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WO2016101104A1 - 一种制备双封端乙二醇醚的方法 - Google Patents

一种制备双封端乙二醇醚的方法 Download PDF

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Publication number
WO2016101104A1
WO2016101104A1 PCT/CN2014/094535 CN2014094535W WO2016101104A1 WO 2016101104 A1 WO2016101104 A1 WO 2016101104A1 CN 2014094535 W CN2014094535 W CN 2014094535W WO 2016101104 A1 WO2016101104 A1 WO 2016101104A1
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WO
WIPO (PCT)
Prior art keywords
ethylene glycol
raw material
glycol monoether
ether
alcohol ether
Prior art date
Application number
PCT/CN2014/094535
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English (en)
French (fr)
Inventor
倪友明
朱文良
刘红超
刘勇
刘中民
李利娜
刘世平
周慧
Original Assignee
中国科学院大连化学物理研究所
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Filing date
Publication date
Priority to US15/537,928 priority Critical patent/US10040739B2/en
Priority to EA201791358A priority patent/EA031545B1/ru
Priority to JP2017533195A priority patent/JP6450847B2/ja
Priority to BR112017013558-2A priority patent/BR112017013558A2/zh
Priority to KR1020177020165A priority patent/KR101961055B1/ko
Priority to AU2014415514A priority patent/AU2014415514B2/en
Application filed by 中国科学院大连化学物理研究所 filed Critical 中国科学院大连化学物理研究所
Priority to EP14908675.3A priority patent/EP3239124B1/en
Priority to MYPI2017702258A priority patent/MY172782A/en
Priority to PCT/CN2014/094535 priority patent/WO2016101104A1/zh
Priority to SG11201705071SA priority patent/SG11201705071SA/en
Publication of WO2016101104A1 publication Critical patent/WO2016101104A1/zh
Priority to ZA2017/04703A priority patent/ZA201704703B/en

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Classifications

    • 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
    • B01J29/7007—Zeolite Beta
    • 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
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/10—Saturated ethers of polyhydroxy compounds
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present application belongs to the field of chemistry and chemical industry, and in particular to a method for preparing a double-capped glycol ether.
  • the double-capping glycol ether refers to a glycol ether obtained by substituting a hydrogen on both hydroxyl groups of the ethylene glycol with a hydrocarbon group.
  • Double-terminated glycol ether has no active hydrogen, strong chemical stability, low pour point, small change in viscosity temperature, good heat resistance, enhanced acid-base stability, good emulsifying ability, low foaming and good lipophilicity, and anti-coking property. Good, with low viscosity and density. Therefore, double-terminated polyethylene glycol ethers have a wide range of applications in high-speed spinning oils, low-foaming detergents, food processing and bio-fermentation.
  • the preparation of the double-capping glycol ether mainly includes a halogenated hydrocarbon and sodium alkoxide (Williamson synthesis) method and a direct etherification method, wherein the Williamson synthesis method refers to a reaction between a halogenated hydrocarbon and sodium alkoxide under anhydrous conditions to form an ether.
  • the pollution is serious, the operation is dangerous, and the economy is low;
  • the direct etherification method refers to a method of directly etherifying ethylene glycol or ethylene glycol monoether with monohydric or monohydric alcohol ether.
  • ethylene glycol monomethyl ether and dimethyl ether can be used to prepare ethylene glycol dimethyl ether (US 4321413) by using anion exchange resin as a catalyst; ethylene glycol and methanol are prepared by using perfluorosulfonic acid resin as a catalyst to prepare ethylene glycol dimethyl ether. (US2004/0044253).
  • the catalysts used in these methods have low yield, selectivity and longevity, and the resin catalyst is difficult to regenerate, and a large amount of 1,4-dioxane and high-boiling polyglycol double-terminated ether are also easily formed. by-product.
  • a process for preparing a double-capping glycol ether which has a long single-pass catalyst and can be repeatedly regenerated, has high yield and selectivity of a target product, and has low energy consumption for separation of products.
  • the reaction temperature is 50 to 300 ° C, and the reaction pressure is 0.1 to 15 MPa;
  • the mass space velocity of the ethylene glycol monoether in the raw material is 0.01 to 15.0 h-1;
  • the double-capping glycol ether refers to a glycol ether obtained by substituting hydrogen in both hydroxyl groups of ethylene glycol with a hydrocarbon group.
  • the ethylene glycol monoether is selected from at least one of the compounds having the structural formula of formula I:
  • the monohydric alcohol ether is selected from at least one of the compounds having the structural formula shown in Formula II:
  • the double-capping glycol ether is selected from at least one of the compounds having the structural formula shown in Formula III:
  • R 1 is one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms
  • R 2 is one selected from the group consisting of alkyl groups having 1 to 20 carbon atoms. Wherein R 1 and R 2 may be the same or different.
  • the alkyl group having 1 to 20 carbon atoms refers to a group formed by losing any one hydrogen atom on any linear alkane, branched alkane or cycloalkane molecule having 1 to 20 carbon atoms.
  • reaction equation for the preparation of the double-capped glycol ether of the present application is as follows:
  • R 1 and R 2 of the ethylene glycol monoether and the monohydric alcohol ether are any carbon atoms in the raw material can realize the reaction for preparing the double-capping glycol ether in the reaction system.
  • One skilled in the art can select the type of starting material having the corresponding substituents R 1 , R 2 depending on the type of product double-capping glycol ether.
  • R 1 and R 2 are independently selected from alkyl groups having a carbon number of not more than 10.
  • R 1 and R 2 are independently selected from an alkyl group having a carbon number of not more than 5.
  • R 1 and R 2 are independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl.
  • the R 1 is selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl.
  • the R 2 is selected from one of methyl, ethyl, n-propyl, isopropyl, n-butyl.
  • the acidic molecule is screened from one or more of the molecular sieves of the structural type MWW, FER, MFI, MOR, FAU, BEA. Further preferably, the acidic molecule is selected from one or more of a hydrogen type MCM-22 molecular sieve, a hydrogen type ferrierite, a hydrogen type ZSM-5 molecular sieve, a hydrogen type mordenite, a hydrogen type Y zeolite, and a hydrogen type Beta molecular sieve.
  • a hydrogen type MCM-22 molecular sieve a hydrogen type ferrierite, a hydrogen type ZSM-5 molecular sieve, a hydrogen type mordenite, a hydrogen type Y zeolite, and a hydrogen type Beta molecular sieve.
  • the upper limit of the reaction temperature range is selected from the group consisting of 200 ° C, 250 ° C, and 300 ° C, and the lower limit is selected from the group consisting of 50 ° C, 90 ° C, and 100 ° C. Further preferably, the reaction temperature is from 100 to 200 °C.
  • the upper limit of the reaction pressure range is selected from the group consisting of 8 MPa, 10 MPa, and 15 MPa
  • the lower limit is selected from the group consisting of 0.1 MPa, 0.9 MPa, 2 MPa, 3.5 MPa, and 4 MPa.
  • the reaction pressure is 3.5 to 8 MPa.
  • the upper limit of the mass space velocity of the ethylene glycol monoether in the raw material is selected from the group consisting of 5.0h -1 , 10h -1 , 15h -1 , and the lower limit is 0.01h -1 , 0.5h -1 , 1.5h -1 .
  • the mass space velocity of the ethylene glycol monoether in the raw material is from 0.5 to 5.0 h -1 .
  • the molar ratio of the monohydric alcohol ether to the ethylene glycol monoether in the raw material is selected from 4:1, 5:1, 15:1, 25:1. 50:1, 100:1, the lower limit is selected from 1:1 and 2:1.
  • the reaction system in the present application may introduce a carrier gas without introducing a carrier gas.
  • the introduction of a carrier gas into the reaction system can buffer the temperature fluctuation of the catalyst bed caused by the thermal effect of the reaction system, maintain a more uniform temperature gradient, and is advantageous for improving reaction stability and catalyst life.
  • the raw material contains a carrier gas selected from one or more of nitrogen, helium and argon.
  • the carrier gas volume space velocity is 0 to 10000 h -1 . Further preferably, the carrier gas volume space velocity is 100 to 2000 h -1 .
  • the reactor is one or more fixed bed reactors. Take the form of continuous reaction.
  • the fixed bed reactor may be one or plural. When multiple fixed bed reactors are employed, the reactors may be in series, in parallel, or in a combination of series and parallel.
  • the method provided by the present application adopts an acidic molecular sieve catalyst, and has the advantages of long single life and re-use after repeated regeneration.
  • the method provided by the present application has a significant increase in the yield and selectivity of the target product.
  • the method provided in the present application has no water formation in the product, which greatly simplifies the rectification and purification process of the product and saves energy consumption.
  • the by-products are mainly double-terminated diethylene glycol ether, diethylene glycol monoether and ethylene glycol with very high economic value, and low economic value of 1,4-dioxane There are few by-products and high economical efficiency.
  • the method provided by this application has a large investment scale and can be applied to small-scale production of small and medium-sized enterprises for small-scale production and flexible application.
  • Ethylene glycol monoether conversion [(ethylene glycol monoether mass in feed) - (mass of ethylene glycol monoether in discharge)] ⁇ (mass of ethylene glycol monoether in feed) ⁇ (100%)
  • Double-terminated glycol ether selectivity (quality of double-terminated glycol ether in discharge) ⁇ [(in the discharge) There is the mass of ethylene glycol derivative) - (the mass of unreacted ethylene glycol monoether in the discharge)] ⁇ (100%)
  • By-product selectivity (mass of by-products in discharge) ⁇ [(mass of all ethylene glycol derivatives in the discharge) - (mass of unreacted ethylene glycol monoether in the discharge)] ⁇ (100%)
  • ethylene glycol derivatives are those containing a structure containing -O-CH 2 -CH 2 -O- in the formula, mainly including a double-terminated glycol ether, 1,4-dioxane, and unreacted Ethylene glycol monoether, double-terminated diethylene glycol ether, diethylene glycol monoether, and ethylene glycol.
  • Comparative Example 1 The catalyst in Comparative Example 1 was replaced with a sulfonated styrene-divinylbenzene copolymer (Amberlyst-15) resin purchased from Rohm and Haas Company. The remaining experimental steps were identical to Comparative Example 1, and the reaction conditions and results are shown in the table. 2.
  • Amberlyst-15 sulfonated styrene-divinylbenzene copolymer
  • Comparative Example 1 The catalyst in Comparative Example 1 was replaced with a sulfonated styrene-divinylbenzene copolymer strong acid cation exchange resin (D005) purchased from Dandong Mingzhu Specialty Resin Co., Ltd., and the remaining experimental steps were the same as in Comparative Example 1, the reaction conditions and The results are shown in Table 2.
  • D005 sulfonated styrene-divinylbenzene copolymer strong acid cation exchange resin
  • Comparative Example 2 The catalyst in Comparative Example 2 was replaced with a sulfonated styrene-divinylbenzene copolymer strong acid cation exchange resin (D005) purchased from Dandong Mingzhu Specialty Resin Co., Ltd., and the remaining experimental steps were the same as in Comparative Example 2, and the reaction conditions and The results are shown in Table 2.
  • D005 sulfonated styrene-divinylbenzene copolymer strong acid cation exchange resin

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

本申请公开了一种制备双封端乙二醇醚的方法，将含有乙二醇单醚与一元醇醚的原料通入反应器与酸性分子筛催化剂接触并反应，生产双封端乙二醇醚；反应温度为50～300℃，反应压力为0.1～15MPa；原料中乙二醇单醚的质量空速为0.01～15.0h-1；原料中一元醇醚与乙二醇单醚的摩尔比为一元醇醚：乙二醇单醚＝1～100:1。本申请的方法具有催化剂单程寿命长且可以反复再生、目标产物的收率及选择性高、产物的分离能耗低、副产物经济价值高、生产规模大小均可、应用灵活的优势。

Description

一种制备双封端乙二醇醚的方法 技术领域
本申请属于化学化工领域，具体而言，涉及一种双封端乙二醇醚的制备方法。
背景技术
双封端乙二醇醚指乙二醇两个端羟基上的氢被烃基取代所得的乙二醇醚。双封端乙二醇醚没有活泼氢，化学稳定性强，流动点低、黏温变化小、耐热性好、酸碱稳定性增强、乳化能力好、泡沫低亲油性强、抗结焦性较好、有较低的黏度和密度等。因此，双封端聚乙二醇醚在高速纺丝油剂、低泡洗涤剂、食品加工和生物发酵等领域有着广泛的应用。
双封端乙二醇醚的制备主要有卤代烃与醇钠(Williamson合成)法和直接醚化法，其中Williamson合成法是指卤代烃与醇钠在无水条件下反应生成醚，其污染严重、操作危险、经济性较低；直接醚化法是指用乙二醇或乙二醇单醚与一元醇或一元醇醚直接醚化的方法。如乙二醇单甲醚与二甲醚利用阴离子交换树脂作为催化剂可以制备乙二醇二甲醚(US 4321413)；乙二醇与甲醇利用全氟磺酸树脂作为催化剂制备乙二醇二甲醚(US2004/0044253)。这些方法采用的催化剂的收率、选择性和寿命均不高，且树脂催化剂难以再生，同时也容易形成大量的1,4-二氧六环和高沸点的多乙二醇双封端醚等副产物。
发明内容
根据本申请的一个方面，提供了一种制备双封端乙二醇醚的方法，该方法具有催化剂单程寿命长且可以反复再生、目标产物的收率及选择性高、产物的分离能耗低、副产物经济价值高、生产规模大小均可、应用灵活的优势。
所述制备双封端乙二醇醚的方法，其特征在于，将含有乙二醇单醚与一元醇醚的原料通入反应器与含有酸性分子筛的催化剂接触并反应，生产双封端乙二醇醚；
反应温度为50～300℃，反应压力为0.1～15MPa；
所述原料中乙二醇单醚的质量空速为0.01～15.0h-1；
所述原料中一元醇醚与乙二醇单醚的摩尔比为一元醇醚：乙二醇单醚＝1～100:1。
本申请中，双封端乙二醇醚是指乙二醇两个羟基上的氢都被烃基取代所得的乙二醇醚。
优选地，所述乙二醇单醚选自具有如式I所示结构式的化合物中的至少一种：
R1-O-CH2-CH2-OH    式I；
所述一元醇醚选自具有如式II所示结构式的化合物中的至少一种：
R2-O-R2    式II；
所述双封端乙二醇醚选自具有如式III所示结构式的化合物中的至少一种：
R1-O-CH2-CH2-O-R2    式III；
其中，R1选自碳原子数为1～20的烷基中的一种；R2选自碳原子数为1～20的烷基中的一种。其中R1与R2可以相同，也可以不同。
本申请中，碳原子数为1～20的烷基指碳原子数为1～20的任意直链烷烃、支链烷烃或环烷烃分子上，失去任意一个氢原子形成的基团。
本申请的制备双封端乙二醇醚的反应方程式如下：
R1-O-CH2-CH2-OH+R2-O-R2＝R1-O-CH2-CH2-O-R2+R2-OH式IV
理论上，原料中乙二醇单醚与一元醇醚的取代基R1和R2为任意碳原子数的各种烃基均能够在此反应体系中实现制备双封端乙二醇醚的反应。本领域技术人员根据产物双封端乙二醇醚的种类需求，可以选取具有相应的取代基R1、R2的原料种类。优选地，R1和R2独立地选自碳原子数不大于10的烷基。进一步优选地，R1和R2独立地选自碳原子数不大于5的烷基。更进一步优选地，R1和R2独立地选自甲基、乙基、正丙基、异丙基、正丁基。
优选地，所述R1选自甲基、乙基、正丙基、异丙基、正丁基中的一种。
优选地，所述R2选自甲基、乙基、正丙基、异丙基、正丁基中的一种。
优选地，所述酸性分子筛选自结构类型为MWW、FER、MFI、MOR、FAU、BEA的分子筛中的一种或多种。进一步优选地，所述酸性分子筛选自氢型MCM-22分子筛、氢型镁碱沸石、氢型ZSM-5分子筛、氢型丝光沸石、氢型Y沸石、氢型Beta分子筛中的一种或多种。
优选地，所述酸性分子筛中的硅和铝的原子比为Si/Al＝4～140。
优选地，所述反应温度范围上限选自200℃、250℃、300℃，下限选自50℃、90℃、100℃。进一步优选地，所述反应温度为100～200℃。
优选地，所述反应压力范围上限选自8MPa、10MPa、15MPa，下限选自0.1MPa、0.9MPa、2MPa、3.5MPa、4MPa。进一步优选地，所述反应压力为3.5～8MPa。
优选地，所述原料中乙二醇单醚的质量空速的范围上限选自5.0h-1、10h-1、15h-1，下限选0.01h-1、0.5h-1、1.5h-1。进一步优选地，所述原料中乙二醇单醚的质量空速为0.5～5.0h-1。
优选地，所述原料中一元醇醚与乙二醇单醚的摩尔比，一元醇醚：乙二醇单醚的范围上限选自4:1、5:1、15:1、25:1、50:1、100:1，下限选自1:1、2:1。进一步优选地，所述原料中一元醇醚与乙二醇单醚的摩尔比为一元醇醚：乙二醇单醚＝1～5:1。
本申请中反应体系可以不引入载气，也可以引入载气。向反应体系中引入载气，可以缓冲反应体系的热效应带来的催化剂床层温度波动，保持更均匀的温度梯度，利于提高反应稳定性和催化剂寿命。
优选地，所述原料中含有载气，所述载气选自氮气、氦气、氩气中的一种或多种。
优选地，所述载气体积空速为0～10000h-1。进一步优选地，所述载气体积空速为100～2000h-1。
优选地，所述反应器为一个或多个固定床反应器。采用连续反应的形式。固定床反应器可以为一个，也可以为多个。当采用多个固定床反应器时，反应器之间可以是串联、并联、或者串联与并联相结合的形式。
本申请能产生的有益效果至少包括：
a)本申请所提供的方法，采用酸性分子筛催化剂，具有单程寿命长，可以经过反复再生重新使用的优点。
b)本申请所提供的方法与现有技术相比，目标产物的收率、选择性均有明显提升。
c)本申请所提供的方法，产物中没有水生成，极大简化了产物的精馏纯化过程，节约了能耗。
d)本申请所提供的方法，副产物主要是经济价值非常高的双封端二乙二醇醚、二乙二醇单醚以及乙二醇，经济价值低的1,4-二氧六环等副产物很少，具有较高的经济性。
e)本申请所提供的方法，投资规模范围大，能够适用于中小企业小投资小规模生产，应用灵活。
具体实施方式
如无特别说明，实施例中的原料和催化剂均通过商业途径购买。
实施例中分析方法以及转化率、选择性计算如下：
利用带有气体自动进样器、FID检测器以及FFAP毛细管柱的Agilent7890气相色谱仪进行气/液相组分的成分自动分析。
在本申请的实施例中，乙二醇单醚转化率以及产物双封端乙二醇醚以及副产物选择性都基于质量进行计算:
乙二醇单醚转化率＝[(进料中乙二醇单醚质量)－(出料中乙二醇单醚质量)]÷(进料中乙二醇单醚质量)×(100％)
双封端乙二醇醚选择性＝(出料中双封端乙二醇醚质量)÷[(出料中所 有乙二醇衍生物质量)－(出料中未反应完乙二醇单醚质量)]×(100％)
副产物选择性＝(出料中副产物质量)÷[(出料中所有乙二醇衍生物质量)－(出料中未反应完乙二醇单醚质量)]×(100％)
上述所有乙二醇衍生物是指含有分子式中含-O-CH2-CH2-O-结构的物质，主要包括双封端乙二醇醚、1,4-二氧六环、未反应完的乙二醇单醚、双封端二乙二醇醚、二乙二醇单醚以及乙二醇。
下面结合具体的实施例，进一步阐述本申请。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。
实施例1
将50g硅铝比(Si:Al)＝45:1的氢型MCM-22分子筛催化剂在马弗炉的空气气氛下550℃焙烧5小时，取其中一部分粉末样品压片、粉碎成20～40目，用于活性测试。称取该氢型MCM-22分子筛催化剂样品10g，装入内径为8.5mm的不锈钢反应管内，在常压、550℃下用氮气活化4小时，然后降到反应温度(简写为T)＝50℃，通入原料的摩尔比为
CH3OCH3:CH3OCH2CH2OH＝1:1，反应压力(简写为P)＝0.1MPa，原料中乙二醇单醚的质量空速(简写为WHSV)＝0.01h-1，无载气，用气相色谱分析产物，反应稳定后，计算乙二醇单醚转化率和产物的选择性，反应条件及结果见表1。
实施例2
将实施例1中的反应条件换成T＝90℃，P＝0.9MPa，通入原料的摩尔 比为CH3CH2OCH3CH2:CH3CH2OCH2CH2OH＝2:1，WHSV＝0.5h-1，载气氮气体积空速(简写为GHSV)＝100h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例3
将实施例1中的催化剂换成氢型镁碱沸石分子筛，Si:Al＝15:1，T＝300℃，P＝15MPa，通入原料的摩尔比为
CH3OCH3:CH3OCH2CH2OH＝100:1，WHSV＝15h-1，载气为氮气，GHSV＝10000h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例4
将实施例1中的催化剂换成氢型镁碱沸石分子筛，Si:Al＝15:1，T＝250℃，P＝10MPa，通入原料的摩尔比为
CH3CH2CH2OCH2CH2CH3:CH3CH2CH2OCH2CH2OH＝50:1，WHSV＝10h-1，载气为氩气，GHSV＝5000h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例5
将实施例1中的催化剂换成氢型ZSM-5分子筛，Si:Al＝140:1，T＝100℃，P＝3.5MPa，通入原料的摩尔比为CH3OCH3:CH3OCH2CH2OH＝1:1，WHSV＝0.5h-1，其余实验步骤与实施例1一致，反应结果见表1。
实施例6
将实施例1中的催化剂换成氢型ZSM-5分子筛，Si:Al＝140:1，T＝150℃，P＝5MPa，通入原料的摩尔比为
(CH3)2CHOCH(CH3)2:(CH3)2CHOCH2CH2OH＝3:1，WHSV＝2.5h-1，载气为氮气，GHSV＝1000h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例7
将实施例1中的催化剂换成氢型丝光沸石分子筛，Si:Al＝4:1，T＝200℃，P＝8MPa，通入原料的摩尔比为CH3OCH3:CH3OCH2CH2OH＝5:1，WHSV＝5h-1，载气为氦气，GHSV＝2000h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例8
将实施例1中的催化剂换成氢型丝光沸石分子筛，Si:Al＝4:1，T＝180℃，P＝7MPa，通入原料的摩尔比为
CH3(CH2)3O(CH2)3CH3:CH3(CH2)3OCH2CH2OH＝4:1，WHSV＝4h-1，载气为氦气，GHSV＝1500h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例9
将实施例1中的催化剂换成氢型Y分子筛，Si:Al＝25:1，T＝130℃，P＝ 5MPa，通入原料的摩尔比为CH3OCH3:CH3OCH2CH2OH＝2:1，WHSV＝2h-1，无载气，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例10
将实施例1中的催化剂换成氢型Y分子筛，Si:Al＝25:1，T＝140℃，P＝6MPa，通入原料的摩尔比为CH3CH2OCH2CH3:CH3CH2OCH2CH2OH＝2.5:1，WHSV＝2.5h-1，载气为氮气，GHSV＝500h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例11
将实施例1中的催化剂换成氢型Beta分子筛，Si:Al＝20:1，T＝230℃，P＝2MPa，通入原料的摩尔比为CH3OCH3:CH3OCH2CH2OH＝15:1，WHSV＝9h-1，载气为氮气，GHSV＝3000h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
实施例12
将实施例1中的催化剂换成氢型Beta分子筛，Si:Al＝20:1，T＝220℃，P＝3MPa，通入原料的摩尔比为
CH3CH2OCH2CH3:CH3CH2OCH2CH2OH＝25:1，WHSV＝6h-1，载气为氮气，GHSV＝1000h-1，其余实验步骤与实施例1一致，反应条件及结果见表1。
表1 实施例1～12的催化反应条件及结果
Figure PCTCN2014094535-appb-000001
注：其他副产物主要为双封端二乙二醇醚、二乙二醇单醚以及乙二醇
对比例1
将50g购买自杜邦公司全氟磺酸树脂(Nafion-H)在鼓风干燥箱中，空气气氛下105℃烘干12小时，冷却后称取10g装入内径为8.5mm的不锈钢反应管内用于活性测试，在常压、100℃下用氮气活化1小时，然后在反应温度(T)＝130℃，通入原料摩尔比为CH3OCH3:CH3OCH2CH2OH＝2:1，反应压力(P)＝5MPa，甲缩醛质量空速(WHSV)＝2h-1，无载气，用气相色谱分析产物，反应稳定后，计算乙二醇单醚转化率和产物的选择性，反应条件及结果见表2。
对比例2
将对比例1中的反应条件换成T＝140℃，P＝6MPa，通入原料的摩尔比为CH3CH2OCH2CH3:CH3CH2OCH2CH2OH＝2.5:1，WHSV＝2.5h-1，载气为氮气，GHSV＝500h-1，其余实验步骤与对比例1一致，反应条件及结果见表2。
对比例3
将对比例1中的催化剂换成购买自罗门哈斯公司的磺化的苯乙烯-二乙烯苯共聚物(Amberlyst-15)树脂，其余实验步骤与对比例1一致，反应条件及结果见表2。
对比例4
将对比例2中的催化剂换成购买自罗门哈斯公司的磺化的苯乙烯-二乙 烯苯共聚物(Amberlyst-15)树脂，其余实验步骤与对比例2一致，反应条件及结果见表2。
对比例5
将对比例1中的催化剂换成购买自丹东明珠特种树脂有限公司的磺化的苯乙烯-二乙烯苯共聚物强酸性阳离子交换树脂(D005)，其余实验步骤与对比例1一致，反应条件及结果见表2。
对比例6
将对比例2中的催化剂换成购买自丹东明珠特种树脂有限公司的磺化的苯乙烯-二乙烯苯共聚物强酸性阳离子交换树脂(D005)，其余实验步骤与对比例2一致，反应条件及结果见表2。
表2 对比例1～6的催化反应条件及结果
Figure PCTCN2014094535-appb-000002
Figure PCTCN2014094535-appb-000003
注：其他副产物主要为双封端二乙二醇醚、二乙二醇单醚以及乙二醇
实施例13
分别将实施例1、3、5、7、9、11中单程反应失活后的催化剂取出再生，再生条件均为空气气氛下550℃焙烧4小时，再生后的催化剂分别按照原实施例的反应条件重复进行反应。反应结果见表3。
表3实施例中催化再生前后反应结果对比
Figure PCTCN2014094535-appb-000004
对比例1～6中的树脂催化剂无法再生。
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，任何本领域技术人员，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. 一种生产双封端乙二醇醚的方法，其特征在于，将含有乙二醇单醚与一元醇醚的原料通入反应器与含有酸性分子筛的催化剂接触并反应，生产双封端乙二醇醚；
    反应温度为50～300℃，反应压力为0.1～15MPa；
    所述原料中乙二醇单醚的质量空速为0.01～15.0h-1；
    所述原料中一元醇醚与乙二醇单醚的摩尔比为一元醇醚：乙二醇单醚＝1～100:1。
  2. 根据权利要求1所述的方法，其特征在于，
    所述乙二醇单醚选自具有如式I所示结构式的化合物中的至少一种：
    R1-O-CH2-CH2-OH   式I；
    所述一元醇醚选自具有如式II所示结构式的化合物中的至少一种：
    R2-O-R2   式II；
    所述双封端乙二醇醚选自具有如式III所示结构式的化合物中的至少一种：
    R1-O-CH2-CH2-O-R2   式III；
    其中，R1选自碳原子数为1～20的烷基中的一种；R2选自碳原子数为1～20的烷基中的一种。
  3. 根据权利要求2所述的方法，其特征在于，所述R1选自甲基、乙基、正丙基、异丙基、正丁基中的一种；所述R2选自甲基、乙基、正丙基、异 丙基、正丁基的一种。
  4. 根据权利要求1所述的方法，其特征在于，所述酸性分子筛选自结构类型为MWW、FER、MFI、MOR、FAU、BEA的分子筛中的一种或多种。
  5. 根据权利要求1所述的方法，其特征在于，所述酸性分子筛含有氢型MCM-22分子筛、氢型镁碱沸石、氢型ZSM-5分子筛、氢型丝光沸石、氢型Y沸石、氢型Beta分子筛中的一种或多种。
  6. 根据权利要求1或4或5所述的方法，其特征在于，所述酸性分子筛中硅和铝的原子比为Si/Al＝4～140。
  7. 根据权利要求1所述的方法，其特征在于，所述反应温度为100～200℃，所述反应压力为3.5～8MPa；
    所述原料中乙二醇单醚的质量空速为0.5～5.0h-1；
    所述原料中一元醇醚与乙二醇单醚的摩尔比为一元醇醚：乙二醇单醚＝1～5:1。
  8. 根据权利要求1所述的方法，其特征在于，所述原料中含有载气，所述载气体积空速为0～10000h-1；所述载气选自氮气、氦气、氩气中的一种或多种。
  9. 根据权利要求8所述的方法，其特征在于，所述载气体积空速为100～2000h-1。
  10. 根据权利要求1所述的方法，其特征在于，所述反应器为一个或多个固定床反应器。
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