CN105777501B - A kind of method for preparing bi-end-blocking glycol ether - Google Patents

A kind of method for preparing bi-end-blocking glycol ether Download PDF

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CN105777501B
CN105777501B CN201410804722.2A CN201410804722A CN105777501B CN 105777501 B CN105777501 B CN 105777501B CN 201410804722 A CN201410804722 A CN 201410804722A CN 105777501 B CN105777501 B CN 105777501B
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ether
ethylene glycol
glycol mono
raw material
monohydric alcohol
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CN105777501A (en
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倪友明
朱文良
刘勇
刘红超
刘中民
李利娜
刘世平
周慧
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Dalian Institute of Chemical Physics of CAS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

This application involves a kind of methods for preparing bi-end-blocking glycol ether, contact reactor is passed through with the raw material of monohydric alcohol containing ethylene glycol mono-ether and reacts with acid molecular sieve catalyst, produce bi-end-blocking glycol ether；Reaction temperature 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 raw material：Ethylene glycol mono-ether=1~100:1.The present processes have catalyst single pass life long and can with repeated regeneration, the yield of target product and high selectivity, the separating energy consumption of product is low, by-product economic value height, production scale size, using flexible advantage.

Description

A kind of method for preparing bi-end-blocking glycol ether
Technical field
The application belongs to chemical field, in particular to a kind of preparation method of bi-end-blocking glycol ether.
Background technology
The hydrogen that bi-end-blocking glycol ether refers on two terminal hydroxy groups of ethylene glycol is substituted the glycol ether of 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, foam is low, lipophile is strong, anti-coking is preferable, has relatively low viscosity and density etc..Therefore, the poly- second of bi-end-blocking Glycol ethers have 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 in anhydrous conditions with sodium alkoxide Danger, economy are relatively low；Direct etherification method refers to what spent glycol or ethylene glycol mono-ether were directly etherified with monohydric alcohol or unitary alcohol ether Method.As glycol monoethyl ether and dimethyl ether can prepare glycol dimethyl ether by the use of anion exchange resin as catalyst (US4321413)；Ethylene glycol and methanol are by the use of 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 substantial amounts of 1,4- dioxane and high boiling more ethylene glycol bi-end-blocking ethers simultaneously.
The content of the invention
According to the one side of the application, a kind of method for preparing bi-end-blocking glycol ether is provided, there is catalyst list Journey long lifespan and can with repeated regeneration, the yield of target product and high selectivity, the separating energy consumption of product is low, the economic valency of by-product It is worth height, production scale size, using flexible advantage.
The method for preparing bi-end-blocking glycol ether, which is characterized in that by the original containing ethylene glycol mono-ether and monohydric alcohol Material is passed through reactor and contacts and react with the catalyst containing acidic molecular sieve, produces bi-end-blocking glycol ether；
Reaction temperature 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 that hydrogen on two hydroxyls of ethylene glycol is all substituted the second two of gained by alkyl Alcohol ether.
Preferably, the ethylene glycol mono-ether, which is selected from, has at least one of compound of structural formula shown in formula I：
R1-O-CH2-CH2- OH Formulas I；
The monohydric alcohol is selected from at least one of compound of structural formula as shown in Formula II：
R2- OH Formula II；
The bi-end-blocking glycol ether is selected from at least one of compound of structural formula as shown in formula III：
R1-O-CH2-CH2-O-R2Formula III；
Wherein, R1One kind in the alkyl that carbon number is 1~20；R2In the alkyl that carbon number is 1~20 One kind.Wherein R1With R2It may be the same or different.
In the application, the alkyl that carbon number is 1~20 refers to arbitrary linear paraffin, branched alkane that carbon number is 1~20 On hydrocarbon or naphthene hydrocarbon molecule, the group of any one hydrogen atom formation is lost.
The reaction equation of the preparation bi-end-blocking glycol ether of the application is as follows：
R1-O-CH2-CH2-OH+R2- OH=R1-O-CH2-CH2-O-R2+H2O formula IVs
Theoretically, the substituent R of ethylene glycol mono-ether and monohydric alcohol in raw material1、R2It is equal for the various alkyl of arbitrary carbon number The reaction for preparing bi-end-blocking glycol ether can be realized in this reaction system.Those skilled in the art are according to product bi-end-blocking second The species demand of glycol ethers, can choose with corresponding substituent R1、R2Raw material type.Preferably, R1, R2Independently select It is not more than 10 alkyl from carbon number.It is further preferred that R1, R2It is not more than 5 alkyl independently selected from carbon number.More It is further preferred that R1, R2Independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl.
Preferably, the R1One kind in methyl, ethyl, n-propyl, isopropyl, normal-butyl.
Preferably, the R2One kind in methyl, ethyl, n-propyl, isopropyl, normal-butyl.
Preferably, the acidic molecular screened from structure type be MWW, FER, MFI, MOR, FAU, BEA molecular sieve in One or more.It is further preferred that the acidic molecular is screened from Hydrogen MCM-22 molecular sieves, Hydrogen ferrierite, hydrogen One or more in type ZSM-5 molecular sieve, h-mordenite, Hydrogen Y zeolites, Hydrogen Beta molecular sieves.
Preferably, the atomic ratio of the silicon in the acidic molecular sieve and aluminium is Si/Al=4~140.
Preferably, the range of reaction temperature upper limit be selected from 200 DEG C, 250 DEG C, 300 DEG C, lower limit be selected from 50 DEG C, 90 DEG C, 100℃.It is further preferred that the reaction temperature is 100~200 DEG C.
The reaction pressure range limit be selected from 8MPa, 10MPa, 15MPa, lower limit be selected from 0.1MPa, 0.9MPa, 2MPa, 3MPa、3.5MPa、5MPa.It is further preferred that the reaction pressure is 3.5~8MPa.
The range limit of the mass space velocity of ethylene glycol mono-ether is selected from 5.0h in the raw material-1、10h-1、15h-1, lower limit choosing 0.01h-1、0.5h-1、2h-1.It is further preferred that the mass space velocity of ethylene glycol mono-ether is 0.5~5.0h in the raw material-1。
The molar ratio range upper limit of monohydric alcohol and ethylene glycol mono-ether is selected from 4 in the raw material:1、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 the molar ratio of monohydric alcohol and ethylene glycol mono-ether in the raw material For monohydric alcohol：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 brought with the fuel factor of buffering reaction system fluctuates, and more uniform temperature gradient is kept, beneficial to raising Reaction stability and catalyst life.
Preferably, carrier gas, one or more of the carrier gas in nitrogen, helium, argon gas are contained in the raw material.
Preferably, the carrier gas volume space velocity is 0~10000h-1.It is further preferred that the carrier gas volume space velocity is 100~2000h-1。
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) method provided herein, it is long with single pass life using acid molecular sieve catalyst, it can pass through repeatedly The advantages of regeneration is reused.
C) compared with prior art, the yield of target product, selectivity are obviously improved method provided herein.
D) method provided herein, by-product are mainly the very high bi-end-blocking diethylene glycol ether of economic value, two The by-products such as ethylene glycol mono-ether and ethylene glycol, the low Isosorbide-5-Nitrae-dioxane of economic value are seldom, have higher economy.
E) method provided herein, scale of investment scope is big, can on a small scale be given birth to suitable for medium-sized and small enterprises scalp Production, using flexible.
Specific embodiment
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 embodiments herein, ethylene glycol mono-ether conversion ratio and product bi-end-blocking glycol ether and by-product select 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, mainly includes 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.
With reference to specific embodiment, the application is expanded on further.It is to be understood that these embodiments are merely to illustrate this Shen It please rather than limit scope of the present application.
Embodiment 1
By 50g silica alumina ratios (Si:Al)=45:1 Hydrogen MCM-22 molecular sieve catalysts are under the air atmosphere of Muffle furnace When 550 DEG C of roastings 5 are small, take a portion pressed powder pellet, be ground into 20~40 mesh, for active testing.Weigh the hydrogen Type MCM-22 molecular sieve catalyst sample 10g are packed into the stainless steel reaction pipe that internal diameter is 8.5mm, are used at normal pressure, 550 DEG C When nitrogen activation 4 is small, reaction temperature (being abbreviated as T)=50 DEG C is then dropped to, mole composition for being passed through raw material is CH3OH: CH3OCH2CH2OH=1:1, reaction pressure (being abbreviated as P)=0.1MPa, the mass space velocity of ethylene glycol mono-ether (is abbreviated as in raw material WHSV)=0.01h-1, no carrier gas with gas chromatographic analysis product, after stable reaction, calculates ethylene glycol mono-ether conversion ratio and product Selectivity, reaction condition and the results are shown in Table 1.
Embodiment 2
Change the reaction condition in embodiment 1 into T=90 DEG C, P=0.9MPa, mole composition for being passed through raw material is CH3CH2OH:CH3CH2OCH2CH2OH=2:1, WHSV=0.5h-1, carrier gas nitrogen volume space velocity (being abbreviated as GHSV)=100h-1, Remaining experimental procedure and embodiment 1 are consistent, reaction condition and the results are 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, mole composition for being passed through raw material is CH3OH:CH3OCH2CH2OH=100:1, WHSV=15h-1, carrier gas is nitrogen, GHSV =10000h-1, remaining experimental procedure and embodiment 1 are consistent, reaction condition and the results are shown in Table 1.
Embodiment 4
Change the catalyst in embodiment 1 into Hydrogen ferrierite molecular sieve, Si:Al=15:1, T=250 DEG C, P= 10MPa, mole composition for being passed through raw material is CH3CH2CH2OH:CH3CH2CH2OCH2CH2OH=50:1, WHSV=10h-1, carrier gas For argon gas, GHSV=5000h-1, remaining experimental procedure and embodiment 1 are consistent, reaction condition and the results are 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, mole composition for being passed through raw material is CH3OH:CH3OCH2CH2OH=1:1, WHSV=0.5h-1, remaining experimental procedure with Embodiment 1 is consistent, reaction condition and the results are shown in Table 1.
Embodiment 6
Change the catalyst in embodiment 1 into Hydrogen ZSM-5 molecular sieve, Si:Al=140:1, T=150 DEG C, P=5MPa, Mole composition for being passed through raw material is (CH3)2CHOH:(CH3)2CHOCH2CH2OH=3:1, WHSV=2.5h-1, carrier gas is nitrogen, GHSV=1000h-1, remaining experimental procedure and embodiment 1 are consistent, reaction condition and the results are 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, mole composition for being passed through raw material is 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 the results are shown in Table 1.
Embodiment 8
Change the catalyst in embodiment 1 into h-mordenite molecular sieve, Si:Al=4:1, T=180 DEG C, P= 7MPa, mole composition for being passed through raw material is CH3(CH2)3OH:CH3(CH2)3OCH2CH2OH=4:1, WHSV=4h-1, carrier gas is helium Gas, GHSV=1500h-1, remaining experimental procedure and embodiment 1 are consistent, reaction condition and the results are 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 A mole composition for raw material is CH3OH:CH3OCH2CH2OH=2:1, WHSV=2h-1, no carrier gas, remaining experimental procedure and embodiment 1 Unanimously, reaction condition and it the results are shown in Table 1.
Embodiment 10
Change the catalyst in embodiment 1 into Hydrogen Y molecular sieve, Si:Al=25:1, T=140 DEG C, P=6MPa is passed through A mole composition for raw material is CH3CH2OH:CH3CH2OCH2CH2OH=2.5:1, WHSV=2.5h-1, carrier gas is nitrogen, GHSV= 500h-1, remaining experimental procedure and embodiment 1 are consistent, reaction condition and the results are 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 Mole composition for entering raw material is CH3OH:CH3OCH2CH2OH=15:1, WHSV=9h-1, carrier gas is nitrogen, GHSV=3000h-1, Remaining experimental procedure and embodiment 1 are consistent, reaction condition and the results are shown in Table 1.
Embodiment 12
Change the catalyst that reaction condition changes into embodiment 1 into Hydrogen Beta molecular sieves, Si:Al=20:1, T=220 DEG C, P=3MPa, mole composition for being passed through raw material is CH3CH2OH:CH3CH2OCH2CH2OH=25:1, WHSV=6h-1, carrier gas is Nitrogen, GHSV=1000h-1, remaining experimental procedure and embodiment 1 are consistent, reaction condition and the results are shown in Table 1.
The catalytic reaction condition and result of 1 embodiment 1~12 of table
Note：Other by-products are mainly bi-end-blocking diethylene glycol ether, diethylene glycol monoether and ethylene glycol
Comparative example 1
50g is bought from E.I.Du Pont Company's perfluorinated sulfonic resin (Nafion-H) in air dry oven, 105 under air atmosphere When DEG C drying 12 is small, 10g is weighed after cooling and is packed into the stainless steel reaction pipe that internal diameter is 8.5mm for active testing, normal pressure, When using nitrogen activation 1 small at 100 DEG C, then at reaction temperature (T)=130 DEG C, material molar ratio is passed through as CH3OH: CH3OCH2CH2OH=2:1, reaction pressure (P)=5MPa, dimethoxym ethane mass space velocity (WHSV)=2h-1, no carrier gas, with gas phase color Spectrum analysis product after stable reaction, calculates the selectivity of ethylene glycol mono-ether conversion ratio and product, reaction condition and the results are shown in Table 2.
Comparative example 2
Change the reaction condition in comparative example 1 into T=140 DEG C, P=6MPa, the molar ratio for being passed through raw material is CH3CH2OH: CH3CH2OCH2CH2OH=2.5:1, WHSV=2.5h-1, carrier gas is nitrogen, GHSV=500h-1, remaining experimental procedure and comparative example 1 is consistent, reaction condition and the results are shown in Table 2.
Comparative example 3
The catalyst in comparative example 1 is changed into purchase to be copolymerized from the styrene-divinylbenzene of the sulfonation of Rhom and Hass Object (Amberlyst-15) resin, remaining experimental procedure and comparative example 1 are consistent, reaction condition and the results are shown in Table 2.
Comparative example 4
The catalyst in comparative example 2 is changed into purchase to be copolymerized from the styrene-divinylbenzene of the sulfonation of Rhom and Hass Object (Amberlyst-15) resin, remaining experimental procedure and comparative example 2 are consistent, reaction condition and the results are shown in Table 2.
Comparative example 5
By the catalyst in comparative example 1 change into purchase from the styrene of the sulfonation of Dandong Mingzhu Special Type Resin Co., Ltd.- Divinylbenzene copolymer storng-acid cation exchange resin (D005), remaining experimental procedure and comparative example 1 are consistent, reaction condition and It the results are shown in Table 2.
Comparative example 6
By the catalyst in comparative example 2 change into purchase from the styrene of the sulfonation of Dandong Mingzhu Special Type Resin Co., Ltd.- Divinylbenzene copolymer storng-acid cation exchange resin (D005), remaining experimental procedure and comparative example 2 are consistent, reaction condition and It the results are shown in Table 2.
The catalytic reaction condition and result of 2 comparative example 1~6 of table
Note：Other by-products are mainly bi-end-blocking diethylene glycol ether, diethylene glycol monoether and ethylene glycol
Embodiment 13
The catalyst after one way reaction inactivation in embodiment 1,3,5,7,9,11 is taken out into regeneration respectively, regeneration condition is When the lower 550 DEG C of roastings 4 of air atmosphere are small, the catalyst after regeneration repeats instead respectively according to the reaction condition of former embodiment It should.Reaction result is shown in Table 3.
Reaction result compares before and after catalytic regeneration in 3 embodiment of table
Resin catalyst in comparative example 1~6 can not regenerate.
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 (7)

  1. A kind of 1. method for producing bi-end-blocking glycol ether, which is characterized in that by the raw material containing ethylene glycol mono-ether and monohydric alcohol It is passed through reactor to contact and react with the catalyst containing acidic molecular sieve, produces bi-end-blocking glycol ether；
    Reaction temperature 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；
    The ethylene glycol mono-ether, which is selected from, has at least one of compound of structural formula shown in formula I：
    R1-O-CH2-CH2- OH Formulas I；
    The monohydric alcohol, which is selected from, has at least one of compound of structural formula as shown in Formula II：
    R2- OH Formula II；
    The bi-end-blocking glycol ether, which is selected from, has at least one of compound of structural formula as shown in formula III：
    R1-O-CH2-CH2-O-R2Formula III；
    Wherein, R1One kind in methyl, ethyl, n-propyl, isopropyl, normal-butyl；R2Selected from methyl, ethyl, n-propyl, One kind in isopropyl, normal-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. 2. 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.
  3. 3. method according to claim 1 or 2, which is characterized in that the atomic ratio of silicon and aluminium in the acidic molecular sieve For Si:Al=4~140:1.
  4. 4. 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 mass space velocity of ethylene glycol mono-ether is 0.5~5.0h 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=1~5:1.
  5. 5. according to the method described in claim 1, it is characterized in that, contain carrier gas in the raw material, the carrier gas volume space velocity For 0~10000h-1；One or more of the carrier gas in nitrogen, helium, argon gas.
  6. 6. according to the method described in claim 5, it is characterized in that, the carrier gas volume space velocity is 100~2000h-1。
  7. 7. 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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分子筛醚化催化剂的发展动态;宋丽娟等;《石油炼制与化工》;19941231(第4期);31-35 *
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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