WO2017054321A1 - 由乙二醇单甲醚直接制备乙二醇二甲醚并联产乙二醇的方法 - Google Patents

由乙二醇单甲醚直接制备乙二醇二甲醚并联产乙二醇的方法 Download PDF

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WO2017054321A1
WO2017054321A1 PCT/CN2015/097160 CN2015097160W WO2017054321A1 WO 2017054321 A1 WO2017054321 A1 WO 2017054321A1 CN 2015097160 W CN2015097160 W CN 2015097160W WO 2017054321 A1 WO2017054321 A1 WO 2017054321A1
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ethylene glycol
molecular sieve
monomethyl ether
glycol monomethyl
reaction
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PCT/CN2015/097160
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English (en)
French (fr)
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石磊
倪友明
朱文良
刘勇
刘红超
刘中民
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中国科学院大连化学物理研究所
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Priority to BR112018006549-8A priority Critical patent/BR112018006549B1/pt
Priority to JP2018515587A priority patent/JP6549793B2/ja
Priority to US15/763,318 priority patent/US10532969B2/en
Priority to EP15905232.3A priority patent/EP3330246B1/en
Priority to EA201890795A priority patent/EA036494B1/ru
Publication of WO2017054321A1 publication Critical patent/WO2017054321A1/zh
Priority to ZA2018/01833A priority patent/ZA201801833B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/14—Preparation of ethers by exchange of organic parts on the ether-oxygen for other organic parts, e.g. by trans-etherification
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • 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
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present application belongs to the field of chemistry and chemical industry, and in particular relates to a method for directly preparing ethylene glycol dimethyl ether from ethylene glycol monomethyl ether to produce ethylene glycol in parallel.
  • Ethylene glycol dimethyl ether Chinese name is 1,2-dimethoxyethane (DME).
  • DME 1,2-dimethoxyethane
  • ethylene glycol dimethyl ether is a colorless transparent liquid with ether flavor. It is an aprotic polar solvent with excellent properties. It is relatively stable in nature, is not easy to react, and can be mixed with water, mostly low.
  • the organic solvent such as carbon (C1-C6) alcohol, ketone or ester is miscible in an arbitrary ratio and has a strong dissolving ability for an alkali metal compound. Therefore, it can be an ideal solvent for many organic synthesis reactions, and it is also widely used as a cleaning agent compound for textile printing, paint and ink auxiliaries, fuel additives, and for organic compounds and pharmaceutical intermediates. Synthesis, etc.
  • the synthesis methods of ethylene glycol dimethyl ether in the literature mainly include: (1) 1,2-dichloroethane reported in US 3699174 reacted with methanol, respectively, in the metal or metal oxide of Group IV of the periodic table. And some of the transition metals in Group VI-VIII are catalysts, the main products are ethylene glycol dimethyl ether and methyl ethyl ether, wherein the conversion of the raw material 1,2-dichloroethane is 50%, ethylene glycol
  • the ether selectivity was 24.6% and the dichloromethyl ethyl ether selectivity was 46.9%.
  • the process produces more by-products, and the yield of the product is not high, wherein the 1,4-dioxane selectivity is higher than 20%.
  • the selectivity of the diol dimethyl ether is 15-20%, the total selectivity of the tris, tetra and pentaethylene glycol dimethyl ether is about 10%, and the selectivity of the 1,4-dioxane is 5-7%.
  • the reaction process has many by-products and relatively more 1,4-dioxane formation.
  • Japanese Patent Laid-Open No. 55-104221 reports that ethylene glycol or ethylene glycol monomethyl ether is reacted with methanol at a reaction temperature of 200-300 ° C to prepare ethylene glycol dimethyl ether, and the product is ethylene glycol.
  • Methyl ether selectivity is 25%, diethylene glycol dimethyl ether selectivity It is 8%, the selectivity of diethylene glycol monomethyl ether is 15%, and 1,4-dioxane is also formed in the process.
  • US4321413 reports that ethylene glycol monomethyl ether and dimethyl ether are used as reaction raw materials to prepare ethylene glycol dimethyl ether at a reaction temperature of 180 ° C, and the conversion ratio of raw material ethylene glycol monomethyl ether is 55.4%.
  • the selectivity of ethylene glycol dimethyl ether in the product was 62.4%, the selectivity to 1,4-dioxane was 20%, and the selectivity of diethylene glycol dimethyl ether was 16.5%.
  • CN104250206A discloses a preparation method of glycol ether, wherein ethylene glycol and low-carbon fatty alcohol are obtained by acid catalysis to obtain glycol ether, and the solid acid catalyst used is molecular sieve or zeolite, and the reaction temperature is 20- The reaction pressure is from 0.1 to 10 MPa at 250 °C.
  • the present invention provides a method for directly preparing ethylene glycol dimethyl ether by ethylene glycol monomethyl ether in parallel to produce ethylene glycol, the method comprising: making the raw material ethylene glycol monomethyl ether and any The selected inert gas as a carrier gas is passed through a reactor carrying a solid acid catalyst at a reaction temperature of 40 to 150 ° C and a reaction pressure of 0.1 to 15.0 MPa, optionally in the presence of water having a volume concentration of 0 to 95%.
  • the reaction is carried out to produce ethylene glycol dimethyl ether and ethylene glycol, wherein the raw material ethylene glycol monomethyl ether has a mass space velocity of 0.05 to 5.0 h -1 ; and the volume concentration of the raw material ethylene glycol monomethyl ether is 1 to 100%, the volume concentration of the carrier gas is 0 to 99%.
  • the water is introduced by addition to the starting ethylene glycol monomethyl ether.
  • the solid acid catalyst is an acidic molecular sieve catalyst or an acidic resin catalyst; preferably the acidic molecular sieve catalyst is of the structural type MWW, FER, MFI, MOR, FAU or BEA.
  • the acidic molecular sieve catalyst is one or more of MCM-22 molecular sieve, ferrierite molecular sieve, ZSM-5 molecular sieve, mordenite molecular sieve, Y zeolite molecular sieve or beta molecular sieve.
  • the acidic molecular sieve contains one or more of an alkali metal, an alkaline earth metal or a rare earth metal in a mass fraction of 0.1 to 10%, preferably 0.1 to 4%; and the acidic molecular sieve contains mass A binder having a fraction of 1 to 40%, the binder being one or more of alumina and silica.
  • the acidic resin catalyst is one or more of a benzenesulfonic acid resin, a p-toluenesulfonic acid resin, a perfluorosulfonic acid resin or a strongly acidic cation exchange resin; preferably a perfluorosulfonic acid; Nafion resin.
  • the reaction temperature is 50 to 150 ° C
  • the reaction pressure is 3.0 to 8.0 MPa
  • the mass space velocity of the raw material ethylene glycol monomethyl ether is 0.3 to 2.0 h -1 .
  • the inert gas is one or more selected from the group consisting of nitrogen, helium, and argon, and the carrier gas has a volume concentration of from 1 to 99%.
  • the reactor is a fixed bed reactor or a tank reactor.
  • the method of the invention adopts a solid acid as a catalyst under low temperature conditions, and directly prepares ethylene glycol dimethyl ether and ethylene glycol with ethylene glycol monomethyl ether as a raw material, and the product is simple and has fewer side reactions.
  • the selectivity of the desired product ethylene glycol dimethyl ether and ethylene glycol can reach 50% of the theoretical value, respectively; at the same time, the method of the invention has no or no by-products which pollute the environment and cause damage to the human or animal body. , 4-dioxane formation.
  • the present application provides a method for directly and efficiently preparing ethylene glycol dimethyl ether in parallel with ethylene glycol monomethyl ether on the surface of a solid acid catalyst to produce ethylene glycol in parallel. More specifically, in the process of the present invention, the raw material ethylene glycol monomethyl ether and optionally the inert gas as a carrier gas are passed through a reactor carrying a solid acid catalyst at a reaction temperature of 40 to 150 ° C and reacted.
  • the reaction is carried out at a pressure of 0.1 to 15.0 MPa, optionally in the presence of water having a volume concentration of 0 to 95%, to produce ethylene glycol dimethyl ether and ethylene glycol, wherein the mass space velocity of the raw material ethylene glycol monomethyl ether It is 0.05 to 5.0 h -1 ; the volume concentration of the raw material ethylene glycol monomethyl ether is 1 to 100%, and the volume concentration of the carrier gas is 0 to 99%.
  • the volume concentrations of the raw materials ethylene glycol monomethyl ether, carrier gas and water are based on the total volume of the raw materials when present in the reaction system, unless otherwise specified.
  • the volume concentration should be 100%; and when only the raw material ethylene glycol monomethyl ether and the carrier gas are present in the reaction system, the raw material ethylene glycol mono
  • the volume concentration of each of the ether and the carrier gas is based on the total volume of both of them; and when the raw materials of ethylene glycol monomethyl ether, carrier gas and water are present in the reaction system, their volume concentration is based on the total of the three of them. volume.
  • the feedstock of the raw material ethylene glycol monomethyl ether may be as follows:
  • the first way is to directly pump the liquid raw material ethylene glycol monomethyl ether into the reactor, such as a fixed bed reactor, at a flow rate, for example, 0.1-10 ml/min, by a feed pump such as a constant flow pump in the absence of a carrier gas. In the middle of the realization of the feed.
  • the second way is to carry the saturated vapor of ethylene glycol monomethyl ether into the fixed gas at a different bath temperature (40-80 ° C) in the presence of a carrier gas by an inert gas such as N 2 as a carrier gas.
  • a carrier gas such as N 2 as a carrier gas.
  • the flow rate of the carrier gas is from 10 to 50 mL/min.
  • the amount of ethylene glycol monomethyl ether material entering the reactor per unit time can be calculated from the saturated vapor pressure and the N 2 flow rate.
  • the calculation method of the saturated vapor pressure of the raw material ethylene glycol dimethyl ether under different temperature conditions is as follows.
  • p 1 * and P 2 * represent the saturated vapor pressures of the raw material ethylene glycol monomethyl ether at different temperature conditions; ⁇ VapHm represents the molar evaporation enthalpy of ethylene glycol monomethyl ether (39.48 KJ/mol); T 1 and T 2 denotes different temperatures (unit K); the saturated vapor pressure is 3.968Kpa at 253K, so that the saturated vapor pressure of ethylene glycol monomethyl ether can be calculated at any temperature.
  • the solid acid catalyst used in the present invention is an acidic molecular sieve catalyst or an acidic resin catalyst; more preferably, the acidic molecular sieve catalyst has a structural type of MWW, FER, MFI, MOR, FAU or BEA.
  • the acidic molecular sieve catalyst used in the present invention is one or more of MCM-22 molecular sieve, ferrierite molecular sieve, ZSM-5 molecular sieve, mordenite molecular sieve, Y zeolite molecular sieve or ⁇ molecular sieve;
  • the silicon-aluminum atomic ratio Si/Al in the Y molecular sieve 3 to 50;
  • the silicon-aluminum atom in the ⁇ molecular sieve has a Si/Al ratio of 5 to 100.
  • the acidic resin catalyst contains various resins of a sulfonic acid functional group such as benzenesulfonic acid, p-toluenesulfonic acid, perfluorosulfonic acid resin, preferably perfluorosulfonic acid Nafion resin, or strong.
  • a sulfonic acid functional group such as benzenesulfonic acid, p-toluenesulfonic acid, perfluorosulfonic acid resin, preferably perfluorosulfonic acid Nafion resin, or strong.
  • acidic cation exchange resins One or more of acidic cation exchange resins;
  • the reaction temperature is 50 to 150 ° C, more preferably 80 to 150 ° C, the reaction pressure is 3 to 8 MPa, and the mass space velocity of the raw material ethylene glycol monomethyl ether is 0.3 to 2.0 h -1 ;
  • the carrier gas is a mixed gas of one or any one selected from the group consisting of nitrogen, helium and argon; more preferably, the carrier gas has a mass space velocity of 50.0 to 12000.0. h -1 , further preferably from 600.0 to 5000.0 h -1 ;
  • the reactor is a fixed bed reactor which can realize a continuous reaction, or a tank reactor, preferably a fixed bed reactor.
  • ethylene glycol monomethyl ether undergoes its own disproportionation reaction to produce ethylene glycol dimethyl ether and ethylene glycol;
  • the starting ethylene glycol monomethyl ether may undergo an intermolecular dehydration reaction to form diethylene glycol dimethyl ether and water in a molar ratio of 1:1.
  • the produced ethylene glycol undergoes an intermolecular dehydration reaction with the starting ethylene glycol monomethyl ether to form diethylene glycol monomethyl ether;
  • the diol is capable of undergoing its own dehydration reaction to form diethylene glycol.
  • the produced diethylene glycol dimethyl ether undergoes an ether exchange reaction with the raw material ethylene glycol monomethyl ether to form diethylene glycol monomethyl ether and ethylene glycol dimethyl ether.
  • the resulting diethylene glycol monomethyl ether can A self-disproportionation reaction occurs to form diethylene glycol dimethyl ether and diethylene glycol.
  • the reaction products which may be obtained from the raw material ethylene glycol monomethyl ether are: ethylene glycol dimethyl ether and ethylene glycol, diethylene glycol monomethyl ether, water, diethylene glycol. Dimethyl ether, diethylene glycol and 1,4-dioxane, as well as very small amounts of methanol and dimethyl ether.
  • the presence of water in the reaction system of the present invention may be preferred because water is pre-existing in water since water is a reaction product of Formula II. In the case of the reaction of Formula II, it may be inhibited or less likely to occur.
  • the water may be introduced by addition to the starting material ethylene glycol monomethyl ether, either by carrier gas or by itself in the reactor.
  • the product is detected and determined by gas chromatography analysis.
  • substantially or completely absent 1,4-dioxane means that by gas chromatography as described above, 1,4-dioxane is present in an undetectable amount.
  • the reactor is a fixed bed reactor with a catalyst filling mass of 1-10 g, a reaction temperature of 40-250 ° C (wherein a temperature higher than 150 ° C as a comparative example of the present invention), a reaction pressure of 0.1-10 MPa, and a raw material ethylene glycol single Methyl ether enters the reactor in two injections:
  • the catalyst pretreatment conditions were: N 2 flow rate of 30 ml/min, rising from 25 ° C to 150 ° C over 150 min, and maintaining at 500 ° C for 180 min.
  • the starting material glycol monomethyl ether under conditions of a bath temperature of 60 °C, 2 in / min flow rate into 30ml of N into the reactor, the reaction pressure 0.5Mpa.
  • Reaction conditions a reaction pressure of 0.5 MPa, a catalyst mass of 1 g, a water bath temperature of 60 ° C, and a N 2 flow rate of 30 ml/min.
  • ethylene glycol can react with ethylene glycol.
  • the raw material ethylene glycol monomethyl ether undergoes a dehydration reaction to form diethylene glycol monomethyl ether, or the ethylene glycol itself undergoes dehydration reaction to form diethylene glycol.
  • the reaction temperature is higher than 150 ° C, although the raw material still maintains 100% conversion, the reaction product is dimethyl ether, methanol, ethylene glycol, 1,4-dioxane due to the increase of the reaction of the above formula III to formula IX.
  • Table 1 when a H- ⁇ molecular sieve having a silica-alumina ratio of 16 is used as a catalyst, the selectivity of ethylene glycol dimethyl ether is 50% at the reaction temperature and reaction pressure of the present invention, and ethylene glycol is used. The selectivity is from 0.6% to 50%, and there is no formation of 1,4-dioxane at all.
  • a HY molecular sieve having a silica-alumina ratio of 10.6 was tableted at a pressure of 40 MPa, and pelletized at 20-40 mesh to obtain a standby catalyst. 1 g of this catalyst was packed into a fixed bed reactor for pretreatment.
  • the pretreatment conditions were: N 2 flow rate 30 ml/min, rising from 25 ° C to 150 ° C over 150 min, and maintaining at 500 ° C for 180 min.
  • the starting material glycol monomethyl ether under conditions of a bath temperature of 60 °C, 2 in / min flow rate into 30ml of N into the reactor, the reaction pressure 0.5Mpa.
  • Reaction conditions a reaction pressure of 0.5 MPa, a catalyst mass of 1 g, a water bath temperature of 60 ° C, and a N 2 flow rate of 30 ml/min.
  • ethylene glycol can be dehydrated with the reaction raw material ethylene glycol monomethyl ether to form diethylene glycol monomethyl ether, or ethylene glycol itself dehydration reaction to form diethylene glycol, so The selectivity of ethylene glycol monomethyl ether and diethylene glycol is increased in the product.
  • the reaction temperature is higher than 170 ° C, although the conversion of the raw material is increased, for example, at 200 ° C, the conversion of the raw material can reach 80%, but the selectivity of ethylene glycol dimethyl ether in the product is drastically lowered, dimethyl ether and 1
  • the selectivity of 4-dioxane is significantly improved.
  • H- ⁇ , HY, H-ZSM-5, H-MOR and F-FER molecular sieves with different ratios of silicon to aluminum were used to compress the tablets under the pressure of 40 Mpa, and granulated 20-40 mesh to obtain a standby catalyst.
  • 1 g of each catalyst was charged into a fixed bed reactor for pretreatment.
  • the pretreatment conditions were: N 2 flow rate 30 ml/min, rising from 25 ° C to 150 ° C over 150 min, and maintaining at 500 ° C for 180 min.
  • the reaction raw material ethylene glycol monomethyl ether was introduced into the reactor from N 2 at a flow rate of 30 ml/min at a water bath temperature of 60 °C. Airspeed, reaction pressure.
  • Reaction conditions a catalyst mass of 1 g, a water bath temperature of 60 ° C, and a N 2 flow rate of 30 ml/min.
  • 0.5 g of perfluorosulfonic acid resin (Nafion-H) was packed into a fixed bed reactor for pretreatment.
  • the pretreatment conditions were: N 2 flow rate 30 ml/min, rising from 25 ° C for 60 min to 150 ° C, and maintaining at 150 ° C for 180 min.
  • the starting material glycol monomethyl ether under conditions of a bath temperature of 60 °C, 2 in / min flow rate into 30ml of N into the reactor, the reaction pressure 0.5Mpa.
  • Table 4 Reactivity and product selectivity of the starting ethylene glycol monomethyl ether on Nafion-H catalyst under different temperature conditions (Note: This table only gives the selectivity of the main products, the data of other related products are not given) .
  • Reaction conditions a reaction pressure of 0.5 MPa, a catalyst mass of 0.5 g, a water bath temperature of 60 ° C, and a N 2 flow rate of 30 ml/min.
  • Benzenesulfonic acid, p-toluenesulfonic acid solid and perfluorosulfonic acid resin were packed into a fixed bed reactor for pretreatment.
  • the pretreatment conditions were: N 2 flow rate 30 ml/min, rising from 60 ° C to 130 ° C over 60 min, and maintaining at 150 ° C for 180 min.
  • the reaction raw material ethylene glycol monomethyl ether was introduced into the reactor from N 2 at a flow rate of 30 ml/min under a water bath temperature of 60 °C.
  • Table 5 Reactivity of raw material ethylene glycol monomethyl ether on different quality resin catalysts under different reaction temperatures and reaction pressures, and ethylene glycol dimethyl ether and 1,4-dioxane selectivity (Note: Only the selectivity of the main product is given, data for other related products are not given).
  • Reaction conditions water bath temperature 60 ° C, N 2 flow rate 30 ml / min.
  • H- ⁇ molecular sieves with a topological structure of H-BEA and a silica-alumina ratio of 16 were pressed at a pressure of 40 MPa, and granulated at 20-40 mesh to obtain a standby catalyst. 3 g of each catalyst was packed into a fixed bed reactor for pretreatment.
  • the pretreatment conditions were: N 2 flow rate 30 ml/min, rising from 25 ° C to 150 ° C over 150 min, and maintaining at 500 ° C for 180 min.
  • the reaction raw material ethylene glycol dimethyl ether was pumped into the reactor from a constant flow pump at a flow rate of 0.03 ml/min, a space velocity of 0.6 h -1 , and a reaction pressure of 0.1 Mpa.
  • reaction pressure 0.1 Mpa, space velocity 0.6 h -1 , N 2 flow rate 50 ml/min.
  • Example 6 The same catalyst as in Example 6 was used, the same pretreatment conditions, and the same injection method, the volume ratio of the raw material ethylene glycol monomethyl ether to water was 1:0.01, 1:0.1, 1:1, 1:4 and 1:10 (i.e., volumetric concentrations of water were 0.99%, 9.09%, 50.00%, 80.00%, and 90.91%, respectively), and the feed space velocity was 3.0 h -1 .
  • Table 7 Reactivity and product selectivity of raw material ethylene glycol monomethyl ether and deionized water mixed feedstock on H- ⁇ catalyst at 110 ° C (Note: This table only gives the selectivity of the main product, other related products The data is not given).
  • reaction pressure 0.1 Mpa, space velocity 3.0 h -1 , N 2 flow rate 50 ml/min.
  • reaction temperature was 110 ° C, and the addition of water in the raw material significantly lowered the selectivity of diethylene glycol and diethylene glycol dimethyl ether in the product.

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Abstract

本发明提供了一种由乙二醇单甲醚直接制备乙二醇二甲醚并联产乙二醇的方法，更具体地，使所述原料乙二醇单甲醚和任选的作为载气的惰性气体通过载有固体酸催化剂的反应器，在反应温度为40～150℃和反应压力为0.1～15.0Mpa的条件下反应，生成乙二醇二甲醚和乙二醇，其中所述原料乙二醇单甲醚质量空速为0.05～5.0h-1；所述原料乙二醇单甲醚的体积浓度为1～100％，所述载气的体积浓度0～99％。本发明方法在低温条件下，采用固体酸为催化剂，以乙二醇单甲醚为原料直接高选择性地制备得到乙二醇二甲醚和乙二醇，同时基本上或完全没有对环境造成污染且对人体或动物体造成损害的副产物1，4-二氧六环生成。

Description

由乙二醇单甲醚直接制备乙二醇二甲醚并联产乙二醇的方法 技术领域
本申请属于化学化工领域，具体而言，涉及一种由乙二醇单甲醚直接制备乙二醇二甲醚并联产乙二醇的方法。
背景技术
乙二醇二甲醚，中文名称为1，2-二甲氧基乙烷(DME)。常温下，乙二醇二甲醚是一种带有醚味的无色透明液体，是一种性能优良的非质子极性溶剂，性质相对稳定，不易发生反应，并能与水、大多数低碳(C1-C6)醇、酮、酯等有机溶剂以任意比例混溶，并对碱金属化合物有较强的溶解能力。因此，它能够成为在许多有机合成反应中所需的理想溶剂，同时它还广泛用作清洗剂复配物，用作纺织印染、油漆油墨助剂、燃料添加剂以及用于有机化合物及医药中间体的合成等。
文献中的乙二醇二甲醚的合成方法主要有：(1)US 3699174中报道的1，2-二氯乙烷与甲醇反应，分别以元素周期表中第I-V族中金属或金属氧化物以及第VI-VIII族中部分过渡金属为催化剂，主要产物为乙二醇二甲醚和甲基乙基醚，其中原料1，2-二氯乙烷转化率为50％，乙二醇二甲醚选择性为24.6％，二氯甲基乙基醚选择性为46.9％。该工艺产生的副产物较多，产物的收率不高，其中1，4-二氧六环选择性高于20％。(2)日本特许公开昭60-12089报道的二甲醚氧化偶联反应，在催化剂表面二甲醚直接氧化偶联得到乙二醇二甲醚。由于该反应中加入了氧气，并且二甲醚以及产物乙二醇二甲醚均为易燃物质，所以该工艺路线存在潜在的危险。(3)US4146736报道的二甲醚与环氧乙烷反应，采用固体酸催化剂，原料环氧乙烷转化率接近100％，产物乙二醇二甲醚选择性为65-70％左右，二乙二醇二甲醚选择性为15-20％，三、四和五乙二醇二甲醚总和选择性为10％左右，1，4-二氧六环选择性为5-7％。该反应工艺副产物较多，而且有相对较多的1，4-二氧六环生成。(4)日本特许公开昭55-104221报道了乙二醇或乙二醇单甲醚在反应温度为200～300℃时与甲醇反应脱水反应制备乙二醇二甲醚，产物中乙二醇二甲醚选择性为25％，二乙二醇二甲醚选择性 为8％，二乙二醇单甲醚选择性为15％，其过程中也有1，4-二氧六环生成。(5)US4321413报道了乙二醇单甲醚和二甲醚二者作为反应原料在反应温度为180℃时制备乙二醇二甲醚，原料乙二醇单甲醚的转化率为55.4％，产物中乙二醇二甲醚选择性为62.4％，1，4-二氧六环选择性为20％，二乙二醇二甲醚选择性为16.5％。(6)CN104250206A公开了一种乙二醇醚的制备方法，其中乙二醇和低碳脂肪醇在酸催化作用下制得乙二醇醚，所用固体酸催化剂为分子筛或沸石，反应温度为20-250℃，反应压力为0.1-10MPa。
上述已报道的由制备乙二醇二甲醚的方法中，要么以多种反应物为原料，涉及复杂的反应过程和复杂的副产物，要么反应条件苛刻例如反应温度高，并且这些方法中均存在副产物1，4-二氧六环。然而，当该副产物溶于废水中时，很难用物理分离的方法除去，并且该副产物在自然环境中不易被生物降解，同时可以通过吸入、食入或经皮肤吸收进入人体或动物体内，其在体内逐步累积并且无法代谢出体外，从而对人体或动物体造成伤害。
发明内容
为了克服上述现有技术的问题之一或全部，本发明的目的在于提供一种反应原料简单且以较高选择性直接制备乙二醇二甲醚并联产乙二醇的方法，同时该方法基本上或完全没有对环境造成污染且对人体或动物体造成损害的副产物1，4-二氧六环生成。
为此，本发明提供了一种由乙二醇单甲醚直接制备乙二醇二甲醚并联产乙二醇的方法，所述方法包括：使所述原料乙二醇单甲醚和任选的作为载气的惰性气体通过载有固体酸催化剂的反应器，在反应温度为40～150℃和反应压力为0.1～15.0Mpa下，任选地在体积浓度为0～95％的水存在下反应，生成乙二醇二甲醚和乙二醇，其中所述原料乙二醇单甲醚的质量空速为0.05～5.0h-1；所述原料乙二醇单甲醚的体积浓度为1～100％，所述载气的体积浓度0～99％。
在优选实施方案中，所述水是通过加入到所述原料乙二醇单甲醚中而引入的。
在优选实施方案中，所述固体酸催化剂为酸性分子筛催化剂或酸性树脂催化剂；优选地所述酸性分子筛催化剂的结构类型为MWW、FER、MFI、MOR、FAU或BEA。
在优选实施方案中，所述酸性分子筛催化剂为MCM-22分子筛、镁碱沸石分子筛、ZSM-5分子筛、丝光沸石分子筛、Y沸石分子筛或β分子筛中的一种或多种。
在优选实施方案中，所述MCM-22分子筛中的硅铝原子比Si/Al＝5～100；所述镁碱沸石分子筛中的硅铝原子比Si/Al＝5～100；所述ZSM-5分子筛中的硅铝原子比Si/Al＝5～100；所述丝光沸石分子筛中的硅铝原子比Si/Al＝5～50；所述Y沸石分子筛中的硅铝原子比Si/Al＝3～50；并且所述β分子筛中的硅铝原子比Si/Al＝5～100。
在优选实施方案中，所述酸性分子筛中含有质量分数为0.1～10％，优选0.1～4％的碱金属、碱土金属或稀土金属中的一种或多种；并且所述酸性分子筛中含有质量分数为1～40％的粘结剂，所述粘结剂是氧化铝和氧化硅中的一种或多种。
在优选实施方案中，所述酸性树脂催化剂是苯磺酸树脂、对甲基苯磺酸树脂、全氟磺酸树脂或强酸性阳离子交换树脂中的一种或多种；优选为全氟磺酸Nafion树脂。
在优选实施方案中，所述反应温度为50～150℃，反应压力为3.0～8.0MPa，并且所述原料乙二醇单甲醚的质量空速为0.3～2.0h-1。
在优选实施方案中，所述惰性气体为选自氮气、氦气和氩气中的一种或多种，并且所述载气的体积浓度1～99％。
在优选实施方案中，所述反应器为固定床反应器或釜式反应器。
本发明方法在低温条件下，采用固体酸为催化剂，以乙二醇单甲醚为原料直接高选择性地制备得到乙二醇二甲醚和乙二醇，产物简单，副反应较少，所需产物乙二醇二甲醚和乙二醇的选择性可分别达到其理论值50％；同时本发明的方法基本上或完全没有对环境造成污染且对人体或动物体造成损害的副产物1，4-二氧六环生成。
具体实施方式
本申请提供了一种在固体酸催化剂表面，在低温条件下，由乙二醇单甲醚直接且高效地制备乙二醇二甲醚并联产乙二醇的方法。更具体地，在本发明方法中，使所述原料乙二醇单甲醚和任选的作为载气的惰性气体通过载有固体酸催化剂的反应器，在反应温度为40～150℃和反应压力为0.1～15.0Mpa下任选地在体积浓度为0～95％的水存在下反应，生成乙二醇二甲醚和乙二醇，其中所述原料乙二醇单甲醚的质量空速为0.05～5.0h-1；所述原料乙二醇单甲醚的体积浓度为1～100％，所述载气的体积浓度0～99％。
在本发明中，除非另有指明，所体积的原料乙二醇单甲醚、载气和水的体积浓度都是基于当在反应体系中存在时，它们的总体积。例如，当反应体系中仅存在原料乙二醇单甲醚时，其体积浓度应为100％；而当反应体系中仅存在原料乙二醇单甲醚和载气时，原料乙二醇单甲醚和载气各自的体积浓度为基于它们二者的总体积；而当反应体系中存在原料乙二醇单甲醚、载气和水三者时，它们的体积浓度为基于它们三者的总体积。
在本发明中，原料乙二醇单甲醚的进料方式可以为如下：
第一种方式是，在没有载气存在下，通过进料泵例如恒流泵将液态原料乙二醇单甲醚以一定流速例如0.1-10ml/min直接泵入到反应器例如固定床反应器中而实现进料。
第二种方式是，在有载气存在下，由作为载气的惰性气体例如N2，在不同的水浴温度(40-80℃)条件下携带乙二醇单甲醚的饱和蒸气进入到固定床反应器中。优选地，载气的流速为10～50mL/min。通过饱和蒸气压和N2流速可以计算出单位时间里进入到反应器中原料乙二醇单甲醚物质的量。不同温度条件下原料乙二醇二甲醚的饱和蒸气压的计算方法如下所示，
ln(p1 */p2 *)＝-ΔVapHm/8.3145×(1/T1-1/T2)
其中p1 *和P2 *分别代表不同温度条件下原料乙二醇单甲醚的饱和蒸气压；ΔVapHm表示乙二醇单甲醚的摩尔蒸发焓(为39.48KJ/mol)；T1和T2分别表示不同的温度(单位K)；253K时其饱和蒸气压为3.968Kpa，这样就可以计算任意温度下乙二醇单甲醚的饱和蒸气压。
优选地，本发明中使用的固体酸催化剂为酸性分子筛催化剂或酸性树脂催化剂；更优选地，所述酸性分子筛催化剂的结构类型为MWW、FER、MFI、MOR、FAU或BEA。
进一步优选地，本发明中使用的酸性分子筛催化剂为MCM-22分子筛、镁碱沸石分子筛、ZSM-5分子筛、丝光沸石分子筛、Y沸石分子筛或β分子筛中的一种或多种；
优选地，在本发明中，所述MCM-22分子筛中的硅铝原子比Si/Al＝5～100；所述镁碱沸石分子筛中的硅铝原子比Si/Al＝5～100；所述ZSM-5分子筛中的硅铝原子比Si/Al＝5～100；所述丝光沸石分子筛中的硅铝原子比Si/Al＝5～50；所述Y分子筛中的硅铝原子比Si/Al＝3～50；所述β分子筛中的硅铝原子比Si/Al＝5～100。
优选地，在本发明中，所述酸性树脂催化剂含有磺酸官能团的各种树脂，如苯磺酸、对甲基苯磺酸、全氟磺酸树脂，优选全氟磺酸Nafion树脂，或强酸性阳离子交换树脂中的一种或多种；
优选地，在本发明中，反应温度为50～150℃，更优选80～150℃，反应压力为3～8MPa，原料乙二醇单甲醚的质量空速为0.3～2.0h-1；
优选地，在本发明中，所述载气为选自氮气、氦气和氩气中的一种或任意几种的混合气；更优选地，所述载气的质量空速为50.0～12000.0h-1，进一步优选为600.0～5000.0h-1；
优选地，在本发明中，所述反应器是可实现连续反应的固定床反应器，或者釜式反应器，优选固定床反应器。
不受限于任何理论，在本发明的反应中，原料乙二醇单甲醚在催化剂表面可能发生的化学反应如下式I-IX所示：
Figure PCTCN2015097160-appb-000001
具体地，在较低的反应温度条件下，如式I所示，大量原料乙二醇单甲醚发生自身的歧化反应，生成乙二醇二甲醚和乙二醇；同时如式II所示，原料乙二醇单甲醚又可能发生分子间的脱水反应，生成摩尔比为1∶1的二乙二醇二甲醚和水。
随着反应温度的逐渐升高，如式III和式IV所示，生成的乙二醇与原料乙二醇单甲醚发生分子间脱水反应，生成二乙二醇单甲醚；同时少量的乙二醇能够发生自身脱水反应生成二甘醇。进一步地，如式V所示，生成的二乙二醇二甲醚与原料乙二醇单甲醚发生醚交换反应，生成二乙二醇单甲醚和乙二醇二甲醚。而如式VI所示，生成的二乙二醇单甲醚又能够 发生自身歧化反应，生成二乙二醇二甲醚和二甘醇。
而当反应温度进一步升高时，如式VII-IX所示的，生成的二乙二醇二甲醚、二乙二醇单甲醚、二甘醇发生分子内脱水生成1，4-二氧六环，导致副产物1，4-二氧六环的选择性大幅上升。
因此，从以上反应过程可以看出，由原料乙二醇单甲醚可能得到的反应产物为：乙二醇二甲醚和乙二醇，二乙二醇单甲醚，水，二乙二醇二甲醚，二甘醇以及1，4-二氧六环，还有极少量的甲醇和二甲醚。
对于本发明而言，理想的是，仅发生式I所示的反应，即仅生成产物乙二醇二甲醚和乙二醇。为此，本发明的发明人经过深入研究发现，将温度控制在40～150℃对于仅发生式I和式II所示的反应是非常关键的，因为当温度低于40℃时，反应不能发生或反应速率很低，所需产物的收率较低；而当温度高于150℃时，发生式III至式VII所示的反应增加，导致副产物增多，尤其是会产生大量的副产物1，4-二氧六环。另一方面，为了减少式II所示反应的发生，从反应平衡可以看出，在本发明的反应体系中水的存在可以是优选的，因为由于水是式II的反应产物，在预先存在水的情况下，式II的反应会被抑制或较少发生。所述水可以是通过加入到原料乙二醇单甲醚中引入的，或者是载气带入的，也或者是反应器中本身存在的。
在本发明中，产物是通过气相色谱法分析进行检测和确定的。因此，如本文中使用的，“基本上或完全没有”1，4-二氧六环表示通过上述气相色谱法，1，4-二氧六环是以不可检测到的量存在的。
实施例
下面结合具体的实施例，进一步阐述本发明。应理解，这些实施例仅用于举例说明本发明而不用于限制本发明的范围。
如无特殊说明，本申请的实施例中的原料和催化剂均通过商业途径购买并直接使用。
实施例中的分析方法如下：
原料及产物均由配有50米HP-FFAP毛细管柱气相色谱Agilent 7890A检测。
在本发明的实施例和比较例中，反应条件如下：
反应器选用固定床反应器，催化剂填充质量为1-10g，反应温度为40-250℃(其中高于150℃的温度作为本发明的比较例)，反应压力0.1-10Mpa；原料乙二醇单甲醚采用两种进样方式进入反应器：
实施例1
将Si/Al＝16的H-β分子筛在40Mpa压力下压片，并造粒20-40目，得到备用催化剂。将1g该催化剂填充到固定床反应器中，进行前处理。催化剂前处理条件为：N2流速30ml/min，从25℃开始经150min升至500℃，并在500℃条件下保持180min。
将反应原料乙二醇单甲醚在水浴温度60℃条件下，由N2以30ml/min流速带入到反应器中，反应压力0.5Mpa。
原料转化率以及产物选择性随温度变化如表1所示。
表1：不同温度条件下原料乙二醇单甲醚在H-β分子筛催化剂上反应活性及产物选择性
Figure PCTCN2015097160-appb-000002
反应条件：反应压力0.5Mpa，催化剂质量1g，水浴温度60℃，N2流速30ml/min。
从表1中可以看到，当使用硅铝比为16的H-β分子筛作为催化剂时，随着反应温度从40℃升高到150℃时，原料乙二醇单甲醚的转化率逐渐增 大，当反应温度达到150℃时，原料转化率可达到100％；并且当反应温度低于150℃时，产物中完全没有1，4-二氧六环生成。在较低的反应温度50-80℃区间时，原料主要发生自身的歧化反应，生成乙二醇二甲醚和乙二醇，当反应温度在90-150℃区间时，乙二醇可以和反应原料乙二醇单甲醚发生脱水反应，生成二乙二醇单甲醚，或者乙二醇自身发生脱水反应生成二甘醇。当反应温度高于150℃时，虽然原料仍保持100％转化，但是由于前述式III至式IX的反应增加，反应产物为二甲醚、甲醇、乙二醇、1，4-二氧六环、二甘醇、二乙二醇二甲醚、二乙二醇单甲醚，其中由于二乙二醇单甲醚和二甘醇分别发生分子内脱水反应，生成1，4-二氧六环，导致1，4-二氧六环的选择性直线上升。从表1中可以看到，使用硅铝比为16的H-β分子筛作为催化剂时，在本发明的反应温度和反应压力下乙二醇二甲醚的选择性为50％，乙二醇的选择性为0.6％-50％，而完全没有1，4-二氧六环的生成。
实施例2
将硅铝比为10.6的H-Y分子筛在40Mpa压力下压片，并造粒20-40目，得到备用催化剂。将1g该催化剂填充到固定床反应器中，进行前处理。前处理条件为：N2流速30ml/min，从25℃开始经150min升至500℃，并在500℃条件下保持180min。
将反应原料乙二醇单甲醚在水浴温度60℃条件下，由N2以30ml/min流速带入到反应器中，反应压力0.5Mpa。
原料转化率以及产物选择性随温度变化如表2所示。
表2：不同温度条件下原料乙二醇单甲醚在H-Y催化剂上反应活性及产物选择性
Figure PCTCN2015097160-appb-000003
反应条件：反应压力0.5Mpa，催化剂质量1g，水浴温度60℃，N2流速30ml/min。
从表2中可以看到，当使用硅铝比为10.6的H-Y分子筛作为催化剂时，当反应温度低于150℃时，原料乙二醇单甲醚转化率低于10％，主要产物为乙二醇二甲醚和乙二醇，说明在较低的反应温度80-120℃之间时，原料主要发生自身的歧化反应。当反应温度为120-150℃时，乙二醇可以和反应原料乙二醇单甲醚发生脱水反应，生成二乙二醇单甲醚，或者乙二醇自身发生脱水反应生成二甘醇，所以产物中乙二醇单甲醚和二甘醇选择性增加。然而，当反应温度高于170℃时，虽然原料转化率提高，例如在200℃时，原料转化率可以达到80％，但产物中乙二醇二甲醚选择性急剧降低，二甲醚和1，4-二氧六环选择性显著提高。反应温度为230℃时，二甲醚选择性为18％，1，4-二氧六环选择性为65％。从表2中可以看到，使用硅铝比为10.6的H-Y分子筛作为催化剂时，在本发明的反应温度和反应压力下乙二醇二甲醚的选择性为50％，乙二醇的选择性为22％-48％，而完全没有1，4-二氧六环的生成。
实施例3
选用不同硅铝比的H-β、H-Y、H-ZSM-5、H-MOR、F-FER分子筛在40Mpa压力下压片，并造粒20-40目，得到备用催化剂。选取1g各催化剂填充到固定床反应器中，进行前处理。前处理条件为：N2流速30ml/min，从25℃开始经150min升至500℃，并在500℃条件下保持180min。反应 原料乙二醇单甲醚在水浴温度60℃条件下，由N2以30ml/min流速带入到反应器中。空速，反应压力。
原料转化率以及产物乙二醇二甲醚和1，4-二氧六环选择性随温度和压力变化如表3所示。
表3：不同反应温度和压力条件下乙二醇单甲醚在具有不同拓扑结构和硅铝比的催化剂上反应活性及乙二醇二甲醚和1，4-二氧六环选择性(注：该表仅给出主要产物的选择性，其他相关产物的数据未给出)。
Figure PCTCN2015097160-appb-000004
反应条件：催化剂质量1g，水浴温度60℃，N2流速30ml/min。
从表3中可以看到，具有不同硅铝比的H-β、H-Y、H-ZSM-5、H-MOR、F-FER分子筛在本发明的反应温度和反应压力下都具有催化活性，且无1，4-二氧六环生成。
实施例4
将0.5g全氟磺酸树脂(Nafion-H)填充到固定床反应器中，进行前处理。前处理条件为：N2流速30ml/min，从25℃开始经60min升至150℃，在150℃条件下保持180min。
将反应原料乙二醇单甲醚在水浴温度60℃条件下，由N2以30ml/min流速带入到反应器中，反应压力0.5Mpa。
原料转化率以及产物选择性随温度变化如表4所示。
表4：不同温度条件下原料乙二醇单甲醚在Nafion-H催化剂上的反应活性及产物选择性(注：该表仅给出主要产物的选择性，其他相关产物的数据未给出)。
Figure PCTCN2015097160-appb-000005
反应条件：反应压力0.5Mpa，催化剂质量0.5g，水浴温度60℃，N2流速30ml/min。
从表4中可以看到，使用全氟磺酸树脂(Nafion-H)为催化剂，当反应温度低于80℃时，原料乙二醇单甲醚反应性较低。当反应温度在100～150℃区间逐渐升高时，乙二醇单甲醚主要发生自身的脱水反应，生成二乙二醇二甲醚，二乙二醇二甲醚和乙二醇单甲醚发生醚交换反应，生成乙二醇二甲醚和二乙二醇单甲醚，但仍然没有1，4-二氧六环生成。
实施例5
将不同质量的苯磺酸、对甲基苯磺酸固体和全氟磺酸树脂(Nafion-H)填充到固定床反应器中，进行前处理。前处理条件为：N2流速30ml/min，从60℃开始经60min升至130℃，在150℃条件下保持180min。
将反应原料乙二醇单甲醚在水浴温度60℃条件下，由N2以30ml/min流速带入到反应器中。
原料转化率以及产物选择性随反应温度和反应压力变化如表5所示。
表5：不同反应温度、反应压力条件下原料乙二醇单甲醚在不同质量的树脂催化剂上反应活性及乙二醇二甲醚和1，4-二氧六环选择性(注：该表仅给出主要产物的选择性，其他相关产物的数据未给出)。
Figure PCTCN2015097160-appb-000006
反应条件：水浴温度60℃，N2流速30ml/min。
从表5中可以看到，使用全氟磺酸树脂、苯磺酸以及对甲基苯磺酸作为催化剂时，在本发明的反应温度和反应压力下乙二醇二甲醚的选择性为16％-46％，乙二醇的选择性为2.5％左右，完全没有1，4-二氧六环的生成。
实施例6
选用拓扑结构为H-BEA、硅铝比为16的H-β分子筛在40Mpa压力下压片，并造粒20-40目，得到备用催化剂。将3g各个催化剂填充到固定床反应器中，进行前处理。前处理条件为：N2流速30ml/min，从25℃开始经150min升至500℃，并在500℃条件下保持180min。
将反应原料乙二醇二甲醚由微量恒流泵泵入反应器，流速为 0.03ml/min，空速0.6h-1，反应压力0.1Mpa。
原料转化率以及产物选择性随温度变化如表6所示。
表6：不同温度条件下原料乙二醇单甲醚在H-β催化剂上反应活性及产物选择性(注：该表仅给出主要产物的选择性，其他相关产物的数据未给出)。
Figure PCTCN2015097160-appb-000007
反应条件：反应压力0.1Mpa，空速0.6h-1，N2流速50ml/min。
从表6中可以看到，当反应温度为110℃～150℃时，产物中完全没有1，4-二氧六环生成。并且随着反应温度的提高，原料转化率明显提高，当反应温度为150℃时，原料转化率可以达到49％，产物中乙二醇二甲醚选择性为52％。而当温度升高至180℃时，尽管原料转化率进一步增大，但是产物中1，4-二氧六环的选择性也显著增大。
实施例7
选用实施例6中同样的催化剂，同样的前处理条件，同样的进样方式，原料乙二醇单甲醚与水的体积比为1∶0.01、1∶0.1、1∶1、1∶4和1∶10(即，水的体积浓度分别为0.99％，9.09％，50.00％，80.00％和90.91％)，进料空速为3.0h-1。
原料转化率以及产物选择性随温度变化如表7所示。
表7：在110℃下原料乙二醇单甲醚与去离子水混合原料在H-β催化剂上的反应活性及产物选择性(注：该表仅给出主要产物的选择性，其他相关产物的数据未给出)。
Figure PCTCN2015097160-appb-000008
反应条件：反应压力0.1Mpa，空速3.0h-1，N2流速50ml/min。
从表7中可以看到，反应温度为110℃，原料中水的加入显著地降低了产物中二甘醇和二乙二醇二甲醚的选择性。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (10)

  1. 一种由乙二醇单甲醚直接制备乙二醇二甲醚并联产乙二醇的方法，所述方法包括：使所述原料乙二醇单甲醚和任选的作为载气的惰性气体通过载有固体酸催化剂的反应器，在反应温度为40～150℃和反应压力为0.1～15.0Mpa下，任选地在体积浓度为0～95％的水存在下反应，生成乙二醇二甲醚和乙二醇，其中所述原料乙二醇单甲醚的质量空速为0.05～5.0h-1；所述原料乙二醇单甲醚的体积浓度为1～100％，所述载气的体积浓度0～99％。
  2. 根据权利要求1所述的方法，其特征在于，所述水是通过添加在所述原料乙二醇单甲醚中而引入的。
  3. 根据权利要求1所述的方法，其特征在于，所述固体酸催化剂为酸性分子筛催化剂或酸性树脂催化剂；优选地所述酸性分子筛催化剂的结构类型为MWW、FER、MFI、MOR、FAU或BEA。
  4. 根据权利要求3所述的方法，其特征在于，所述酸性分子筛催化剂为MCM-22分子筛、镁碱沸石分子筛、ZSM-5分子筛、丝光沸石分子筛、Y沸石分子筛或β分子筛中的一种或多种。
  5. 根据权利要求4所述的方法，其特征在于，
    所述MCM-22分子筛中的硅铝原子比Si/Al＝5～100；
    所述镁碱沸石分子筛中的硅铝原子比Si/Al＝5～100；
    所述ZSM-5分子筛中的硅铝原子比Si/Al＝5～100；
    所述丝光沸石分子筛中的硅铝原子比Si/Al＝5～50；
    所述Y沸石分子筛中的硅铝原子比Si/Al＝3～50；并且
    所述β分子筛中的硅铝原子比Si/Al＝5～100。
  6. 根据权利要求3所述的方法，其特征在于，所述酸性分子筛中含有质量分数为0.1～10％，优选0.1～4％的碱金属、碱土金属或稀土金属中的一种或多种；并且所述酸性分子筛中含有质量分数为1～40％的粘结剂，所述粘结剂是氧化铝和氧化硅中的一种或多种。
  7. 根据权利要求3所述的方法，其特征在于，所述酸性树脂催化剂是苯磺酸树脂、对甲基苯磺酸树脂、全氟磺酸树脂或强酸性阳离子交换树 脂中的一种或多种；优选为全氟磺酸Nafion树脂。
  8. 根据权利要求1所述的方法，其特征在于，所述反应温度为50～150℃，反应压力为3.0～8.0MPa，并且所述原料乙二醇单甲醚的质量空速为0.3～2.0h-1。
  9. 根据权利要求1所述的方法，其特征在于，所述惰性气体为选自氮气、氦气和氩气中的一种或多种，并且所述载气的体积浓度1～99％。
  10. 根据权利要求1所述的方法，其特征在于，所述反应器为固定床反应器或釜式反应器。
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