of the drawings
Fig. 1 is that the application prepares bi-end-blocking glycol ether process flow diagram.
Specific implementation mode
Unless otherwise instructed, the raw material in embodiment and catalyst are bought by commercial sources.
Analysis method and conversion ratio, selectivity calculate as follows in embodiment:
Utilize the Agilent7890 gas-chromatographies with gas automatic sampling device, fid detector and FFAP capillary columns
The ingredient that instrument carries out gas/liquid phase component automatically analyzes.
In an embodiment of the present invention, ethylene glycol mono-ether conversion ratio and the choosing of product bi-end-blocking glycol ether and by-product
Selecting property is all based on quality and is calculated:
Ethylene glycol mono-ether conversion ratio=[(ethylene glycol mono-ether quality in charging)-(ethylene glycol mono-ether quality in discharging)] ÷
(ethylene glycol mono-ether quality in charging) × (100%)
Bi-end-blocking glycol ether selectivity=(bi-end-blocking glycol ether quality in discharging) ÷ [(all ethylene glycol in discharging
Derivative quality)-(the complete ethylene glycol mono-ether quality of unreacted in discharging)] × (100%)
By-product selectivity=and (by-product amount of substance in discharging) ÷ [(all ethylene glycol derivative quality in discharging)-(go out
The complete ethylene glycol mono-ether quality of unreacted in material)] × (100%)
Above-mentioned all ethylene glycol derivatives refer to containing in molecular formula contain-O-CH2-CH2The substance of-O- structures includes mainly
The complete ethylene glycol mono-ether of bi-end-blocking glycol ether, 1,4- dioxane, unreacted, bi-end-blocking diethylene glycol ether, diethylene glycol list
Ether and ethylene glycol.
The application produces a kind of technological process of bi-end-blocking glycol ether:
According to a kind of embodiment of the application, process flow diagram is as shown in Figure 1.Fresh feed ethylene glycol mono-ether
Enter the unitary alcohol ether logistics that entry mixers and separative element obtain, cycle monohydric alcohol, cycle ethylene glycol mono-ether with monohydric alcohol
It mixes with ethylene glycol stream, is reacted subsequently into reactor, reactor discharging enters separative element, is isolated to unitary
Alcohol ether logistics, cycle monohydric alcohol, bi-end-blocking glycol ether, water, 1,4- dioxane, more glycol ethers, cycle ethylene glycol mono-ether,
And ethylene glycol stream.Wherein, bi-end-blocking glycol ether is stored as product;1,4- dioxane and more glycol ethers are as by-product
Produce product store;The logistics of unitary alcohol ether, cycle monohydric alcohol, cycle ethylene glycol mono-ether and ethylene glycol stream return to entry mixers,
With together with fresh feed enter reactor.At least contain the second of 95% (weight content) in wherein isolated ethylene glycol stream
Glycol, those skilled in the art can select ethylene glycol object according to needs of production, the operating condition of equipment and economy
Ethylene glycol content in stream, more preferred scheme are at least to contain the ethylene glycol of 99% (weight content) in ethylene glycol stream.
At least contain the unitary alcohol ether of 95% (weight content) in wherein isolated unitary alcohol ether logistics, those skilled in the art can
To select the monohydric alcohol ether content in second unitary alcohol ether stream according to the operating condition of needs of production, equipment and economy,
More preferred scheme is at least to contain the unitary alcohol ether of 99% (weight content) in unitary alcohol ether logistics.
With reference to specific embodiment, the application is expanded on further.It should be understood that these embodiments are merely to illustrate this Shen
It please rather than limit scope of the present application.
Embodiment 1
By 2.0Kg silica alumina ratios (Si:Al)=45:1 Hydrogen MCM-22 molecular sieve catalysts use aluminium oxide as binder
Extruded moulding is roasted 5 hours for 550 DEG C under the air atmosphere of Muffle furnace, is obtained a diameter of after ammonium nitrate fully exchanges
3mm, length 3mm, the rodlike preformed catalyst that quality of alumina content is 20%.Take catalyst 1.0Kg be packed into internal diameter be
In the stainless steel reaction pipe of 32mm, nitrogen activation is used at normal pressure, 550 DEG C 4 hours, then drop to reaction temperature (being abbreviated as T)
=50 DEG C, the molar ratio for the fresh feed being passed through is CH3OH:CH3OCH2CH2OH=1:1, reaction pressure (being abbreviated as P)=
0.1MPa, ethylene glycol mono-ether mass space velocity (being abbreviated as WHSV)=0.01h in fresh feed-1, no carrier gas after stable reaction, uses
Gas chromatographic analysis product calculates the one way selectivity of ethylene glycol mono-ether conversion ratio and product.Then reactor is discharged and is detached
Obtained unitary alcohol ether logistics, cycle ethylene glycol mono-ether, cycle monohydric alcohol and ethylene glycol stream return to entry mixers, and fresh
Raw material enters reactor together.After stable reaction, with gas chromatographic analysis product, total conversion and the production of ethylene glycol mono-ether are calculated
The overall selectivity of object, reaction condition and the results are shown in Table 1, wherein the total conversion of ethylene glycol mono-ether is after being recycled in each embodiment
100%, therefore do not listed in table 1.
Embodiment 2
By in embodiment 1 raw material and molar ratio change into
CH3CH2OH:CH3CH2OCH2CH2OH=1:1, remaining experimental procedure is consistent with embodiment 1.Reaction condition and result
It is shown in Table 1.
Embodiment 3
Change the catalyst in embodiment 1 into Hydrogen ferrierite molecular sieve, Si:Al=15:1, T=300 DEG C, P=
15MPa, the molar ratio for being passed through raw material are CH3OH:CH3OCH2CH2OH=100:1, WHSV=15h-1, carrier gas is nitrogen, carrier gas nitrogen
Air volume air speed (being abbreviated as GHSV)=10000h-1, remaining experimental procedure and embodiment 1 are consistent.It reaction condition and the results are shown in Table
1。
Embodiment 4
By in embodiment 3 raw material and molar ratio change into
CH3CH2OH:CH3CH2OCH2CH2OH=100:1, remaining experimental procedure is consistent with embodiment 3.Reaction condition and knot
Fruit is shown in Table 1.
Embodiment 5
Change the catalyst in embodiment 1 into Hydrogen ZSM-5 molecular sieve, Si:Al=140:1, T=100 DEG C, P=
3.5MPa, the molar ratio for being passed through raw material are CH3OH:CH3OCH2CH2OH=3:1, WHSV=0.5h-1, carrier gas is argon gas, GHSV=
100h-1, remaining experimental procedure and embodiment 1 are consistent.Reaction condition and it the results are shown in Table 1.
Embodiment 6
By in embodiment 5 raw material and molar ratio change into
CH3CH2OH:CH3CH2OCH2CH2OH=3:1, remaining experimental procedure is consistent with embodiment 5.Reaction condition and result
It is shown in Table 1.
Embodiment 7
Change the catalyst in embodiment 1 into h-mordenite molecular sieve, Si:Al=4:1, T=200 DEG C, P=
8MPa, the molar ratio for being passed through raw material are CH3OH:CH3OCH2CH2OH=5:1, WHSV=5h-1, carrier gas is helium, GHSV=
2000h-1, remaining experimental procedure and embodiment 1 are consistent.Reaction condition and it the results are shown in Table 1.
Embodiment 8
By in embodiment 7 raw material and molar ratio change into
CH3CH2OH:CH3CH2OCH2CH2OH=5:1, remaining experimental procedure is consistent with embodiment 7.Reaction condition and result
It is shown in Table 1.
Embodiment 9
Change the catalyst in embodiment 1 into Hydrogen Y molecular sieve, Si:Al=25:1, T=130 DEG C, P=5MPa is passed through
The molar ratio of raw material is CH3OH:CH3OCH2CH2OH=2:1, WHSV=2h-1, carrier gas is nitrogen, GHSV=1000h-1, remaining
Experimental procedure is consistent with embodiment 1.Reaction condition and it the results are shown in Table 1.
Embodiment 10
By in embodiment 9 raw material and molar ratio change into
CH3CH2OH:CH3CH2OCH2CH2OH=2:1, remaining experimental procedure is consistent with embodiment 9.Reaction condition and result
It is shown in Table 1.
Embodiment 11
Change the catalyst in embodiment 1 into Hydrogen Beta molecular sieves, Si:Al=20:1, T=230 DEG C, P=2MPa, lead to
The molar ratio for entering raw material is CH3OH:CH3OCH2CH2OH=15:1, WHSV=9h-1, carrier gas is nitrogen, GHSV=3000h-1,
Remaining experimental procedure is consistent with embodiment 1.Reaction condition and it the results are shown in Table 1.
Embodiment 12
By in embodiment 11 raw material and molar ratio change into
CH3CH2OH:CH3CH2OCH2CH2OH=15:1, remaining experimental procedure is consistent with embodiment 11.Reaction condition and knot
Fruit is shown in Table 1.
The catalytic reaction condition and result of 1 embodiment 1~12 of table
The above is only several embodiments of the application, not does any type of limitation 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, makes 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 technical proposal scope.
Claims (8)
1. a kind of method producing bi-end-blocking glycol ether, which is characterized in that at least include the following steps:
A) reactor is passed through with the fresh feed of monohydric alcohol containing ethylene glycol mono-ether to contact with the catalyst containing acidic molecular sieve
And react, product is isolated to bi-end-blocking glycol ether product, unreacted ethylene glycol mono-ether, unreacted monohydric alcohol, pair
Product component, remaining component;
It b) will be described in the return of unreacted ethylene glycol mono-ether isolated step a), unreacted monohydric alcohol and side components
Reactor;
Reaction temperature in reactor described in step a) is 50~300 DEG C, and reaction pressure is 0.1~15MPa;
The mass space velocity of ethylene glycol mono-ether is 0.01~15.0h in the fresh feed-1;
The molar ratio of monohydric alcohol and ethylene glycol mono-ether is monohydric alcohol in the fresh feed:Ethylene glycol mono-ether=1~100:1;
The ethylene glycol mono-ether is selected from least one of the compound with structural formula shown in formula I:
R-O-CH2-CH2- OH Formulas I;
The monohydric alcohol is selected from least one of the compound with the structural formula as shown in Formula II:
R-OH Formula II;
The bi-end-blocking glycol ether is selected from least one of the compound with the structural formula as shown in formula III:
R-O-CH2-CH2- O-R formula IIIs;
Wherein, the one kind of R in methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tertiary butyl;
The acidic molecular is one kind or more in the molecular sieve of MWW, FER, MFI, MOR, FAU, BEA screened from structure type
Kind.
2. according to the method described in claim 1, it is characterized in that, R is methyl or ethyl.
3. according to the method described in claim 1, it is characterized in that, the acidic molecular screened from Hydrogen MCM-22 molecular sieves,
Hydrogen ferrierite, Hydrogen ZSM-5 molecular sieve, h-mordenite, Hydrogen Y zeolites, one kind in Hydrogen Beta molecular sieves or
It is a variety of.
4. method according to claim 1 or 3, which is characterized in that the atomic ratio of silicon and aluminium is in the acidic molecular sieve
Si/Al=4~140.
5. according to the method described in claim 1, it is characterized in that, the reaction temperature be 100~200 DEG C, the reaction pressure
Power is 3.5~8MPa;
The side components contain ethylene glycol and/or unitary alcohol ether;
The mass space velocity of ethylene glycol mono-ether is 0.5~5.0h in the fresh feed-1;
The molar ratio of monohydric alcohol and ethylene glycol mono-ether is monohydric alcohol in the fresh feed:Ethylene glycol mono-ether=1~5:1.
6. according to the method described in claim 1, it is characterized in that, containing ethylene glycol and/or unitary in the side components
Alcohol ether, the weight content of ethylene glycol and/or unitary alcohol ether in side components are not less than 95%.
7. according to the method described in claim 1, it is characterized in that, carrier gas can be contained in the raw material, the carrier gas volume
Air speed is 0~10000h-1;The carrier gas is one or more in nitrogen, helium, argon gas.
8. according to the method described in claim 1, it is characterized in that, the reactor is one or more fixed bed reactors.
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沸石催化剂上醇的醚化反应;张怀彬等;《燃料化学学报》;19971031;第25卷(第5期);419-422 * |
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