WO2016187773A1 - 制备乙二醇醚用的催化剂及其制备方法和应用 - Google Patents

制备乙二醇醚用的催化剂及其制备方法和应用 Download PDF

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WO2016187773A1
WO2016187773A1 PCT/CN2015/079691 CN2015079691W WO2016187773A1 WO 2016187773 A1 WO2016187773 A1 WO 2016187773A1 CN 2015079691 W CN2015079691 W CN 2015079691W WO 2016187773 A1 WO2016187773 A1 WO 2016187773A1
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catalyst
weight
ether
molecular sieve
acid
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PCT/CN2015/079691
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English (en)
French (fr)
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袁兴东
京堂真大
山下雅由
李永烨
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高化学株式会社
袁兴东
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Priority to PCT/CN2015/079691 priority Critical patent/WO2016187773A1/zh
Priority to CN201580059141.3A priority patent/CN107107042B/zh
Publication of WO2016187773A1 publication Critical patent/WO2016187773A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—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
    • B01J29/40—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
    • B01J29/42—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 containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • 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
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • 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
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups

Definitions

  • the invention relates to a catalyst for preparing glycol ether, a preparation method and application thereof.
  • the glycol ether comprises ethylene glycol monoether, ethylene glycol diether, and polyglycol monoether and polyglycol diether, among which ethylene glycol monomethyl ether (MMET) and ethylene glycol II Methyl ether (DMET) is a typical representative. Since the glycol ether molecule contains both a hydroxyl group and an ether group and is miscible with various organic compounds, it is not only a good solvent but also an intermediate for many organic synthesis. In recent years, glycol ethers have opened up new applications such as extraction of drugs, use as liquid crystal aligning agents, and the like.
  • MMET ethylene glycol monomethyl ether
  • DMET ethylene glycol II Methyl ether
  • glycol ethers especially ethylene glycol dimethyl ether, have good stability and high cetane number, they can also be used as diesel fuel additives for reducing soot emissions. Therefore, the synthesis and application of glycol ethers is a very significant topic.
  • the current commercialization method is the Williamson phase transfer method.
  • the method uses ethylene glycol or ethylene glycol monoether as a raw material, methyl chloride as a methylation reagent, crown ether or quaternary ammonium salt as a phase transfer catalyst to obtain a glycol diether.
  • This method has the disadvantage that the catalyst is expensive and cannot be recovered, and additionally generates hydrogen and salt and is dangerous.
  • CN 101190876A discloses a preparation method involving a glycol ether, which uses ethylene oxide and a low-carbon fatty alcohol as raw materials, and cerium oxide as a main active component, and is selected from vanadium, molybdenum, tungsten, tin, A catalyst composed of one or more of elements of lead, bismuth, antimony and bismuth and a compound thereof, wherein the reaction temperature is 100-300 ° C, the reaction pressure is 0.1-3.0 MPa, and the alcohol to alkane ratio is 1-5.
  • the glycol ether is prepared under the conditions of 0.5-8.0 h to solve the problems of low selectivity of the target product glycol ether and high molar ratio of alcohol to ethylene oxide (alcohol ratio) in the prior art.
  • this method inevitably has a large amount of by-product carbon dioxide.
  • the process of the method is complicated, consumes a large amount of energy, and is not suitable for industrial production.
  • CN 1005133A reports the preparation of ZSM-5 molecular sieve as a precursor and exchange with inorganic acid.
  • CN1033742C is based on CN1005133A, which is used for strengthening the acidity of the catalyst by hydrothermal treatment and then used for the reaction of ethylene oxide and ethanol. Under the same reaction conditions, the process increases the conversion of ethylene oxide, but does not increase the selectivity of the glycol ether, and a large amount of ethylene glycol is produced. In addition, the ethylene oxide used in the process is susceptible to explosion.
  • Chinese patent CN102952003A discloses a method for preparing ethylene glycol monomethyl ether on a catalyst containing titanium silicon molecular sieve directly using ethylene, methanol and hydrogen peroxide as raw materials.
  • the method has the disadvantages of using hydrogen peroxide as an oxidant, using a toxic solvent, easily decomposing hydrogen peroxide, and high industrial cost.
  • U.S. Patent No. 2004/0044253 discloses a method for synthesizing glycol ether on a perfluorosulfonic acid resin catalyst by a batch method using ethylene glycol or ethylene glycol monoether and a lower alcohol as raw materials.
  • the conversion rate was up to 77.2% and the selectivity of total ether was 94.3%.
  • the method has the advantages of wide source of raw materials and low price, but the biggest problem of the method is that the catalyst perfluorosulfonic acid resin used is very expensive, and the catalyst is easily deformed by the influence of temperature during use, and the regeneration is difficult and cannot be industrialized.
  • the industrialization method is the Williamson phase transfer method, but the highly toxic methyl chloride is used in this method, which is disadvantageous to the operating environment.
  • the method uses strong alkali NaOH, which is highly corrosive to equipment.
  • the ethylene oxide used has the risk of being explosive.
  • the selectivity of the glycol ether, especially ethylene glycol dimethyl ether is low in this method, and the by-product dioxane and ethylene glycol are relatively large.
  • the method using ethylene glycol and methanol as raw materials is the most economical and environmentally friendly, but it is required to improve the performance of the catalyst.
  • ethylene glycol is guaranteed as a raw material for the production of glycol ethers.
  • a technique for preparing a glycol ether from a lower alkyl alcohol and/or a lower alkyl ether and ethylene glycol and/or ethylene glycol monoether is expensive and difficult to regenerate.
  • the current status of perfluorosulfonic acid resin as a catalyst can have a good conversion of ethylene glycol and / ethylene glycol monoether and glycol ether selectivity and low dioxane by-products
  • a solid catalyst is substituted for the perfluorosulfonic acid resin catalyst to effect the industrialization of the glycol ether by etherification of ethylene glycol with a lower alkyl alcohol and/or a lower alkyl ether.
  • the inventors of the present invention have extensively carried out catalysts for preparing glycol ethers from lower alkyl alcohols and/or lower alkyl ethers and ethylene glycol and/or ethylene glycol monoethers. Further intensive studies have been made to find a catalyst for preparing glycol ethers from lower alkyl alcohols and/or lower alkyl ethers and ethylene glycol and/or ethylene glycol monoethers which overcomes the above disadvantages of the prior art. Moreover, the catalyst is inexpensive and has a high ethylene glycol conversion rate and selectivity for glycol ethers.
  • zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 50-350, wherein the zeolite molecular sieve has a pore size of 3-10 angstroms;
  • a metal oxide improver wherein the metal is selected from one or more of Group IIA metals, La, Ga and Cu;
  • Another object of the present invention is to provide a process for the preparation of the catalyst of the present invention which comprises the steps of:
  • Zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 50-350 is kneaded with a binder, a molding aid, water and an acid, and then shaped, dried, calcined, and then crushed and sieved.
  • the acid is selected from one or more of nitric acid, phosphoric acid, sulfuric acid, formic acid, acetic acid, propionic acid, oxalic acid or citric acid;
  • the amount of each component is based on the total weight of the catalyst, and the catalyst comprises the following components:
  • zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 50-350, wherein the zeolite molecular sieve has a pore size of 3-10 angstroms;
  • a metal oxide improver wherein the metal is selected from one or more of Group IIA metals, La, Ga and Cu;
  • a further object of the present invention is to provide a process for preparing a glycol ether, the method comprising: contacting a material a and a material b with a catalyst provided by the present invention under etherification conditions, wherein the material a is B
  • the diol and/or ethylene glycol monoether, material b is a C 1 -C 6 alkyl alcohol and/or a di C 1 -C 6 alkyl ether.
  • the catalyst of the invention is especially suitable for the preparation of glycol ethers from lower alkyl alcohols and/or lower alkyl ethers and ethylene glycol and/or ethylene glycol monoethers, which are inexpensive, have a high conversion of ethylene glycol and have a high ethylene glycol conversion rate and The selectivity of the alcohol ether.
  • the method for preparing a glycol ether provided by the invention has high ethylene glycol conversion rate and selectivity of glycol ether.
  • Figure 1 illustrates the effect of reaction temperature on the synthesis of glycol ethers.
  • Figure 2 illustrates the stability of the catalyst prepared in Example 1.
  • Figure 3 illustrates the stability of the catalyst prepared in Example 1 after regeneration.
  • Figure 4 illustrates NH 3 -TPD patterns of different silica-alumina ratios and metal modified beta zeolites.
  • a catalyst for preparing a glycol ether wherein the catalyst comprises the following components based on the total weight of the catalyst:
  • zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 50-350, wherein the zeolite molecular sieve has a pore size of 3-10 angstroms;
  • a metal oxide improver wherein the metal is selected from one or more of Group IIA metals, La, Ga and Cu;
  • the catalyst comprises the following components, based on the total weight of the catalyst:
  • zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 50-350, wherein the zeolite molecular sieve has a pore size of 3-10 angstroms;
  • a metal oxide improver wherein the metal is selected from one or more of a Group IIA metal, La, Ga and Cu;
  • the zeolite molecular sieve used in the present invention is based on a zeolite molecular sieve known to those skilled in the art, for example, the zeolite molecular sieve may be one of USY, Ferrierite, ZSM-5, ZSM-11, ZSM-23, MCM-22, ⁇ and mordenite molecular sieves or A plurality, preferably one or more of ZSM-5, USY, Ferrierite and ⁇ molecular sieves, further preferably ⁇ and/or Ferrierite molecular sieves, particularly preferably ⁇ molecular sieves.
  • the present invention has no particular requirement for the source of the zeolite molecular sieve, and is commercially available or can be obtained by synthesizing a zeolite molecular sieve by the prior art, for example, hydrothermal synthesis.
  • the zeolite molecular sieve may have a silica to alumina molar ratio of 50 to 350, but a glycol ether process is carried out by converting ethylene glycol and a C 1 -C 6 alkyl alcohol and/or a di C 1 -C 6 alkyl ether.
  • a glycol ether process is carried out by converting ethylene glycol and a C 1 -C 6 alkyl alcohol and/or a di C 1 -C 6 alkyl ether.
  • the zeolite molecular sieve has a silica-alumina molar ratio of from 75 to 300.
  • the metal in the metal oxide improver of the present invention is one or more selected from the group consisting of Group IIA metals, La, Ga and Cu. From the viewpoint of selectivity of the glycol ether, the metal is preferably one or more of Mg, La, Ca, Ga, and Cu, and more preferably one or more of Mg, Cu, and Ca, and more preferably More preferably, it is Mg and/or Ca.
  • the type of the binder to be used in the present invention is not particularly limited, and can be selected according to actual needs.
  • the binder may be clay, aluminum sol, pseudoboehmite, silica sol, or the like, or a mixture thereof.
  • the content of the binder is also not particularly limited, and it may be carried out in accordance with a conventional binder amount.
  • the catalyst comprises the following components, based on the total weight of the catalyst:
  • zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 75-300, wherein the zeolite molecular sieve has a pore size of 4.5-9 angstroms, and the zeolite molecule is selected from ZSM-5.
  • zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 75-300, wherein the zeolite molecular sieve has a pore size of 4.5-9 angstroms, and the zeolite molecule is selected from ZSM-5.
  • USY, Ferrierite, and beta molecular sieves One or more of USY, Ferrierite, and beta molecular sieves;
  • a metal oxide improver wherein the metal is one or more of Mg, Cu and Ca;
  • the catalyst thus obtained has a particularly high selectivity and conversion when reacting a C 1 -C 6 alkyl alcohol and/or a di C 1 -C 6 alkyl ether with ethylene glycol to produce a glycol ether.
  • a method of preparing a catalyst of the present invention comprising the steps of:
  • Zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 50-350 is kneaded with a binder, a molding aid, water and an acid, and then shaped, dried, calcined, and then crushed and sieved.
  • the acid used includes one or more of a mineral acid (such as nitric acid, phosphoric acid, sulfuric acid, etc.) or an organic acid (such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid, etc.);
  • the amount of each component is based on the total weight of the catalyst, and the catalyst comprises the following components:
  • zeolite molecular sieve having a silica-alumina molar ratio (SiO 2 /Al 2 O 3 ) of 50-350, wherein the zeolite molecular sieve has a pore size of 3-10 angstroms;
  • a metal oxide improver wherein the metal is selected from one or more of Group IIA metals, La, Ga and Cu;
  • the type of the molding aid in the step (1) of the present invention is not particularly limited, and may be selected according to actual needs.
  • it may be one or more of glutinous rice flour, polyvinyl alcohol or polyethylene glycol.
  • the amount of the molding aid to be used is also not particularly limited, and it may be carried out in accordance with a molding aid in a conventional catalyst preparation process.
  • the molding aid may be used in an amount of 1 to 20 parts by weight, preferably 3 to 15 parts by weight, more preferably 5 to 10 parts by weight per 100 parts by weight of the catalyst.
  • the type of the acid in the step (1) is not particularly limited in the present invention, and can be selected according to actual needs.
  • it may be one or more of an inorganic acid (such as nitric acid, phosphoric acid, sulfuric acid, etc.), an organic acid (such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid, etc.).
  • the amount of the acid is also not particularly Unless otherwise defined, the acid may be fed in accordance with the conventional catalyst preparation process.
  • the acid may be used in an amount of 1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 to 10 parts by weight per 100 parts by weight of the catalyst.
  • the amount of water used in the step (1) of the present invention is also not particularly limited, and it may be carried out according to the amount of water used in the preparation of the conventional catalyst.
  • the water may be used in an amount of 40 to 80 parts by weight, preferably 50 to 70 parts by weight, per 100 parts by weight of the catalyst.
  • the kind of the water-soluble metal salt can be selected in a larger range.
  • the water-soluble metal salt may be a metal salt of a Group IIA, a water-soluble salt of La, Ga, Cu or a mixture thereof, and specifically The nitrate, carbonate, hydrochloride or a mixture thereof of the Group IIA metal, La, Ga or Cu, preferably a nitrate, a carbonate, a hydrochloride or a mixture thereof of Mg, Cu or Ca, further preferably Mg And/or a nitrate, carbonate, hydrochloride or a mixture of Ca.
  • the present invention has no particular requirement for the kneading conditions of the step (1).
  • the kneading conditions may include: the kneading temperature is 20-50 ° C, the kneading time is 20-90 minutes; and the kneading temperature is preferably 20-30. °C, the kneading time is 25-45 minutes.
  • the method of the present invention further comprises the steps of molding, drying and calcining after the kneading of the step (1).
  • the method of molding, the method of drying, and the method of firing can be carried out by methods well known in the art.
  • the method of forming may be extrusion molding.
  • the drying may be a conventional drying method such as oven drying, and the drying temperature may be 50 to 250 ° C, preferably 100 to 200 ° C; and the drying time may be 5 to 96 hours, preferably 5 to 20 hours.
  • the calcination may be a conventional calcination condition for preparing the H-type zeolite molecular sieve.
  • the calcination temperature may be 500 to 750 ° C, preferably 500 to 650 ° C; and the calcination time may be 1 to 10 hours, preferably 3 to 8 hours.
  • the water-soluble metal salt is contacted with the formed zeolite molecular sieve by a dipping method commonly used in the art.
  • the contact conditions may include: the contact temperature is 30-90 ° C, and the contact time It is 2-15 hours; the temperature of the contact is preferably 50-80 ° C, and the contact time is 2-10 hours.
  • the drying of the step (2) may be a conventional drying condition of the molecular sieve.
  • the drying temperature may be 50-250 ° C, preferably 100-200 ° C; the drying time may be 4-20 hours, preferably 4-16 hours. .
  • the calcination of the step (2) may be a conventional calcination condition for preparing a zeolite molecular sieve; for example, the calcination temperature may be 500 to 750 ° C, preferably 500 to 650 ° C; and the calcination time may be 1 to 10 hours, preferably 3 to 8 hour.
  • the type and amount of the metal in the zeolite molecular sieve, the water-soluble metal salt, and the kind and the preferred conditions of the binder are as described above, and will not be described herein.
  • a process for the preparation of a glycol ether using the catalyst of the invention comprising: under the etherification conditions, the material a and the material b and the catalyst provided by the invention or according to the invention
  • the catalyst prepared by the method is contacted, wherein the material a is ethylene glycol and/or ethylene glycol monomethyl ether, and the material b is a C 1 -C 6 alkyl alcohol and/or a di C 1 -C 6 alkyl ether.
  • the molar ratio of the material b to the material a is not particularly limited.
  • the molar ratio of the material b to the material a may be from 0.1 to 20:1, preferably from 1 to 10:1, further preferably 2-6:1.
  • the conditions for contacting the material a and the material b with the catalyst are not particularly limited.
  • the contact conditions may include: a contact temperature of 100-400 ° C, a contact pressure of 0.1-10.0 MPa, and a material.
  • the mass flow rate of the total flow meter of a and material b is 0.05-15 h -1 .
  • the contact temperature is 180-220 ° C
  • the contact pressure is 3.5-7.0 MPa
  • the mass space velocity of the total flow meter of material a and material b is 1.0- 10h -1 .
  • the selection of the C 1 -C 6 alkyl alcohol in the present invention is not particularly limited. Specifically, examples thereof include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol and isomers thereof, n-pentanol and isomers thereof, n-hexanol and one of its isomers Or one or more; preferably one or more of methanol, ethanol, n-propanol, n-butanol, n-pentanol and n-hexanol; further preferably one of methanol, ethanol, n-propanol and n-butanol or A variety.
  • the selection of the di-C 1 -C 6 alkyl ether of the present invention is not particularly limited. Specifically, examples thereof include, but are not limited to, dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether and isomers thereof, di-n-pentyl ether and isomers thereof, di-n-hexyl ether And an isomer thereof; preferably one or more of dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether and di-n-hexyl ether; further preferably dimethyl ether.
  • the source of ethylene glycol includes not only pure ethylene glycol but also industrial
  • the initial product of the ethylene glycol plant was prepared.
  • the source of the ethylene glycol monoether includes not only the pure ethylene glycol monoether commodity, but also the initial product of the industrial preparation of the ethylene glycol monoether device.
  • material a is ethylene glycol.
  • the form of the reactor in which the contacting is carried out is not particularly limited, and the reactor may be a fixed bed reactor, a slurry bed reactor, a batch reactor, a stream.
  • the monolithic reactor refers to a reactor employing a monolithic catalyst of a foam monolith, and preferably the reactor is a fixed bed reactor.
  • X EG is the conversion rate of ethylene glycol
  • m o raw material EG is the mass of ethylene glycol raw material
  • m product EG is the mass of ethylene glycol in the product.
  • S i is the selectivity of component i and n i is the mass of component i in the product.
  • the pore size of the molecular sieve is measured by the BJH method.
  • the silica sol used was a silica sol having a SiO 2 content of 40% by weight;
  • the aluminum sol used was an aluminum sol having an Al 2 O 3 content of 10% by weight.
  • H-type ⁇ molecular sieve 30g of clay, 5g of glutinous rice flour, 60g of H 2 O, add 5g of concentrated nitric acid, knead at 25 ° C for 30 minutes, extrude with a mold of 3.0 mm diameter, dry, set It was baked in an oven at 120 ° C for 12 hours and then calcined in a muffle furnace at 550 ° C for 5 hours under an air atmosphere. Then, it was crushed and sieved to obtain solid particles having a particle diameter of 1 mm.
  • Example 1 The experimental conditions of Example 1 were repeated except that the H-type ⁇ molecular sieve (SiO 2 /Al 2 O 3 molar ratio of 300) was all used in the H-type ZSM-5 zeolite (the SiO 2 /Al 2 O 3 molar ratio was 100) instead.
  • H-type ⁇ molecular sieve SiO 2 /Al 2 O 3 molar ratio of 300
  • H-type ZSM-5 zeolite the SiO 2 /Al 2 O 3 molar ratio was 100
  • Example 1 The experimental conditions of Example 1 were repeated except that the H-type ⁇ molecular sieve (SiO 2 /Al 2 O 3 molar ratio of 300) was all replaced with USY molecular sieve (SiO 2 /Al 2 O 3 molar ratio of 110). Other properties of the catalyst are shown in Table 1.
  • Example 1 The experimental conditions of Example 1 were repeated except that the H-type ⁇ molecular sieve (SiO 2 /Al 2 O 3 molar ratio of 300) was all replaced with Ferrierite (SiO 2 /Al 2 O 3 molar ratio of 100). Other properties of the catalyst are shown in Table 1.
  • Example 1 The experimental conditions of Example 1 were repeated except that the H-type ⁇ molecular sieve (SiO 2 /Al 2 O 3 molar ratio of 300) was not subjected to CaO modification.
  • H-type ⁇ molecular sieve SiO 2 /Al 2 O 3 molar ratio of 300
  • Example 1 The experimental conditions of Example 1 were repeated except that the molar ratio of silicon to aluminum in the ammonium type beta molecular sieve used was 150.
  • Example 1 The experimental conditions of Example 1 were repeated except that the molar ratio of silicon to aluminum in the ammonium type beta molecular sieve used was 75.
  • Example 2 The experimental conditions of Example 1 were repeated except that 1.58 g of Mg(NO 3 ) 2 ⁇ 6H 2 O was used instead of 1.05 g of Ca(NO 3 ) 2 ⁇ 4H 2 O to obtain a MgO-modified catalyst.
  • the catalyst comprised 69.3% by weight of zeolite beta, 1.0% by weight of magnesium oxide and 29.7% by weight of clay, based on the total weight of the catalyst obtained.
  • Example 2 The experimental conditions of Example 1 were repeated except that 0.90 g of Cu(NO 3 ) 2 ⁇ 6H 2 O was used instead of 1.05 g of Ca(NO 3 ) 2 ⁇ 4H 2 O to obtain a CuO-modified catalyst.
  • the catalyst comprised 69.3% by weight of beta molecular sieve, 1.0% by weight of copper oxide and 29.7% by weight of clay, based on the total weight of the catalyst obtained.
  • Example 2 The experimental conditions of Example 1 were repeated except that the clay was entirely replaced with pseudo-boehmite to obtain a catalyst having a binder of Al 2 O 3 .
  • the catalyst contained 69.3% by weight of ⁇ molecular sieve, 1.0% by weight of calcium oxide and 29.7% by weight of Al 2 O 3 based on the total weight of the obtained catalyst.
  • Example 2 The experimental conditions of Example 1 were repeated except that the clay was entirely replaced with a silica sol to obtain a catalyst in which a silica sol was used as a binder source.
  • the catalyst contained 69.3% by weight of ⁇ molecular sieve, 1.0% by weight of calcium oxide and 29.7% by weight of SiO 2 based on the total weight of the obtained catalyst.
  • Example 1 The experimental conditions of Example 1 were repeated except that the clay was entirely replaced with an aluminum sol (Nissan Chemical Industry Co., Ltd., AS-200) to obtain a catalyst in which an aluminum sol was used as a binder source.
  • the catalyst contained 69.3% by weight of ⁇ molecular sieve, 1.0% by weight of calcium oxide and 29.7% by weight of Al 2 O 3 based on the total weight of the obtained catalyst.
  • Example 1 The experimental conditions of Example 1 were repeated except that the weight of the H-type ⁇ molecular sieve was 80 g and the weight of the clay was 20 g during the molding process, and the weight of Ca(NO 3 ) 2 ⁇ 4H 2 O during the impregnation was 3.15g.
  • the catalyst contained 77.6% by weight of zeolite beta, 3.0% by weight of calcium oxide and 19.4% by weight of clay, based on the total weight of the catalyst obtained.
  • Example 1 The experimental conditions of Example 1 were repeated except that the weight of the H-type ⁇ molecular sieve was 50 g and the weight of the clay was 50 g during the molding process, and the weight of Ca(NO 3 ) 2 ⁇ 4H 2 O during the impregnation was 0.52g.
  • the catalyst comprises 49.75% by weight of zeolite beta, 0.5% by weight of calcium oxide and 49.75% by weight of clay, based on the total weight of the catalyst obtained.
  • Example 2 The experimental conditions of Example 1 were repeated except that the weight of the H-type ⁇ molecular sieve was 40 g and the weight of the clay was 60 g during the molding process, and the weight of Ca(NO 3 ) 2 ⁇ 4H 2 O during the impregnation was 0.104g.
  • the catalyst comprised 39.96 wt% of zeolite beta, 0.1 wt% of calcium oxide and 59.94 wt% of clay, based on the total weight of the catalyst obtained.
  • This example is intended to illustrate the preparation of glycol ethers from ethylene glycol and methanol using the catalyst of the present invention.
  • Example 1 In a stainless steel tube reactor having an inner diameter of 6 mm, 2.0 g of the shaped catalyst prepared in Example 1 was filled, and methanol and ethylene glycol having a molar ratio of 4.0/1.0 were introduced at 5.0 MPa, and the reaction temperature was 210 ° C.
  • the mass space velocity of the total flow meter of material a and material b was 1.2 h -1 , and the experimental results are shown in Table 1.
  • Example 15 The experimental conditions of Example 15 were repeated except that the catalysts used were replaced with the catalysts prepared in Examples 2-14, respectively. The experimental results are shown in Table 1.
  • Example 15 The experimental conditions of Example 15 were repeated except that the catalysts used were replaced with the catalysts prepared in Comparative Examples 1-2, respectively. The experimental results are shown in Table 1.
  • Example 15 The same experimental conditions as in Example 15 were repeated except that methanol as a raw material was replaced with ethanol, n-propanol, n-butanol and dimethyl ether, respectively, and the results are shown in Table 2.
  • Example 15 The experimental conditions of Example 15 were repeated except that the methanol in the raw material was replaced with a mixture of methanol, ethanol, n-propanol and n-butanol in a molar ratio of 1/1/1/1, and the results are shown in the table. 2 in.
  • Example 15 The experimental conditions of Example 15 were repeated except that the molar ratio of methanol to ethylene glycol in the raw material was changed to 2/1, 3/1, 5/1, 6/1 feed, and the results are shown in Table 2. in.
  • Example 15 The experimental conditions of Example 15 were repeated except that the reaction temperatures were changed to 180 ° C, 190 ° C, 200 ° C and 220 ° C, respectively, and the results are shown in Fig. 1.
  • Example 15 The experimental conditions of Example 15 were repeated except that the reaction pressure was changed to 0.1 MPa, 3.5 MPa, and 7.0 MPa, respectively.
  • Example 15 Experimental conditions of Example 15 was repeated, except that: the total mass flow meter airspeed material and a material b respectively 1.0h -1, 4.8h -1 and 9.6h -1, the reaction result; glycol The conversion rates were 89.76%, 46.69% and 25.52%, respectively; the selectivity of monoglycol ether was 89.81%, 99.67% and 99.66%, respectively, and the selectivity of dioxane was 7.38%, 0.14% and 0.15%, respectively. The selectivity to polyglycol ethers was 2.81%, 0.18% and 0.19%, respectively.
  • Example 15 The experimental conditions of Example 15 were repeated except that the reaction time was extended to 2000 hours. The experimental results are shown in Figure 2.
  • Example 48 After the completion of the preparation of Example 48, the ethylene glycol and methanol feeds were stopped, the catalyst bed was purged with 50 ml/min of nitrogen for 30 minutes, and then air was introduced at a rate of 50 ml/min at a rate of 8 ° C/min. Raise the temperature from 210 ° C to 550 ° C, then hold at 550 ° C for 8 hours, will be The catalyst in Example 36 was regenerated. After the end of regeneration, the catalyst bed temperature dropped to 210 °C.
  • reaction temperature is 210 ° C
  • reaction pressure is 5.0 MPa
  • the molar ratio of material b to ethylene glycol is 4 / 1
  • the weight of the catalyst is 2.0 g
  • the mass space velocity of the total flow meter of material b and ethylene glycol is 1.2h -1 .
  • Reaction conditions a reaction temperature of 210 ° C, a reaction pressure of 5.0 MPa, a catalyst weight of 2.0 g, and a mass space velocity of 1.2 h -1 of the total flow meter of the material b and ethylene glycol.
  • the perfluorosulfonic acid resin catalyst prolonged with time and its activity gradually decreased, which may be related to the loss of sulfonic acid. In addition, when the reaction was over, it was found that the perfluorosulfonic acid resin catalyst had been severely deformed, indicating that the stability of the catalyst could not be industrialized. s level. When using a catalyst containing a minimum pore size Ferrierite molecular sieve, it has the highest ethylene glycol conversion rate of 90.71% and 100% glycol ether selectivity, but the selectivity of ethylene glycol dimethyl ether is only 24.53%.
  • ⁇ (SiO 2 /Al 2 O 3 molar ratio 300) molecular sieve is used as the catalyst, although the conversion of ethylene glycol and the selectivity of glycol ether are lower than that of the Ferrierite molecular sieve, after the modification by Ca 2+ ,
  • the selectivity of glycol ether is up to 98.67%
  • the selectivity of ethylene glycol dimethyl ether is up to 41.44%
  • the selectivity of dioxane is below 1.0%
  • the stability is the best, indicating the pore structure of ⁇ molecular sieve.
  • the reaction for synthesizing a glycol ether from ethylene glycol and methanol is advantageous.
  • the ⁇ molecular sieve is acid-modulated. From the results of metal modification, the modification with the addition of alkali metal Mg 2+ and Ca 2+ is better, and the selectivity of glycol ether, especially ethylene glycol dimethyl ether. The selectivity is improved, the selectivity of the by-product dioxane and heavy components is inhibited, and the catalyst is relatively stable, wherein the Ca 2+ modified ⁇ molecular sieve catalyst is optimal, the stability of the fresh catalyst is higher than 2000 hours, and more Secondary regeneration.

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Abstract

提供一种制备乙二醇醚的催化剂及其制备方法，其中以该催化剂的总重量计，该催化剂包含以下组分：a)30-85重量％的硅铝摩尔比(SiO 2/Al 2O 3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；b)0.01-5重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及c)15-65重量％的粘结剂，且各组分的总和总是加起来为100重量％。该催化剂尤其适用于由低级烷基醇和/或低级烷基醚及乙二醇和/或乙二醇单醚制备乙二醇醚且价格便宜、具有较高的乙二醇转化率和乙二醇醚的选择性。还提供一种采用上述催化剂制备乙二醇醚的方法。

Description

制备乙二醇醚用的催化剂及其制备方法和应用 技术领域
本发明涉及一种制备乙二醇醚用的催化剂及其制备方法和应用。
背景技术
乙二醇醚包含乙二醇单醚，乙二醇二醚，以及多乙二醇单醚和多乙二醇二醚等，其中又以乙二醇单甲醚(MMET)和乙二醇二甲醚(DMET)为典型代表。由于乙二醇醚分子中同时含有羟基和醚基，能够与多种有机化合物混溶，所以其不仅是良好的溶剂，而且是许多有机合成的中间体。近年来，乙二醇醚又开拓了一些新的应用，如用于提取药物、用作液晶取向剂等。由于乙二醇醚，特别是乙二醇二甲醚具有较好的稳定性，且十六烷值较高，也可用作减少炭烟排放的柴油添加剂。因此，对乙二醇醚的合成及应用研究是一个非常有意义的课题。
目前合成乙二醇醚主要有下几种方法：
(1)目前商业化的方法为Williamson相转移法。该方法使用乙二醇或乙二醇单醚为原料，氯甲烷为甲基化试剂，冠醚或季铵盐等为相转移催化剂，得到乙二醇二醚。该方法存在催化剂价格高且不能回收，另外产生氢气和盐以及具有危险性的缺点。
(2)环氧乙烷法。该方法采用环氧乙烷与甲醇在高温高压下反应，可以以一些固体酸性物质为催化剂，也可以不需要催化剂。CN 101190876A公开了一种涉及乙二醇醚的制备方法，该方法以环氧乙烷和低碳脂肪醇为原料，以氧化铌为主要活性组分，以选自钒、钼、钨、锡、铅、镧、镨、钕的元素及其化合物中一种或多种为助剂组成的催化剂，在反应温度100-300℃、反应压力为0.1-3.0MPa，醇烷比为1-5、反应时间0.5-8.0h的条件下制备乙二醇醚，以解决现有技术中存在目的产物乙二醇醚选择性低、醇与环氧乙烷摩尔比(醇烷比)高等问题。但该方法不可避免有大量副产物二氧化碳生成。且该方法的工艺过程较为复杂，能耗大，不太适合工业生产。CN 1005133A报道了以ZSM-5分子筛为母体，用无机酸交换后而制得 的NKC-01固体酸催化剂，由环氧乙烷和低碳醇在间歇釜中制备乙二醇醚。在原料中醇与环氧乙烷的摩尔比为5时，其催化活性很高，环氧乙烷的转化率接近100％，但是，乙二醇醚特别是乙二醇二甲醚的选择性低，当环氧乙烷与醇的摩尔比较低时，反应不能进行。CN1033742C在CN1005133A的基础上，采用水热处理法加强催化剂的酸性后用于环氧乙烷和乙醇的反应。在相同反应条件下，该方法提高了环氧乙烷的转化率，但是没有提高乙二醇醚的选择性，会有大量的乙二醇产生。此外，该方法中使用的环氧乙烷存在易爆炸的危险性。
(3)乙烯法。中国专利CN102952003A公开了一种直接以乙烯、甲醇及过氧化氢为原料，在含有钛硅分子筛的催化剂上制备乙二醇单甲醚的方法。该方法存在需使用双氧水作为氧化剂、需使用有毒的溶剂、双氧水容易分解以及工业化价格高的缺陷。
(4)以乙二醇(EG)与甲醇或者二甲醚为原料。美国专利US2004/0044253报道了一种由乙二醇或乙二醇单醚与低碳醇为原料，采用间歇法，在全氟磺酸树脂催化剂上合成乙二醇醚的方法，乙二醇的转化率最高达到77.2％，总醚的选择性为94.3％。该方法的优点是原料来源广泛，价格便宜，但是该方法的最大问题是所用催化剂全氟磺酸树脂的价格非常贵，在使用过程中受温度的影响催化剂容易变形，而且再生困难，不能工业化。
综上所述，现有的乙二醇醚制备方法中，工业化的方法为Williamson相转移法，但在此法中使用了剧毒的氯甲烷，对操作环境不利。此外，该方法使用了强碱NaOH，对设备腐蚀较大。以环氧乙烷与低碳醇为原料的工艺中，使用的环氧乙烷存在易爆炸的危险性。另外，这种方法中乙二醇醚特别是乙二醇二甲醚的选择性低，副产物二噁烷和乙二醇比较多。在上述的几种制备乙二醇醚的工艺中，以乙二醇和甲醇为原料的方法最为经济和环境友好，但需要提高催化剂的性能。
随着煤制乙二醇工艺的成功工业化，乙二醇作为生产乙二醇醚的原料得到保障。基于现有技术中由低级烷基醇和/或低级烷基醚与乙二醇和/或乙二醇单醚为原料制备乙二醇醚的技术中，需要采用价格昂贵的且难于再生 的全氟磺酸树脂作为催化剂的现状，亟需找到价格比较低、能兼具较好的乙二醇和/乙二醇单醚转化率和乙二醇醚选择性且二噁烷类副产物低的固体催化剂来代替全氟磺酸树脂催化剂以实现乙二醇与低级烷基醇和/或低级烷基醚进行醚化反应生产乙二醇醚的工业化。
发明内容
鉴于上述现有技术状况，本发明的发明人在由低级烷基醇和/或低级烷基醚与乙二醇和/或乙二醇单醚为原料制备乙二醇醚用的催化剂方面进行了广泛而又深入的研究，以期发现一种能够克服现有技术的上述缺点的用于由低级烷基醇和/或低级烷基醚及乙二醇和/或乙二醇单醚制备乙二醇醚的催化剂，且该催化剂价格便宜及具有较高的乙二醇转化率和乙二醇醚的选择性。
本发明的一个目的是提供一种制备乙二醇醚的催化剂，其中以该催化剂的总重量计，该催化剂包含以下组分:
a)30-85重量％的硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；
b)0.01-5重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及
c)15-65重量％的粘结剂，且各组分的总和总是加起来为100重量％。
本发明的另一目的是提供一种制备本发明催化剂的方法，该方法包括以下步骤:
(1)将硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛与粘结剂、成型助剂、水和酸捏合，然后成型、干燥、焙烧，之后破碎和筛分，得到固体颗粒，其中所述酸选自硝酸、磷酸、硫酸、甲酸、乙酸、丙酸、草酸或柠檬酸中的一种或多种；以及
(2)将步骤(1)得到的固体颗粒与水溶性金属盐的水溶液接触，然后干燥、焙烧，得到催化剂，所述金属选自IIA族金属、La、Ga和Cu中的一种或多种，
其中各组分的用量以该催化剂的总重量计，该催化剂包含以下组分:
a)30-85重量％的硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；
b)0.01-5重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及
c)15-65重量％的粘结剂，且各组分的总和总是加起来为100重量％。
本发明的再一目的是还提供一种制备乙二醇醚的方法，该方法包括：在醚化条件下，将物料a和物料b与本发明提供的催化剂接触，其中所述物料a为乙二醇和/或乙二醇单醚，物料b为C1-C6烷基醇和/或二C1-C6烷基醚。
本发明的催化剂尤其适用于由低级烷基醇和/或低级烷基醚及乙二醇和/或乙二醇单醚制备乙二醇醚且价格便宜、具有较高的乙二醇转化率和乙二醇醚的选择性。本发明提供的制备乙二醇醚的方法，具有较高的乙二醇转化率和乙二醇醚的选择性。
附图说明
图1说明反应温度对乙二醇醚合成的影响。
图2说明实施例1制备的催化剂的稳定性。
图3说明实施例1制备的催化剂再生后的稳定性。
图4说明不同硅铝比和金属改性后β分子筛的NH3-TPD图。
具体实施方式
根据本发明的一方面，本发明提供一种制备乙二醇醚的催化剂，其中以该催化剂的总重量计，该催化剂包含以下组分:
a)30-85重量％的硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；
b)0.01-5重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及
c)15-65重量％的粘结剂，且各组分的总和总是加起来为100重量％。
优选地，以该催化剂的总重量计，该催化剂包含以下组分:
a)35-80重量％的硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；
b)0.1-3重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及
c)20-60重量％的粘结剂，且各组分的总和总是加起来为100重量％。
本发明所用沸石分子筛基于本领域技术人员所公知的沸石分子筛，例如沸石分子筛可以为USY、Ferrierite、ZSM-5、ZSM-11、ZSM-23、MCM-22、β和丝光沸石分子筛的一种或多种，优选为ZSM-5、USY、Ferrierite和β分子筛中的一种或多种，进一步优选为β和/或Ferrierite分子筛，尤其优选为β分子筛。
本发明对沸石分子筛的来源没有特别要求，可以通过商购得到，也可以通过现有技术合成沸石分子筛的方式得到，例如可以采用水热法合成得到。
根据本发明，所述沸石分子筛的硅铝摩尔比可以为50-350，但从乙二醇和C1-C6烷基醇和/或二C1-C6烷基醚转化制备乙二醇醚过程中的原料转化率和乙二醇醚选择性考虑，优选沸石分子筛的硅铝摩尔比为75-300。
本发明金属氧化物改进剂中的金属为选自IIA族金属，La、Ga和Cu中的一种或多种。从乙二醇醚的选择性进行考虑，优选所述金属为Mg、La、Ca、Ga和Cu中的一种或多种，进一步优选为Mg、Cu和Ca中的一种或多种，更进一步优选为Mg和/或Ca。
本发明对所用粘结剂的种类没有特别的限定，可以根据实际需要进行选择。例如粘结剂可以为粘土、铝溶胶、拟薄水铝石、硅溶胶等或其混合物。所述粘结剂的含量也没有特别的限定，按照常规的粘结剂用量进行投料即可。
在本发明的一种优选实施方案中，以该催化剂的总重量计，该催化剂包含以下组分:
a)35-80重量％的硅铝摩尔比(SiO2/Al2O3)为75-300的沸石分子筛，其中沸石分子筛的孔径大小为4.5-9埃，所述沸石分子筛选自ZSM-5、USY、Ferrierite和β分子筛中的一种或多种；
b)0.1-3重量％的金属氧化物改进剂，其中所述金属为Mg、Cu和Ca中的一种或多种；以及
c)20-60重量％的粘结剂，且各组分的总和总是加起来为100重量％。如此得到的催化剂在由C1-C6烷基醇和/或二C1-C6烷基醚和乙二醇反应制乙二醇醚时选择性和转化率尤其高。
根据本发明的另一方面，提供了一种制备本发明催化剂的方法，该方法包括如下步骤：
(1)将硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛与粘结剂、成型助剂、水和酸捏合，然后成型、干燥、焙烧，之后破碎和筛分，得到固体颗粒，其中使用的酸包括无机酸(如硝酸、磷酸、硫酸等)或有机酸(如甲酸、乙酸、丙酸、草酸、柠檬酸等)中的一种或多种；以及
(2)将步骤(1)得到的固体颗粒与水溶性金属盐的水溶液接触，然后干燥、焙烧，得到催化剂，所述金属选自IIA族金属、La、Ga和Cu中的一种或多种，
其中各组分的用量以该催化剂的总重量计，该催化剂包含以下组分:
a)30-85重量％的硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；
b)0.01-5重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及
c)15-65重量％的粘结剂，且各组分的总和总是加起来为100重量％。
本发明对步骤(1)中成型助剂的种类没有特别地限定，可以根据实际需要进行选择。例如可以为田箐粉、聚乙烯醇或聚乙二醇中的一种或多种。所述成型助剂的用量也没有特别的限定，按照常规催化剂制备过程中成型助剂进行投料即可。例如，相对于100重量份的所述催化剂，所述成型助剂以干基计的用量可以为1-20重量份，优选为3-15重量份，更优选为5-10重量份。
本发明对步骤(1)中酸的种类没有特别地限定，可以根据实际需要进行选择。例如可以为无机酸(如硝酸、磷酸、硫酸等)，有机酸(如甲酸、乙酸、丙酸、草酸、柠檬酸等)中的一种或多种。所述酸的用量也没有特 别的限定，按照常规催化剂制备过程中酸进行投料即可。例如，相对于100重量份的所述催化剂，所述酸以干基计的用量可以为1-20重量份，优选为1-15重量份，更优选为1-10重量份。
本发明对步骤(1)中水的用量也没有特别的限定，按照常规催化剂制备过程中水的用量进行投料即可。例如，相对于100重量份的所述催化剂，所述水以干基计的用量可以为40-80重量份，优选为50-70重量份。
根据本发明，水溶性金属盐的种类可以在较大的范围内进行选择，例如，所述水溶性金属盐可以为IIA族金属、La、Ga、Cu的水溶性盐或其混合物，具体可以为IIA族金属、La、Ga或Cu的硝酸盐、碳酸盐、盐酸盐或其混合物，优选为Mg、Cu或Ca的硝酸盐、碳酸盐、盐酸盐或其混合物，进一步优选为Mg和/或Ca的硝酸盐、碳酸盐、盐酸盐或其混合物。
本发明对步骤(1)的捏合的条件没有特别要求，一般地，捏合的条件可以包括：捏合的温度为20-50℃，捏合的时间为20-90分钟；优选捏合的温度为20-30℃，捏合的时间为25-45分钟。
本发明方法还包括在步骤(1)的捏合后进行成型、干燥和焙烧的步骤。成型的方法、干燥的方法和焙烧的方法可以采用本领域公知的方法进行。例如，成型的方法可以为挤条成型。干燥可以为常规的干燥方法，例如烘箱烘干，干燥的温度可以为50-250℃，优选为100-200℃；干燥的时间可以为5-96小时，优选为5-20小时。焙烧可以为制备H型沸石分子筛的常规焙烧条件，例如，焙烧的温度可以为500-750℃，优选为500-650℃；焙烧的时间可以为1-10小时，优选为3-8小时。
本发明方法的步骤(2)中将水溶性金属盐与成型后沸石分子筛接触可以采用本领域常用的浸渍法，一般地，接触的条件可以包括:接触的温度为30-90℃，接触的时间为2-15小时；优选接触的温度为50-80℃，接触的时间为2-10小时。
步骤(2)的干燥可以为分子筛的常规干燥条件，具体地，干燥的温度可以为50-250℃，优选为100-200℃；干燥的时间可以为4-20小时，优选为4-16小时。
步骤(2)的焙烧可以为常规的制备沸石分子筛的焙烧条件；例如焙烧的温度可以为500-750℃，优选为500-650℃；焙烧的时间可以为1-10小时，优选为3-8小时。
本发明的制备方法中，沸石分子筛、水溶性金属盐中金属的种类和粘结剂的种类和用量以及优选条件如上所述，在此不再赘述。
根据本发明的再一个方面，提供了一种采用本发明催化剂制备乙二醇醚的方法，该方法包括：在醚化条件下，将物料a和物料b与本发明提供的催化剂或根据本发明的方法制备的催化剂接触，其中所述物料a为乙二醇和/或乙二醇单甲醚，物料b为C1-C6烷基醇和/或二C1-C6烷基醚。
根据本发明，本发明对于物料b与物料a的摩尔比没有特别限制，例如，所述物料b与物料a的摩尔比可以为0.1-20：1，优选为1-10：1，进一步优选为2-6：1。
根据本发明，本发明对于物料a和物料b与催化剂接触的条件没有特别限制，例如所述接触的条件可以包括：接触的温度为100-400℃，接触的压力为0.1-10.0MPa，以物料a和物料b的总流量计的质量空速为0.05-15h-1。从反应转化率与乙二醇醚选择性的角度进行考虑，优选接触的温度180-220℃，接触的压力3.5-7.0MPa，以物料a和物料b的总流量计的质量空速为1.0-10h-1。
根据本发明，本发明对所述C1-C6烷基醇的选择没有特别的限制。具体地，其实例包括但不限于：甲醇、乙醇、正丙醇、异丙醇、正丁醇及其异构体、正戊醇及其异构体、正己醇及其异构体中的一种或多种；优选为甲醇、乙醇、正丙醇、正丁醇、正戊醇和正己醇中的一种或多种；进一步优选为甲醇、乙醇、正丙醇和正丁醇中的一种或多种。
根据本发明，本发明对所述二C1-C6烷基醚的选择没有特别的限制。具体地，其实例包括但不限于为：二甲醚、乙醚、二正丙醚、二异丙醚、二正丁醚及其异构体、二正戊醚及其异构体、二正己醚及其异构体；优选为二甲醚、乙醚、二正丙醚、二正丁醚、二正戊醚和二正己醚中的一种或多种；进一步优选为二甲醚。
根据本发明，乙二醇的来源不仅包括纯的乙二醇商品，也可以为工业 上制备乙二醇装置的初产品。乙二醇单醚的来源不仅包括纯的乙二醇单醚商品，也可以为工业上制备乙二醇单醚装置的初产品。优选物料a为乙二醇。
根据本发明的制备乙二醇醚的方法，本发明对接触进行的反应器的形式没有特别的限定，所述反应器可以为固定床反应器、浆态床反应器，间歇釜反应器、流化床反应器、移动床反应器和独石反应器中的一种或者多种的组合。本发明中，所述独石反应器是指采用泡沫独石整体型催化剂的反应器，优选所述反应器为固定床反应器。
实施例
下面借助实施例和对比例详细描述本发明，但本发明的范围并不限于这些实施例。
以下实施例中，采用气相色谱进行体系中各组分的分析，通过校正归一法进行定量，均可参照现有技术进行，在此基础上计算反应物的转化率、产物的收率和选择性等评价指标。
本发明中，乙二醇(EG)的转化率计算公式如下:
Figure PCTCN2015079691-appb-000001
其中，XEG为乙二醇的转化率，mo 原料EG为乙二醇原料的质量，m产物EG为产物中乙二醇的质量。
各产物的选择性:
Figure PCTCN2015079691-appb-000002
其中Si为组分i的选择性，ni为产物中组分i的质量。
分子筛的孔径大小采用BJH法测量。
以下实施例和对比实施例中，所用的硅溶胶均为SiO2含量为40重量％的硅溶胶；所用铝溶胶均为Al2O3含量为10重量％的铝溶胶。
实施例1
将商购的硅铝摩尔比(SiO2/Al2O3)为300的铵型β分子筛100克在550℃下在空气中焙烧5小时，得到H型β分子筛。
称取70g制得的H型β分子筛，30g粘土，5g田箐粉，60g H2O，加入5g浓硝酸在25℃捏合30分钟，用直径为3.0毫米的模具挤条成型，晾干，置于120℃的烘箱中12小时，然后在马弗炉中在空气氛围下于550℃下焙烧5小时。然后破碎，筛分，得到粒径为1mm的固体颗粒。
称取1.05g Ca(NO3)2·4H2O溶于100ml去离子水中，加入24g上述成型后的1mm固体颗粒，在60℃下浸渍6小时，蒸发掉多余的水分，将蒸发后的固体物置于120℃的烘箱中12小时，然后在马弗炉中于550℃下焙烧5小时，得到CaO改性催化剂。以所得催化剂的重量为基准，包含69.3重量％的β分子筛，1.0重量％的CaO和29.7重量％的粘土。该催化剂的其他性能如表1所示。
实施例2
重复实施例1的实验条件，所不同的是：将H型β分子筛(SiO2/Al2O3摩尔比为300)全部用H型ZSM-5沸石(SiO2/Al2O3摩尔比为100)代替。该催化剂的其他性能如表1所示。
实施例3
重复实施例1的实验条件，所不同的是：将H型β分子筛(SiO2/Al2O3摩尔比为300)全部用USY分子筛(SiO2/Al2O3摩尔比为110)代替。该催化剂的其他性能如表1所示。
实施例4
重复实施例1的实验条件，所不同的是：将H型β分子筛(SiO2/Al2O3摩尔比为300)全部用Ferrierite(SiO2/Al2O3摩尔比100)代替。该催化剂的其他性能如表1所示。
对比例1
重复实施例1的实验条件，所不同的是：不对H型β分子筛(SiO2/Al2O3摩尔比为300)进行CaO改性。
对比例2
称取5.0g购买的全氟磺酸树脂，加入100.00g去离子水，再加入5.0g浓度为35重量％的盐酸，搅拌30分钟，然后静置12小时，过滤，洗净，在120℃下烘干。
实施例5
重复实施例1的实验条件，所不同的是：使用的铵型β分子筛中硅铝摩尔比为150。
实施例6
重复实施例1的实验条件，所不同的是：使用的铵型β分子筛中硅铝摩尔比为75。
实施例7
重复实施例1的实验条件，所不同的是：用1.58g Mg(NO3)2·6H2O代替1.05g Ca(NO3)2·4H2O，得到MgO改性的催化剂。以所得催化剂的总重量计，该催化剂包含69.3重量％的β分子筛，1.0重量％的氧化镁和29.7重量％的粘土。
实施例8
重复实施例1的实验条件，所不同的是：用0.90g Cu(NO3)2·6H2O代替1.05g Ca(NO3)2·4H2O，得到CuO改性的催化剂。以所得催化剂的总重量计，该催化剂包含69.3重量％的β分子筛，1.0重量％的氧化铜和29.7重量％的粘土。
实施例9
重复实施例1的实验条件，所不同的是：将粘土全部用拟薄水铝石代替，得到粘结剂为Al2O3的催化剂。以所得催化剂的总重量计，该催化剂包含69.3重量％的β分子筛，1.0重量％的氧化钙和29.7重量％的Al2O3。
实施例10
重复实施例1的实验条件，所不同的是：将粘土全部用硅溶胶代替，得到硅溶胶为粘结剂源的催化剂。以所得催化剂的总重量计，该催化剂包含69.3重量％的β分子筛，1.0重量％的氧化钙和29.7重量％的SiO2。
实施例11
重复实施例1的实验条件，所不同的是：将粘土全部用铝溶胶(日产化学工业株式会社，AS-200)代替，得到铝溶胶为粘结剂源的催化剂。以所得催化剂的总重量计，该催化剂包含69.3重量％的β分子筛，1.0重量％的氧化钙和29.7重量％的Al2O3。
实施例12
重复实施例1的实验条件，所不同的是：在成型过程中，H型β分子筛的重量为80g，粘土的重量为20g，在浸渍过程中Ca(NO3)2·4H2O的重量为3.15g。以所得催化剂的总重量计，该催化剂包含77.6重量％的β分子筛，3.0重量％的氧化钙和19.4重量％的粘土。
实施例13
重复实施例1的实验条件，所不同的是：在成型过程中，H型β分子筛的重量为50g，粘土的重量为50g，在浸渍过程中Ca(NO3)2·4H2O的重量为0.52g。以所得催化剂的总重量计，该催化剂包含49.75重量％的β分子筛，0.5重量％的氧化钙和49.75重量％的粘土。
实施例14
重复实施例1的实验条件，所不同的是：在成型过程中，H型β分子筛的重量为40g，粘土的重量为60g，在浸渍过程中Ca(NO3)2·4H2O的重量为0.104g。以所得催化剂的总重量计，该催化剂包含39.96重量％的β分子筛，0.1重量％的氧化钙和59.94重量％的粘土。
实施例15
该实施例用来说明采用本发明催化剂由乙二醇与甲醇制备乙二醇醚。
在内径为6毫米的不锈钢管反应器中，填充2.0g实施例1制备的成型催化剂，在5.0MPa下，通入摩尔比为4.0/1.0的甲醇和乙二醇，反应温度为210℃，以物料a和物料b的总流量计的质量空速为1.2h-1，实验结果列于表1中。
实施例16-28
重复实施例15的实验条件，所不同的是：将所用催化剂分别替换为实施例2-14制备的催化剂。实验结果列于表1中。
对比例3-4
重复实施例15的实验条件，所不同的是：将所用催化剂分别替换为对比例1-2制备的催化剂。实验结果列于表1中。
实施例29-32
重复实施例15相同的实验条件，所不同的是：将作为原料的甲醇分别替换为乙醇、正丙醇、正丁醇和二甲醚进料，结果列于表2中。
实施例33
重复实施例15的实验条件，所不同的是：将原料中的甲醇替换为甲醇、乙醇、正丙醇和正丁醇的摩尔比为1/1/1/1的混合物进料，结果列于表2中。
实施例34-37
重复实施例15的实验条件，所不同的是：将原料中的甲醇与乙二醇的摩尔比改变为2/1，3/1，5/1，6/1进料，结果列于表2中。
实施例38-41
重复实施例15的实验条件，所不同的是：将反应温度分别改变为180℃、190℃、200℃和220℃，结果示于图1中。
实施例42-44
重复实施例15的实验条件，所不同的是：将反应压力分别改变为0.1MPa、3.5MPa和7.0MPa。反应结果：乙二醇的转化率分别为67.46％，72.81％和74.83％；单乙二醇醚的选择性分别为10.47％，58.93％和99.46％，二噁烷的选择性分别为77.59％，20.04％和0.05％，多乙二醇醚的选择性分别为31.94％，21.03％和0.49％。
实施例45-47
重复实施例15的实验条件，所不同的是：以物料a和物料b的总流量计的质量空速分别为1.0h-1、4.8h-1和9.6h-1，反应结果；乙二醇的转化率分别为89.76％，46.69％和25.52％；单乙二醇醚的选择性分别为89.81％，99.67％和99.66％，二噁烷的选择性分别为7.38％，0.14％和0.15％，多乙二醇醚的选择性分别为2.81％，0.18％和0.19％。
实施例48
重复实施例15的实验条件，所不同的是：将反应时间延长到2000小时。实验结果示于图2中。
实施例49
在实施例48的制备结束后，停止乙二醇和甲醇进料，用50ml/min的氮气吹扫催化剂床层30分钟，然后再以50ml/min的速度通入空气，以8℃/分钟的速度将温度从210℃升到550℃，然后在550℃下保持8小时，将实 施例36中的催化剂进行再生。再生结束后，催化剂床层温度降到210℃。
将再生后的催化剂采用实施例48相同的实验条件，进行催化剂的稳定性实验，实验结果如图3所示。
表1.各种催化剂合成乙二醇醚的反应结果
Figure PCTCN2015079691-appb-000003
反应条件：反应温度为210℃，反应压力为5.0MPa，物料b与乙二醇的摩尔比为4/1，催化剂重量2.0g，以物料b与乙二醇的总流量计的质量空速为1.2h-1。
表2.物料b的种类和组成对乙二醇醚合成反应的影响
Figure PCTCN2015079691-appb-000004
反应条件：反应温度为210℃，反应压力为5.0MPa，催化剂重量2.0g，以物料b与乙二醇的总流量计的质量空速为1.2h-1。
从表1和表2的结果看，所选几种分子筛和全氟磺酸树脂催化剂都能够将乙二醇与甲醇转化成为乙二醇醚，但是，当用孔径大的USY分子筛或者全氟磺酸树脂作为催化剂的活性中心时，乙二醇的转化率比较高，但产物中有害物质二噁烷和多醇醚选择性高，USY分子筛催化剂失活速率快，可能和其孔径大、大分子副产物比较多，容易在孔道内堵塞有关。全氟磺酸树脂催化剂随时间延长，活性逐渐下降，可能和磺酸的流失有关，另外，当反应结束后，发现全氟磺酸树脂催化剂已经严重变形，说明该催化剂的稳定性还不能达到工业化的水平。当使用含孔径最小的Ferrierite分子筛的催化剂时，具有最高的乙二醇转化率90.71％和100％的乙二醇醚选择性，但是其中乙二醇二甲醚的选择性低，只有24.53％，催化剂经过120小时后，乙二醇的转化率只有43.73％，失活快；同样孔径小的ZSM-5分子筛催化剂的活性高达77.94％，乙二醇醚的选择性达到98％，但是乙二醇二甲醚的选择性只有35.61％，有1.75％的二噁烷产生，同样催化剂失活比较快，240小时后乙二醇的转化率下降到55.74％，说明产物选择性及稳定性和分子筛的孔径较小有关。而以β(SiO2/Al2O3摩尔比300)分子筛为催化剂，虽然乙二醇的转化率和乙二醇醚选择性比Ferrierite分子筛的低，但是在经 过Ca2+改性后，乙二醇醚的选择性最高达到98.67％，乙二醇二甲醚的选择性也最高达到41.44％，二噁烷的选择性达到1.0％以下，而且稳定性最好，说明β分子筛的孔结构对从乙二醇和甲醇合成乙二醇醚的反应有利。
从分子筛的NH3-TPD图看，当硅铝比从75升高到300，β分子筛的酸强度变化不大，酸密度降低，乙二醇的转化率仅从84.51％下降到75.42％，但是产物的选择性明显发生改变，其中副产物二噁烷从20.32％下降到0.73％以下，说明乙二醇的转化率和分子筛的酸性有关，酸密度大，乙二醇容易转化，但是乙二醇分子内脱水生成的二噁烷越多，对目的产物不利，随硅铝比的升高，酸量减少，活性降低，乙二醇的转化率降低，但是酸强度提高，有利于甲醇和乙二醇的反应，因此乙二醇醚选择性高。
同样对β分子筛进行酸性调变，从金属改性后的结果看，以添加碱金属Mg2+、Ca2+的改性较好，乙二醇醚特别是乙二醇二甲醚的选择性得到提高，副产物二噁烷和重组分的选择性得到抑制，催化剂也比较稳定，其中以Ca2+改性的β分子筛催化剂为最佳，新鲜催化剂的稳定性高于2000小时，而且可以多次再生。

Claims (14)

  1. 一种制备乙二醇醚的催化剂，其中以该催化剂的总重量计，该催化剂包含以下组分:
    a)30-85重量％的硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；
    b)0.01-5重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及
    c)15-65重量％的粘结剂，且各组分的总和总是加起来为100重量％。
  2. 根据权利要求1的催化剂，其中以该催化剂的总重量计，该催化剂包含以下组分:
    a)35-80重量％的硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；
    b)0.1-3重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及
    c)20-60重量％的粘结剂，且各组分的总和总是加起来为100重量％。
  3. 根据权利要求1或2的催化剂，其中硅铝摩尔比(SiO2/Al2O3)为75-300。
  4. 根据权利要求1-3中任一项的催化剂，其中沸石分子筛为USY、Ferrierite、ZSM-5、ZSM-11、ZSM-23、MCM-22、β和丝光沸石分子筛中的一种或多种，优选为ZSM-5、USY、Ferrierite和β分子筛中的一种或多种，进一步优选为β和/或Ferrierite分子筛，尤其优选为β分子筛。
  5. 根据权利要求1-4中任一项的催化剂，其中所述金属为Mg、Ga、La、Ca和Cu中的一种或多种，优选为Mg、Cu和Ca中的一种或多种，进一步优选为Mg和/或Ca。
  6. 根据权利要求1-5中任一项的催化剂，其中粘结剂为粘土、铝溶胶、拟薄水铝石和硅溶胶中的一种或多种。
  7. 根据权利要求1-6中任一项的催化剂，其中沸石分子筛的孔径大小 为4.5-9埃。
  8. 一种制备根据权利要求1-7中任一项的催化剂的方法，该方法包括如下步骤：
    (1)将硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛与粘结剂、成型助剂、水和酸捏合，然后成型、干燥、焙烧，之后破碎和筛分，得到固体颗粒，其中所述酸选自硝酸、磷酸、硫酸、甲酸、乙酸、丙酸、草酸或柠檬酸中的一种或多种；以及
    (2)将步骤(1)得到的固体颗粒与水溶性金属盐的水溶液接触，然后干燥、焙烧，得到催化剂，所述金属选自IIA族金属、La、Ga和Cu中的一种或多种，
    其中各组分的用量使得以该催化剂的总重量计，该催化剂包含以下组分：
    a)30-85重量％的硅铝摩尔比(SiO2/Al2O3)为50-350的沸石分子筛，其中沸石分子筛的孔径大小为3-10埃；
    b)0.01-5重量％的金属氧化物改进剂，其中所述金属选自IIA族金属、La、Ga和Cu中的一种或多种；以及
    c)15-65重量％的粘结剂，且各组分的总和总是加起来为100重量％。
  9. 根据权利要求8的方法，其中所述成型助剂选自田箐粉、聚乙烯醇和聚乙二醇中的一种或多种。
  10. 根据权利要求7或8的方法，其中所述水溶性金属盐为所述金属的硝酸盐、碳酸盐、盐酸盐或其混合物。
  11. 一种制备乙二醇醚的方法，包括：在醚化条件下，将物料a和物料b与根据权利要求1-7中任一项的催化剂或根据权利要求8-10中任一项的方法制备的催化剂接触，其中所述物料a为乙二醇和/或乙二醇单甲醚，物料b为C1-C6烷基醇和/或二C1-C6烷基醚。
  12. 根据权利要求11的方法，其中物料a与物料b的摩尔比为0.1-20：1，优选为1-10：1，进一步优选为2-6：1。
  13. 根据权利要求11或12的方法，其中醚化条件包括：接触的温度为100-400℃，接触的压力为0.1-10.0MPa，以物料a和物料b的总流量计的质量空速为0.05-15h-1；优选接触的温度180-220℃，接触的压力 3.5-7.0MPa，以物料a和物料b的总流量计的质量空速为1.0-10h-1。
  14. 根据权利要求11-13中任一项的方法，其中C1-C6烷基醇为甲醇、乙醇、正丙醇、异丙醇、正丁醇及其异构体、正戊醇及其异构体、正己醇及其异构体中的一种或多种，优选为甲醇、乙醇、正丙醇、正丁醇、正戊醇和正己醇中的一种或多种，进一步优选为甲醇、乙醇、正丙醇和正丁醇中的一种或多种；二C1-C6烷基醚为二甲醚、乙醚、二正丙醚、二异丙醚，二正丁醚及其异构体、二正戊醚及其异构体，二正己醚及其异构体；优选为二甲醚、乙醚、二正丙醚、二正丁醚、二正戊醚和二正己醚中的一种或多种；进一步优选为二甲醚。
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